... . .. .. ... . . . .. . . . .... .... . . .. ... ... . .

ORN L- 2 988
UC-25 - Metallurgy aiid Ceramics
TID-4500 (15th e d . )

Contract No. W-7405-eng-26

METALLURGY DIVISION

ANNUAL PROGRESS REPORT

f o r P e r i o d Ending J u l y 1, 1960

J. H. Frye, Jr., D i r e c t o r
W . D . Manly, A s s o c i a t e D i r e c t o r
J. E . Cunningham, A s s i s t a n t D i r e c t o r

DATE ISSUED

This document is

OAK RIDGE NATIONAL LABORATORY

Oak Ridge, Tennessee
o p e r a t e d by
UNION CARBIDE CORPORATION
Y
for t h e
U. S. ATOMIC ENERGY COMMISSION

.- I
 DISCLAIMER

This report was prepared as an account of work sponsored by an

agency of the United States Government. Neither the United States
Government nor any agency Thereof, nor any of their employees,
makes any warranty, express or implied, or assumes any legal
liability or responsibility for the accuracy, completeness, or
usefulness of any information, apparatus, product, or process
disclosed, or represents that its use would not infringe privately
owned rights. Reference herein to any specific commercial product,
process, or service by trade name, trademark, manufacturer, or
otherwise does not necessarily constitute or imply its endorsement,
recommendation, or favoring by the United States Government or any
agency thereof. The views and opinions of authors expressed herein
do not necessarily state or reflect those of the United States
Government or any agency thereof.
 DISCLAIMER

Portions of this document may be illegible in

electronic image products. Images are produced
from the best available original document.
 PART I . FUNDAMENTAL METALLURGY

Crystal Physics

F a c i l i t i e s have been completed f o r s i n g l e - c r y s t a l - g r o w t h s t u d i e s

u s i n g t h e flame-fusion method and t h e hydrothermal a u t o c l a v e technique.
I n v e s t i g a t i o n s a r e i n p r o g r e s s f o r c r y s t a l growth of some oxides by hy-
d r o l y s i s of f u s e d h a l i d e m e l t s . An arc-image system and a c o n s t r i c t e d -
a r c furnace a r e being assembled.
A s a p a r t of an e x p l o r a t o r y i n v e s t i g a t i o n of mineral s y n t h e s i s by
hydrothermal techniques, t h e r a r e mineral k a l s i l i t e h a s been s y n t h e s i z e d
from muscovite mica. S i m i l a r experiments designed t o grow macroscopic
c r y s t a l s of MgO a r e i n p r o g r e s s .
Small c r y s t a l s of MgO and Z r O 2 have been grown by h y d r o l y s i s of MgC12
m e l t s and ZrF4-LiF-NaF m e l t s , and t h i s work i s c o n t i n u i n g .
Crystal boules of N i O and A1203 a r e being grown i n t h e flame-fusion
a p p a r a t u s t o e v a l u a t e i t s performance. Later other c r y s t a l materials w i l l
be t r i e d .

Deformation of C r y s t a l l i n e S o l i d s
3
O f t h e p h y s i c a l p r o p e r t i e s which a r e s i g n i f i c a n t l y a l t e r e d by d e f o r -
mation, t h e one of perhaps g r e a t e s t importance i s t h e change i n i n t e r n a l
L energy ( s t o r e d energy) of t h e m e t a l . This energy i s i n t i m a t e l y a s s o c i a t e d
w i t h t h e changes during deformation and with subsequent recovery and r e -
c r y s t a l l i z a t i o n on h e a t i n g . Work i s under way t o measure t h i s energy during
deformation as t h e d i f f e r e n c e between t h e mechanical energy i n p u t and t h e
heat liberated. This h e a t i s used t o vaporize a f l u i d , and t h e volume of
t h e r e s u l t i n g g a s i s measured, providing a measure of t h e h e a t .
Some d i f f i c u l t i e s have been encountered with t h e p r e s e n t design, b u t
it i s f e l t t h a t those problems n o t a l r e a d y solved can be t a k e n c a r e of
with minor changes. R e s u l t s t o d a t a i n d i c a t e t h a t t h e method h o l d s con-
s i d e r a b l e promise. Immediate p l a n s a r e t o study copper, n i c k e l , aluminum,
zirconium, and b r a s s from 24°C down t o -190°C.

iii

i
1

High-Temperature Reactions

Absorption s p e c t r a have been measured f o r d i l u t e s o l u t i o n s of bismuth

m e t a l i n molten B i C 1 3 over t h e wavelength, c o n c e n t r a t i o n , and temperature
ranges 400 t o 800 mp, 0.001 t o 0 . 7 m o l e / l i t e r , and 237 t o 433”C, respec-
tively. A broad, very i n t e n s e band with maximum a t 560 nyi. w a s observed.
Apparent Beer’s l a w d e v i a t i o n s were l a r g e and q u i t e temperature s e n s i t i v e ,
i n d i c a t i n g a p a r t i t i o n i n g of bismuth metal i n t o a t l e a s t two d i f f e r e n t
species i n solution.
The lowest-energy t r a n s i t i o n ( n 3 IT*)of t h e n i t r a t e i o n w a s found

t o s h i f t i n a simple way over t h e s e r i e s of molten a l k a l i n i t r a t e s from

CsN03 through LiN03. A p o s s i b l e e l e c t r o n i c o r i g i n of t h i s behavior w a s
considered. S p e c t r a l p r o f i l e s of t h e molten a l k a l i n i t r a t e s were meas-
u r e d a t s e v e r a l temperatures, over a wavelength range of -
c a . 250 t o 360
mp, and w i t h c a l i b r a t e d p a t h l e n g t h s down t o 19 p.. The p r o f i l e s c o n s i s t e d
of t h e w e a k band (11) of t h e n --+fix- t r a n s i t i o n , skewed toward h i g h e n e r g i e s ,
and overlapped by an a b s o r p t i o n edge. -
The d a t a , c a . 50 p o i n t s p e r spectrum,
were f i t t e d w i t h a l e a s t - s q u a r e s c r i t e r i o n t o s e v e r a l p r o f i l e models of
which t h e most usef’ul w a s a Gauss f u n c t i o n , symmetrical on a wavelength
s c a l e , p l u s an e x p o n e n t i a l f u n c t i o n . For t h i s p r o f i l e model, a t y p i c a l
s t a n d a r d d e v i a t i o n w a s 0.04 liter-mole-’. cm-I f o r a range of e x t i n c t i o n
c o e f f i c i e n t s from 0.06 t o 25.5 1iters.mole-’.cm-l. The energy E of t h e
maximum of band I1 v a r i e d w i t h t h e r e c i p r o c a l of t h e c a t i o n i c r a d i u s r i n
a n approximately l i n e a r way and a t 360°C ( e x t r a p o l a t e d f o r C s N O 3 ) w a s rep-
r e s e n t e d by t h e r e l a t i o n E ( i n e l e c t r o n v o l t s ) s 0 . 0 3 / r + 3.83. The t e m -
p e r a t u r e dependence (d.E/dT) w a s E. -m4ev/deg and i n c r e a s e d i n magnitude
with increasing c a t i o n i c l / r . The f number changed by only a s m a l l amount
L
from CsN03 t o RbN03 t o KpJO3, a l l a t -
c a . l r 4 ,and t h e n i n c r e a s e d t o e a .
1.7 x f o r NaN03 and t o -
e a , 4.0 x f o r LiNO3. The thermal c o e f f i -
c i e n t (l/f) (df/dT) w a s i n t h e range of t o lo-’ deg-l. The band
width changed by only a very s m a l l amount f o r changes e i t h e r i n c a t i o n o r
i n temperature. The way i n which cohesive f o r c e s i n a melt can s h i f t a
molecule-ion t r a n s i t i o n w a s shown by a p p l i c a t i o n of t h e Franck-Condon and
conservation-of-energy p r i n c i p l e s t o a l o c a l i z e d t r a n s i t i o n i n a c l a s s i c a l
ionic melt. A d d i t i o n a l c o n s i d e r a t i o n s were invoked t o show how Coulomb
f o r c e s can p l a u s i b l y account f o r t h e observed s h i f t .

iv

J
 Microstresses i n Crystals

A m o d i f i c a t i o n of our x-ray d i f f r a c t o m e t e r f o r automatic d i f f u s e s c a t -

t e r i n g measurements h a s been planned and i s now being c a r r i e d o u t . Upon
completion of t h e m o d i f i c a t i o n , our instrument w i l l g a t h e r d a t a by count
r a t e measurements a t predetermined i n t e r v a l s i n 28, r a t h e r t h a n by con-
t i n u o u s scanning. The data output w i l l be i n t h e form of a p r i n t e d paper
tape. A s modified, our d i f f r a c t o m e t e r w i l l a l l o w t h e measurement of d i f f u s e
s c a t t e r i n g c o n s i d e r a b l y more r a p i d l y w i t h no compromise o f p r e c i s i o n .
Expressions f o r t h e v a r i o u s o r d e r s of temperature d i f f u s e s c a t t e r i n g
(TDS) f o r cubic elements a r e developed which show t h a t t h e d i f f u s e peaks
a t t h e Bragg maxima a r e broader f o r t h e h i g h e r o r d e r TDS c o n t r i b u t i o n s ,
and which a l s o show t h a t t h e average value of l t h o r d e r TDS ( i n e l e c t r o n
R
u n i t s p e r atom) i s f2e-2M(2M) / J ! . These r e s u l t s are shown t o be s t r i c t l y
v a l i d only i n t h e case of t h e Debye l a t t i c e model. T h e i r relevance t o t h e
Warren t h e o r y and t h e more r e c e n t Paskin t h e o r y f o r TDS -Cor cubic powders
i s d i s c u s s e d , and i t i s shown t h a t t h e Warren t h e o r y i s more a c c u r a t e .
X-ray d i f f r a c t i o n l i n e broadening measurements of Cu20 f i l m s grown
on copper have been i n t e r p r e t e d i n terms of s t r a i n s induced i n t h e films
a s t h e y grow because of t h e coherence of t h e films w i t h t h e s u b s t r a t e .
It i s expedient t o c o n s i d e r t h e growth of t h e f i l m t o be i n two s t a g e s .
Probable d i f f e r e n c e s i n t h e s t r u c t u r e of t h e f i l m s and t h e i r i n f l u e n c e on
t h e growth r a t e i n t h e two s t a g e s are d e s c r i b e d and d i s c u s s e d .

Reactions a t Metal S u r f a c e s

S t u d i e s o f t h e r o l e of s t r a i n i n t h e oxide f i l m s i n t h e o x i d a t i o n o f
m e t a l s have been continued. The r e s e a r c h c o n s i s t e d of (1) an i n v e s t i g a t i o n
of t h e s t r a i n - i n d u c e d a n i s o t r o p y i n t h i n cuprous oxide f i l m s on copper
s i n g l e c r y s t a l s , and ( 2 ) 'a study of "break-away'' phenomena i n t h e oxide
f i l m s on niobium s i n g l e c r y s t a l s .
Oxide f i l m s on t h e (110) and (311) p l a n e s of copper e x h i b i t e d o p t i c a l
a n i s o t r o p y while t h o s e on t h e (111) and (100) p l a n e s d i d n o t . A marked
v a r i a t i o n i n t h e degree of a n i s o t r o p y as a f u n c t i o n of f i l m t h i c k n e s s w a s
a l s o noted f o r oxide f i l m s on t h e (110) and (311) p l a n e s . A t e n t a t i v e ex-
p l a n a t i o n of t h e s e r e s u l t s based on t h e expected c h a r a c t e r o€ e p i t a x i a l l y
induced s t r a i n s between t h e oxide and metal w a s p r e s e n t e d .

V
 O x i d a t i o n - r a t e measurements and oxide morphology s t u d i e s on s i n g l e -
c r y s t a l specimens of niobium i n d i c a t e d t h a t t h e p r o c e s s of gaseous oxida- BL
t i o n i n t h e temperature range 4OC-425°C w a s p a r t i c u l a r l y dependent upon
t h e c r y s t a l l o g r a p h i c o r i e n t a t i o n of t h e m e t a l . Specimens o r i e n t e d w i t h i n
about 25" of (100) oxidized, a t l e a s t i n t h e i n i t i a l s t a g e s , a t a much
slower o v e r - a l l r a t e t h a n t h a t f o r t h e remaining o r i e n t a t i o n s . These d i f -
f e r e n c e s i n o x i d a t i o n c h a r a c t e r i s t i c s were a t t r i b u t e d i n p a r t t o t h e e f f e c t
of s u b s t r a t e o r i e n t a t i o n on t h e manner i n which t h e t r a n s i t i o n from p r o t e c -
t i v e t o n o n p r o t e c t i v e o x i d a t i o n behavior occurred.

S t r u c t u r e of Metals

An x-ray study of s t a c k i n g f a u l t s produced by deformation a t 4.2"K h a s

shown a f a u l t i n g frequency of t h e same o r d e r i n u l t r a - h i g h - p u r i t y l e a d as
i n copper, s i l v e r , and g o l d . T h i s behavior i s c o n t r a r y t o t h a t p r e d i c t e d
by c u r r e n t theory r e g a r d i n g f a u l t i n g . The a d d i t i o n of s i l v e r t o l e a d had
no e f f e c t on t h e f a u l t i n g behavior, whereas 20 a t . $ indium completely sup-
p r e s se d f a u l t f ormat i on.
The ORNL method f o r p r e f e r r e d - o r i e n t a t i o n d e t e r m i n a t i o n was used t o
show t h e t e x t u r e i n a n Fe-3$ S i sample. The r e s u l t s were compared w i t h
t h o s e o b t a i n e d by t h e conventional p o l e f i g u r e method. The s e v e r a l com-
ponents deduced from t h e a x i s c h a r t s were shown t o e x p l a i n t h e magnetic-
t o r q u e curve o b t a i n e d f o r t h e same m a t e r i a l , whereas t h e components de-
duced from p o l e figures were only i n g e n e r a l agreement w i t h t h e torque
4
data.
High-purity vanadium s i n g l e c r y s t a l s were found t o deform by mechanical
twinning when loaded i n compression a t 77°K. This concludes a study which
showed t h a t t h e group VA body-centered cubic m e t a l s r e a d i l y twin when t h e
i n t e r s t i t i a l i m p u r i t y c o n t e n t i s low and t h e g r a i n s i z e i s l a r g e .

Theory of Alloying

For zirconium a l l o y s , t h e d e r i v a t i v e w i t h r e s p e c t t o s o l u t e concentra-

t i o n of t h e r e l a t i v e f r e e energy of t h e a and l3 phases, t h e %phase density
of s t a t e s , a x i a l r a t i o , and e l e c t r i c a l r e s i s t i v i t y were found t o be l i n e a r l y
p r o p o r t i o n a l t o t h e number of e l e c t r o n s i n t h e s o l u t e s Ag, C d , I n , Sn, and
Sb. A zero p o i n t o r null e f f e c t of t h e s o l u t e occurs f o r t h e r e l a t i v e f r e e

vi
e n e r g i e s a t s o l u t e valence n e a r two, b u t f o r d e n s i t y of s t a t e s and a x i a l
r a t i o s t h i s occurs n e a r zero s o l u t e valence. If one assumes t h a t each of
t h e s e p r o p e r t i e s depends on t h e p o s i t i o n of t h e Fermi l e v e l , t h e r e i s no
c l e a r r e s o l u t i o n of t h e d i f f e r e n t e f f e c t i v e zirconium valences i n d i c a t e d
by t h e s e r e s u l t s . However, because t h e f r e e e n e r g i e s are a more complicated
p r o p e r t y , t h e p r e s e n t p r e f e r e n c e i s f o r n e a r l y z e r o - v a l e n t zirconium.
The r i g i d - b a n d model and t h e assumption t h a t t h e u n f i l l e d d band of
zirconium does n o t e x t e n d i n t o t h e Wigner-Seitz c e l l s of t h e s o l u t e atoms
permit t h e d e r i v a t i o n of a r e l a t i o n between t h e change i n t h e d e n s i t y of
s t a t e s and t h e s o l u t e c o n c e n t r a t i o n . The experimental curve f o r t h e s o l u t e s
Ag, I n , and Sn a g r e e s with t h i s r e l a t i o n and shows t h a t t h e number of s-type
e l e c t r o n s i n zirconium i s small, t h a t t h e band s t r u c t u r e i s probably over-
lapped, and t h a t t h e d e n s i t y of s t a t e s i n c r e a s e s r a p i d l y w i t h i n c r e a s i n g
electron concentration.
Measurements of t h e a x i a l r a t i o s of a-zirconium w i t h a d d i t i o n s of Ag,
Cd, I n , Sn, and Sb show t h a t t h e change i n t h e a x i a l r a t i o i s p r o p o r t i o n a l
to t h e product of t h e s o l u t e c o n c e n t r a t i o n and t h e v a l e n c e . The propor-
t i o n a l i t y t o s o l u t e valence w a s found t o be p r i n c i p a l l y due t o a similar
dependence of t h e e - l a t t i c e c o n s t a n t upon s o l u t e valence, s u g g e s t i n g a
B r i l l o u i n zone i n t e r a c t i o n with t h e e l e c t r o n g a s i n t h e [OOl] d i r e c t i o n
i n (&zirconium.

The e l e c t r i c a l r e s i s t i v i t y change p e r u n i t s o l u t e c o n c e n t r a t i o n a t
4.2'K i s i n c r e a s e d by t h e s o l u t e s Ag, C d , I n , Sn, and Sb i n p r o p o r t i o n
t o t h e i r normal chemical valence. Norbury's r u l e w a s found n o t t o be
valid f o r these alloys. The l a r g e e f f e c t found even w i t h t h e lowest-
valence s o l u t e i s a s s o c i a t e d w i t h t h e f i l l e d d s h e l l i n each o f t h e s e
s o l u t e s and the d i s c o n t i n u i t i e s which would appear i n t h e zirconium
u n f i l l e d d band i n such a l l o y s . The dependence upon valence i s probably
due t o t h e sane mechanism proposed by Mott and J o n e s f o r n i c k e l a l l o y s .
A t h i g h e r temperatures n e g a t i v e d e v i a t i o n s from M a t t h i e s s e n ' s r u l e i n -
c r e a s e w i t h a l l o y composition and temperature. A t l e a s t some of t h i s
d e v i a t i o n appears t o be r e l a t e d t o an i n c r e a s e i n t h e number of over-
lapping e l e c t r o n s .
The i n t e g r a l f r e e energy of formation o f a and f3 s o l i d s o l u t i o n s of
C d - Z r a l l o y s h a s been e s t a b l i s h e d by measurement of t h e cadmium vapor

vii
 n
p r e s s u r e over t h e a l l o y s . Equations a r e g i v e n f o r t h e a/@phase bound-
a r i e s i n terms of t h e measured thermodynamic p r o p e r t i e s , and t h e phase
boundaries of t h e Zr-Cd a l l o y s a r e c a l c u l a t e d numerically.

X-Ray D i f f r a c t i o n

D i f f r a c t i o n examinations of s e v e r a l r a r e - e a r t h phosphides, n i t r i d e s ,
and antimonides have been completed and s t r u c t u r e s determined. A struc-
t u r a l i n v e s t i g a t i o n of a new c l a s s of compound AMn03, where A = Lu, Yb,
Tm, E r , and Y , i s n e a r i n g completion.
. S i n g l e c r y s t a l s of a new compound Sr2Be305 have been obtained, and
t h e s t r u c t u r e of t h i s phase i s being s t u d i e d .
Aging t r a n s f o r m a t i o n s i n quenched U-Nb, Ti-Nb, and T i - T a a l l o y s a r e
being s t u d i e d by x-ray d i f f r a c t i o n t e c h n i q u e s i n an e f f o r t t o understand
the s t r u c t u r e s of i n t e r m e d i a t e phases and t h e n a t u r e of t h e t r a n s f o r m a t i o n s
involving them.
The i n v e s t i g a t i o n of t h e o r d e r - d i s o r d e r t r a n s i t i o n s i n nonstoichio-
m e t r i c Cu-Au a l l o y s h a s been extended by high-temperature d i f f r a c t i o n ex-
periments w i t h Cu-25 a t . ’$ Au and 37.5 a t . ‘$ Au compositions. Intermediate
o r d e r e d s t r u c t u r e s were n o t found a t e i t h e r g o l d content; t h e r e s u l t s a t
37.5 a t . ’$ Au tended t o support t h e commonly assumed phase diagram of t h e
Cu-Au system.

PART 11. L O N G - W G E APPLIED METALLURGY 6

Phy si c a1 Prope r t i e s

A program t o study t h e mechanisms of h e a t t r a n s p o r t i n nonmetallic

m a t e r i a l s of i n t e r e s t f o r r e a c t o r f u e l s , moderators, o r cladding, and
t h e v a r i a t i o n of thermal c o n d u c t i v i t y w i t h such v a r i a b l e s a s composition,
d e f e c t s t r u c t u r e , g r a i n s i z e , and i r r a d i a t i o n h a s been s t a r t e d . A Powell
b a l l a p p a r a t u s and t h e equipment f o r a quenching technique have been de-
signed and a r e being b u i l t . Supporting s t u d i e s t o provide U02 i n varying
known c o n d i t i o n s have been s t a r t e d . These s t u d i e s i n c l u d e a d e t e r m i n a t i o n
o f t h e Debye temperature, phase composition a s a f u n c t i o n of h e a t t r e a t m e n t
and chemical composition, and g r a i n growth.

...
Vlll
%-

s Sintering Studies

An i n v e s t i g a t i o n of t h e f a c t o r s i n f l u e n c i n g t h e s i n t e r i n g of o x i d e s
having t h e CaF2 s t r u c t u r e h a s been i n i t i a t e d . The i n f l u e n c e o f s u r f a c e
p r o p e r t i e s o f t h e oxides, p a r t i c l e s i z e and shape, and s u b s t r u c t u r e a r e
being s t u d i e d . Work h a s been s t a r t e d on e v a l u a t i n g t h e s i n t e r i n g char-
a c t e r i s t i c s of Tho2 prepared by a number of d i f f e r e n t methods. Oxides
showing d i f f e r e n c e s i n s i n t e r i n g behavior w i l l be f u r t h e r s t u d i e d i n o r d e r
t h a t t h e c o n t r o l l i n g f a c t o r s might become c l e a r .

S o l i d Reaction S t u d i e s

A l a b o r a t o r y t o be used i n connection w i t h t h e i n v e s t i g a t i o n of v a r i o u s
s o l i d s t a t e d i f f u s i o n phenomena h a s been designed and s e t up. Cursory ex-
periments have been performed f o r t h e purpose of technique e v a l u a t i o n . A
long-range program h a s been i n i t i a t e d t o study t h e d i f f u s i o n of s o l i d f i s -
s i o n p r o d u c t s i n r e a c t o r f u e l and cladding m a t e r i a l s . The s e l f - d i f f u s i o n
c h a r a c t e r i s t i c s of aluminum w i l l a l s o be determined.
The ORR f u e l - i r r a d i a t i o n program w a s t e r m i n a t e d a f t e r completion of
a gamma-heating experiment. P a r t i c i p a t i o n i n t h e ORNL F a s t Breeder A s s i s t -
ance Program was c a r r i e d t o completion by t h e d e s i g n and f a b r i c a t i o n of
c a p s u l e s f o r i r r a d i a t i o n of UO2-stainless s t e e l specimens.
E v a l u a t i o n of p r e v i o u s experiments on t h e U02-Al r e a c t i o n h a s been
made. Planned experimental work w i l l be d i r e c t e d a t l e a r n i n g t h e r o l e of
gases i n the reaction.

Zirconium Alloys

Zirconium-base a l l o y s a r e of c o n s i d e r a b l e i n t e r e s t t o s e v e r a l r e a c t o r
systems because of t h e i r c o r r o s i o n r e s i s t a n c e and low thermal-neutron-ab-
sorption cross section. A zirconium a l l o y development study o r i g i n a l l y
confined t o a l l o y s o f i n t e r e s t t o t h e Aqueous Homogeneous Reactor h a s been
broadened t o i n c l u d e zirconium-base a l l o y s of i n t e r e s t t o o t h e r r e a c t o r
systems. A continuing study of t h e t r a n s f o r m a t i o n k i n e t i c s and p r o d u c t s
o f t h e Zr-Nb-X a i l o y systems h a s i n d i c a t e d t h a t t h e vacancy c o n c e n t r a t i o n
i n r e t a i n e d B-Zr-15 JTb a l l o y s s t r o n g l y a f f e c t s the n u c l e a t i o n r a t e and
c o n c e n t r a t i o n of t h e m e t a s t a b l e t r a n s i t i o n w phase, an i n c r e a s e d number
of vacancies d e c r e a s i n g t h e i n c u b a t i o n t i m e f o r formation of ,,I phase.

ix

e
 c
h
P r e l i m i n a r y s t u d i e s of a l l o y s of t h e Zr-Mo system, u s i n g c o n t e n t s of
4 and 7 . 5 w t % Mo, have shown t h a t metallography i s of l i t t l e a i d i n f o l -
lowing t h e t r a n s f o r m a t i o n s , t h e p r i n c i p a l changes being only t h e disappear-
ance of a Widmanstztten p l a t e l e t phase on aging t o produce a c l e a r g r a i n
s t r u c t u r e s i m i l a r t o t h a t r e p o r t e d p r e v i o u s l y f o r t h e Z r - N b a l l o y system.
Hardness d a t a f o r t h e @-quench and r e h e a t t r a n s f o r m a t i o n suggest t h a t an
age-hardening r e a c t i o n had s t a r t e d a t 500°C and below.
S i m i l a r s t u d i e s have been s t a r t e d on t h e Zr-Cu a l l o y system, using
1 . 0 and 1 . 6 wt % Cu a l l o y s . Metallography of transformed specimens d i d
n o t show a p p r e c i a b l e d i f f e r e n c e s i n t h e m i c r o s t r u c t u r e s , r e g a r d l e s s of
time, temperature, t r a n s f o r m a t i o n type ( i s o t h e r m a l o r @-quench and r e h e a t ) ,
o r composition. The m i c r o s t r u c t u r e s of t h e @-quenched specimens showed a
f i n e r e c t a n g u l a r block p r e c i p i t a t e e x i s t i n g i n a needle m a t r i x . Hardness -.
F

d a t a f o r t h e i s o t h e r m a l t r a n s f o r m a t i o n s u g g e s t s t h a t an age-hardening r e -
a c t i o n occurs a t 500°C and below, and t h a t , if it occurs a t temperatures
above 500"C, t h e a l l o y s overage i n l e s s t h a n 1 5 min.

A study of t h e f a b r i c a t i o n v a r i a b l e s on t h e p r e f e r r e d o r i e n t a t i o n
and a n i s o t r o p y of mechanical p r o p e r t i e s of Z i r c a l o y - 2 h a s been completed
and r e p o r t e d i n two t o p i c a l r e p o r t s . The p r i n c i p a l conclusions were t h a t
s m a l l v a r i a t i o n s i n t h e e x a c t d e t a i l s of t h e f a b r i c a t i o n procedure can
a-i"fect a p p r e c i a b l y t h e p r e f e r r e d o r i e n t a t i o n and a n i s o t r o p y of mechanical
p r o p e r t i e s produced and t h a t t h e ORNL-HRP f a b r i c a t i o n schedule f o r Z i r -
caloy-2 used f o r s e v e r a l y e a r s produced t h e most i s o t r o p i c m a t e r i a l . A
subsequent study of t h e r e s o l v e d s h e a r s t r e s s f o r s e v e r a l a x i s o r i e n t a t i o n s
f o r some of t h e f a b r i c a t i o n schedules which produced m a t e r i a l having a h i g h
.)-
degree of t e x t u r e h a s e x p l a i n e d t h e h i g h degree of t e n s i l e d u c t i l i t y ob-
served i n specimens whose t e n s i l e axes were along t h e c a x i s of t h e t e x t u r e .
L i t t l e s t r a i n occurred i n t h e d i r e c t i o n of t h e c a x i s when i t w a s a t 90"
t o the tensile axis. I n +.ension along t h e c a x i s , twinning r e a l i g n s s l i p
systems f a v o r a b l y f o r deformation by s l i p . Compressive s t r e s s e s , on t h e
o t h e r hand, produce twinning such t h a t l i t t l e deformation by s l i p can occur,
f o r c i n g most of t h e s t r a i n t o occur by twinning, l e a d i n g t o cleavage and
early fracture.
A program of study of t h e e f f e c t s of a l l o y i n g elements and o x i d i z i n g
environment on t h e o x i d a t i o n r a t e s and mechanisms f o r zirconium-base a l l o y s @a

X
 h a s been s t a r t e d . The i n i t i a l study w i l l be confined t o o x i d a t i o n i n pure
oxygen and i n w a t e r . Oxidation equipment for t h e d e t e r m i n a t i o n of t h e o x i -
d a t i o n r a t e s t o a h i g h degree of p r e c i s i o n d u r i n g t h e t h i n - f i l m s t a g e of
o x i d a t i o n h a s been b u i l t and i s undergoing t e s t s . Duplicate runs f o r
checks of r e p r o d u c i b i l i t y have i n d i c a t e d t h a t t h e equipment can produce
t h e d a t a d e s i r e d b u t t h a t s e v e r a l m o d i f i c a t i o n s must be made.
R e l a t i v e l y l a r g e s i n g l e c r y s t a l s of zirconium-base a l l o y s a r e needed
i n t h e oxidation study. Attempts t o grow t h e d e s i r e d s i n g l e c r y s t a l s a s
l a r g e g r a i n s i n s t r i p specimens are under way, u s i n g a s t e e p thermal g r a -
F
4 d i e n t moving a l o n g a specimen w h i l e t h e specimen i s s t r e s s e d by a c o n s t a n t
load. I n i t i a l r e s u l t s show t h a t g r a i n s as l a r g e as 5 mm i n diameter were
grown f r o m g r a i n s 0.01 mm i n diameter by 150 p a s s e s of t h e thermal g r a d i e n t
I3

-! while t h e specimen w a s s t r e s s e d a t 1600 p s i . The r a t e o f growth o f t h e

l a r g e g r a i n s seems t o be a f u n c t i o n o f t h e passage of t h e thermal g r a d i e n t
zone, and n o t t h e r a t e of passage.

PART 111. REACTOR METALLURGY

Ceramics Laboratory

A method w a s developed f o r p r e p a r i n g h i g h l y s i n t e r a b l e U 0 2 powder of

r e p r o d u c i b l e forming and s i n t e r i n g c h a r a c t e r i s t i c s from U F 6 by t h e ammonium
diuranate process. A r e c y c l e p r o c e s s , i n v o l v i n g p r e c i p i t a t i o n of ammonium
d i u r a n a t e from n i t r a t e s o l u t i o n s , f o r converting U 0 2 f a b r i c a t i o n s c r a p t o
UO2 powder produced powder which i n some c a s e s was i d e n t i c a l in forming and
s i n t e r i n g c h a r a c t e r i s t i c s t o t h a t p r e p a r e d from U F 6 , although O/U r a t i o s
we re abnormally h i g h .
K i n e t i c s t u d i e s on t h e formation of UC and UC2 from U 0 2 and g r a p h i t e
showed t h a t a t 1 2 0 0 ° C i n vacuum t h e r e a c t i o n followed a p a r a b o l i c r a t e l a w
and t h a t a t 1 4 5 0 ° C it w a s e s s e n t i a l l y complete i n 1 h r . The UC2/UC r a t i o
i n c r e a s e d w i t h i n c r e a s i n g temperature. The r e a c t i o n r a t e i n c r e a s e d w i t h
d e c r e a s i n g p a r t i c l e s i z e a t t e m p e r a t u r e s below about 1 3 5 0 ° C b u t was r e l -
a t i v e l y i n s e n s i t i v e t o p a r t i c l e s i z e a t higher temperatures.
Attempts t o p r e p a r e uniform, equiaxed orthorhombic bipyramidal c i y s t a l s
of U 0 3 . H 2 0 from h i g h l y a c i d aqueous m i x t u r e s of s p a r i n g l y s o l u b l e U 0 2 and
U308 by t h e hydrothermal p r o c e s s y i e l d e d impure p r o d u c t s w i t h wiae ranges
o f c r y s t a l s i z e s and shapes.

xi

E
 S t u d i e s on t h e e f f e c t of h e a t i n g r a t e d u r i n g t h e c a l c i n a t i o n i n a i r of
[email protected] on t h e s i n t e r a b i l i t y o f Be0 i n d i c a t e d t h a t i n f e r i o r s i n t e r i n g
c h a r a c t e r i s t i c s were a s s o c i a t e d w i t h r a p i d decomposition t o B C 2 0 4 . H 2 O ,
accompanied by t h e formation of an u n i d e n t i f i e d l i q u i d phase.
The l i t h i u m c o n t e n t o f Be0 w a s reduced from 100 t o 1 0 ppm by use of
t h e s t a n d a r d s i n t e r i n g procedure of h e a t i n g t o 1650°C i n 1 h r .
Phase s t u d i e s i n t h e systems C a O - B O , La203-Be0, SrO-BO, Y * O 3 - B e O ,
and MgO-Be0 showed t h a t compound formation occurred i n a l l b u t t h e M g O - B O
system. I n CaO-BO, a e u t e c t i c r e a c t i o n w a s i n d i c a t e d a t 60 BO-40 CaO
(mole $) and about 1365°C; on quenching l i q u i d o f t h i s composition a meta-
s t a b l e face-centered-cubic phase ( a 0 = 14.06 A ) w a s formed. Compound f o r -
mation a t 90 BO-10 C a O (mole $) occurred s l u g g i s h l y on prolonged h e a t i n g
a t 1000°C. I n La203-B0, a e u t e c t i c r e a c t i o n w a s observed a t 85 La203-15
B O ( w t %) and about 1350'C.
The o x i d a t i o n of UC d u r i n g c o n s t a n t - r a t e h e a t i n g i n a i r w a s observed
t o occur over a p e r i o d of 20 t o 3 G min between 225 and 6OOoC, r a t h e r t h a n
i n s t a n t a n e o u s l y a s was expected. It was found t h a t volume and weight
changes d u r i n g complete o x i d a t i o n of e n c a p s u l a t e d UC were small so t h a t
r e a c t i o n p r o d u c t s could be r e t a i n e d .
Twelve specimens of Cr-Al203 f u e l e d w i t h 0 . 5 g of f u l l y e n r i c h e d UO;!
were p r e p a r e d f o r use i n ORR i r r a d i a t i o n experiments.
Procedures f o r t h e p r e p a r a t i o n of h i g h - d e n s i t y , low-porosity g r a p h i t e
b o d i e s w e r e developed through a comprehensive i n v e s t i g a t i o n of f a b r i c a t i o n
variables. The formation of a U02 c o a t i n g on UC p a r t i c l e s i n f u e l e d graph-
i t e p r e p a r e d by t h e admixture method and f i r e d i n argon w a s a t t r i b u t e d t o
a r e a c t i o n between UC and t h e b i n d e r . i
Bulk d e n s i t i e s of 8 . 5 t o 8 . 7 g/cm3 were e a s i l y o b t a i n e d by v i b r a t o r y
compaction of g r a n u l a r , fused ThO2-3.4 U02 ( w t $) i n s i n g l e s t a i n l e s s s t e e l
tubes. P a r t i c l e - s i z e d i s t r i b u t i o n appeared t o be t h e primary c o n t r o l l i n g
factor. P r e l i m i n a r y s t u d i e s i n d i c a t e d t h a t d e n s i t i e s of a t l e a s t 8 . 5 g/cm3
can be achieved by t h i s method in m u l t i t u b e a s s e m b l i e s .
S u c c e s s f u l s l i p c a s t i n g o f Tho2 w a s shown t o r e q u i r e p a r t i c l e s l e s s
t h a n 2 t o 3 p i n s i z e , w i t h about 50 v o l % below 1 p and a s o l u t i o n of
t e t r a s o d i u m phosphate as b a s i c d e f l o c c u l a n t .

xi i

1
 The a d d i t i o n of 3 t o 5 v o l $, A1203 t o 7302 bodies d r y p r e s s e d and
f i r e d a t 1700°C i n a i r r e s u l t e d i n s l i g h t l y i n c r e a s e d b u l k d e n s i t y , low
p o r o s i t y , and s i g n i f i c a n t enhancement of t h e a b r a s i o n r e s i s t a n c e . These
e f f e c t s were a t t r i b u t e d t o t h e formation d u r i n g s i n t e r i n g of a h a r d c o a t i n g
of an A1203-rich e u t e c t i c mixture on t h e Tho2 p a r t i c l e s .
The performance o f an a p p a r a t u s designed t o measure t h e thermal con-
d u c t i v i t y of r e f r a c t o r y oxides by t h e s t e a d y - s t a t e method w a s e v a l u a t e d by
use of i n g o t i r o n specimens. Data f o r t h i s m a t e r i a l i n t h e temperature
range 600 t o 1000°C were c o n s i s t e n t and agreed w e l l w i t h t h a t of p f e v i o u s
investigators.
More t h a n 1000 r e f e r e n c e s t o r e p o r t s and a r t i c l e s r e l a t i n g t o thermal
p r o p e r t i e s o f r e f r a c t o r y r e a c t o r f u e l m a t e r i a l s have been compiled, and
about h a l f o f t h e r e f e r e n c e s have been a b s t r a c t e d .
A mercury vacuum system f o r t h e a c c u r a t e d e t e r m i n a t i o n o f bulk d e n s i t y
of s m a l l (approximately 2 em3), low-porosity ceramic b o d i e s was designed
and i s being b u i l t .
P r e l i m i n a r y experiments i n d i c a t e d t h a t t h e r e s i n embedding technique
h o l d s promise as a r e l i a b l y a c c u r a t e means f o r determining b u l k d e n s i t i e s
of g r a n u l a t e d m a t e r i a l s .

Corrosion Engineering

A three-phase o u t - o f - p i l e c o r r o s i o n t e s t program i s c o n t i n u i n g i n
P o r d e r t o . e v a l u a t e t h e behavior o f I n c o n e l and I N O R - 8 i n c o n t a c t with f l u -
i
oride s a l t mixtures. Results o f t h e t e s t s completed t o d a t e show Inconel
t o be q u i t e s u s c e p t i b l e t o t h e c o r r o s i v e a t t a c k o f t h e v a r i o u s f u s e d f l u -
o r i d e mixtures, while I N O R - 8 c o n t i n u e s t o show e x c e l l e n t c o r r o s i o n r e s i s t -
ance. I n s e r t s contained i n an I N O R - 8 forced-convection t e s t a t t h e p o i n t
of maximum temperature e x h i b i t e d weight l o s s e s d u r i n g a 15,000-hr p e r i o d
of from 1.7 t o 2 . 1 mg/cm2.
A m a t e r i a l s c o m p a t i b i l i t y program h a s been i n p r o g r e s s t o study e f -
f e c t s of contaminants outgassed from g r a p h i t e on s t r u c t u r a l materials t o
be i n c o r p o r a t e d i n t h e Experimental Gas-Cooled Reactor. Polythermal s t a t i c
p o t t e s t s have been completed w i t h t y p e 304 s t a i n l e s s s t e e l specimens h e a t e d
t o temperatures as h i g h as 1800'F. The n a t u r e of t h e r e a c t i o n films found
on t h e s e specimens w a s s t r o n g l y i n f l u e n c e d by t h e t o t a l m e t a l s u r f a c e area

...
. Xlll

?
I

w i t h i n t h e t e s t chambers. Low-pressure thermal-convection l o o p s have been

o p e r a t e d w i t h impurity l e v e l s continuously maintained i n t h e range of t h e
Experimental Gas-Cooled Reactor s p e c i f i c a t i o n s . S t a i n l e s s s t e e l s demon-
s t r a t e d e x c e l l e n t Compatibility w i t h t h e environments i n t h e l a t t e r t e s t s ,
b u t r e a c t i o n f i l m s formed on low-alloy s t e e l s were r e l a t i v e l y heavy and
as a consequence were s u b j e c t t o s p a l l i n g . E f f e c t s of g a s p r e s s u r e and
v e l o c i t y on c o m p a t i b i l i t y were i n v e s t i g a t e d and were found t o be incon-
sequential. A t e s t a p p a r a t u s i s p r e s e n t l y being assembled t o provide an
e v a l u a t i o n of c a r b u r i z a t i o n o c c u r r i n g i n g r a p h i t e - m e t a l couples under var-
ious contact pressures.

Fuels Evaluation

The r e l e a s e - r a t e parameter f o r Xe133 h a s been measured f o r approxi-

mately 95% dense U02 p e l l e t s from d i f f e r e n t vendors over t h e temperature
range of i n t e r e s t i n t h e Experimental Gas-Cooled Reactor. The experimental
method used c o n s i s t s in a low-temperature in-pile a c t i v a t i o n of t h e f u e l
followed by an o u t - o f - p i l e high-temperature a n n e a l .
R e s u l t s showed t h a t t h e mechanism of r e l e a s e below t h e s i n t e r i n g
temperature c o n s i s t s i n a n i n i t i a l r a p i d ''burst" of Xe followed by a
slower d i f f u s i o n - c o n t r o l l e d r e l e a s e which i n c r e a s e s w i t h temperature.
P r e l i m i n a r y v a l u e s of t h e release r a t e parameter range between 10-l'
and see-' a t 1400°C. P r e l i m i n a r y r e s u l t s a l s o i n d i c a t e t h a t t h e
a c t i v a t i o n energy f o r d i f f u s i o n of Xe133 from UO2 i s i n t h e range 47
t o 100 kcal/mole . Above t h e s i n t e r i n g temperature, r e l e a s e r a t e param-
e t e r s are h i g h e r t h a n would be expected i f d i f f u s i o n c o n t r o l l e d . These

h i g h v a l u e s might be e x p l a i n e d by v a p o r i z a t i o n of U02.
I

Materials C o m p a t i b i l i t y

Thirty-one d i f f e r e n t grades of g r a p h i t e have been t e s t e d f o r t h e i r

p e r m e a b i l i t y by molten f l u o r i d e s i n 100-hr s c r e e n i n g t e s t s a t 1300°F and
150 p s i g . Four grades, B-1, S-4-LB, GT-123-82, and CS-112-S,had l e s s
t h a n 0.5$ of t h e i r b u l k volume permeated by molten f l u o r i d e s i n t h e
screening t e s t . It a p p e a r s t h a t f o r some g r a d e s of g r a p h i t e s i g n i f i c a n t
d e c r e a s e s i n molten f l u o r i d e s a l t permeation can be accomplished by proper
pressure reductions. Moderately low-permeability g r a d e s of g r a p h i t e ( R - 4

I xiv
i
 and S-4) were permeated t o t h e same e x t e n t by molten f l u o r i d e s under 150
p s i g a t 1300°F a f t e r 1 - h r exposures as t h e y were i n 100-hr exposures.
Grade AGOT g r a p h i t e w a s impregnated with molten bismuth and subse-
q u e n t l y s u b j e c t e d t o a s t a n d a r d fuel-permeation t e s t . R e s u l t s showed
t h a t t h e bismuth p r e t r e a t m e n t suppressed t h e f u e l pickup, b u t t h e bismuth
w a s not completely r e t a i n e d i n t h e g r a p h i t e p o r e s d u r i n g t h e f u e l permeation
test.
Two t e s t s have been conducted t o remove t h e oxygen contamination from
graphite. P a s t t e s t s have shown t h a t a p o r t i o n o€ t h e uranium i n LiF-BeF2-
UFr, (62-37-1 mole $, f u e l 130) p r e c i p i t a t e s as U 0 2 when t h i s f u e l i s ex-
posed t o t h e g r a p h i t e a t 1300°F i n a vacuum. A 50-hr exposure of AGOT
grade g r a p h i t e t o hydrogen p r e h e a t e d t o 1300°F f a i l e d t o d e t e c t a b l y de-
c r e a s e t h e oxygen contamination. However, purging t h e g r a p h i t e with
molten f u e l 130 o r t h e r m a l l y decomposing c r y s t a l s of ammonium b i f l u o r i d e
i n s i d e t h e g r a p h i t e c r u c i b l e a p p a r e n t l y w a s s u c c e s s f u l i n removing t h e
oxygen contamination.

I N O R - 8 w a s c a r b u r i z e d t o a depth of 1 4 m i l s while i n d i r e c t c o n t a c t
f o r 3400 h r with grade TSF g r a p h i t e i n NaF-ZrFr,-UFr, (50-46-4 mole $I, f u e l
30) a t 1300°F.
Three nickel-base b r a z i n g a l l o y s , an 82$ Au-l@% N i a l l o y , and pure
copper showed good c o r r o s i o n r e s i s t a n c e t o LiF-BeFz-UFr, (62-37-1 mole $I,

.'I f u e l 130) a t 1300°F during a 10,000-hr thermal-convection-loop t e s t of

brazed I N O R - 8 joints.
It was noted t h a t t h e commercial nickel-base a l l o y s
were corroded when used with Inconel as t h e base m e t a l . R e s u l t s of i n i t i a l
c o r r o s i o n s t u d i e s on experimental Au-Ni-Ta a l l o y s have i n d i c a t e d t h a t t h e y
have good r e s i s t a n c e t o f'uels based on both NaF-ZrFr, and LiF-BeF2. These
a l l o y s a r e being developed t o i n v e s t i g a t e p o s s i b l e g r a p h i t e - t o - g r a p h i t e
and g r a p h i t e - t o - m e t a l j o i n i n g methods.
S t u d i e s conducted t o determine t h e c o m p a t i b i l i t y of type 304 s t a i n -
l e s s s t e e l and b e r y l l i u m i n a N a K environment were conducted a t 1112,
1292, and 1472°F (600, 700, and 800°C). R e s u l t s r e v e a l e d t h a t a t r a n s f e r
of b e r y l l i u m t o t h e s t a i n l e s s s t e e l occurred. The amount of t r a n s f e r de-
pended on t h e s e p a r a t i o n d i s t a n c e between t h e two m a t e r i a l s , t h e g r e a t e r
t r a n s f e r o c c u r r i n g where t h e s e p a r a t i o n was l e a s t .

. xv

4
 A program t o i n v e s t i g a t e t h e c o m p a t i b i l i t y o f b o i l i n g potassium w i t h
s e v e r a l p o t e n t i a l c o n t a i n e r m a t e r i a l s a t 1600°F was i n i t i a t e d . Refluxing
potassium capsule t e s t s on Inconel and t y p e s 310 and 316 s t a i n l e s s s t e e l
have been conducted f o r p e r i o d s of 500 h r . Metallographic and weight-
change d a t a i n d i c a t e no s i g n i f i c a n t c o r r o s i o n i n t h e v a r i o u s zones of
t h e t e s t systems. A b o i l i n g potassium-type 316 s t a i n l e s s s t e e l loop
t e s t w a s o p e r a t e d a t a b o i l e r temperature of 1550°F f o r 200 h r . The
r e s u l t s i n d i c a t e d no a t t a c k on t h e l o o p o r specimens suspended i n t h e
loop. An a d d i t i o n a l t e s t w i t h a b o i l e r temperature of 1600'F h a s op-
e r a t e d f o r 1800 h r and w i l l be o p e r a t e d f o r 1200 more hours. The p o t a s -
sium-vapor flow r a t e i n t h i s l o o p i s approximately 54 0 s .
A program h a s been i n i t i a t e d t o study t h e phenomenon of m a s s t r a n s -
p o r t i n systems i n which t h e c i r c u l a t i n g f l u i d i s a l i q u i d m e t a l . This
program w i l l i n c l u d e t e s t s t o o b t a i n t h e s o l u b i l i t y of c o n t a i n e r m a t e r i a l s
i n an a l k a l i metal and t h e r a t e o f s o l u t i o n o f t h e c o n t a i n e r m a t e r i a l .
Thermal-convection-loop s t u d i e s w i l l follow these preliminary s t u d i e s .
A thermal-convection loop was o p e r a t e d w i t h sleeve-type i n s e r t s p e c i -
mens l i n i n g t h e h o t and c o l d s e c t i o n s of t h e l o o p . A n a l y s i s of r e s u l t s
i n d i c a t e s t h a t t h e use of i n s e r t specimens i s a s a t i s f a c t o r y method of
e v a l u a t i n g m a s s t r a n s f e r q u a n t i t a t i v e l y i n a thermal-convection-loop sys-
tem.
Continued a s s i s t a n c e w a s g i v e n t o t h e Chemical Technology D i v i s i o n
i n connection w i t h c o r r o s i o n , s e l e c t i o n o f m a t e r i a l s o f c o n s t r u c t i o n , t
f a b r i c a t i o n , welding, b r a z i n g , and f a i l u r e a n a l y s i s . Most o f t h i s support
w a s a l l o c a t e d t o t h e ORNL F l u o r i d e V o l a t i l i t y P r o c e s s .

Mechanical P r o p e r t i e s

The e f f o r t s of t h e Mechanical P r o p e r t i e s Laboratory a r e c h a n n e l l e d

along t h r e e g e n e r a l c a t e g o r i e s which c o n s i s t of (1) o b t a i n i n g t h e n e c e s s a r y
data f o r t h e s o l u t i o n of s p e c i f i c r e a c t o r d e s i g n problems, ( 2 ) studying
t h e f a c t o r s which c o n t r o l t h e flow and f r a c t u r e of m a t e r i a l s a t e l e v a t e d
t e m p e r a t u r e s , and ( 3 ) developing new t y p e s of t e s t i n g d e v i c e s t o accomplish
t h e t a s k s r e l e v a n t t o b o t h of t h e s e programs.
A new a p p a r a t u s w a s c o n s t r u c t e d t o p e r m i t t h e s t u d y of t h e g e o m e t r i c a l
r e l a t i o n s h i p of U02 f u e l p e l l e t s and t h e s t a i n l e s s s t e e l c y l i n d e r used t o

xvi
L
encapsulate t h e f u e l . A r a d i o g r a p h i c technique w a s developed and used t o
r e v e a l t h e r e l a t i v e expansion of t h e two materials under temperature g r a -
d i e n t s simulating service conditions.
An extensometer working on t h e p r i n c i p l e of an a i r gage has been de-
veloped; it i s capable of measuring s t r a i n s of l x low6. Since t h e s e n s i n g
d e v i c e would appear t o be i m u n e t o i r r a d i a t i o n e f f e c t s , it may be p a r t i c -
u l a r l y a t t r a c t i v e f o r i n - p i l e c r e e p experiments.
Two a l l o y s r e c e n t l y developed by Haynes S t e l l i t e and t h e I n t e r n a t i o n a l
Nickel Company have been e v a l u a t e d i n t h e c a s t c o n d i t i o n f o r s e r v i c e i n
t h e temperature range from 1500 t o 1700°F. T h e i r c r e e p s t r e n g t h s were su-
p e r i o r t o t h o s e of most of t h e a l l o y s s u i t a b l e f o r a r e a c t o r . Tube-burst
t e s t s and creep-buckling t e s t s on type 304 s t a i n l e s s s t e e l were continued
i n an e f f o r t t o determine t h e behavior of t h i s a l l o y under t h e v a r i e t y of
s e r v i c e c o n d i t i o n s a n t i c i p a t e d f o r t h e Experimental Gas-Cooled Reactor.
Creep p r o p e r t i e s i n t h e t y p e s of g a s e s which may contaminate t h e helium
c o o l a n t were conducted and no pronounced d e l e t e r i o u s e f f e c t s were noted.
I r r a d i a t i o n t e s t s were conducted on u n s t r e s s e d , h e a t e d coupons of
b e r y l l i u m t o a s c e r t a i n t h e magnitude of t h e problem produced by t h e gen-
e r a t i o n of helium i n t h e l a t t i c e of t h e m e t a l as a r e s u l t of n e u t r o n bom-
bardment. Contrary t o p r e d i c t i o n s based on work by o t h e r i n v e s t i g a t o r s
t h e r e s u l t s o f t h e f i r s t experiment r e v e a l e d an unexpected amount of s w e l l -
ing.
Research on t h e flow and f r a c t u r e of metals was continued w i t h r e g a r d
t o dynamic l o a d s , combined s t r e s s e s , and environmental e f f e c t s . Some prog-
r e s s i s r e p o r t e d i n a t t e m p t s t o r e l a t e s t r e s s - s t r a i n parameters t o f r a c -
t u r e under c y c l i c l o a d s . Development of new t e s t equipment p e r m i t t e d t h e
combined s t r e s s work t o be extended i n t o new s t r e s s states. Results tend
t o confirm t h e e a r l i e r hypotheses t h a t t h e maximuni p r i n c i p a l s t r e s s i s t h e
determining f a c t o r i n e l e v a t e d temperature r u p t u r e .
The a n a l y s i s r e l a t i n g c r e e p t o combined s t r e s s s t a t e s w a s a p p l i e d t o
t h e c a s e of a hexagonal metal, Z i r c a l o y - 2 . The r e s u l t s of u n i a x i a l c r e e p
t e s t s f o r specimens of d i f f e r e n t t e x t u r e o r i e n t a t i o n s w e r e i n t e r p r e t e d i n
terms of t h e a n a l y t i c a l model d e r i v e d f o r f a c e - c e n t e r e d - c u b i c metals. The
d a t a i n d i c a t e t h a t t h e e f f e c t of a n i s o t r o p y i s t o reduce t h e s t r a i n f o r
f r a c t u r e i n c e r t a i n combinations of p r i n c i p a l s t r e s s e s and t h a t t h i s e f f e c t
becomes more pronounced a t e l e v a t e d t e m p e r a t u r e s .
xvii
 A

T h e o r i e s developed through mechanical m e t a l l u r g y r e s e a r c h were a p p l i e d

t o t h e problem of p r e d i c t i n g t h e f a i l u r e of f u e l elements of t h e d i s p e r s i o n
type. Good c o r r e l a t i o n w a s found between t h e a n a l y t i c a l model proposed
and a c t u a l o p e r a t i n g experience of one p a r t i c u l a r t y p e of f u e l element.
I n a d d i t i o n it w a s p o s s i b l e t o d e s c r i b e t h e r e l a t i v e e f f e c t s on f u e l e l e -
ment performance of t h e more important f u e l - e l e m e n t parameters.
F u r t h e r evidence w a s o b t a i n e d t o show t h a t r e l a x a t i o n t e s t s a r e u s e f u l
i n e s t i m a t i n g v a l u e s €or m a t e r i a l c o n s t a n t s used i n e m p i r i c a l c r e e p equa-
tions. A graphic s o l u t i o n i s shown t o be a simple and d i r e c t method of
computation, and d a t a a r e p r e s e n t e d f o r t y p e 304 s t a i n l e s s s t e e l and Z i r -
c aloy-2.
I n t h e area of environmental r e s e a r c h , t h e s p e c i f i c e f f e c t s of oxygen,
n i t r o g e n , and hydrogen w e r e explored i n r e l a t i o n t o niobium. Small a d d i -
t i o n s were found t o s t r e n g t h e n t h e metal; however, t h r e s h o l d v a l u e s were
found for each gas which s e v e r e l y e m b r i t t l e d niobium a t room t e m p e r a t u r e .
A t e l e v a t e d t e m p e r a t u r e s c r e e p v a l u e s were enhanced by oxygen and n i t r o g e n ,
b u t hydrogen produced an a c c e l e r a t i o n i n t h e p l a s t i c f l o w r a t e .

Metal Forming and C a s t i n g

Development work d u r i n g t h e p a s t y e a r can be c a t e g o r i z e d i n t o t h r e e

areas of material development: aluminum-base f u e l elements f o r low- and
medium-temperature r e a c t o r a p p l i c a t i o n s , s t a i n l e s s - s t e e l - b a s e components
k'
f o r medium-temperature r e a c t o r s , and b e r y l l i u m t u b i n g ' a n d uranium mono-
c a r b i d e a r c -melted shapes f o r high-temperature systems.
I n t h e low-temperature aluminum-base r e s e a r c h r e a c t o r f i e l d , a s i g -
Y-
n i f i c a n t c o n c l u s i o n tha-t a d i s p e r s i o n o f U,08 i n aluminum i s an a t t r a c t i v e
f u e l material i n a p p l i c a t i o n s l i m i t i n g t h e U235 enrichment t o 2@ vas ar-
r i v e d a t a f t e r demonstrating t h a t t h e c o n v e n t i o n a l p l a t e - t y p e f u e l element
can be f a b r i c a t e d r e l a t i v e l y economically even though 1000 g of uranium
i s r e q u i r e d p e r f u e l element. T h i s c o n c l u s i o n w a s based on d a t a o b t a i n e d
a f t e r f a b r i c a t i n g more t h a n 70 e x p e r i m e n t a l f u e l elements f o r t h e p o o l -
t y p e r e a c t o r a t t h e F u e r t o Rico Nuclear C e n t e r . A d d i t i o n a l s t u d i e s aimed
a t e v a l u a t i n g t h e i r r a d i a t i o n behavior of b o t h U 0 2 and U308 as a d i s p e r s o i d
i n aluminum w i t h and w i t h o u t a boron a d d i t i v e , f o r h i g h s p e c i f i c power ap- n

p l i c a t i o n s i n t h e low- and medium-temperature range, h a s shown t h a t b o t h

xviii
 t h e f i s s i l e compound and t h e boron can be i n c o r p o r a t e d i n aluminum by
powder m e t a l l u r g y p r o c e s s i n g w i t h a c c e p t a b l e homogeneity. The a l l o y t y p e
X8001 i s of i n t e r e s t f o r medium-temperature r e a c t o r s . Current r e s u l t s ,
however, r e v e a l t h a t although conventional t e s t s of roll-bonded X8001 ma-
t e r i a l i n d i c a t e achievement of m e t a l l u r g i c a l bonding, b l i s t e r s develop a t
t h e bonded i n t e r f a c e a t t h e p e r i p h e r y of r o l l - c l a d p l a t e s when t h e s p e c i -
mens a r e s u b j e c t e d t o a u t o c l a v e t e s t s a t 290°C.
Considerable e f f o r t i n t h e aluminum-base medium-temperature r e a c t o r
f i e l d h a s been d i r e c t e d toward development of a 6 0 0 - p l a t e f u e l element f o r
t h e High Flux I s o t o p e Reactor, which i s designed t o o p e r a t e a t a h e a t f l u x
of 1 . 5 x lo6 Btu.hr-1.ft-2, and a neutron flux i n t h e t r a p of 5 x
neutrons.cm-2 - see-’. The r e f e r e n c e f u e l material i s an aluminum-base a l l o y
c o n t a i n i n g 30 w t % U-2.0 wt % Si-0.05 wt % B. P r e l i m i n a r y r e s u l t s i n d i c a t e
t h a t boron and uranium can be d i s t r i b u t e d uniformly i n 30 wt % U-2 w t $ Si-
0.05 w t % B-Al a l l o y , t h a t t h e f u e l material can be r o l l c l a d i n t o com-
p o s i t e p l a t e s , and t h a t t h e p l a t e s can be marformed i n t o an i n v o l u t e shape
and mechanically j o i n e d between two c o n c e n t r i c t u b e s i n t o a f u e l - e l e m e n t
array.
I n t h e development of f u e l , n e u t r o n a b s o r b e r s and burnable poison
materials f o r medium-temperature water-cooled and -moderated r e a c t o r s ,
s t u d i e s on U02 swage c l a d w i t h a u s t e n i t i c s t a i n l e s s s t e e l have shown t h a t
i n t e r n a l c r a c k i n g of t h e s t a i n l e s s s t e e l c l a d d i n g i s a problem when work-
i i n g above 6OOOC and r e d u c t i o n s i n a r e a g r e a t e r t h a n 65%. Postirradiation
r e s u l t s on f u l l - s i z e p l a t e - t y p e U02-stainless s t e e l f u e l elements have r e -
v e a l e d no s i g n i f i c a n t damage i n m a t e r i a l c o n t a i n i n g 26 w t $ U02 a f t e r a
m a x i m u m burnup of 32% a t 260°C i n t h e SM-1 r e a c t o r . P o s t i r r a d i a t i o n exam-
i n a t i o n of f u l l - s i z e 3 w t $ B-Fe n e u t r o n a b s o r b e r s from t h i s r e a c t o r showed
evidence of s i g n i f i c a n t damage t o t h e material a f t e r 18 a t . $I burnup of
t h e B”. However, c a l c u l a t i o n s based on a boron g r a d i e n t d e s i g n i n d i c a t e
t h a t it may be p o s s i b l e t o i n c r e a s e t h e BIO burnup t o 25 a t . $ burnup w i t h
no damage. S t u d i e s on t h e c o m p a t i b i l i t y of boron and boron compounds i n
s t a i n l e s s s t e e l r e v e a l e d r e a c t i o n s between SrB6 and YB6 and t h e a u s t e n i t i c
stainless steel. It w a s a l s o demonstrated t h a t 4 w t $ e l e m e n t a l boron w a s
compatible i n t y p e 200 s t a i n l e s s s t e e l powder m e t a l l u r g y compacts b u t n o t
w i t h type 347 s t a i n l e s s s t e e l . A d d i t i o n a l work on d i s p e r s i o n s of Eu203

xix
i n d i c a t e t h a t c h a r a c t e r i s t i c s of t h e b a s i c oxide may be r e s p o n s i b l e f o r
s w e l l i n g d u r i n g s i n t e r i n g of a u s t e n i t i c s t a i n l e s s s t e e l compacts c o n t a i n i n g
d i s p e r s i o n s of t h i s m a t e r i a l . A d d i t i o n a l work on t h e UOZ-type 430 s t a i n -
l e s s s t e e l i r r a d i a t i o n program w a s l i m i t e d t o f u e l element d e s i g n .
Development i n t h e high-temperature sodium-cooled r e a c t o r f i e l d h a s
demonstrated t h a t f l a t , t h i c k - p l a t e s t a i n l e s s s t e e l f u e l elements, con-
t a i n i n g a d i s p e r s i o n of 33 w t $ s p h e r i c a l U 0 2 can be f a b r i c a t e d and t h a t
uranium a l l o y s c o n t a i n i n g 1 0 t o 17 w t $ Mo can be vacuum i n d u c t i o n melted
and extruded i n t o r o d w i t h no d i f f i c u l t y . Gas-cooled development has i n -
cluded procurement of b e r y l l i u m t u b i n g produced by v a r i o u s f a b r i c a t o r s and
t h e e s t a b l i s h m e n t of a s u b c o n t r a c t w i t h Nuclear Metals, Incorporated, t o
e v a l u a t e v a r i o u s e x t r u s i o n parameters involved i n t h e f a b r i c a t i o n of be-
ryllium tubing. Arc-melted uranium monocarbide shapes have a l s o been p r e -
pared i n support of an i r r a d i a t i o n t e s t i n g program of t h i s h i g h l y regarded
f u e l compound.

Metallography

A requirement has been f u l f i l l e d t h i s y e a r i n t h e development of ad-

d i t i o n a l s p e c i a l equipment t o extend t h e c a p a b i l i t i e s of metallographic
investigation. Micro and macro hot-hardness t e s t e r s have been completed
and t e s t e d f o r use w i t h vacuum and i n e r t atmospheres up t o 900°C, and u l -
t r a s o n i c c h i s e l t e c h n i q u e s have been r e f i n e d . These i n v e s t i g a t i o n a l t o o l s
now t a k e t h e i r p l a c e w i t h e l e c t r o n microscopy and d i l a t o m e t r y .
r
There h a s been a c o n c e n t r a t i o n of e f f o r t i n c o o p e r a t i n g w i t h t h e En-
g i n e e r i n g D i v i s i o n i n developing remote metallographic equipment f o r t h e
High R a d i a t i o n Level Examination Laboratory. A f u l l - s c a l e mockup c e l l now
r
p r o v i d e s a t e s t f a c i l i t y f o r t e s t i n g remote v i b r a t o r y p o l i s h i n g equipment.
The i n c r e a s i n g requirements f o r ceramic materials i n r e a c t o r s have
p l a c e d a demand f o r t h e e x t e n s i o n of metallographic t e c h n i q u e s t o ceramo-
graphic s t u d i e s . For example, a v e r y s a t i s f a c t o r y p o l i s h and e t c h i n g pro-
cedure h a s been developed t o r e v e a l t h e g r a i n s i z e of Tho,.
The main manpower e f f o r t c o n t i n u e s i n t h e metallographic support f o r
t h e v a r i o u s r e a c t o r programs i n t h e Metallurgy D i v i s i o n . During t h e p e r i o d
covered by t h i s r e p o r t , t h e Metallography S e c t i o n processed over 5000 spec-
imens, made over 6000 photographs and photomicrographs, and made approxi-
mately 1800 l a n t e r n s l i d e s .

xx
5

Nondestructive T e s t Development

A new t r a n s i s t o r i z e d , eddy-current i n s t r u m e n t , t h e Metal I d e n t i f i c a -

t i o n Meter, f o r t h e s o r t i n g of m e t a l s and a l l o y s according t o t h e i r e l e c -
t r i c a l c o n d u c t i v i t y and magnetic p e r m e a b i l i t y , has been designed and b u i l t
by t h e I n s t r u m e n t a t i o n and C o n t r o l s D i v i s i o n i n c o n j u n c t i o n w i t h t h e Non-
d e s t r u c t i v e T e s t Development Group. This l i g h t w e i g h t instrument o f f e r s
s e v e r a l advantages over i t s p r e d e c e s s o r .
A new eddy-current instrument has been designed and developed f o r use
with probe-coil techniques. A f e a t u r e of t h i s equipment i s t h e i n s e n s i -
t i v i t y t o t h e probe-to-sample spacing.
A program of i n v e s t i g a t i o n i s c o n t i n u i n g f o r t h e f a b r i c a t i o n of r e -
a l i s t i c , reproducible standards f o r tubing inspection. The most promising
technique t h u s f a r i s e l e c t r i c a l spark-discharge machining which can p r o -
duce o u t s i d e - d i a m e t e r notches w i t h a d e p t h accuracy of 0.0002 i n .
Requirements f o r t h e measurement of f u e l element spacing i n t h e High
Flux I n t e n s i t y Reactor c o r e have l e d t o t h e development of equipment and
t e c h n i q u e s f o r u s i n g t h e eddy-current " l i f t o f f " e f f e c t t o accomplish t h i s .

Much of t h e e f f o r t h a s been d i r e c t e d toward t h e i n s p e c t i o n develop-

ment requirements f o r t h e Experimental Gas-Cooled Reactor f u e l element.
Techniques have been recommended f o r t h e f u e l element components and t h e
c a p s u l e c l o s u r e weld.
S t u d i e s of u l t r a s o n i c behavior i n t h i n s e c t i o n s are b e i n g expanded
t o i n c l u d e q u a n t i t a t i v e measurements o r r e f l e c t i o n , t r a n s m i s s i o n , and Lamb-
wave propagation as a f u n c t i o n of v a r i a t i o n i n metal t h i c k n e s s and t h e u l -
t r a s o n i c frequency and i n c i d e n t a n g l e . Instrumentation i s being c a l i b r a t e d
f o r frequency response, and equipment has been assembled which w i l l permit
complete €reedom of movement € o r t h e t r a n s d u c e r s .
S t u d i e s of exposure requirements f o r helium and a i r atmospheres f o r
low-voltage radiography have demonstrated t h e advantage of t h e helium a t -
mosphere. S p e c i f i c t e c h n i q u e s have been developed f o r t h e radiography of
c e r t a i n b e r y l l i u m and g r a p h i t e shapes.
Nondestructive t e s t i n g t e c h n i q u e s a r e b e i n g developed f o r t h e i n s p e c -
t i o n of b e r y l l i u m t u b i n g . These t e c h n i q u e s are b e i n g a p p l i e d t o t h e e v a l -
u a t i o n of a q u a n t i t y of t u b i n g which has been r e c e i v e d from American,
B r i t i s h , and French s o u r c e s .

xxi
 U l t r a s o n i c t e c h n i q u e s have been used t o measure t h e w a l l t h i c k n e s s of
t h e Zircaloy-2 c o r e v e s s e l f o r t h e Homogeneous Reactor T e s t . Utilization
of s e v e r a l e l e c t r o n i c i n s t r u m e n t s p e r m i t s a d i g i t a l p r e s e n t a t i o n of t h e
thickness. Successive measurements i n d i c a t e a s l i g h t decrease i n t h e av-
erage w a l l t h i c k n e s s .
A p r e l i m i n a r y i n v e s t i g a t i o n w a s made on t h e use of u l t r a s o n i c s f o r
weld i n s p e c t i o n i n t h i c k p l a t e s . C o r r e l a t i o n w a s good between i n s p e c t i o n
r e s u l t s and d e f e c t s l o c a t e d i n s e c t i o n e d areas of t h e weld.
Equipment h a s been modified and t e c h n i q u e s have been developed f o r
t h e a s s a y of U235 c o n t e n t i n Al-U f u e l element c o r e b l a n k s . Good c o r r e -
l a t i o n h a s been o b t a i n e d between instrument measurements and a n a l y t i c a l
chemistry r e s u l t s .
A number of s h o r t - t e r m i n s p e c t i o n and e v a l u a t i o n problems have been
solved d u r i n g t h e p a s t y e a r . These have included niobium t u b i n g , s t a i n l e s s
s t e e l c l a d f u e l r o d s , and t h e measurement of b u r i e d b o l t s .
Physic a1 Metallurgy

C o m p a t i b i l i t y s t u d i e s of type 304 s t a i n l e s s s t e e l w i t h low concen-

t r a t i o n s of CO and CO, i n d i c a t e t h a t c a r b u r i z a t i o n may be governed by t h e
e q u i l i b r i a Fe-Fe3C-CO-C02. Unlike i r o n , o x i d a t i o n appears t o occur i r r e -
s p e c t i v e of t h e CO and CO, c o n c e n t r a t i o n s o r t h e i r r a t i o s . The o x i d e s
which formed i n CO, atmospheres s p a l l e d upon c o o l i n g and may t h e r e f o r e be
a problem when p r e s e n t as p a r t i c l e s i n a h i g h - v e l o c i t y helium stream. Ad-
h e r e n t o x i d e s are formed a t h i g h CO/CO, ratios.
Beryllium r e a c t s w i t h CO, t o form a p r o t e c t i v e f i l m of BeO. The su-
p e r f i c i a l n a t u r e of t h e Be0 remained unchanged d u r i n g r e a c t i o n t i m e s up t o
1000 h r . A n i n c r e a s e i n t h e CO, p r e s s u r e by a f a c t o r of lo6 resulted i n \.-
only a s l i g h t increase i n t h e r e a c t i o n rate.
Thermodynamic c a l c u l a t i o n s of p o s s i b l e r e a c t i o n s of molybdenum w i t h
gases have been made. The d a t a show t h a t from t h e s t a n d p o i n t of o x i d a t i o n ,
t h e metal can be exposed t o w e t hydrogen and t o c e r t a i n CO/CO2 composi-
tions. The f e a s i b i l i t y of exposing t h e metal t o h i g h c o n c e n t r a t i o n s of
CO, depends upon t h e p r o p e r t i e s of MOO,.
The o x i d a t i o n of unalloyed niobium i n oxygen a t p r e s s u r e s between
3 x and 5 x mm Hg and t e m p e r a t u r e s of 850, 1000, and 1200°C p r o -
ceeds p r i n c i p a l l y by s o l u t i o n of oxygen, i n t e r n a l o x i d a t i o n , f i l m forma-
t i o n , and by an oxide-gas r e a c t i o n . C h a r a c t e r i s t i c r a t e c u r v e s f o r each

xxii
A.
 of t h e o x i d a t i o n s t a g e s were observed and c o r r e l a t e d w i t h t h e formation of
IS%-0 s o l i d s o l u t i o n s , NbO, D O 2 , and N b 2 0 5 . The f o u r o x i d a t i o n s t a g e s were
found t o be dependent on temperature, p r e s s u r e , and time. Three d i f f e r e n t
l i n e a r and two p a r a b o l i c r e a c t i o n r a t e s were observed.
The r a t e - c o n t r o l l i n g r e a c t i o n s were governed by t h e a d s o r p t i o n of
oxygen, d i f f u s i o n of t h e r e a c t a n t s through a p r o t e c t i v e Nb02 l a y e r , and
by a r e a c t i o n between Nb02 and oxygen t o form Nb205.
Under t h e proper c o n d i t i o n s of time and temperature, Nb-nominal 1% Z r
a l l o y s w i l l undergo an a g i n g r e a c t i o n which c a u s e s an i n c r e a s e i n t h e t e n -

4 s i l e p r o p e r t i e s and a d e c r e a s e i n t h e d u c t i l i t y of t h e metal. Data w e r e

o b t a i n e d on t h e aging c h a r a c t e r i s t i c s of Nb-Zr a l l o y s r a n g i n g from 0.6 t o
1.25% Z r . O f t h e s e a l l o y s , f i v e showed d e f i n i t e a g i n g and f o u r showed no
-* a g i n g response. A c o r r e l a t i o n w a s found between t h e aging response and t h e

i m p u r i t y l e v e l s of carbon, oxygen, and n i t r o g e n i n t h e a l l o y s . It i s p r o -

posed t h a t t h e aging r e s u l t s from t h e p r e c i p i t a t i o n of n i t r i d e s and/or
c a r b i d e s of zirconium. When s u f f i c i e n t oxygen i s p r e s e n t i n t h e a l l o y t h e
aging r e a c t i o n i s neutralized.

P o s t i r r a d i a t i o n Examination Laboratory

F i n a l d e s i g n work on t h e High R a d i a t i o n Level Examination Laboratory

h a s been completed by t h e a r c h i t e c t - e n g i n e e r , and a c o n t r a c t w a s awarded
f o r c o n s t r u c t i o n of t h e new h o t - c e l l f a c i l i t y d u r i n g t h e next 14-month
period. Much of t h e s p e c i a l i z e d equipment r e q u i r e d t o perform v a r i o u s i n -
c e l l m e t a l l u r g i c a l o p e r a t i o n s h a s p r o g r e s s e d t o an advanced s t a g e of de-
velopment.
D e s p i t e t h e l i m i t a t i o n s of t h e p r e s e n t f a c i l i t i e s f o r handling h i g h l y
r a d i o a c t i v e m a t e r i a l s , continued support w a s given t o t h e i n - r e a c t o r c o r -
r o s i o n e f f o r t of t h e Aqueous Thermal Breeder Program. I n addition, a fail-
u r e a n a l y s i s of a gamma-heating probe w a s performed and support given t o
t h e ORR Core Corrosion and t h e Beryllium E v a l u a t i o n Program.
Exploratory work i n t h e f i e l d of remote r e p l i c a t i o n f o r examination
of s u r f a c e topography of i r r a d i a t e d samples i s encouraging. The t e c h n i c a l
f e a s i b i l i t y of p r e p a r i n g r e l i a b l e r e p l i c a s w i t h a minimum of e f f o r t and
low exposure t o o p e r a t i n g p e r s o n n e l h a s been demonstrated.

xxiii
 M
Powder Metallurgy and F u e l Cycle

Attempts a r e b e i n g made t o develop a f u e l m a t e r i a l c o n s i s t i n g of UO,

o r UC d i s p e r s e d i n a U-Mo, y-uranium matrix. L i m i t e d success i n c o l d
p r e s s i n g UO2 w i t h p r e a l l o y e d U-Mo powders w a s r e a l i z e d , b u t c o n s i d e r a b l e
d i f f i c u l t y w a s experienced i n s i n t e r i n g t h e s e compacts. High d e n s i f i c a t i o n
of U-10 w t % Mo powders w a s o b t a i n e d through swaging; however, t h e bonding
between p a r t i c l e s w a s poor. Work i s c o n t i n u i n g i n o r d e r t o improve f a b -
r i c a t i o n f o r t h e s e materials.
Experiments have been performed t o develop f u e l c o r e s having a de-
s i r e d f u e l c o n c e n t r a t i o n and a c o n s t a n t l o a d i n g of burnable poison. In
o b t a i n i n g c o r e s which c o n t a i n U308, B,C, and aluminum, d i r e c t c o l d p r e s s i n g

of f u e l c o r e s and f i l l e r p i e c e s w a s employed. To improve dimensional and

d e n s i t y c o n t r o l of t h e p r e s s i n g s , t h e d i e t o p i s b e i n g f i t t e d w i t h a gage
f o r p r e c i s i o n spacing o f t h e powder l e v e l p r i o r t o p r e s s i n g .
A s a p a r t of t h e Army Package Power Reactor (APPR) Program, i n v e s t i -
g a t i o n of boronated g l a s s e s as burnable poisons was s t a r t e d . When r o l l e d
i n s t a i n l e s s s t e e l , s e v e r e s t r i n g e r i n g of normal Pyrex g l a s s occurred.
Two programs aimed a t development of advanced f u e l m a t e r i a l s have been
initiated. The f a b r i c a t i o n of uranium monocarbide b o d i e s by l i q u i d - p h a s e
s i n t e r i n g w i t h n i c k e l , vanadium, o r U3Si2 as b i n d e r i s expected t o l e a d
t o improved d e n s i t y and performance c h a r a c t e r i s t i c s . I n a n o t h e r program,
t h e mechanical and i r r a d i a t i o n p r o p e r t i e s of y-uranium ( c o n t a i n i n g 10-15
wt % Mo) and thorium a l l o y s , s t r e n g t h e n e d b y f i n e - p a r t i c l e d i s p e r s i o n , w i l l
be s t u d i e d .

Welding and Brazing

The developmental programs c a r r i e d out i n t h e Welding and Brazing Labo-

r a t o r y a r e p r i m a r i l y p r o ject-connected and, consequently, v a r y q u i t e widely
i n scope. The development of s u i t a b l e j o i n i n g t e c h n i q u e s f o r unique and
unusual m a t e r i a l s of i n t e r e s t i n r e a c t o r technology comprises a major e f f o r t .
Beryllium-joining development h a s been c o n c e n t r a t e d on high-temperature
b r a z i n g , d i f f u s i o n bonding, and f u s i o n welding, and s u c c e s s f u l j o i n t s have
been produced by a l l t h r e e methods. Corrosion-resistant brazing a l l o y s

xxiv

.
 which r e a d i l y flow on g r a p h i t e have been developed, and procedures have
been developed f o r s u c c e s s f u l l y j o i n i n g g r a p h i t e t o s t r u c t u r a l metals f o r
high-temperature s e r v i c e .

By t h e use of s u i t a b l e g a s - s h i e l d i n g procedures, contamination-free

niobium welds can be made without t h e use of controlled-atmosphere chambers.
The aging c h a r a c t e r i s t i c s of -1% Zr a l l o y welds have been determined and
methods developed f o r circumventing t h i s c o n d i t i o n .
The use of a nickel-base a l l o y f i l l e r metal (BP-85) h a s been i n v e s t i -
g a t e d f o r j o i n i n g f e r r i t i c s t e e l s t o a u s t e n i t i c s t a i n l e s s s t e e l s , and suc-
cessf’ul welding procedures have been developed. The impact behavior of
v a r i o u s weld h e a t - a f f e c t e d zone m i c r o s t r u c t u r e s i n ASTM SA-212 p r e s s u r e -
v e s s e l s t e e l i s under study.
The development of s u i t a b l e procedures f o r f a b r i c a t i n g f u e l elements
and o t h e r components of i n t e r e s t i n t h e v a r i o u s r e a c t o r p r o j e c t s i s a l s o
under way. Techniques f o r f a b r i c a t i n g t h e Experimental Gas-Cooled Reactor
f u e l element were developed and u t i l i z e d s u c c e s s f u l l y i n a p i l o t p l a n t con-
s t r u c t i o n of 50 T i t l e I f u e l assembiies. The Arvac p r o c e s s w a s s u c c e s s f u l l y
developed f o r s e a l i n g advanced f u e l c a p s u l e s c o n t a i n i n g helium a t l e s s t h a n
atmospheric p r e s s u r e . S u i t a b l e techniques have been developed for t h e pene-
t r a t i o n of a m u l t i t u d e of t h i n - w a l l e d b u r s t - s l u g d e t e c t i o n t u b e s and small-
diameter thermocouples through t h e EGCR p r e s s u r e s h e l l . The i n e r t - g a s con-
sumable-electrode p r o c e s s h a s been found t o be a f e a s i b l e means f o r remotely
j o i n i n g t h e EGCR experimental through t u b e s t o t h e surrounding s t r u c t u r e .
The development of techniques f o r f a b r i c a t i n g compartmented f l a t - p l a t e f u e l
elements and high-vacuum s o l i d i f i e d - m e t a l s e a l s i s d e s c r i b e d . Successful
. welding procedures have been developed f o r f a b r i c a t i n g p r o t o t y p e HFIR alu-
minum f u e l elements with extremely c l o s e dimensional c o n t r o l . The e l e c t r o n -
beam welding p r o c e s s w a s s u c c e s s f u l l y used f o r c o n s t r u c t i n g HFIR dynamic-
c o r r o s i o n t e s t specimens w i t h i n very t i g h t t o l e r a n c e l i m i t a t i o n s .

xxv
 CONTENTS

SUMMARY .............................................................. iii

PART I . FUNDAMENTAL METALLURGY

1. CRYSTAL PHYSICS ................................................. 3

C r y s t a l Growth by t h e Hydrothermal Method ..................... 3
C r y s t a l Growth from Fused S a l t Melts .......................... 4
C r y s t a l Growth by t h e Flame-Fusion ( V e r n e u i l ) Method .......... S
Constricted-Arc Method f o r C r y s t a l Growth ..................... 5
2. DEFORMATION OF CRYSTALLINE SOLIDS ............. .................. 6
Calorimetry of Deformation of Metals .......................... 6

3. HIGd-TEMPERA_TURF: REACTIONS ...................................... 9

V i s i b l e Absorption S p e c t r a of Molten Bismuth-Bismuth
Trichloride Solutions ....................................... 9
E f f e c t of A l k a l i C a t i o n s on t h e Lowest Energy E l e c t r o n i c
T r a n s i t i o n of t h e N i t r a t e I o n i n Molten A l k a l i N i t r a t e s . . ... 17

4. MICROSTRESSES I N CRYSTALS ........................................ 45

D i f f r a c t o m e t e r Modification f o r Automatic D i f f u s e
.....................................
S c a t t e r i n g Measurements 45
Temperature D i f f u s e S c a t t e r i n g f o r Cubic Powder P a t t e r n s ...... 47
.......
X-Ray D i f f r a c t i o n S t u d i e s of Cu20 Films Grown on Copper s4

5. RF,ACTIONS AT METAL SWACES ..................................... 61

Oxidation S t u d i e s on Copper ................................... 61
" Break-Away" Phenomena i n t h e Oxidation of Niobium S i n g l e
....................................................
Crystals 68

6. STRUCTURE: OF METALS ............................................. 85

Deformation S t a c k i n g F a u l t s i n Face-Centered Cubic Metals.. ... 85
On a Complex R e c r y s t a l l i z a t i o n Texture i n Fe-3$ S i ............ 89
Twinning i n Vanadi urn.........................,................. 96

7. THEORY OF ALLOYING .............................................. 97

The M e t a l l i c Valence of Z i r c o n i............................... 97
S p e c i f i c Heats a t Low Temperatures of Zirconium A l l o y s . . ...... 102
The L a t t i c e Spacings and Axial R a t i o s of Alpha-Zirconium
Alloys ...................................................... 107
The Z r - G a Phase Diagram i n t h e V i c i n i t y of t h e A l l o t r o p i c
T r a n s i t i o n of Z i r c o n i....................................... 110
E l e c t r i c a l R e s i s t i v i t i e s of Zirconium and Zirconium
Alloys ...................................................... 11s
...........................
Vapor P r e s s u r e s i n t h e Zr-Cd System 122

xxvi i
 8 . X-RAY DIFFRACTION............................................... 135
Routine Analyses .............................................. 135
Ceramic Research .............................................. 137
Aging Transformation of Metastable Alloys ..................... 140
Ordering of Copper-Gold Alloys ................................ 141

PART I1 . LONG-RANGE APPLIED METALLURGY

9. PHYSICAL PROPERTIES ............................................. 149

10. SINTERING STUDIES ............................................... 153

11 . SOLID REACTION STUDIES .......................................... 155

D i f f u s i o n S t u d i e s ............................................. 155
F u e l I r r a d i a t i o n Programs ..................................... 157
Uranium Dioxide-Aluminum Reaction ............................. 160

12 . ZIRCONIUM ALLOYS ................................................ 167

Zirconium Alloy Development ................................... 167
Oxidation o f Zirconium-Base Alloys ............................ 180
Production of S i n g l e C r y s t a l s o f Zirconium-Base Alloys ........ 181

PART I11 . REACTOR METALLURGY

13 . CERAMICS LABORATORY ............................................. 185

Uranium Dioxide Technology S t u d i e s ............................ 185
Beryllium Oxide Technology S t u d i e s ............................ 188
Advanced F u e l Element Development ............................. 191
Thorium Dioxide Technology S t u d i e s ............................ 194
P h y s i c a l P r o p e r t y S t u d i e s ..................................... 195

14 . CORROSION ENGINEERING ........................................... 197

Molten-Salt Reactor Program ................................... 197
GCR M a t e r i a l s C o m p a t i b i l i t y T e s t s ............................. 209
i

15 . ................................................
FUELS EVALUATION 213
The Release of F i s s i o n P r o d u c t s from UO ...................... 213

16 . MATERIALS COMPATIBILITY ......................................... 221

C o m p a t i b i l i t y o f Graphite, Fused S a l t s , and S t r u c t u r a l
Materials ................................................... 221
Corrosion S t u d i e s of Brazing Alloys ........................... 230
.......
C o m p a t i b i l i t y o f a Beryllium-NaK-Stainless S t e e l System 231
.......................
B o i l i n g Potassium C o m p a t i b i l i t y S t u d i e s 235
.........................
Mass T r a n s f e r i n Liquid Metal Systems 239
Corrosion of Process Container M a t e r i a l s Used i n
Reprocessing Spent Reactor F u e l s ............................ 241
.
xxviii
 17 . MECHANICAL PROPERTIES ........................................... 244
Dimensional Behavior of Encapsulated UO ...................... 244
I n - P i l e Extensometer .......................................... 246
An E v a l u a t i o n of I N C O 713C and Haynes 8294 a t 1500
t o 1700°F ................................................... 247
..............................................
Graphite T e s t i n g 251
................
Mechanical T e s t i n g o f Type 304 S t a i n l e s s S t e e l 254
F r a c t u r e of Metals Under Dynamic Loads ........................ 258
Zircaloy-2 .................................................... 262
...............
P r e d i c t i o n of Creep Rates from R e l a x a t i o n Tests 267
........................................
Complex S t r e s s S t u d i e s 269
.................................
Beryllium I r r a d i a t i o n E f f e c t s 271
A n a l y t i c a l Work on t h e F a i l u r e of U 0 2 - S t a i n l e s s S t e e l
4
Dispersion Fuels ............................................ 273
E f f e c t of Oxygen, Nitrogen, and Hydrogen on t h e Mechanical
.......................................
P r o p e r t i e s of Niobium 279
E f f e c t o f Environment on t h e Creep P r o p e r t i e s of Type 304
....................
S t a i n l e s s S t e e l a t E l e v a t e d Temperatures 280

1 8 . METAL FORMING AND CASTING ....................................... 283

Development o f Aluminum-Base F u e l Elements .................... 283
Development of S t a i n l e s s - S t e e l - B a s e F u e l Elements ............. 297
Burnable Poisons and Control-Rod M a t e r i a l Development ......... 312
Advanced F u e l Element Materials Development ................... 325
Beryllium F a b r i c a t i o n ......................................... 330

341
341

348
361
. 371
374

377
Metallographic Support f o r t h e Homogeneous Reactor
v
1 ...............................................
P r o j e c t (HRP) 3 85
Metallographic Support f o r t h e High Flux I s o t o p e
..............................................
Reactor ( H F I R ) 391
Metallographic Support f o r t h e E n r i c o Fermi Reactor (FERMI)
and Molten S a l t Reactor (MSR) Program; ...................... 396
Metallographic Support f o r t h e A i r c r a f t Nuclear P r o p u l s i o n
(ANP) Program ............................................... 403

20 . NONDESTRUCTIVE TEST DEVELOPMENT ................................. 406

Eddy-Current Development ...................................... 406
H i gh Flux I s o t ope R e ac t o r C o o l m t -Channel - Spac i n g
Measurement ................................................ 409
Experimental Gas-Cooled Reactor F u e l Assembly I n s p e c t i o n
Development ................................................. 411

xxix

L
 ....................
U l t r a s o n i c Behavior i n Thin Metal S e c t i o n s 412
Low-Voltage Radiography ....................................... 413
f

........
Beryllium I n s p e c t i o n Development and Tubing E v a l u a t i o n 415
Measurement of Homogeneous Reactor T e s t Core V e s s e l Wall
Thickness ................................................... 416
...............
P r e s s u r e Vessel Weldment I n s p e c t i o n Development 417
Gamma-Scintillation Spectrometry .............................. 418
...................
I n s p e c t i o n Problems and Material E v a l u a t i o n 419
2 1 . PHYSICAL METALLURGY ............................................. 421
The Reactions of Type 304 S t a i n l e s s S t e e l w i t h CO and CO ..... 421
Beryllium Oxidation S t u d i e s ................................... 424
Molybdenum .................................................... 426
Oxidation o f Niobium a t Low Oxygen P r e s s u r e s .................. 428
Niobium-Zirconium Aging S t u d i e s ............................... 431

22 . POSTIRRADIATION EXAMINATION LABORATORY .......................... 436

High R a d i a t i o n Level Examination Laboratory ................... 436
Homogeneous Reactor Program Support ........................... 437
Other Support A c t i v i t i e s ...................................... 43%
Adaptation of R e p l i c a t i o n Techniques f o r Hot-Cell
Application ................................................. 439

23 . POWDER METALLURGY AND FUEL CYCLE ................................ 443

F u e l s w i t h F e r t i l e U-Mo Matrix Containing U02 o r UC
Dispersoid ................................................... 443
Development of., Aluminum-Matrix F u e l Cores ..................... 450
Boronated Glass P a r t i c l e s i n S t a i n l e s s S t e e l as Burnable
Poison ...................................................... 451
Advanced F u e l Materials ....................................... 452

24 . WELDING AND BRAZING ............................................. 453

M a t e r i a l s - J o i n i n g Development ................................. 453
Gas-Cooled Reactor Component Development ...................... 460
Component F a b r i c a t i o n Development f o r Other Reactor
A p p l i c a t i o n s ................................................ 463 ..

PUBLICATIONS ......................................................... 4’70

PAPERS PRESENTED AT SCIENTIFIC AID TECHNICAL MEETINGS ................ 4’72
ORGANIZATION CHART ................................................... 475

xxx

.............. ... .- .. ............... ..... ........

 Part I

FUNDAMENTAL METALLURGY
 1. CRYSTAL PH!iSICS-

G . W . Clark

The a i m s of t h i s program a r e t o e x p l o r e methods f o r growing nonme-

t a l l i c c r y s t a l s , t o s t u d y t h e d e f e c t s t r u c t u r e s of t h e grown c r y s t a l s , and
t o i n v e s t i g a t e t h e electromagnetic b e h a v i o r o f c e r t a i n of t h e s e c r y s t a l s .
F a c i l i t i e s f o r growth s t u d i e s i n c l u d e flame-f-ision and c o n s t r i c t e d - a r c
f u r n a c e s , hydrothermal a u t o c l a v e s , and a system i n which oxide c r y s t a l s
have been grown from f u s e d h a l i d e s a l t m e l t s . Components o f a n arc-image
system have been n e a r l y assembled.
F u t u r e work w i l l involve a c o n t i n u a t i o n of c r y s t a l growth s t u d i e s by
t h e methods o u t l i n e d . I n a d d i t i o n , t h e i n v e s t i g a t i o n of two a d d i t i o n a l
t e c h n i q u e s i s planned: growth from t h e melt [Czochralski method), and
t h e i n c o r p o r a t i o n of an e l e c t r o n i c t o r c h similar t o t h a t d e s c r i b e d by
Cobine2 i n t o a crystal-growing f u r n a c e . A double-crystal diffractometer
w i l l b e used t o measure t h e x - r a y - l i n e widths f o r c r y s t a l s grown by t h e
v a r i o u s methods i n o r d e r t o provide a c r i t e r i o n f o r t h e q u a l i t y of t h e
crystals.

CRYSTAL GROWTH BY THE HYDROTHERMAL mTHOD

G . 14. Clark 0. c. K O ~ P ~

The hydrothermal method has been used i n a t t e m p t s t o grow q u a r t z

(SiOZ), MgO, and s e v e r a l o t h e r m a t e r i a l s . Q u a r t z s i n g l e c r y s t a l s of i n -
termediate quality, as judged by t h e presence o f l i n e a g e and occluded
growth l i q u o r , w i t h dimensions up t o 1 X 1 X 2 ern have been grown. Simi-
l a r experiments designed t o produce MgO are i n p r o g r e s s although t h u s f a r
t h e y have been u n s u c c e s s f u l .
The use of r e t r o g r a d e s o l u b i l i t y e f f e c t s t o s y n t h e s i z e q u a r t z whisk-
e r s and t h e m i n e r a l s acmite and o s a n n i t e h a s been superseded by a more
g e n e r a l e x p l o r a t o r y program. One r e s u l t of t h i s program w a s t h e conver-
s i o n of muscovite mica t o a n i r o n - r i c h mica and t h e r a r e m i n e r a l k a l s i -
lite. This w a s achieved d u r i n g a t t e m p t s t o grow muscovite s i n g l e c r y s t a l s

-
'J. Czochralski, Z . physik. Chem. -
72, 219 (1717).
2J. D. Cobine and D . A. Wilbur, J. Appl. Phys.
--- 22, 835-41 (1751).
3Consultant from U n i v e r s i t y of Tennessee.

3
1

using muscovite cleavage plates as seeds and shredded muscovite as nutri-

ent.

Several improvements in experimental technique are under considera-

tion. The initial experiments were conducted in a Walker-type': welded
closure. Various modifications to this basic design are under test, and
these efforts should lead to the development of autoclaves in which in-
ternal pressure and temperature may be measured conveniently. The use of
new mineral solvents such as KOH and Na3ALF6 is also being explored.

CRYSTAL GROWTH FROM FUSED SAW MELTS

C. B. Finch G. W. Clark

Many fused salts are excellent solvents for a variety of materials,

and attempts were made to obtain MgO crystals by a simple solution-pre-
cipitation process from fused salt melts. This technique proved to be
unsuccessful because of the difficulty encountered in finding a suitable
solvent for MgO. The maximum concentration of Mg
++ in NU-LiF melts held
in contact with MgO for several days at 750°C was only approx 5000 ppm.
Several other fluoride melts were also investigated, and only in cryolite
(Na3AD6) was a slight increase in M g
++ solubility observed. The tech-
nique has been abandoned until a better solvent is found.

A more promising method involves the hydrolysis of halide melts. Im-

perfect crystals of MgO up to 0.5 cm on an edge were obtained by hydro-
lyzing a previously dehydrated MgClz melt at 800°C in a quartz container.
This method shows promise as a means of producing medium-sized MgO crys-
tals at temperatures less than 1000°C.

Crystals of Zr02 slightly less than 1 m m in diameter were grown also

by this general method through the hydrolysis of ZrF4-LiF-NaF melts. Pres-
ent investigations are designed to determine the optimum conditions of
temperature, melt composition, and hydrolysis rates for the production
of high-quality crystals.

':A. C . Walker, Ind. Eng . Chem, -

46, 167G76 (1954).
-
4
4
,*
 CRYSTAL GROWTH BY THE FW-FUSION (VERNEUIL) METHOD

T . L. Boswell G. W . Clark

The flame-fusion method of c r y s t a l growth5 i n v o l v e s t h e use of an

oxyhydrogen flame which extends down i n t o a t h e r m a l l y i n s u l a t e d r e g i o n .
The s t a r t i n g m a t e r i a l f o r t h e c r y s t a l i s i n t h e form of a powder which
i s s i f t e d down through t h e flame and i s c o l l e c t e d on t h e molten cap of
t h e boule. The h e i g h t of t h e cap i s a d j u s t e d so t h a t a shallow l a y e r
of molten m a t e r i a l i s maintained on t h e s u r f a c e of t h e growing b o u l e .

A flame-fusion f u r n a c e h a s been c o n s t r u e z e d and p l a c e d i n o p e r a t i o n .

Crystals of N i O and A1203 have been grown by :;his method i n o r d e r t o evalu-
a t e t h e performance of t h e a p p a r a t u s . Growth of c r y s t a l s of o t h e r oxides
w i l l be considered i n t h e f u t u r e .

CONSTRICTED-ARC METHOD FOR CRYSTAL GROWTH

C . B . Finch G . W . Clark

The c o n s t r i c t e d - a r c method f o r c r y s t a l growth o f f e r s t h e advantages

of v e r y h i g h temperatures (approx 10,OOO°K) and, a t l e a s t i n p r i n c i p l e ,
a c o n t r o l l e d atmosphere around t h e growing c r y s t a l . I n i t s s i m p l e s t form
t h e c o n s t r i c t e d - a r c t o r c h , o r "plasma j e t , " ccrnsists of a r o d e l e c t r o d e
mounted on t h e axis of an a n n u l a r e l e c t r o d e . A direct-current arc i s
s t r u c k between t h e two e l e c t r o d e s , and a gas i s caused t o flow through
t h e a n n u l a r space, emerging as a n e x c i t e d gas plasma w i t h temperatures
of t h e o r d e r of 10,OOO°K. Hydrogen, n i t r o g e n , t h e r a r e g a s e s , . a n d o t h e r
gases may be used i n t h i s scheme. Such a c o n s t r i c t e d - a r c f u r n a c e i s i n
t h e p r o c e s s of c o n s t r u c t i o n .

~~

5A. Verneuil, Compt. rend. 135 791-94 (1902)

-'

5
 A
2. DEFOFWATION OF CRYSTALLINE SOLIDS

R . 0 . Williams

CALQRIMETRY OF DEFORMATION OF METALS

When m e t a l s a r e deformed, p a r t of t h e mechanical energy i s converted

i n t o h e a t ; t h e r e s t remains s t o r e d w i t h i n t h e m e t a l . This s t o r e d energy
can b e subsequently r e l e a s e d by a n n e a l i n g a t e l e v a t e d temperatures; t h e
f i r s t energy r e l e a s e d i s a s s o c i a t e d w i t h recovery, and t h e remaining en-
ergy i s r e l e a s e d d u r i n g r e c r y s t a l l i z a t i o n . A knowledge of t h i s energy i s
fundamental i n understanding t h e n a t u r e of deformed metals. Until the
p r e s e n t t i m e t h e b e s t i n f o r m a t i o n on t h i s energy has been o b t a i n e d from
measurements of i t s r e l e a s e u s i n g i s o t h e r m a l , anisothermal, o r r e a c t i o n
methods. Such methods s u f f e r , however, from complexity and l i m i t e d accu-
racy, s o t h a t t h e i r use f o r t h e d e t e r m i n a t i o n of t h e s t o r e d energy a t l o w
s t r a i n s would be a v e r y d i f f i c u l t t a s k . The p r e s e n t i n v e s t i g a t i o n i s an
a t t e m p t t o measure t h i s energy d i r e c t l y as t h e d i f f e r e n c e between t h e me-
c h a n i c a l energy and t h e t h e r m a l energy r e l e a s e d by t h e samples d u r i n g t h e
deformation. Such an approach i s a p p r e c i a b l y more a t t r a c t i v e a t low s t r a i n s
s i n c e it i s a l r e a d y known t h a t t h e f r a c t i o n of t h e energy s t o r e d i s h i g h e r
w i t h lower s t r a i n s .
The manner i n which t h e s e measurements a r e t o be c a r r i e d out i s shown
i n F i g . 2.1. The e n t i r e assembly i s designed t o f i t i n t o an I n s t r o n t e n -
-
s i l e machine, which deforms t h e sample a t a uniform r a t e of e l o n g a t i o n and f

r e c o r d s b o t h t h e e l o n g a t i o n and t h e f o r c e , s o t h a t t h e mechanical i n p u t
can be c a l c u l a t e d a t any g i v e n s t r a i n . The h e a t which i s r e l e a s e d w i t h i n
t h e sample i s u t i l i z e d i n v a p o r i z i n g t h e l i q u i d immediately around t h e
I
sample and i s t h u s measured by t h e volume of gas formed. A calculation
r e q u i r e s knowledge of t h e h e a t of v a p o r i z a t i o n of t h e l i q u i d a t i t s b o i l -
i n g p o i n t and t h e d e n s i t y of t h e g a s a t room temperature.
This method i s i n p r i n c i p l e t h e same as w i t h t h e Bunsen i c e c a l o r i m e t e r
except t h a t one i s u s i n g v a p o r i z a t i o n r a t h e r t h a n m e l t i n g . The p o t e n t i a l
advantages of t h e p r e s e n t method a r e t h a t one does n o t depend upon t h e
volume of t h e chamber remaining c o n s t a n t and one presumably has a s e n s i -
t i v i t y down t o perhaps 0 . 1 c a l .

6
 UNCLASSIFIED
ORNL-LR-DWG 5 0 2 2 8

h
TO GAS

.
DEWAR F L A S K -

FREON

-SAMPLE

HEATER -

F i g . 2.1. Apparatus for Stored-Energy Measure-

ments During Deformation.

7
 It i s s e e n t h a t h e a t should n o t flow i n t o o r away from t h e sample
chamber, s i n c e t h e e n t i r e surroundings a r e kept a t t h e same temperature
by means of t h e same l i q u i d . The sample chamber i s i s o l a t e d reasonably
w e l l by t h e surrounding gas space and t h e use of s t a i n l e s s s t e e l , which
h a s a low t h e r m a l c o n d u c t i v i t y r e l a t i v e t o i t s s t r e n g t h .
S e v e r a l runs have shown t h a t it i s easy t o o p e r a t e t h i s c a l o r i m e t e r ,
b u t no e n t i r e l y s a t i s f a c t o r y data have y e t been o b t a i n e d because of c e r t a i n
difficulties. It h a s been e s t a b l i s h e d t h a t some of t h e d i f f i c u l t y a r o s e
from t h e open cup, where t h e Freon could and d i d evaporate below i t s b o i l -
ing point. This problem w i l l b e s o l v e d b y t h e e l i m i n a t i o n of t h i s b a t h
through s u i t a b l e d e s i g n . There p o s s i b l y remains a problem of s u p e r h e a t i n g .
The h e a t e r added t o p r e v e n t t h i s around t h e sample appears t o have overcome
this difficulty. A t t h e p r e s e n t time t h e r e remains t h e problem of an ap-
p a r e n t i n t e r n a l source of h e a t which i s s t r e s s dependent. This e f f e c t i s
SO strong that it m a s k s any stored energy after t h e stress becomes high
enough. The o n l y r e a s o n a b l e e x p l a n a t i o n seems t o b e t h a t m a r t e n s i t e forms
i n t h e s t a i n l e s s s t e e l p u l l rods. The p r o c e s s i s time dependent even under
constant load. The b e s t s o l u t i o n t o t h i s problem remains t o b e worked o u t .
The u l t i m a t e accuracy which can b e a c h i e v e d ' h a s not been e s t a b l i s h e d
b u t w i l l presumably b e b e t t e r t h a n 1%. Even i f t h e accuracy i s no g r e a t e r
t h a n t h i s , good r e s u l t s can s t i l l b e o b t a i n e d a t low s t r a i n s , s i n c e t h e
s t o r e d energy i s t h e n a n a p p r e c i a b l e f r a c t i o n of t h e s u p p l i e d energy. P r e -
sumably t h i s f r a c t i o n w i l l i n c r e a s e w i t h d e c r e a s i n g t e m p e r a t u r e s , and it T

i s a l r e a d y known t h a t t h e f r a c t i o n i s l a r g e , around 0.3, f o r a l l o y s .

The immediate p l a n s f o r t h i s i n v e s t i g a t i o n c a l l f o r t h e measurement
of t h e s t o r e d energy v s s t r a i n and temperature (down t o -19OOC) f o r t h e
following materials : copper, aluminum, n i c k e l , zirconium, and b r a s s . Some
work may b e done a l s o on a few o t h e r pure m e t a l s , p a r t i c u l a r l y s i l v e r .
E x a c t l y what i s done next w i l l depend i n p a r t on what i s found i n t h e above
i n v e s t i g a t i o n b u t w i l l probably i n c l u d e one o r more of t h e f o l l o w i n g prob-
lems: s i m i l a r measurements on nonmetals such as s i l v e r c h l o r i d e , a s t u d y
of s i n g l e c r y s t a l s of copper, s y s t e m a t i c s t u d y o f t h e e f f e c t o f a l l o y i n g ,
and a s t u d y of t h e e f f e c t s of p r e c i p i t a t i o n hardening on s t o r e d energy.
i

‘accs 3. HIGH-TEMPERATURE REACTIONS

G. P. Smith, Jr.

VISIBLE ABSORPTION SPECTRA OF MOLTEN BISMUTH-BISMUTH

TRICHLORIDE SOLUTIONS

C. R. Boston G. P. Smith, Jr.

Solutions of metals in molten halide salts are of current interest
because of unanswered questions concerning the fate of the valency elec-
trons from the metal atoms. Recently, considerable attention has centered
on solutions of bismuth metal in bismuth trihalides because of the possi-
bility that dissolved bismuth may exist in several oxidation states and
several polymeric forms at different temperatures and total bismuth con-
centrations.
Measurements of vapor pressure,” density,3-5 phase equilibria,
6 j

and electrical properties‘’ have been reported. Although this work has
contributed to a better understanding of these systems, the species and
equilibria in solution are still not adequately defined. Further, it has
been known for some time that metal-molten-salt systems are frequently
highly colored; yet, quantitative measurements of this property have not
been reported. Therefore, the present study was undertaken to explore the
feasibility of spectral measurements on metalinolten-salt systems and to

ID. Cubicciotti, T. J. Keneshea, Jr., and C. M. Kelley, J. Phys. Chem.

-62, 463 (1958).
2D. Cubicciotti and T. J. Keneshea, Jr.,’J. Phys. Chem. 62, 999 (1958).
-
3T. J. Keneshea, Jr., and D. Cubicciotti, J. Phys. Chem. 62, 843
(1958). -
‘T. J. Keneshea, Jr., and D. Cubicciotti, J. Phys. Chem. 63, 1112
(1959). -
-
5T. J. Keneshea, Jr., and D. Cubicciotti, J. Phys. Chem. 63, 1472
(1959). -
-
6S. J. Yosim - al., J. Phys. Chem. 63, 230 (1959).
et -
-
7M. A. Sokolova, G. G. Urazov, and V. G. Kuznetsov, Khim. Redkikh
Elementov, Akad. Nauk S.S.S.R., Inst. Obshche? i Neorg. Khim. No. 1,
p 102 (1954).
_. 8A. H. W. Aten, Z. physik. Chem. -66, 641 (1909).
-
9D. Cubicciotti and N. L. Lofgren, Trans. N.Y. Acad. Sei. (in press).

9
provide a d d i t i o n a l evidence which might be u s e f u l f o r t h e determination
of s p e c i e s and e q u i l i b r i a which occur i n E i - B i C 1 3 s o l u t i o n s .

Experimental

Bismuth t r i c h l o r i d e w a s p r e p a r e d b y D . E . LaValle o f t h e A n a l y t i c a l
Chemistry D i v i s i o n of t h i s Laboratory. About 100 g of reagent-grade b i s -
muth m e t a l w a s r e a c t e d w i t h c h l o r i n e gas i n t h e f i r s t chamber of a two-
chamber Vycor a p p a r a t u s . The f i r s t chamber was 50 mm X 15 em and w a s p r e -
ceded by a s t a n d a r d - t a p e r j o i n t t o permit m e t a l a d d i t i o n and a two-way
stopcock to permit c h l o r i n e and argon e n t r y . The second chamber w a s 50 mm x
30 em and w a s followed by a two-way stopcock connected t o atmospheric p r e s -
s u r e exhaust and t o vacuum. The two h o r i z o n t a l l y arranged chambers were
connected by a 4-em l e n g t h o f 15-mm t u b i n g c o n t a i n i n g q u a r t z wool. All

ground j o i n t s were l u b r i c a t e d w i t h a fluorocarbon l u b r i c a n t . The c h l o r i n e -

bismuth r e a c t i o n w a s s t a r t e d by g r a d u a l l y r a i s i n g t h e temperature up t o
approx 40OoC, where t h e r e a c t i o n proceeded f a i r l y r a p i d l y . As the reaction
continued, c h l o r i n e gas flow c a r r i e d B i C 1 3 vapor over t o t h e second chamber
(which w a s cooled b y w a t e r o r a i r ) , where it condensed. A f t e r a l l of t h e
bismuth m e t a l had r e a c t e d and B i C 1 3 had sublimed i n t o t h e second chamber,
t h e furnace w a s moved over t o m e l t t h e B i C 1 3 . While g r a d u a l l y r a i s i n g t h e
temperature d u r i n g t h i s m e l t i n g o p e r a t i o n , a flow of argon c o n t a i n i n g a
s m a l l amount of c h l o r i n e gas w a s passed through t h e system. Finally, a f t e r
i
t h e B i C 1 3 had melted, a flow of h i g h - p u r i t y argon w a s maintained over t h e
melt. The product w a s allowed t o c o o l , and b o t h ends of t h i s second cham-
b e r were s e a l e d o f f under s l i g h t l y l e s s t h a n 1 a t m of argon and s t o r e d
u n t i l needed. This m a t e r i a l w a s extremely s e n s i t i v e t o a i r contamination,
and a l l handling, i n c l u d i n g a n a l y t i c a l weighing, w a s performed i n a c a r e -
f u l l y c o n t r o l l e d vacuum-type dry box. Analysis of t h e s a l t showed 33.68
wt % C1, as compared w i t h t h e t h e o r e t i c a l v a l u e of 33.73%.
Bismuth m e t a l w a s p u r i f i e d by bubbling hydrogen through molten r e a -
gent-grade metal h e l d on a s i n t e r e d g l a s s d i s k . The a p p a r a t u s used w a s
s i m i l a r t o t h a t d e s c r i b e d previously'' f o r t h e p u r i f i c a t i o n of LiC1-KC1
eutectic. The o x i d e - f r e e m e t a l w a s f i l t e r e d through t h e s i n t e r e d g l a s s

'OC. R . Boston and G. P. Smith, J. Phys. Chem. -

62, 409 ( 1 9 5 8 ) .
-

10
s
 disk into a Pyrex tube, sealed off under vacuum, and later opened in the
dry box, where the mete ingot was broken up in a mortar and placed in a
weighing bottle. Subsequent handling of bismuth metal was performed in
air with minimum exposure time. As an added precaution, the metal was
stored in a desiccator. No weight change was detected when bismuth was
stored in this way for periods of several months.
Measurements. - A Cary model llMS spectrophotometer modified'' for
high-temperature work was used to make the spectral measurements. Fused
silica cell-insert combinations'' were used to provide path lengths as
short as 24 p. Cells were loaded with weighed amounts (1C-12 g) of BiC13
in the dry box and held under a flow of argon during spectral measurements.
Melt composition was changed between spectral scans by adding bismuth metal
through the top of the cell while keeping a stream of argon passing over
the melt. In some cases, the weight of bismuth added was quite small (1-
2 mg), requiring the use of a microbalance to obtain sufficient accuracy.

Results

Concentrations in moles of bismuth atoms per liter were calculated on

the basis of the density measurements of Keneshea and Cubicciotti3 and
will be referred to as initial or formal bismuth concentrations, since the
actual species occurring in solution are still not defined. The formal
z molar extinction coefficient E was then calculated from the relation
f
E = A./M d, where A is the absorbance of a solution layer d: cm thick
f 1 f i
with a formal metal concentration M
f'
Typical spectra of Bi-BiC13 solutions are shown in Fig. 3.1, in which
formal extinction coefficients are plotted against wavelength. The effect
of temperature and composition on the spectra is obvious. A Beer's law
plot of (Ai)max/d vs [Bi] (formal bismuth concentration) is shown in Fig.
3.2. A plot of this kind should give a straight line with slope equal to
the extinction coefficient if there were only a single species of chromo-
phore present. It can be seen that apparent Beer's law deviations are
substantial even in these very dilute solutions and become greater with
increasing concentration and decreasing temperature. The limiting slope
at very low concentrations is approx 8 x lo3.

11
 UNCLASSIFIED
ORNL-LR-DWG 44361 R
7000
I 1
SPECTRA OF Bi-BiC13 C, = 0,009 moles B i / l i t e r

I
6000

5000

-+
c

G-
2
w
0
5
0
4000
V
z
II
I-
V
z 3000
W
1
a
H
a
?
2000

1000

0
450 500 550 600 650 700 750
i
WAVELENGTH ( m p )

Fig. 3.1. Absorption Spectra of Solutions of Bismuth in Bismuth Trichloride.

It i s e v i d e n t from F i g . 3.1 t h a t t h e 560-mp band i s overlapped by

t h e edge of a n o t h e r band a t s h o r t e r wavelengths. To compare s p e c t r a a t
d i f f e r e n t temperatures and t o c o r r e c t f o r band o v e r l a p it i s u s e f u l t o
determine t h e band a r e a o r i n t e g r a t e d absorbancy, which may be w r i t t e n
I(Ai/d)dE, where E i s t h e photon energy i n e l e c t r o n v o l t s . The 560-mp
band unquestionably corresponds t o an allowed t r a n s i t i o n , and t h e i n t e -
g r a t e d absorbancy should be a f f e c t e d only weakly by temperature. Figure
3.3 shows t h e i n t e g r a t e d absorbancy p l o t t e d a g a i n s t formal bismuth con-
centration. Band a r e a s were determined g r a p h i c a l l y from A./d
1 vs E p l o t s ,

12
 UNCLASSIFIED
O R N L - L R - D W G 443
70C

I I

600

500

d 300
\
x
4
- 300
d 250

W
X
0

2u 200
2
a
m
IT
200
2m 150
a

x:: 100
-5
I00 50

0
0 0.02 0.04 0.06 0.08 0.1
FORMAL BISMUTH CONCENTRATION (rnoles/liter)

0 ‘
0 0.1 0.2 0.3 0.4 0.5
FORMAL BISMUTH CONCENTRATION ( m o l e s / l l t e r )

Fig. 3.2. Beer’s L a w Type of P l o t Employing the Absorbance Index as a Measure of In-
tensity. T h e data are for t h e maximum o f the band which occurs at about 560 mp.

13
 UNCLASSIFIED
ORNL-LR-DWG 46738R
900 /
I I I

FORMAL BISMUTH CONCENTRATION (moles/liter)

Fig. 3.3. Beer's L a w Type of Ptot Employing the Integrated Absorb-

ance Index as a Measure of Intensity. T h e data are from the same
t
spectra displayed in Fig. 3.1.

and t h e approximate e r r o r l i m i t s i n t r o d u c e d i n t h i s procedure are i n d i -

c a t e d f o r each p o i n t i n F i g . 3 . 3 . The e r r o r l i m i t s , of c o u r s e , become z
g r e a t e r with increasing overlap. This i s e s s e n t i a l l y a Beer's l a w p l o t
c o r r e c t e d f o r band o v e r l a p e x c e p t t h a t i n t h i s c a s e t h e s l o p e s h o u l d be
a f f e c t e d o n l y weakly by t e m p e r a t u r e . Apparent B e e r ' s l a w d e v i a t i o n s a r e
a g a i n v e r y l a r g e even i n t h e s e d i l u t e s o l u t i o n s and become l a r g e r w i t h i n -
c r e a s i n g c o n c e n t r a t i o n and d e c r e a s i n g t e m p e r a t u r e . A constant limiting
s l o p e , shown by t h e dashed l i n e , w a s approached a t a l l t h r e e t e m p e r a t u r e s ,
i n d i c a t i n g t h a t t h e o s c i l l a t o r s t r e n g t h i s v i r t u a l l y temperatsure independ-
e n t , as e x p e c t e d f o r an allowed t r a n s i t i o n . I n t h e v e r y d i l u t e range ( i n -
s e t , F i g . 3 . 3 ) t h i s l i m i t i n g s l o p e was followed v e r y c l o s e l y even a t t h e
lowest t e m p e r a t u r e .

14
5
 The strong Beer's law deviations shown in Figs. 3.2 and 3.3 show that
at least one species other than the chromophore is present in solution.
The influence of temperature on these deviations indicates that the chromo-
phore is in equilibrium with at least one other species which is more stable
than the chromophore at the lower temperatures.

Discuss ion

Previous attempts to identify species and equilibria in Bi-BiCl, solu-

tions have been made largely on the basis of thermodynamic measurements,
and the present status of this subject has been well summarized in a re-
cent paper by S. J. Yosim -
et -
a1.6 Interpretation of thermodynamic data for
fused salt systems in terms of species necessarily involves rather broad
assumptions as to activity coefficients, s o l i d solution formation, etc.,
and it is not surprising that attempts along this line have met with rather
limited success. The cryoscopic datal' near both ends of the phase dia-
gram indicate a polymeric subhalide, namely, Bi2C12, as a principal con-
stituent of moderately concentrated solutions near the liquidus. In the
vapor pressure studies, activities of BiC13, calculated from the vapor
pressures, obeyed Raoult's law in very dilute solutions, especially at
higher temperatures, but positive deviations became very large at moderate
bismuth concentrations. In order to explain both the vapor pressure and
cryoscopic results, BredigT2 proposed the equilibrium
f
2Bi2 + 2BiC13 = 3Bi2C1,

The nonthermodynamic evidence presently available consists of elec-

trical conductivity, ' 1' magnetic susceptibility,l 3 'I density,3--5 and vis-
cosity' data. Of these only magnetic susceptibility measurements have
helped significantly in the identification of species. Solutions of bis-
muth in molten bismuth trichloride are strongly diamagnetic. However, the
accuracy of the measurements does not permit one to exclude the presence

I1S. W. Mayer, S. J. Yosim, and L. E. Topol, J. Phys. Chem. -

6 4 , 238
(1960).
I2M. 63, 978 (1959).
A. Bredig, J. Phys. Chem. -
I3J. ->79
D. Corbett, S. Winbush, and J. C. Albers, J. Am. Chem. SOC.-
3020 (1957).
l 4 O . C. Holecek, thesis, University of Southern California, 1953.

15
 i

of a paramagnetic species in low concentrations. In fact, the latter

species are indicated in the work of Ho1ecekl4 described below.
The spectral data reported here give the first direct evidence for
the existence in solution of more than one species derived from bismuth
metal. One of these species has a very intense absorption band near 560
mp and is referred to as the chromophore. In very dilute solutions (0.01-
M),
as seen in Fig. 3.3, virtually all of the bismuth metal is present as the
chromophore. However, at moderate concentrations and especially at lower
temperatures, species other than the chromophore rapidly become predomi-
nant.
Species which have been proposed for this system are bismuth atoms,
n+
neutral bismuth dimer, Biz, and the subhalides, Bin , where values of n
of 1 through 4 have been suggested. The simplest model consistent with
the spectral data requires an equilibrium between two such species. If
one assumes that the tendency toward polymer formation decreases with in-
creasing temperature, then any of the following equilibria w o u l d be in
qualitative agreement with the spectral evidence:

2Bi = Bi2
4Bi + 2BiC13 = 3Bi2C12
2Bi + BiC1, = Bi3C1,
8Bi + 4BiC13 = 3Bi4C1,
2BiC1 = Bi2C1,
3BiCl = Bi3C13

In each case the monomeric species Bi or Bi' would be the chromophore.

The magnetic susceptibility measurements of Holecek14 in very dilute
solutions show an increase in susceptibility with decreasing metal con-
centration, indicating the presence of a paramagnetic species in low con-
centrations. The prominence in dilute solutions of both a paramagnetic
species and a strong (visible) light-absorbing species suggests that per-
haps they are the same species, with a bismuth atom or a Bi' ion being
reasonable choices.

c
 E F F E C T OF ALKALI CATIONS ON THE LOWEST ENERGY ELECTRONIC
T F L U S I T I O N O F THE NITRATE I O N I N MOLTEN ALKALI N I T R A T E S

G. P. Smith, Jr. C. R . Boston

An electronic transition of a given molecule frequently occurs at
somewhat different energies when the molecule is dissolved in different

and 5 -
solvents, as, for example, in the well-known ''solvent shifts" of n
fi transitions. Presumably this effect of solvent on the absorp-
tion spectrum of a solute arises because of a change in the interaction
-+ fi

between the solute molecules and their solvent environment in going from
the ground state to the excited state. Some of the importance of this
phenomenon lies in the expectation that, when it is better understood, it
may become a tool for making direct measurements of intermolecular inter-
actions. In systems of importance to chemistry and allied sciences solute-
solvent interactions are commonly too complex for a priori quantum mechani-
cal analysis, and significant theoretical understanding rests to a great
extent on initial experimental disclosure of the relative importance of
different molecular parameters. In the case of spectral "solvent shifts"
the limited theoretical progress thus far sterns largely from the experi-
mental discovery of instances in which the transition energy of a solute
changes in a systematic way when certain molecular properties of the sol-
vent are changed in a systematic way. However, examples of such syste-
matic changes are of limited variety, so that further empirical disclosures
of systematic behavior are an essential prelude to theoretical advances.
The preponderance of work on the spectral shifts of internal molecu-

solvent and d -
lar transitions (as distinguished, for example, from charge-transfer-to-
d transitions) has been done with organic molecules and
has been attributed in different cases to permanent dipole forces, dis-
persion forces, hydrogen bonding, and repulsive overlap forces.
The present work is an extension of the solvent-shift type of phe-
nomenon to ion-ion interactions in molten salts, and reports a systematic
shift in transition enerw for an internal transition of a molecule anion
which accompanies a systematic change from one cation to another. Other
spectral parameters were also checked for systematic changes.
The lowest energy transition of the nitrate ion gives rise to a weak
absorption band in the neighborhood of 300 mp which has been assigned to

17
t h e e x c i t a t i o n of a l o n e - p a i r , nonbonding e l e c t r o n ( n o r b i t a l ) on oxygen
i n t o an a n t i b o n d i n g IT o r b i t a l (IT* o r b i t a l ) of t h e n i t r a t e i o n , t h a t i s ,
an n + IT* transition. This i s a c h a r a c t e r i s t i c t r a n s i t i o n f o r ortho-
oxyanions .l5
S p e c t r a l p r o f i l e s of t h e molten a l k a l i n i t r a t e s were measured a t sev-
e r a l t e m p e r a t u r e s o v e r a wavelength range of approx 250 t o 360 mp. The
l o w e s t energy band w a s found t o be overlapped by t h e edge of a much s t r o n g e r
band, and t h e amount of t h i s o v e r l a p w a s deduced t h r o u g h a q u a n t i t a t i v e

a n a l y s i s of t h e shape of t h e spectrum. From t h i s a n a l y s i s t h e p a r a m e t e r s

of t h e l o w e s t energy band were computed. The band energy and t h e f num-
b e r were found t o change from one a l k a l i n i t r a t e t o a n o t h e r i n a way which
w a s s y s t e m a t i c and which c o u l d be c o r r e l a t e d w i t h d i f f e r e n c e s i n c a t i o n
size. T h i s b e h a v i o r i s a t t r i b u t e d t o t h e e f f e c t which c a t i o n f o r c e f i e l d s
have on t h e change i n e l e c t r o n d i s t r i b u t i o n which i s c h a r a c t e r i s t i c of an
n + n* t r a n s i t i o n . The s h i f t i n band energy i s e m p i r i c a l l y analogous t o
t h e " b l u e - s h i f t ' ' e f f e c t which p o l a r s o l v e n t s have on t h e n ----f IT* transi-
t i o n i n organic s o 1 u t e s . l 6

Expe riment a1

Materials. - The l i t h i u m , sodium, and potassium n i t r a t e s were r e a g e n t

grade. The b e s t o b t a i n a b l e rubidium and cesium n i t r a t e s were s u p p l i e d by
t h e Fairmount Chemical Company and t h e Maywood Chemical Works, r e s p e c -
tively. A l l of t h e n i t r a t e s were f i r s t r e c r y s t a l l i z e d and t h e n oven d r i e d I

a t 140°C. The o p t i c a l c e l l s were l o a d e d i n a i r w i t h -

c a . 5 g of m a t e r i a l .
S i n c e t h e s e compounds do n o t r e a c t r e a d i l y w i t h s m a l l amounts of w a t e r ,
it w a s p o s s i b l e t o c a r r y o u t t h e f i n a l d e h y d r a t i o n i n t h e o p t i c a l c e l l s
by b u b b l i n g d r y argon t h r o u g h t h e m e l t f o r about 1 h r .
Apparatus. - The s p e c t r o p h o t o m e t e r used i n t h i s work w a s a Cary model
llMS modified f o r h i g h - t e m p e r a t u r e work. The i n s t r u m e n t a t i o n f o r t h e meas-
urement and c o n t r o l o f t e m p e r a t u r e w a s more t h a n adequate t o e n s u r e an a c -
curacy and c o n t r o l w i t h i n 0.5OC. Melts were k e p t under an argon atmosphere.
S h o r t p a t h l e n g t h s were o b t a i n e d by use of p r e c i s i o n f u s e d - s i l i c a i n s e r t s .

15S. P. McGlynn and M. Kasha, J. Chem. Phys. -

24, 481 (1956).
16J. W . Sidman, Chem. Revs. -
58, 689 (1958).
-

18
.A.

The spectrophotometer and c e l l s have been described.17 The v a r i o u s m i s -

alignment e r r o r s u s u a l l y a s s o c i a t e d w i t h t h e use of i n s e r t s i n work w i t h
aqueous s o l u t i o n s were s t u d i e d by f o r c i n g an i n s e r t i n t o p o s i t i o n s of m i s -
alignment w i t h a f u s e d n i t r a t e i n t h e c e l l and t h e n measuring t h e absorb-
ance curve. Such e r r o r s were v e r y small, presumably because geometric
r e s t r i c t i o n s l i m i t e d c o n s i d e r a b l y t h e amount of misalignment and because
t h e f u s e d n i t r a t e s have r e f r a c t i v e c l o s e t o t h a t of f u s e d
silica.
P a t h Length. - The s p e c t r a l p r o f i l e s which a r e r e p o r t e d h e r e w e r e
o b t a i n e d a t two p a t h l e n g t h s f o r each n i t r a t e except RbN03. One p a t h
l e n g t h w a s chosen s o t h a t band maxima l a y i n t h e absorbance range of 1 . 5

t o 2.7. The o t h e r p a t h l e n g t h w a s s h o r t e r by a f a c t o r of 2 t o 3.5 and

w a s used t o extend t h e s p e c t r a a l o n g a t e r m i n a l a b s o r p t i o n edge. This
e x t e n s i o n w a s n o t considered n e c e s s a r y f o r RbN03. The p a t h l e n g t h s were
a s follows: 1 9 . 1 and 60.4 y f o r LiN03, 60.4 and 115 IJ- f o r NaN03, 60.4
and 212 p f o r b o t h KN03 and CsN03, and 212 i ~ - f o r RbNO3. Additional data
were o b t a i n e d a t o t h e r p a t h l e n g t h s t o a s s i s t i n e s t i m a t i n g e r r o r s i n t h e
extinction coefficient.
The well-known d i f f i c u l t i e s of determining such s h o r t p a t h l e n g t h s
w i t h u s e f u l accuracy a r e t e r s e l y summarized by Kelly and Svensson.20 In
t h e p r e s e n t work, p a t h l e n g t h c a l i b r a t i o n s were made mechanically by meas-
u r i n g t h e t h i c k n e s s of t h e i n s e r t and t h e i n s i d e dimensions of t h e c e l l
( a t s e v e r a l p o i n t s ) by means of s e v e r a l d i f f e r e n t p r e c i s i o n micrometer
d e v i c e s each i n v o l v i n g d i f f e r e n t s o u r c e s of e r r o r , and by a b s o r p t i o n m e a s -
urements u s i n g t h e Bouguer-Lambert l a w . The r e s u l t s f e l l w i t h i n a p r e c i -
's.
s i o n of 1%.
The a b s o r p t i o n measurements f o r c a l i b r a t i o n purposes were made a t
370.0 my u s i n g K 2 C r O 4 s o l u t i o n s up t o 0.06 - M i n 0.05 - N aqueous KOH. The
e x t i n c t i o n c o e f f i c i e n t s f o r somewhat l e s s c o n c e n t r a t e d K2Cr04 i n aqueous
NaOH s o l u t i o n s ( r a t h e r t h a n KOH) a r e known t o be s l i g h t l y c o n c e n t r a t i o n

1 7 C . R . Boston and G. P. Smith, J. Phys. Chem. -

62, 409 ( 1 9 5 8 ) .
l8H. Bloom and D. C . Rhodes, J . Phys. Chem. -
6 0 , 7 9 1 (1956).
-
"0. H. Wagner, Z . physik. Chem. 131, 409 (1928).
-
-
2oJ. W . Kelly and G. Svensson, J, Phys. Chem. -
62, 1076 ( 1 9 5 8 ) .

19
dependent.21 However, t h e a u t h o r s made measurements a t 7 t o 13 p a t h l e n g t h s
f o r each of f o u r s o l u t i o n s ranging from 0.004339 t o 0.06045 -
M i n K2Cr04 and
0.05 -
N i n KOH. Within t h e p r e c i s i o n of t h e measurements (about 0 . 5 % ) , no
s i g n i f i c a n t t r e n d w a s found, and t h e average e x t i n c t i o n c o e f f i c i e n t of 4,842
liters-mole-l-crn-l a t 370.0 mp was only 0.6% g r e a t e r t h a n t h e v a l u e r e p o r t e d
by Gibson22 f o r 0.0002060 -
M K2Cr04 i n 0.05 -
N KOH.
N i t r i t e I n t e r f e r e n c e . - S p e c i a l a t t e n t i o n w a s given t o t h e p o s s i b i l i t y
of s p e c t r a l i n t e r f e r e n c e from t h e n i t r i t e i o n , s i n c e t h i s substance, a prod-
u c t of t h e thermal decomposition of t h e n i t r a t e i o n , absorbs i n t h e n e a r
ultraviolet. The n i t r i t e i o n i n f u s e d n i t r a t e s o l u t i o n w a s found t o have
an a b s o r p t i o n minimum i n t h e neighborhood of t h e lowest energy n i t r a t e band
and an a b s o r p t i o n maximum a t approx 360 mp, where t h e f u s e d n i t r a t e s a r e
substantially transparent. Thus, inasmuch as a l l s p e c t r a l measurements
i n c l u d e d t h e 360-mp r e g i o n , it w a s p o s s i b l e t o d e t e c t t h e presence of n i -
t r i t e i o n s b e f o r e t h e y became c o n c e n t r a t e d enough t o a f f e c t appreciably
t h e n i t r a t e spectrum.
N i t r a t e melts were s u b j e c t e d t o thermal t r e a t m e n t s which were more
s e v e r e t h a n t h o s e involved i n t h e s p e c t r a l measurements. These m e l t s were
t h e n cooled, d i s s o l v e d i n water, and analyzed f o r n i t r i t e by a c o l o r i m e t r i c
method which involved t h e formation of an aminoazo complex. The concen-
t r a t i o n of n i t r i t e i o n s i n t h e s e m e l t s w a s found t o be only a few p a r t s
p e r m i l l i o n , which i s w e l l below a n y t h i n g of s p e c t r a l s i g n i f i c a n c e .
C o r r e c t i o n f o r L i g h t Losses. - The q u a n t i t y which was measured w a s
log (11/12), where 11 w a s t h e i n t e n s i t y i n c i d e n t on t h e a b s o r p t i o n c e l l
and I2 w a s t h e i n t e n s i t y t r a n s m i t t e d through t h e a b s o r p t i o n c e l l . I n o r d e r
t o o b t a i n t h e i n t e r n a l absorbance A of t h e molten n i t r a t e l a y e r s it w a s i
i
n e c e s s a r y t o c o r r e c t f o r l i g h t l o s s e s due t o r e f l e c t i o n s a t i n t e r f a c e s and
due t o a b s o r p t i o n by t h e s i l i c a i n t h e c e l l w a l l s and i n s e r t . A detailed
numerical computation of t h e magnitudes of t h e s e l i g h t l o s s e s , t o g e t h e r
w i t h auxiliary measurements, showed t h a t t h e n e c e s s a r y c o r r e c t i o n s could
be made a c c u r a t e l y by u s i n g as a r e f e r e n c e a s i l i c a p l a t e a t t h e same t e m -
p e r a t u r e as t h e sample and of a t h i c k n e s s e q u a l t o t h e combined t h i c k n e s s e s

21G. K b ' r l u m , Z . physik. Chem. -

B33, 243 (1936).
-
22K. S. Gibson, N a t l . Bur. Standards ( U . S . ) , C i r c . No. 484 (September
1949).
of t h e two c e l l w a l l s and i n s e r t . T h i s simple method of c o r r e c t i o n w a s
made p o s s i b l e by t h e f o r t u i t o u s c l o s e n e s s of t h e r e f r a c t i v e i n d i c e s of
s i l i c a and t h e f u s e d n i t r a t e s . I 8 9'' The c o r r e c t i o n s were s m a l l ( a b o u t
0.03 absorbance u n i t a t 300 mp) and v a r i e d only s l i g h t l y w i t h temperature.
Computations f o r r e f l e c t i v e l o s s e s a t a s i n g l e i n t e r f a c e were based on
t h e Cauchy-Beer formula. Of t h e s e v e r a l i n f i n i t e s e r i e s r e q u i r e d t o de-
s c r i b e f i r s t - o r d e r m u l t i p l e r e f l e c t i o n s from a system of s i x s u c c e s s i v e
i n t e r f a c e s only one, t h a t f o r t h e two a i r - s i l i c a i n t e r f a c e s , gave a s e n s -
i b l e correction.
Molar E x t i n c t i o n C o e f f i c i e n t . - S p e c t r a were o b t a i n e d as c h a r t record-
i n g s , which were c o r r e c t e d f o r l i g h t l o s s e s , as d i s c u s s e d above, t o give
the i n t e r n a l absorbance A . ( h ) as a continuous f u n c t i o n of wavelength. L i g h t
1
a b s o r p t i o n w a s a t t r i b u t e d t o t h e n i t r a t e ion, and, hence, t h e molar ex-
tinction coefficient €(A) w a s o b t a i n e d from t h e r e l a t i o n ~ ( h =) A . (A)/Md,
1 -
M t h e c o n c e n t r a t i o n of n i -
where d i s t h e p a t h l e n g t h i n c e n t i m e t e r s and -
t r a t e i o n s i n moles p e r l i t e r . The molar c o n c e n t r a t i o n a t a temperature
of t " C was'calculated from t h e formula - M = a - p t , where a and p a r e em-
p i r i c a l c o n s t a n t s . Values of a and p used h e r e were determined r e c e n t l y
by G. F. P e t e r s e n of t h i s Laboratory and a r e l i s t e d i n Table 3.1.

Table 3.1. Molar Concentration of N i t r a t e I o n s i n Melts

-
M=a-@t

Nitrate Q: (rnoles/liter) p ~rnoles.liter-'-("~)-']

x
LiN03 27.88 8.06
NaNO3 25.00 8.25
mo3 20.87 7.25
RbN0-j 18.86 6.58
CsN03 16.82 5.82

The r e p r o d u c i b i l i t y of A i ( A ) was about 0.3% or e l s e 0.003 absorbance

u n i t , whichever w a s g r e a t e r . Absolute v a l u e s of E a t band maxima are t o
w i t h i n about 5$, w i t h t h e primary u n c e r t a i n t y r e s i d i n g i n t h e p a t h l e n g t h .

21
 h

Results

General C h a r a c t e r i s t i c s o f Molten N i t r a t e S p e c t r a . - F i g u r e 3.4 shows

t y p i c a l molten n i t r a t e s p e c t r a p l o t t e d as l o g E vs A. The p o i n t s marked

o f f a t 2-mp i n t e r v a l s r e p r e s e n t d a t a used i n a numerical p r o f i l e a n a l y s i s

d e s c r i b e d below.
I n keeping w i t h t h e n o t a t i o n of Rhodes and U b b e l ~ h d et ~
h e~ band whose
maximum i s shown i n F i g . 3.4 w i l l be n m b e r e d 11. T h i s i s t h e l o w e s t en-
e r g y e l e c t r o n i c band. The n e x t band, of which o n l y t h e a b s o r p t i o n edge
appears i n F i g . 3.4, w i l l be numbered I .

23E. R. Rhodes and A. R. Ubbelohde, P r o c . Roy. SOC. (London) A251,

156 (1959).
UNCLASSI FlED
ORNL-LR-DWG 50229

E (ev)
50 44 40 36 32

240 260 280 300 320 340 360 380 400

h (rnp)

Fig. 3.4. T y p i c a l Spectra o f Molten A l k a l i Nitrates i n the

Neighborhood o f the L o w e s t Energy Absorption Band. The
logarithm o f t h e molar extinction coefficient (liters/mole-crn)
i s plotted on a linear wavelength scale w i t h t h e corresponding
photon energy i n electron v o l t s shown a i t h e top o f the graph.
The spectra shown are for LiNO, at 273”C, represented by
circles; NaNO, a t 314”C, represented by triangles; and CsNO,
a t 425T, represented by squares. T h e open symbols represent
data taken w i t h “long” path-length c e l l s w h i l e t h e f i l l e d symbols
represent data taken w i t h “short” path-length c e l l s . The sizes
o f long and short path-length cells, which were different for
different nitrates, are specified i n t h e text.
 The s p e c t r a shown i n F i g . 3 . 4 a r e m i l d v a r i a t i o n s of t h e c h a r a c t e r i s -
t i c spectrum of t h e n i t r a t e i o n i n n o n - f u s e d - s a l t media. The maximum of
band I1 has g e n e r a l l y been found i n the neighborhood of 300 mp, w i t h an
e x t i n c t i o n c o e f f i c i e n t between 6 and 1 2 liters-mole-l.cm'-l, depending on
t h e s o l v e n t composition. The maximum of band I has n o t o f t e n been meas-
u r e d , b u t i n d i l u t e aqueous s o l u t i o n s it h a s been r e p ~ r t e d ~ ' a, t~ approx
~
200 mp w i t h an e x t i n c t i o n c o e f f i c i e n t of 12,000 liters.mole-l.cm-l and i n
c r y s t a l l i n e potassium n i t r a t e 2 5 a t between 200 and 220 mp w i t h an absorp-
t i o n c o n s t a n t only 20 t i m e s g r e a t e r t h a n t h a t of band 11.
Some c h a r a c t e r i s t i c f e a t u r e s of molten n i t r a t e s p e c t r a a r e l i s t e d i n
Table 3 . 2 . The c o o r d i n a t e s of t h e maximum of band I1 a r e s t i p u l a t e d by
€
max'
Amax' and Emax' where Emax i s t h e photon energy i n ev which c o r r e -
sponds t o A
max
. The p o s i t i o n s of t h e long-wavelength edges of bands I and
I1 a r e given, r e s p e c t i v e l y , by t h e wavelength A
I
a t which €(A) f o r band I
equals and by t h e wavelength A a t which €(A) f o r band I1 e q u a l s
E
max ' I1
E The s p e c t r a l range over which p r e c i s e €(A) v a l u e s c o u l d be de-
max/2.
t e r m i n e d a r e g i v e n under "A range'' and t h e molar e x t i n c t i o n c o e f f i c i e n t
a t t h e s h o r t - w a v e l e n g t h end of t h i s range i s denoted E*. Table 3 . 2 t o -
g e t h e r w i t h F i g . 3 . 4 p r o v i d e s a survey of t h e i n f l u e n c e which c a t i o n and
t e m p e r a t u r e have on t h e g r o s s e r f e a t u r e s of t h e n i t r a t e spectrum.
A l l a v a i l a b l e d a t a on E e x c e p t f o r CsN03, a r e c o l l e c t e d i n F i g .
max'
3 . 5 , where t h e photon energy E minus an a r b i t r a r y c o n s t a n t Q i s p l o t t e d
rnax
a g a i n s t t e m p e r a t u r e . The c o n s t a n t Q, which i s d i f f e r e n t f o r d i f f e r e n t
n i t r a t e s , w a s chosen s o as t o b r i n g t h e data t o g e t h e r on a p l o t of con-
v e n i e n t dimensions. Values of Q a r e s p e c i f i e d i n t h e c a p t i o n . The quan-
t i t y Amax, from which Emax w a s determined, w a s t a k e n t o be t h e l i m i t a t
t h e band maximum of t h e midpoints of a s e r i e s of chords drawn a c r o s s a
band p a r a l l e l t o t h e wavelength a x i s . C e s i u m n i t r a t e m e l t s above t h e t e m -
p e r a t u r e range o v e r which t h e o t h e r n i t r a t e s were s t u d i e d , s o t h a t it w a s
n o t convenient t o d i s p l a y values of E f o r t h i s compound i n F i g . 3 . 5 .
max
It w a s found t h a t Emax f o r CsN03 d e c r e a s e d by about 0.002 e v o v e r t h e
range from 418 t o 458°C. For a l l of t h e n i t r a t e s (d.E max/dT) w a s of t h e

2 4 G . Scheibe, Ber. d e u t . chem. Ges. -59, 1321 ( 1 9 2 6 ) .

251.Maslakowez, Z . Physik - 51, 696 ( z 2 8 ) .
-

23
 i
r- O co r-
N O a rl
-t
a N rl
M 0 0 N
a a 0
cd
k
-P
0
a,

f
;?;
m
I
N
O
N

m
NI
a
c\I

2
O
N
a
m . .
r--t
r l c -
. .
Or-
CDN
. . m. o.
M r l
a 0 Flnco
2
P
O
N N
O ina
c \ I N
a c- N P
N N
-
( v
0
a,
rl
a,
a. m.
a m
. .
mr- o. m.
aP- 0
. .
0 - t
0
cn 0 0
r - M
r i d N N m m
k m m m m m m m m
0
m 0 0 r - 0 + r - r - C P
m r i inn m N 0 0
0
.d
-P . .
m m . .
r - r l 0
+ +
. 0. 0
+ m
. .
C P
rn + i t - t +
.d
k
a,
P
+ .r - . m. c o. + C P
. .
r - r0
-
0 r -
. .
ar- M c o 0 0
2k coco N
N
6 0
N N
0
m m
o r -
m m
cd
E
N
m
0 0 r- co + . u \ N c o
a,
rl mr- . . m m 3 - t. . d o . .
2
?E
r - Q
r l r -
co co + i t l n O
m r - -t in con inco
F a rl a r i a N . u \
a m m m m m - t +
m m m m
0 0 0 0
5 73 2
fz
73
V
l-2 zl
24
 UNCLASSIFIED
ORNL-LR-DWG 50233

0.08

0.07

01 I I I I I I I
250 275 300 325 350 375 400 425
TEMPERATURE f"C)
b
Fig. 3.5. Effect of Temperature on the Energy
Emax of Band II. The quantity plotted i s (E,,, - e),
where i s an arbitrary constant which has the
following values: 4.240 for LiNO,, 4.100 for
NaNO,, 4.030 for KNO,, and 4.020 for RbNO,.

o r d e r of ev/deg and d e c r e a s e d p r o g r e s s i v e l y o v e r t h e r i e s from

LiN03 t h r o u g h CsN03.

Discuss i o n

P r e v i o u s l y Measured S p e c t r a of Molten A l k a l i N i t r a t e s . - I n 1916,

8 -

fj S c h a e f e r 2 6 determined t h e u l t r a v i o l e t spectrum of molten KN03, w i t h r e -

s u l t s which compare w e l l w i t h t h o s e d e s c r i b e d h e r e . (The " l o g m" s c a l e
used by S c h a e f e r e q u a l s -log E p l u s an unknown c o n s t a n t . ) I n 1957, S a k a i 2 7
r e p o r t e d wavelength values f o r a b s o r p t i o n edges of RbN03, C s N 0 3 , and NH4N03
from room t e m p e r a t u r e t o above t h e i r m e l t i n g p o i n t s . H i s v a l u e s f o r molten
RbNO3 and C s N O 3 c o r r e s p o n d t o t h e energy v a l u e s of t h e edge of band I g i v e n
i n Table 3 . 2 , T h i s i s i n a c c o r d w i t h t h e v e r y s h o r t p a t h l e n g t h of 0.5 p
which he used. Sundheim and Greenberg28 measured a b s o r p t i o n edges of a
l a r g e number of f u s e d s a l t s i n c l u d i n g t h e n i t r a t e s of l i t h i u m and p o t a s -
sium. The wavelength v a l u e s which t h e y r e p o r t f o r t h e s e n i t r a t e s l i e f a r

26K. S c h a e f e r , Z . anorg. 'u. allgem. Chem. 97, 285 (1916).

27K. S a k a i , J. Phys. Chem. - 61, 1131 (1957)-
-
28B. R. Sundheim and J. Greenberg, J. Chem. Phys. - 28, 439 ( 1 9 5 8 ) .

25
out on t h e low-energy s - 11, a s w i l l be seen by a comparison of h

their A0 values with t h e A values i n Table 3.1. This agrees with t h e

I1
f a c t t h a t they worked a t a path l e n g t h of 2000 p. Rhodes and U b b e l ~ h d e ~ ~
measured u l t r a v i o l e t s p e c t r a of t h i n films of LiN03, NaNO3, and KNO3 i n
both t h e c r y s t a l l i n e and molten s t a t e s . From t h e i r p l o t s t h e coordinates
of t h e maximum of band I1 may be estimated f a i r l y w e l l f o r a melt of LiNO3
and r a t h e r roughly f o r a melt of Na;N03. Assuming t h a t they c a l c u l a t e d t h e
"absorption constant" as A . /d r a t h e r than t h e f r e q u e n t l y used q u a n t i t y
1
2.303A./d, we estimate t h a t t h e i r values f o r t h e maximum of band I1 agree
1
approximately with ours.
The p r o f i l e a n a l y s i s which w i l l be described r e q u i r e s t h a t band I be
much s t r o n g e r than band 11. The d a t a of Rhodes and LJbbelohde support t h i s
requirement f o r melts of N d O 3 and KN03 b u t not f o r melts of LiN03. They
r e p o r t t h a t band I f o r molten LiN03 a t 264,"C peaks a t about 740 cm-', which
i s only a l i t t l e higher than t h e maximum of band 11. I n c o n t r a s t with t h i s ,
t h e authors followed t h e absorption edge o f band I a t 273°C up t o an A . / d
1
of about 1600 cm-l ( s e e @ i n Table 3.2) and found t h a t a t t h i s p o i n t it
was r i s i n g a t a r a t e which w a s only a l i t t l e slower than exponential. (See
following s e c t i o n s . )
P r o f i l e Models. - Inasmuch a s band I1 i s overlapped by band I it was
necessary t o devise a procedure f o r s e p a r a t i n g t h e bands i n t h e region of
overlap i n order t o s p e c i f y t h e s p e c t r a l parameters of t h e t r a n s i t i o n as-
s o c i a t e d with band 11. The procedure which w a s followed was t o c o n s t r u c t
T

numerical models of €(A) functions and t o a d j u s t parameters i n t h e s e models

so a s t o o b t a i n a "best" f i t with t h e experimentally measured €(A) func-
tions. The models were chosen t o be t h e sum of two functions, one of which
could be i d e n t i f i e d with band I and t h e o t h e r with band 11. I n order t o
permit t h e use of numerical methods t h e continuous, experimental €(A) func-
t i o n s were d i g i t i z e d a t 2-mp i n t e r v a l s so as t o obtain approx 50 p o i n t s
p e r spectrum. Such d i g i t i z e d p o i n t s a r e shown i n F i g . 3.4.
It w i l l be necessary t o d i s c u s s e x t i n c t i o n c o e f f i c i e n t functions both
on a A s c a l e and on an E s c a l e . For s i m p l i c i t y t h e following n o t a t i o n w i l l
be used. I f €(E) i s a p r o f i l e model on a uniform E s c a l e , then t h e same
model on a uniform A s c a l e , t h a t i s , ~ ( 1 2 4 0 / A ) , w i l l be designated ;(A).
A q u a l i t a t i v e examination of p l o t s of l o g E vs E o r vs A, such a s
shown i n Fig. 3.4, provides c l u e s t o a proper choice of p r o f i l e models.

26

i
 For a l l of t h e n i t r a t e s , t h e long-A edge of band I1 i s e s s e n t i a l l y p a r a -
b o l i c , s o t h a t t h e band shape i s e s s e n t i a l l y Gaussian. This i s t o be ex-
p e c t e d from previous s t u d i e s of t h e p r o f i l e s of bands without s i g n i f i c a n t
overlap.29 On t h e o t h e r hand, t h e edge of band I, beyond t h e range w i t h i n
which o v e r l a p a f f e c t s it, i s almost l i n e a r w i t h a v e r y s l i g h t c u r v a t u r e .
Thus, whatever t h e complete shape of band I may be, t h e segment of it which
w a s measured can be approximated q u i t e w e l l by an e x p o n e n t i a l f u n c t i o n .
These q u a l i t a t i v e c o n s i d e r a t i o n s l e a d one t o seek a s u i t a b l e Gaussian func-
t i o n t o r e p r e s e n t band I1 combined w i t h a s u i t a b l e e x p o n e n t i a l f u n c t i o n t o
r e p r e s e n t band I.
It w i l l be noted from F i g . 3.4 t h a t band I1 f o r CsN03 has an i n f l e c -
t i o n and b r e a k s away from a p a r a b o l i c shape below l o g E of a b o u t - 0 . 5 .
T h i s b e h a v i o r cannot be accounted f o r by an e x p o n e n t i a l o r Gaussian e x t r a -
p o l a t i o n of t h e edge of band I a c r o s s band 11, b u t it can be accounted f o r
by a v e r y weak band, denoted band 11’, p a r t i a l l y hidden under t h e wing o f
band 11. Traces of a s i m i l a r d e v i a t i o n were noted f o r RbN03, b u t t h e s e
l a y almost w i t h i n e r r o r l i m i t s of t h e p r o f i l e a n a l y s i s and hence were i g -
nored.
Two models were s e l e c t e d f o r c l o s e stuciy. Each c o n s i s t s of t h e sum
of a Gaussian f u n c t i o n i d e n t i f i e d w i t h band 11, and an e x p o n e n t i a l
I1’
E

function E i d e n t i f i e d w i t h t h e edge of band I . The f i r s t model, t o be

I’
r e f e r r e d t o a s t h e Kuhn-Braun model,30 w a s of t h e form

and t h e second, t o be r e f e r r e d t o as t h e Lowry-Hudson model,31 w a s of t h e

form

I n t h e s e models eo and Eo o r A. are t h e c o o r d i n a t e s of t h e maximum of E

I1
and a r e t o be d i s t i n g u i s h e d from E and Emax, t h e coordinates of t h e
max

29C. K. Jargensen, Acta 8, 1495 ( 1 9 5 4 ) .

Chem. Scand. -
3%. Kuhn and E . Braun, Z . physik. Chem. 8B, 281 ( 1 9 3 0 ) .
-
31T. M. Lowry and H. Hudson, P h i l . Trans. Roy. SOC. London A232, 117
(1933).

27
maximum of t h e composite f u n c t i o n € ( E ) . The c o n s t a n t s 0 and u a r e band-
width c o n s t a n t s although w i t h a d i f f e r e n t p h y s i c a l s i g n i f i c a n c e because
0 i s on an E s c a l e and u i s on a A s c a l e . The c o n s t a n t s ( a , b ) and (w,v)
d e s c r i b e t h e e x p o n e n t i a l e x t r a p o l a t i o n of band I on E and A s c a l e s , r e -
spectively.

The d i g i t i z e d d a t a were f i t t e d t o t h e s e p r o f i l e models s o as t o mini-

mize t h e sum of t h e squares of t h e r e s i d u a l s by methods developed by D. A.
Gardiner and coded f o r d i g i t a l computer by G. J. A t t a , b o t h of t h e Mathe-
m a t i c s Panel of t h i s Laboratory. Two methods of f i t t i n g were t e s t e d . In
b r i e f , t h e s e were t h e f o l l o w i n g .

F i r s t w a s t h e g e n e r a l i z e d Newton method. The model w a s expanded i n

a T a y l o r ' s s e r i e s about i n i t i a l guesses of t h e parameters. Then t h e model
was l i n e a r i z e d by dropping second-order and h i g h e r terms. The e x p e r i -
mental v a l u e s (about 50 p o i n t s i n a l l c a s e s ) w e r e s u b s t i t u t e d i n t o t h e
l i n e a r i z e d model and a l e a s t - s q u a r e s s o l u t i o n obtained. This gave cor-
r e c t i o n s t o t h e i n i t i a l guesses of t h e parameters. The r e s u l t a n t f i r s t -
c o r r e c t e d parameters were used f o r an i t e r a t i o n . This procedure w a s con-
t i n u e d u n t i l s u c c e s s i v e i t e r a t i o n s gave sums of t h e squares of t h e r e s i d u a l s
which d i f f e r e d by no more t h a n a few p a r t s i n lo8. Convergence w a s t e s t e d
over t h e s e r i e s of i t e r a t i o n s and w a s always s a t i s f a c t o r y .

Second w a s Garwood's method.32 This d i f f e r e d from t h e g e n e r a l i z e d

Newton method i n t h a t t h e model was l i n e a r i z e d by expanding i t s f i r s t de- V

r i v a t i v e about i n i t i a l guesses of t h e parameters and dropping terms above

f i r s t order. Computations which used Garwood's method proved t o be slower
i
t h a n t h o s e which used t h e g e n e r a l i z e d Newton method and did n o t lead t o
b e t t e r e s t i m a t e s of t h e parameters.

The same computing procedures were used on p r o f i l e models which con-

s i s t e d of t h e sum of two Gauss f u n c t i o n s . However, t h e c a l c u l a t i o n s d i d
n o t converge i n a s a t i s f a c t o r y way and such models were abandoned. This
b e h a v i o r i s presumed t o have a r i s e n from t h e f a c t t h a t t h e edge of band I
d e p a r t e d from an e x p o n e n t i a l f u n c t i o n by only a s l i g h t amount.

32F. Garwood, Biometrika -

32, 48 (1941).
-

28
 P r o f i l e s t u d i e s were a l s o made i n which t h e shape of € ( E ) w a s e s t i -
mated by t h e f u n c t i o n s proposed by Mead33 and J E r g e n ~ e n . ~ ' Mead's func-
t i o n does n o t give much b e t t e r results t h a n t h e Kuhn-Braun model, while
JErgensen's f u n c t i o n gave r e s u l t s comparable w i t h t h e Lowry-Hudson model.
The presence of band 11' i n t h e CsN03 spectrum w a s q u a n t i t a t i v e l y
handled i n t h e f o l l o w i n g way. The spectrum w a s f i t t e d t o t h e Lowry-Hudson
model over a wavelength range which excluded t h e more pronounced d e v i a t i o n
due t o band 11' (262-348 m p ) . The model w a s e x t r a p o l a t e d from 348 mp t o
t h e long-wavelength l i m i t of t h e measurement a t 392 mp and s u b t r a c t e d from
t h e experimental e x t i n c t i o n c o e f f i c i e n t curve t o give a r e s i d u a l f u n c t i o n
o v e r ' t h e range from 348 t o 392 mp. This r e s i d u a l f u n c t i o n was r e a d i l y
f i t t e d t o a Gaussian curve.
I n t e n s i t y c o n s i d e r a t i o n s f o r a band are c o n v e n i e n t l y p r e s e n t e d i n
terms of an i n t e g r a t e d photon c r o s s s e c t i o n . The e m p i r i c a l f number i s
used h e r e f o r t h i s purpose, as d e f i n e d by t h e r e l a t i o n
m
f = 2.303 X J E ( E ) dE = 3.483 x
flzm0
J E ( E ) dE , (3)

where and 2 a r e , r e s p e c t i v e l y , t h e mass and charge of t h e e l e c t r o n , h

i s P l a n c k ' s c o n s t a n t , No i s Avogadro's number, and t h e i n t e g r a t i o n i s t a k e n
over a l l s e n s i b l e i n t e n s i t y of band 11. It w i l l be n o t e d t h a t E q . ( 3 ) i s
t h e e x p r e s s i o n f o r t h e o s c i l l a t o r s t r e n g t h of an a b s o r b i n g gas3' o r of a
chromophore d i s s o l v e d i n a h y p o t h e t i c a l medium of u n i t r e f r a c t i v e index.
When E ~ ~ ( fEu n) c t i o n s from E q s . (1) and ( 2 ) are s u b s t i t u t e d i n t o E q .
( 3 ) one o b t a i n s for the Kuhn-Braun model

'r
and f o r t h e Lowry-Hudson model

+ 1>!
f = 0.07'653 2@
A$
m

r=O
(g) r (2r
rl (5)

Convergence of t h e s e r i e s i n Eq. ( 5 ) depends on t h e r a t i o of o- t o 2Ao.

For t h e s p e c t r a r e p o r t e d h e r e t h i s r a t i o ' w a s always i n t h e neighborhood
i
of 0.04 and t h e s e r i e s converged very r a p i d l y .

33A. Mead, Trans. Faraday SOC. - 30, 1052 ( 1 9 3 4 ) .

Repts. Progr. i n Phys. 8, 231 ( 1 9 4 1 ) .
3 4 R . S. Mulliken and C . A. Rieke, -
-

29
 i

R e s u l t s of P r o f i l e A n a l y s i s . - Twelve s p e c t r a were f i t t e d t o b o t h t h e
Lowry-Hudson and Kuhn-Braun p r o f i l e models. R e s u l t s f o r t h e Lowry-Hudson
model are l i s t e d i n Table 3.3, and a r e p r e s e n t a t i v e s e l e c t i o n of r e s u l t s
f o r t h e Kuhn-Braun model a r e l i s t e d i n Table 3.4. Both t a b l e s give v a l u e s
f o r t h e f i v e parameters i n t h e models, t h e s t a n d a r d d e v i a t i o n 6 of t h e
r e s i d u a l s , and t h e f number. Both models were f i t t e d over t h e same A
ranges, and t h e s e a r e l i s t e d i n Table 3.3.
The Lowry-Hudson model g i v e s a s i g n i f i c a n t l y b e t t e r f i t t h a n t h e Kuhn-
Braun model. For a l l of t h e s p e c t r a , t h e s t a n d a r d d e v i a t i o n f o r t h e Kuhn-
Braun model was 1 . 6 t o 5.8 times as g r e a t as t h a t f o r t h e Lowry-Hudson
model. A correspondingly l a r g e divergence was found f o r t h e 95$ confidence
l i m i t s on t h e parameters f o r band I1 and on t h e f number. Values of t h e
f number e s t i m a t e d by t h e Lowry-Hudson model a r e from 4 t o 10% ( a v e r a g e
about 6%) above t h o s e e s t i m a t e d by t h e Kuhn-Braun model and w i l l be t a k e n
as being more n e a r l y c o r r e c t . V a l u e s of A and A i n Table 3 . 2
max' 71' I1
d i f f e r from t h o s e o b t a i n e d from t h e Lowry-Hudson model by no more t h a n
0.6 rnp and g e n e r a l l y by much l e s s . Values of E i n Table 3 . 2 d i f f e r
max
from t h o s e computed by s u b s t i t u t i n g A. f o r A i n t h e Lowry-Hudson model by
no more t h a n t h e s t a n d a r d d e v i a t i o n .
An important consequence of f i t t i n g a model t o t h e d a t a by t h e l e a s t -
s q u a r e s c r i t e r i o n i s t h a t t h e model l i e s f i r s t above and t h e n below t h e
data i n a c y c l i c fashion. Thus, when t h e d i f f e r e n c e s between d a t a and
c a l c u l a t e d p o i n t s are p l o t t e d as a f u n c t i o n o f wavelength, a s i n u s o i d a l -
l i k e function i s obtained. Because o f t h i s c y c l i n g , t h e l e a s t - s q u a r e s
c r i t e r i o n causes even a moderately poor model, such as t h e Kuhn-Braun pro-
f i l e , t o g i v e a moderately good f i t . 1

The p r o f i l e a n a l y s e s show t h a t band I1 h a s a Gaussian shape which i s

skewed toward h i g h e r e n e r g i e s . It i s now g e n e r a l l y recognized t h a t smooth
e l e c t r o n i c bands n e a r l y always have a near-Gaussian shape. Although it i s
o f t e n assumed t h a t t h e Gaussian i s symmetrical on an E s c a l e , a skewness
of t h e magnitude and d i r e c t i o n r e p o r t e d h e r e has been found f o r o t h e r e l e c -
t r o n i c bands.29p31 I n a c a r e f u l s t u d y of t h e o r i g i n s of band shape Lax35
found t h a t a p o s i t i v e skewness w a s t o be expected f o r c e r t a i n t r a n s i t i o n s

35M. Lax, J . Chem. Phys. -

20, 1752 ( 1 9 5 2 ) .
-

30
0
i,

Table 3.3. Profile Analysis with Lowry-Hudson Model

Temperature
Melt
(“c) (”mole em/ ’-,--’

x ioe4
LiN03 273 17.29 286.2 24.34 0.1829 48.73 0.048 3.98 24S348
367 16.56 288.0 26.14 0.1568 42.83 0.076 4.05 25 2-35 2

NaNO3 314 8.33 298.0 23.62 0.1587 43.22 0.048 1.713 256-360
347 8.32 298.5 24.09 0.1521 41.79 0.053 1.738 258-360
365 8.32 298.8 24.39 0.1493 41.22 0.057 1,74 258-360
mo3 342 4.75 305.2 23.66 0.1515 41.91 0.037 0.933 258-360
368 4.78 305.5 24.00 0.1450 40.42 0.038 0.950 258-360
405 4.81 306.0 24.57 0.1394 39.25 0.041 0.973 26>360

RbNO3 318 4.41 306.8 23.15 0.1524 42.09 0.038 0.838 262-360
341 4.46 307.3 23.51 0.1503 41.77 0.035 0.849 264-360
365 4.41 307.6 23.83 0.1427 39.93 0.032 0.857 266-360

CsNO3 425. 5.07 310.2 24.68 0.1307 37.46 0.039 1.005 262-348

I
 c
m
.
t
' o lrm-.
0
m
a
0
(3

to
0
to
*cn
c\1
k r
m rl 0 0 0
x
to d to to a
c\1 4 0 0 0
0 0 0 0 0
0 -4- m to 0
0-
c-
m
c\l
m z it
m
d
m
cn c- a
0 c\1 c-
in
tc 2
co P- F. c- c-
it d a 0 it
D c- in a m
z
0

rl
m
0

0
m
0

(3
cv
0

0
m
0
0 (3 a m nl
a 0
it
m
in
d 0 8 0
it it if it it
rl m (3 nl m
if m c- if 0
D to if it in
d
m D to d In
c-
cv z a
m $ c\1
-4-
m m m
0 0 (? 0" 0
5
4
723 0E 2
P
ffi
5
u
32
i n c r y s t a l s a t e l e v a t e d temperatures as a m a n i f e s t a t i o n of t h e Stokes r u l e
t h a t phonon emission i s e a s i e r t h a n phorton a b s o r p t i o n .
The Lowry-Hudson band p r o f i l e i s art approximate r e p r e s e n t a t i o n of t h e
p o s i t i v e skewness (on an E s c a l e ) of barid I1 and has t h e advantage f o r
c u r v e - f i t t i n g purposes of a minimum number of parameters t o be a d j u s t e d .
I t should be emphasized t h a t no s p e c i a l meaning i s a t t a c h e d t o t h e f a c t
t h a t t h i s p r o f i l e i s symmetrical on a A s c a l e .
The parameters f o r band 11' f o r CsTJ03 a t 425OC a r e as f o l l o w s : 0.16
for E a t t h e band maximum, 350 mp f o r A a t t h e band maximum, 31 f o r t h e
width c o n s t a n t B on a A s c a l e , and 3 x for f . Using t h e s e parameters
and t h o s e i n Table 3.3 t h e experimental p r o f i l e over t h e wavelength range
from 262 t o 392 mp i s r e p r e s e n t e d w i t h a s t a n d a r d d e v i a t i o n of 0.031.
Empirical Regularities. - The primary f a c t s t o b e deduced from t h e
experimental d a t a i n c o r p o r a t e d i n F i g . 3.5 and Table 3 . 3 are t h e i n f l u -
ences which temperature a t t h e 600°K l e v e l and a m o l t e n - s a l t environment
f r e e of complex-forming c a t i o n s have on t h e lowest energy t r a n s i t i o n of
the n i t r a t e ion. A c u r s o r y scan of t h e d a t a r e v e a l s t h a t t h e e f f e c t which
a 10% change i n a b s o l u t e temperature has on t h e parameters of band I1 i s
i n every i n s t a n c e s o small t h a t it can be a s c e r t a i n e d only i n a r a t h e r
approximate way. I n c o n t r a s t , t h e e f f e c t of changing from one a l k a l i n i -
t r a t e t o a n o t h e r i s s u b s t a n t i a l i n a l l b u t a few i n s t a n c e s . O f t h e s e en-
vironmental e f f e c t s , t h e most s t r i k i n g i.s t h e s y s t e m a t i c way i n which t h e
energy of t h e maximum of band I1 d e c r e a s e s over t h e s e r i e s from LiN03
through CsN03.
It has l o n g been recognized t h a t very h i g h c o n c e n t r a t i o n s ( t h e o r d e r
of 2 t o 1 0 -
M) of c a t i o n s of noble-gas e l e c t r o n c o n f i g u r a t i o n s w i l l s h i f t
t h e lowest energy band of t h e n i t r a t e i o n r e l a t i v e t o i t s p o s i t i o n i n d i -
l u t e aqueous s o l u t i o n . 3 6 The r a t i o of w a t e r molecules t o c a t i o n s i n such
s o l u t i o n s i s s u f f i c i e n t l y small t o ensure t h a t t h e r e w i l l be many c a t i o n -
anion p a i r s s e p a r a t e d by no more t h a n a s i n g l e w a t e r molecule. K a t ~ i n ~ ~
used -
t - b u t y l a l c o h o l as a s o l v e n t s o as t o produce a h i g h degree of i o n
c l u s t e r i n g and t h e r e b y o b t a i n d i r e c t c a t i o n - a n i o n c o n t a c t . He found t h a t
p o l y v a l e n t c a t i o n s of noble-gas c o n f i g u r a t i o n s , such as ,
'
"
l
A w e r e more
36H. v. Halban and J. Eisenbrand, 2;. physik. Chem. 132, 401 ( 1 9 2 8 ) .
-
18, 789 ( 1 9 5 0 ) .
37L. I . Katzin, J. Chem. Phys. -

33
 effective than L i
+ i n s h i f t i n g band I1 t o h i g h e r e n e r g i e s and p o i n t e d out
t h a t t h e s h i f t w a s "a f u n c t i o n of e l e c t r o s t a t i c charge and e f f e c t i v e i o n i c
r a d i u s . I'
I n a molten a l k a l i n i t r a t e two simple forms of s t r u c t u r a l o r d e r can
b e recognized. F i r s t , t h e n i t r a t e i o n does n o t d e p a r t g r e a t l y from t h e
D3h symmetry of t h e i s o l a t e d i o n . The most convincing evidence f o r t h i s
comes from Raman measurements on molten nitrate^.^' Thus, it i s p o s s i b l e
t o r e g a r d t h e s p e c t r a l e f f e c t s produced by changing from one a l k a l i n i t r a t e
t o a n o t h e r as p e r t u r b a t i o n s of t h e m o l t e n - s a l t environment on t h e proper-
t i e s of an i s o l a t e d n i t r a t e i o n . Second, t h e n i t r a t e i o n i s surrounded
11
by a cage" o r n e a r e s t neighbor s h e l l of a l k a l i c a t i o n s which i s deeply
p e n e t r a t e d by n i t r a t e anions because of t h e i r l a r g e r e l a t i v e s i z e . That
i s , t h e a l k a l i n i t r a t e s behave l i k e Hnormal" i o n i c m e l t s f o r t h e u s u a l
reasons of Coulombic a t t r a c t i o n and r e p u l s i o n . 3 9 Furthermore, radial d i s -
t r i b u t i o n f u n c t i o n s o b t a i n e d from x-ray s c a t t e r i n g measurements4' on molten
NaN03 and KN03 show t h a t c r y s t a l r a d i i p e r s i s t i n t h e m e l t . Thus, t h e
c a t i o n i c c r y s t a l r a d i u s i s a meaningful parameter i n t h e m e l t d e s p i t e t h e
f a c t t h a t t h e p r e c i s e d i s t r i b u t i o n of c a t i o n - a n i o n d i s t a n c e s i s unknown.
The c o r r e l a t i o n between t h e t r a n s i t i o n energy of band I1 and t h e r e -
c i p r o c a l of t h e c a t i o n r a d i u s proves t o be q u a n t i t a t i v e l y simple, as i l l u s -
t r a t e d by F i g . 3 . 6 . O f t h e v a r i o u s energy parameters which were d e t e r -
mined, Emax ( s e e Table 3 . 2 and F i g . 3 . 5 ) g i v e s t h e b e s t e s t i m a t e of t h e
mean t r a n s i t i o n energy of band I1 f o r two r e a s o n s . F i r s t , Emax may b e de-
termined w i t h g r e a t e r p r e c i s i o n t h a n t h e p r o f i l e - a n a l y s i s parameter E o ;
and, second, Emax i n t r i n s i c a l l y d i f f e r s from t h e energy of t h e maximum of
band I1 by a v e r y s m a l l amount because t h e s l o p e of E I( E ) i s very s m a l l

at Emax*
The v a l u e s of E i n F i g . 3.6 a r e chosen a t 365°C from F i g . 3 . 4 p l u s
max
I t h e n e c e s s a r y a d d i t i o n a l d a t a f o r CsN03. Values of t h e i o n i c r a d i i a r e

38The most e x t e n s i v e r e c e n t measurements a r e as f o l l o w s : E . F. Gross

and V. A. Kolesova, Akad. Nauk S.S.S.R., Pamyati S . I . Vavilova, p 231
( 1 9 5 2 ) , and W. Bues, Z . physik. Chem. ( F r a n k f u r t ) - -
10, 1 ( 1 9 5 7 ) .

I 39T. Fbrland, Norg. Tek. Vitenskapsakad., S e r . 2, No. 4 (1957).

"V. I . Danilov and S. Ia. K r a s n i t s k i i , Doklady Akad. Nauk S.S.S.R. n

101, 661 ( 1 9 5 5 ) .

34
3
c

UNCLASSIFIED
ORNL-LR-DWG 39673R

did 4 35

4 30

4 25

4 20

-
-
2 415
4
:

4 10

4 05

4 oc

05 07 09 1 1 13 15 t7
i/r (ii-'

Fig. 3.6. T h e Energy of the Maximum of Band 11, E m a xat,

365y as a Function of the Reciprocal of the Cation Radius rO.
Values of the radii are those of Pouting, represented by circles,
and those o f Zachariasen for Li' and Na', represented by
triangles. T h e values of E m a xfor CsNO, were extrapolated to
365OC from measurements at higher temperatures.

those o f Pau1ing4' (represented by c i r c l e s ) and those of Z a ~ h a r i a s e nf~o ~

r
-z Li
+ and Na
+ (represented by t r i a n g l e s ) . These two s e t s of r a d i i f o r t h e
small ions a r e p l o t t e d t o emphasize t h e f a c t t h a t too g r e a t a weight should
not be placed on p r e c i s e radius values f o r t h e smaller c a t i o n s under c i r -
cumstances of uncertain geometry. From Fig. 3.4 it i s seen t h a t E in-
max
creases i n an approximately l i n e a r way w i t h l / r o . The e f f e c t o f tempera-
t u r e on E as expressed by ( a m a x / d T ) i s a small negative quantity which
max

"L. Pauling, The Nature of t h e Chemical Bond, 2d ed., p 346, Cornell

University Press, Ithaca, N.Y., 1945.
"W. H. Zachariasen, Z . K r i s t . -
80:,137 (1931).-

35
p r o g r e s s i v e l y i n c r e a s e s i n a b s o l u t e magnitude f o r t h e s e r i e s CsN03 through
LiN03. Thus, an i n c r e a s e i n t e m p e r a t u r e o v e r t h e ranges s t u d i e d t e n d s t o
d e c r e a s e t h e e f f e c t which t h e c a t i o n p o t e n t i a l has i n s h i f t i n g t h e band
energy.
The f number of band I1 i n c r e a s e s as a smoothly a c c e l e r a t i n g f u n c t i o n
of l / r o f o r a l l of t h e n i t r a t e s e x c e p t CsN03, as shown i n Table 3.3. The
f number f o r CsN03 l i e s s l i g h t l y above t h e f numbers f o r RbN03 and KNO,.
The small t h e r m a l c o e f f i c i e n t ( l / f ) ( d f / d T ) amounts t o about to
deg-l i n a l l cases.
The width of band I1 i s n o t a b l e f o r i t s r e l a t i v e i n s e n s i t i v i t y t o
change from one a l k a l i n i t r a t e t o a n o t h e r e x c e p t f o r a s m a l l i n c r e a s e i n
going from Nm03 t o LiN03. The band width on an E s c a l e i s c o n v e n i e n t l y
measured by t h e r a t i o of t h e f number t o EO. T h i s r a t i o i s i n t h e range
of 1 . 9 t o 2 . 1 x a t a l l t e m p e r a t u r e s f o r a l l of t h e a l k a l i n i t r a t e s
e x c e p t LiN03. F o r LiN03 t h e r a t i o i s about 2.4 x lo-? F o r each n i t r a t e
t h e band w i d t h i n c r e a s e s by a s m a l l anount w i t h i n c r e a s i n g t e m p e r a t u r e .
T h i s t h e r m a l b r o a d e n i n g i s almost u n i v e r s a l f o r smooth e l e c t r o n i c bands
a t e l e v a t e d t e m p e r a t u r e s and undoubtedly a r i s e s from phonon-photon i n t e r -
actions.
Band-Energy C o n s i d e r a t i o n . - The e l e c t r o n i c assignment of t h e l o w e s t
e n e r a n i t r a t e band i n terms of t h e LCAO m o l e c u l a r - o r b i t a l t r e a t m e n t h a s
been d i s c u s s e d by W a l ~ h , ' ~McGlynn and K a ~ h a F
, r~i e~n d and Lyons,C5 and
Sayre.46 These t r e a t m e n t s a g r e e on t h e o r i g i n of t h e e x c i t e d e l e c t r o n
as a n e s s e n t i a l l y l o n e - p a i r , nonbonding o r b i t a l on oxygen ( n - t y p e o r b i t a l )
and on i t s d e s t i n a t i o n as an a n t i b o n d i n g
c u l e i o n (n*-type o r b i t a l ) ; t h a t i s , an n
r[

- o r b i t a l s p r e a d o v e r t h e mole-
fl* t y p e of t r a n s i t i o n .
were s e v e r a l p o i n t s of disagreement among t h e s e a u t h o r s , one of which w a s
There

t h e c h o i c e of e l e c t r o n i c symmetry s p e c i e s f o r t h e e x c i t e d s t a t e . I n terms

a s s i g n e d t h e t r a n s i t i o n as Ai -
of t h e D3h p o i n t - g r o u p symmetry of t h e i s o l a t e d , n o n v i b r a t i n g i o n Sayre
E ' , which i s symmetry allowed, w h i l e t h e

43D. A . Walsh, J. Chem. Soc. 1953, 2301.

4 4 S . P. McGlynn and M. Kasha, J. Chem. Phys. -
24, 481 ( 1 9 5 6 ) .
4 5 J . A. F r i e n d and L . E . Lyons, J. Chem. SOC. 1'359, 1572.
4 6 E . V. Sayre, J. Chem. Phys. -
31, 73 (1959). - cs,
o t h e r a u t h o r s a s s i g n e d t h e t r a n s i t i o n as Ai ,
:
A which i s symmetry f o r -
bidden.
An e m p i r i c a l r e g u l a r i t y which c h a r a c t e r i z e s n - fl* transitions i n

i n g p o l a r i t y have i n p r o g r e s s i v e l y s h i f t i n g an n
molecule toward h i g h e r e n e r g i e s . 47
-
o r g a n i c molecules i s t h e e f f e c t which s c l v e n t s of p r o g r e s s i v e l y i n c r e a s -
n* band f o r a s o l u t e
Superficially, t h i s polar-solvent

s i t i o n f o r t h e n i t r a t e i o n i n molten s a l t s . However, many of t h e known

-
" b l u e - s h i f t ' ' e f f e c t a p p e a r s t o be p a r a l l e l e d by t h e b l u e - s h i f t e f f e c t
which c a t i o n s of p r o g r e s s i v e l y i n c r e a s i n g l / r o have on t h e n fl* tran-

p o l a r - s o l v e n t b l u e s h i f t s o c c u r i n h y d r o x y l i c media where t h e b a n d - s h i f t -
i n g mechanism i n v o l v e s s t a b i l i z a t i o n of n - t y p e e l e c t r o n s i n t h e ground
s t a t e by hydrogen bonding.48 C l e a r l y , t h i s mechanism does n o t apply t o
a l k a l i n i t r a t e melts.
The n i t r a t e i o n b l u e s h i f t must a r i s e from t h e i o n - i o n i n t e r a c t i o n
forces. The dominant f o r c e s a r e o v e r l a p r e p u l s i o n and Coulomb f o r c e s . A s
w i l l be p o i n t e d o u t i n more d e t a i l , o v e r l a p r e p u l s i o n may w e l l be an i m -
p o r t a n t f a c t o r i n t h e b l u e - . s h i f t mechanism; however, t h e dependence of
b l u e s h i f t on c a t i o n i c l / r o o r , inc1udin.g K a t z i n ' s o b s e r v a t i o n s , on c a t -
i o n i c Z / r o s u g g e s t s t h a t t h e Coulomb f o r c e s p l a y a dominant r o l e i n s h i f t -
i n g t h e t r a n s i t i o n energy. Working from e x i s t i n g d a t a one cannot d i s t i n -
g u i s h s e p a r a t e c o n t r i b u t i o n s of o v e r l a p and Coulomb f o r c e s , b u t one can
s e t up a model i n which t h e s e f o r c e s occur i n s e p a r a t e , a d d i t i v e terms
and, t h e r e b y , examine from a t h e o r e t i c a l view t h e way i n which atomic
p a r a m e t e r s are i n v o l v e d i n t h e Coulomb c o n t r i b u t i o n a l o n e .
The m e l t w i l l be r e g a r d e d as a c l a s s i c a l i o n i c medium i n t h e s e n s e
t h a t i t s c o h e s i v e energy" U i s assumed t o a r i s e from p a i r w i s e i o n - i o n
interactions. That i s , f o r a n e l t c o n s i s t i n g of i o n s numbered 1 t h r o u g h
m

where 2' i s t h e summation o v e r a l l i and. j from 1 t h r o u g h m b u t e x c l u d i n g

terms f o r which i = j ; i s t h e Coulortb p o t e n t i a l energy between t h e
@i
j
58, 689 (1958).
4 7 J . W . Sidman, Chem. Revs. -
48G. J. B r e a l e y and M. K a s h a T J . Am. Chem. SOC. -
77, 4 4 6 2 (1955).
4 9 N . F. Mott and R. W . Gurney, E l e c t r o n i c P r o c e s s e s i n I o n i c Crystals,
2d e d . , p 1-10, Oxford U n i v e r s i t y P r e s s , 194.8.

37
i t h and j t h i o n s , a f u n c t i o n o f t h e v e c t o r c o o r d i n a t e s r and r over
-i -3
t h e c o n f i g u r a t i o n spaces of t h e i t h and j t h i o n s , r e s p e c t i v e l y ; and y
ij
i s t h e o v e r l a p p o t e n t i a l energy between t h e i t h and j t h i o n s . The e l e c -

vidual n i t r a t e ions.
-
t r o n i c p o l a r i z a t i o n of one i o n by i t s n e i g h b o r s w i l l be n e g l e c t e d , s o t h a t
the electronic transition n fi* w i l l be r e g a r d e d as l o c a l i z e d on i n d i -

o v e r t h e band width of t h e n -
L e t t h e m e l t , c o n t a i n i n g m i o n s , be i r r a d i a t e d w i t h a p u l s e of photons
rr* t r a n s i t i o n s o as t o e x c i t e
i o n s i n t o t h e Franck-Condon-metastablee x c i t e d s t a t e w i t h t h e a b s o r p t i o n
m' n i t r a t e

of a t o t a l photon energy m ' E . Number t h e e x c i t e d n i t r a t e i o n s 1 through

m'. Denote t h e c o h e s i v e energy of t h e m e l t w i t h t h e s e i o n s i n t h e e x c i t e d
s t a t e as U' and t h e c o r r e s p o n d i n g Coulomb and o v e r l a p terms as @
i j
' and
yij, r e s p e c t i v e l y . From t h e Franck-Condon p r i n c i p l e p l u s t h e r e s t r i c t i o n
on e l e c t r o n i c p o l a r i z a t i o n it f o l l o w s t h a t ( @ ' - @ . . ) and ( y i j - y . . ) a r e
i j 1J 1J
z e r o when n e i t h e r i n o r j e q u a l s 1 t h r o u g h m'. Thus, t h e change i n co-
h e s i v e energy which accompanies l i g h t a b s o r p t i o n i s

where t h e a s t e r i s k * s i g n i f i e s t h a t terms f o r which j i s 1 t h r o u g h m' a r e

d i v i d e d by 2 and terms f o r which j e q u a l s i a r e excluded.
The term z*J @i j' i n Eq. ( 7 ) i s t h e Coulomb p o t e n t i a l energy due t o
t h e i n t e r a c t i o n of t h e i t h e x c i t e d n i t r a t e i o n w i t h a l l of t h e r e s t of
the ions i n the melt. T h i s term i s g i v e n more e x p l i c i t l y by t h e r e l a t i o n

where 5 i s t h e u n i t of e l e c t r o n i c charge,
'i
' i s t h e c h a r g e - d e n s i t y func-
t i o n o v e r t h e i t h e x c i t e d n i t r a t e i o n , V . i s t h e Coulomb p o t e n t i a l which
1
a l l of t h e o t h e r i o n s e x e r t o v e r t h e space of t h e i t h i o n , dv. i s a v o l -
1
ume element i n t h e i t h i o n , and t h e i n t e g r a t i o n i s over a l l o f t h e space
of t h e i t h i o n . E l e c t r o n charge d e n s i t y i s t a k e n t o be n e g a t i v e and nu-
c l e a r c h a r g e s as p o s i t i v e , s o t h a t p ' may be e x p r e s s e d as t h e sum of f o u r
i
d e l t a f u n c t i o n s f o r t h e n u c l e a r c h a r g e s minus t h e e l e c t r o n d e n s i t y func-
tion \$;I2, where 9'
i
i s t h e t o t a l e l e c t r o n i c e i g e n f u n c t i o n of t h e i t h

38

3
c

excited ion. The Coulomb p o t e n t i a l V i s given by t h e r e l a t i o n

i

where D i s an e f f e c t i v e d i e l e c t r i c c o n s t a n t , t h e v e c t o r c o o r d i n a t e s r
Ni
over t h e i t h i o n and r over t h e j t h i o n a r e measured from t h e same p o i n t
-j
(say, t h e nitrogen of t h e i t h i o n ) , p i s t h e charge-density function f o r
j
t h e j t h i o n , and t h e volume i n t e g r a l i s t a k e n over t h e space of t h e j t h
ion.
The g r o u n d - s t a t e term 2; O i j i n Eq. ( 7 ) can be expressed by an equa-
t i o n l i k e Eq. ( 8 ) i n which p ' i s r e p l a c e d by t h e g r o u n d - s t a t e charge-den-
i
s i t y f u n c t i o n p which, i n t u r n , c o n t a i n s t h e n e g a t i v e of a g r o u n d - s t a t e
i
electron-density function I$.1I 2 . The Coulomb p o t e n t i a l V f o r t h e ground
i
s t a t e i s s l i g h t l y d i f f e r e n t from t h a t f o r t h e e x c i t e d s t a t e s i n c e t h e l a t -
t e r c o n t a i n s t h e c h a r g e - d e n s i t y f u n c t i o n s of m ' - 1 e x c i t e d n i t r a t e i o n s .
However, s i n c e t h e t o t a l number of n i t r a t e i o n s m/2 i s enormously g r e a t e r
t h a n m', v a l u e s of Ir - r.1 f o r b o t h i and j e q u a l t o numbers 1 through
-j -1
m ' can be assumed t o be very l a r g e and, hence, t o make a n e g l i g i b l e con-
tribution t o V
i
. Therefore, t h e d i f f e r e n c e between V
i
i n t h e ground and
e x c i t e d s t a t e s can be s a f e l y ignored.
It i s convenient t o i n t r o d u c e t h e n o t a t i o n

where A@ i s , by d e f i n i t i o n , t h e t o t a l change i n Coulomb p o t e n t i a l energy

which accompanies t h e t r a n s i t i o n and AI? i s t h e corresponding t o t a l change
i n o v e r l a p energy. I n t o Eq. ( l o a ) s u b s t i t u t e Eq. ( 8 ) f o r t h e e x c i t e d -
s t a t e term and a l i k e e x p r e s s i o n f o r t h e g r o u n d - s t a t e terms, and n o t e t h a t
t h e Franck-Condon p r i n c i p l e r e q u i r e s t h a t t h e change i n charge d e n s i t y
( p i - p . ) which c o n s t i t u t e s t h e t a n s i t i o n be e n t i r e l y a change i n e l e c -
1
t r o n i c charge. This y i e l d s

39
 If one does an energy b a l a n c e on t h e photon-absorbing p r o c e s s which
w a s d e s c r i b e d above and n e g l e c t s a s m a l l change i n t h e r m a l energy, t h e n
one o b t a i n s f o r m'E, t h e t o t a l photon energy absorbed,

m ' E = U' - U + m'Em , (12)

where m'Em i s t h e t r a n s i t i o n e n e r m of m ' n i t r a t e i o n s s e p a r a t e d t o i n -

finity. Combining Eqs. ( 8 ) , (ll), and (12), one o b t a i n s

E - Em =
I
-
m ' (AQ + AI') . (13)

Now, c o n s i d e r t w o a l k a l i n i t r a t e s , e a c h w i t h a d i f f e r e n t s p e c i e s o f c a t i o n ,
+ + c
C1 and C 2 , r e s p e c t i v e l y . Denoting t h e energy terms f o r each n i t r a t e by
a p p r o p r i a t e s u p e r s c r i p t s and r e c o g n i z i n g t h a t Em i s t h e same f o r b o t h n i -
t r a t e s , one o b t a i n s from Eq. (13)
t

A q u a l i t a t i v e s t a t e m e n t of t h e e x p e r i m e n t a l o b s e r v a t i o n i s t h a t i f r o(1)
and rL2) a r e t h e i o n i c r a d i i of C 1 and
+ C2,
+ respectively, then the experi-
mental s h i f t - E ( 2 ) has t h e same sign as l/rL1) - l/ri2). E q u a t i o n
(14) r e l a t e s t h i s o b s e r v a t i o n t o t h e average change i n i n t e r a c t i o n energy
between t h e m e l t and t h e n i t r a t e i o n s , and Eqs. ( 9 ) and (11) r e l a t e t h e
Coulomb p a r t of t h i s change t o atomic p a r a m e t e r s .
L e t us examine t h e i m p l i c a t i o n s of Eq. (11). I f t h e t r a n s i t i o n does
n o t i n v o l v e a s i g n i f i c a n t r e d i s t r i b u t i o n of e l e c t r o n i c charge d e n s i t y ,
then the function ;$I 1 - I would be v e r y s m a l l and t h e Coulomb t e r m
AQ i n Eqs. (13) and (14) w i l l make l i t t l e c o n t r i b u t i o n t o a s h i f t i n en-
ergy. Furthermore, s i n c e e l e c t r o n i c charge i s conserved d u r i n g t h e t r a n -
s i t i o n , t h e volume i n t e g r a l of I$! 1 1 - l2 over t h e space of t h e i t h
n i t r a t e ion exactly vanishes. T h e r e f o r e , i f Vi i s a c o n s t a n t , t h a t i s ,
h a s no g r a d i e n t a c r o s s a n i t r a t e i o n , AQ v a n i s h e s and, a g a i n , t h e Coulomb
terms i n Eqs. (13) and (14) make no c o n t r i b u t i o n t o a s h i f t i n t r a n s i t i o n
energy. Thus, n e c e s s a r y r e q u i r e m e n t s f o r a Coulomb c o n t r i b u t i o n t o an
energy s h i f t a r e a s i g n i f i c a n t g r a d i e n t i n V and a s i g n i f i c a n t r e d i s t r i -
i
b u t i o n i n charge d e n s i t y as a r e s u l t of t h e t r a n s i t i o n . The c o n t r i b u t i o n
may b e toward a b l u e s h i f t (A0 p o s i t i v e ) o r toward a r e d s h i f t (A0 nega-
t i v e ) depending on t h e way i n which t h e r e d i s t r i b u t i o n and t h e g r a d i e n t

40
 combine. A b l u e s h i f t may be thought of as a "movement" of e l e c t r o n s
a g a i n s t t h e f i e l d o r i n t o p o s i t i o n s of l e s s s t a b i l i t y w i t h r e s p e c t t o t h e
field.

F o r a l o c a l i z e d a n i o n . t r a n s i t i o n i n a simple p u r e s a l t t h e q u a l i t a -
t i v e dependence of A@ on t h e c a t i o n i c c h a r g e - t o - r a d i u s r a t i o Z / r o f o l l o w s
from Eq. ( 9 ) . [Equations ( 8 ) and ( 9 ) i n v o l v e no s p e c i a l assumptions as
t o t h e n e t c h a r g e s on t h e i o n s . ] The c o n t r i b u t i o n made by a s h e l l of i o n s
about t h e i t h n i t r a t e i o n t o t h e g r a d i e n t i n V decays v e r y r a p i d l y ' a s t h e
i
d i a m e t e r of t h e s h e l l of i o n s i n c r e a s e s . Consequently, t h e major c o n t r i -
b u t i o n comes from t h e n e a r e s t neighbor s h e l l , and as one changes from one
n i t r a t e t o a n o t h e r t h e major change i n t h e n e a r e s t n e i g h b o r s h e l l i s t h e
change i n t h e s p e c i e s of c a t i o n . The Coulomb p o t e n t i a l due t o a c a t i o n
o f r a r e - g a s c o n f i g u r a t i o n i s e s s e n t i a l l y t h e same as t h a t of a p o i n t charge,
s o t h a t t h e i n t e g r a l i n Eq. ( 9 ) may be r e p l a c e d by Z/l r -
-j
%I,
where r
-j
i s t h e v e c t o r from t h e n i t r a t e n i t r o g e n t o t h e c a t i o n n u c l e u s and r ranges
-i
o v e r t h e volume of t h e n i t r a t e i o n . It f o l l o w s t h a t t h e p o t e n t i a l c l o s e t o
a c a t i o n i s approximately s c a l e d a c c o r d i n g t o Z / r o . T h i s p o t e n t i a l h a s an
average p o s i t i v e v a l u e because n i t r a t e i s n e g a t i v e . It i s a maximum a t
c a t i o n n u c l e i and p a s s e s through minima. a l o n g l i n e s which i n t e r c o n n e c t
cation nuclei.

If t h e LCAO m o l e c u l a r o r b i t a l trea.tment of t h e n - I* transition is

even q u a l i t a t i v e l y c o r r e c t , t h e n t h i s t r a n s i t i o n s h i f t s charge d e n s i t y
from t h e neighborhood of oxygens t o the. neighborhood of n i t r o g e n s w i t h a
c o n s e r v a t i o n of t o t a l c h a r g e . Consequently, it i s p o s s i b l e t o d i v i d e t h e
'Z s p a c e of a n i t r a t e i o n i n t o two r e g i o n s , one around n i t r o g e n and t h e o t h e r
around oxygens, such t h a t t h e volume i n t e g r a l of l$i12 - /Ci12 h a s some
p o s i t i v e value a o v e r t h e s p a c e around n i t r o g e n and h a s t h e c o r r e s p o n d i n g
n e g a t i v e v a l u e -2 o v e r t h e space around oxygens. Thus, f o r purposes of
q u a l i t a t i v e d i s c u s s i o n choose IC!
1
I* - I* t o be a s t e p f u n c t i o n w i t h
t h e value a o v e r a r e g i o n around n i t r o g e n and t h e v a l u e -a o v e r a r e g i o n
around oxygens. I n l i k e manner choose V . t o be a similar s t e p f u n c t i o n
1

4
41

a
 w i t h t h e value Vi( O x ) over t h e r e g i o n around oxygens and over t h e r e -
i
gion around n i t r o g e n . S u b s t i t u t i n g t h e s e f u n c t i o n s i n t o E q . (11)one ob-
tains

Elementary e l e c t r o n i c c o n s i d e r a t i o n s 5 a r e s u f f i c i e n t t o show t h a t
nitrogen-oxygen bonds on t h e n i t r a t e i o n i n i t s ground s t a t e a r e p o l a r i z e d
i n such a d i r e c t i o n t h a t t h e n e t charge around oxygens i s more n e g a t i v e
t h a n t h e n e t charge around n i t r o g e n . Therefore, t h e most s t a b l e m e l t con-
f i g u r a t i o n s w i l l t e n d t o be t h o s e i n which nitrogen-oxygen bonds l i e along
d i r e c t i o n s i n which V y ) - Vfox) i s negative. A t a s u f f i c i e n t l y low tem-
p e r a t u r e such c o n f i g u r a t i o n s w i l l predominate. Hence, t h e summation i n
E q . ( 1 5 ) w i l l t e n d t o be n e g a t i v e , A0 w i l l be p o s i t i v e , and t h e Coulomb
i n t e r a c t i o n w i l l c o n t r i b u t e t o a b l u e s h i f t i n t r a n s i t i o n energy. In a
melt, of course, t h e r e w i l l be c o n f i g u r a t i o n s which a r e n o t e n e r g e t i c a l l y
f a v o r a b l e , and t h e i r i n c r e a s i n g prevalence w i t h i n c r e a s i n g temperature
w i l l m a n i f e s t i t s e l f i n a d e c r e a s i n g c o n t r i b u t i o n of t h e Coulomb p o t e n t i a l
t o a blue s h i f t . The observed thermal s h i f t f o r a l l n i t r a t e s i s of t h e
o r d e r of --lo-' ev/deg (-2 c a l / d e g ) , which corresponds t o t h e energy of
s m a l l thermal motions.
The f o r e g o i n g c o n s i d e r a t i o n s d e s c r i b e i n terms of a c l a s s i c a l model
t h e way i n which Coulomb i n t e r a c t i o n f o r c e s i n a simple melt can c o n t r i b -
u t e t o a l o c a l i z e d anion t r a n s i t i o n . The a p p l i c a t i o n of t h e model t o e
a l k a l i n i t r a t e m e l t s involved u n c e r t a i n t i e s concerning t h e d i r e c t i o n of
t h e e x t e r n a l Coulomb g r a d i e n t . However, a p o s s i b l e basis was suggested
f o r supposing t h a t t h i s d i r e c t i o n i s such as t o c o r r e l a t e t h e c o n t r i b u -
t i o n of t h e Coulomb i n t e r a c t i o n f o r c e s w i t h t h e observed i n f l u e n c e of
c a t i o n i c Z / r o and temperature.
Repulsive o v e r l a p f o r c e s decay r a p i d l y w i t h i n t e r i o n i c d i s t a n c e , s o

The n -
t h a t , i n t h e ground s t a t e , t h e y may b e c o n s i d e r e d as e x i s t i n g only be-
tween n e a r e s t neighbor i o n s . fl* t r a n s i t i o n involves a n e t ex-
pansion of t h e n i t r a t e charge cloud because of t h e occupancy of an a n t i -
bonding o r b i t a l i n t h e e x c i t e d s t a t e , and most of t h i s expansion probably
5 0 L . Pauling, The Nature of t h e Chemical Bond, 2d ed., p 209, Cornel1
U n i v e r s i t y P r e s s , I t h a c a , N.Y., 1945.

42
 o c c u r s i n t h e neighborhood of n i t r o g e n . Consequently, c o l l i s i o n between
n i t r a t e n i t r o g e n and a neighbor i o n r e s u l t s i n an i n c r e a s e i n o v e r l a p upon
t r a n s i t i o n w i t h a consequent i n c r e a s e :in r e p u l s i v e o v e r l a p energy of t h e
system Ar and a b l u e s h i f t i n t r a n s i t i o n energy.
B a n d - I n t e n s i t y C o n s i d e r a t i o n s . - The s i m p l e s t b a s i s f o r e x p l a i n i n g
t h e observed i n c r e a s e i n f number w i t h c a t i o n i c l / r o over t h e s e r i e s from
RbN03 t h r o u g h LiNO, i s i n terms of t h e A ' A" assignment mentioned i n
1 1
t h e preceding s e c t i o n . The f o r b i d d e n c h a r a c t e r of t h i s t r a n s i t i o n i s p r e -
sumably r e l a x e d i n p a r t by c o u p l i n g w i t h a p p r o p r i a t e v i b r a t i o n s and i n
p a r t by an asymmetric e x t e r n a l Coulomb p o t e n t i a l V . [ s e e Eq. (9)] which
1
modifies t h e D Clear
p o i n t - g r o u p symmetry of t h e n u c l e a r - c h a r g e f i e l d .
3h
e x p e r i m e n t a l evidence f o r t h e l a t t e r e f ' f e c t and i t s p r o p e r dependence on
cationic Z/r, f o r i o n s of r a r e - g a s c o n f i g u r a t i o n s i s g i v e n by t h e Raman
s t u d i e s of t h e b r o a d e n i n g and s p l i t t i n g of t h e doubly d e g e n e r a t e "valencet'
frequency v 3 i n n i t r a t e m e l t s . 3 8
The o r i g i n of t h e s m a l l d e c r e a s e i n f number i n going from CsN03 t o
RbN03 i s unknown.
CsN03 Band 11'. - S t u d i e s of t h e CsN03 p r o f i l e d i s c l o s e d a v e r y weak
band, d e s i g n a t e d 11'. There i s t h e i n t e r e s t i n g p o s s i b i l i t y t h a t t h i s band
may b e t h e t r a n s i t i o n from t h e s i n g l e t ground s t a t e t o t h e l o w e s t energy
t r i p l e t s t a t e , namely, 3 ( n + TI*),t h e s i n g l e t - t r i p l e t c o u n t e r p a r t of band

m
11.

The assignment 3 ( n ~r*)

-
The l a t t e r band i s almost c e r t a i n l y a t r a n s i t i o n t o t h e f i r s t e x c i t e d

-
singlet s t a t e , t h a t is, the singlet-singlet t r a n s i t i o n '(n TI*).

a c c o r d s w i t h t h e t h r e e i m p o r t a n t observa-
t i o n s , namely, t h e energy of band 11' -is about 0.45 e v l e s s t h a n t h e en-
ergy of band 11, t h e i n t e n s i t y of band 11' i s v e r y small ( f = and
band 11' i s c l e a r l y observed o n l y f o r CsN03. The f i r s t t r i p l e t l e v e l
f o r m a l l y l i e s lower i n energy t h a n t h e f i r s t e x c i t e d s i n g l e t l e v e l , and
Sidman" h a s given r e a s o n s f o r e x p e c t i n g t h e energy d i f f e r e n c e between
'(n --f TI*)and 3 ( n +n*) t o b e a few t e n t h s of an e l e c t r o n v o l t . The ob-
s e r v a n c e of t h e 3 ( n + fl*) band would r e q u i r e some s p i n - o r b i t c o u p l i n g ,
b u t t h i s i s unexpected i n a " l i g h t - a t o m " molecule i o n such as n i t r a t e .
However, it i s known t h a t o r g a n i c s o l v e n t s which c o n t a i n "heavy atoms"

51J. W . Sidman, J. Chem. Phys. -

27, 429 (1957).
-

43
like iodine can perturb light-atom solute molecules so as to permit tran-
sitions between states of different m u l t i p l i ~ i t y . ~The
~ mechanism by which
spin-orbit coupling is induced in such instances presumably involves inter-
cs
molecular collisions which are strong enough to give some charse-density
overlap between the solute molecule and the heavy atom in the solvent.
Such a mechanism could work just as well in the case of cation-anion col-
lisions in molten CsN03.

Concluding Remarks

Certain molecular electronic transitions are quite sensitive to the

environment of the light-absorbing molecule. The importance of this phe-
nomenon is the expectation that it may become a tool for making direct
measurements of intermolecular interactions. At the present time the theo-
retical analysis of this phenomenon is sufficiently formidable that prog-
ress is keyed to the experimental disclosure of correlations between changes
in spectral parameters and corresponding changes in molecular parameters
of the environment. The work described here extends these considerations
to molten salts.
Systematic changes are reported in the lowest energy transitions of
the nitrate ion over the series of molten alkali nitrates. The most strik-

-
ing of these systematic changes is the almost linear correlation between
band energy and the reciprocal of the cationic radius. Another, less
simple, correlation is reported between the empirical f number and the
cationic radius. The procurement and analysis of these data were made
possible by advances in the technique of molten-salt spectrophotometry
and in the technique of numerical profile analysis. I

Theoretical considerations are invoked, but the value of the work

rests largely on its empiricism.

52W. W. Robertson and R. E. Reynolds, J. Chem. Phys. 29, 138 (1958).

-

c
 4. MICROSTRESSES I N CRYSTALS

13. B o r i e

DIFFRACTOMETEB MODIFICATION FOR AUTOMATIC DIFFUSE

SCATTERING MEIZSUREMENTS

C . J. Sparks B. Borie

During t h e p a s t y e a r a G-E x - r a y d i f f r a c t o m e t e r w a s a c q u i r e d and ex-

t e n s i v e m o d i f i c a t i o n undertaken t o enhance t h e u s e f u l n e s s of t h e i n s t r u -
ment f o r x-ray d i f f u s e s c a t t e r i n g measurements. Such d i f f u s e s c a t t e r i n g
i s u s u a l l y slowly v a r y i n g , g i v i n g r i s e t o b r o a d peaks w i t h s h a l l o w v a l -
leys. I t s measurement may p r o v i d e i n f o r m a t i o n about s h o r t - r a n g e o r d e r ,
l o c a l i z e d l a t t i c e d i s t o r t i o n s , and t h e r m a l motion. The measurement of
t h i s i n t e n s i t y r e q u i r e s on t h e average 1200 t o 2500 d a t a p o i n t s f o r two-
dimensional d a t a , which r e s u l t s i n l o n g p e r i o d s o f x - r a y machine opera-
tion.
It i s t h e purpose of t h i s m o d i f i c a t i o n t o d e c r e a s e t h e time neces-
s a r y t o accumulate d a t a and/or improve t h e accuracy by s t e p scanning au-
t o m a t i c a l l y while providing a d a t a p r i n t o u t attachment. The continuous
c h a r t r e c o r d p r e v i o u s l y u s e d n e c e s s i t a t e d a v i s u a l e s t i m a t i o n of count
r a t e from t h e s t r i p c h a r t and i n t r o d u c e d an e r r o r of approx 15$ i n our
data. F i g u r e 4 . 1 i s a t y p i c a l example of x-ray d i f f u s e s c a t t e r i n g from
a n a l l o y of Cu-16 a t . $I Al which e x h i b i t s s h o r t - r a n g e o r d e r . The two
t r a c e s a r e r u n s made w i t h a n i c k e l t h e n a c o b a l t f i l t e r i n t h e beam t o
e l i m i n a t e s u b m u l t i p l e wavelength components i n t h e n e a r l y monochromatic
i n c i d e n t beam. The i n t e n s i t y i s t a k e n t o be t h e d i f f e r e n c e of t h e two
scans. This c o n t i n u o u s r e c o r d p r o v i d e s u n i n t e r r u p t e d d a t a ; however, be-
cause t h e i n t e n s i t y i s slowly v a r y i n g , p o i n t c o u n t i n g a t i n t e r v a l s of 2"
28 c o u l d b e u s e d w i t h o u t m i s s i n g any s t r u c t u r e . Hence, t h e time u s e d t o
s c a n t h e 2" i n t e r v a l c o u l d b e u s e d f o r p o i n t c o u n t i n g w i t h a r e s u l t i n g
i n c r e a s e i n accuracy.
The t r a c e shown i n F i g . 4 . 1 w a s t a k e n a t a s c a n n i n g r a t e of 2 deg/min.
Hence, s i n c e two s c a n s a r e r e q u i r e d , it t a k e s 120 s e e p e r 2" i n t e r G a 1 . This
i s i n c r e a s e d t o about 150 s e e if' account i s t a k e n of time n e c e s s a r y f o r
s e r v i c i n g t h e r e c o r d e r and count r a t e m e t e r .

45
 100

75
I

"*
0)

>
+
c
0
3

2 50
>-
L
In
z
W
c
z
25 5

0
54 58 62 66 70 74 78 82 86 90
6
2 8 (deq)

Fig. 4.1. X-Ray Diffuse Scattering from an Alloy of Cu-16 at. % AI Slowly Cooled from 750T.

The d i f f r a c t o m e t e r as modified s c a n s a t 5 deg/min, s o t h e t i m e be-

tween c o u n t s i s 2 / 5 min, p l u s about 10 s e e f o r programring. Hence, t h e r e
remains about 115 s e e t o measure t h e i n t e n s i t y w i t h o u t i n c r e a s i n g t h e t i m e
f o r each measurement compared t o c o n t i n u o u s s c a n n i n g .
The q u e s t i o n a r i s e s as t o t h e b e s t method f o r measuring t h e i n t e n s i t y
w i t h minimum e r r o r i n a g i v e n c o u n t i n g t i m e . Minimum e r r o r i n t h e d i f f e r -
8
ence of t h e n i c k e l and c o b a l t r e a d i n g s i s a c h i e v e d when d i f f e r e n t c o u n t s
o r t i m e s are u s e d f o r each of t h e two r e a d i n g s , s i n c e t h e i n t e n s i t i e s d i f -
f e r by about a f a c t o r of 7. But i n our c a s e , it i s e x p e d i e n t t o u s e t h e i
same p r e s e t count o r t i m e f o r b o t h t h e n i c k e l and t h e c o b a l t f i l t e r meas-
urements t o e l i m i n a t e an e x t r a m a n i p u l a t i o n of t h e d a t a and t o minimize
t h e complexity of t h e equipment. The advantage of t h e f i x e d - c o u n t method
as opposed t o f i x e d - t i m e c o u n t i n g i s t h a t it allows t h e p r e c i s i o n t o b e
predetermined. However, t h e p r e s e t f i x e d count i n c r e a s e s t h e t i m e neces-
s a r y t o make a measurement because of t h e extremely l o n g t i m e t h a t would
be s p e n t measuring t h e weak c o b a l t f i l t e r i n t e n s i t y . On t h e b a s i s of t h e
above c o n s i d e r a t i o n s w e have chosen t o d e s i g n our i n s t r u m e n t f o r e q u a l
f i x e d t i m e counting f o r both f i l t e r s .

46
 In general, the average count rate with the nickel filter is about
50 counts/sec and that for the cobalt filter is 7 counts/sec. In such a
case, with 57 sec for each measurement, the resulting most probable error
in the difference of the measurements is 2.3%. Hence, the accuracy of
the measurements can be increased considerably with no increase in the
time necessary to accumulate the data. Conversely, with an accuracy of
about 476, the time spent per 2" interva.1 can be reduced by more than a
factor of 3.
The modification of the instrument. includes a provision for automat-
ically interchanging the filters at each step of the diffractometer so
that a complete radial scan can be made automatically. Additional fea-
tures which have been incorporated in the modification to provide in-
creased flexibility of operation are:
1. Preset, time for each count may be selected from 1 to 1000 sec.
2. Data output in counts is automatically registered and printed on
paper tape.
3. The step between measurements may be varied from 0.01 to 17" 28 in
increments of 0.01".
4. The instrument may be operated either manually or automatically,
with or without balanced filters, ,and as a continuously scanning
diffractometer.

Positive control of each step of the diffractometer is necessary so

that no large accumulative error arises when many steps are made in the
e course of a run. This feature was provided by counting each revolution
of the drive gear and by means of a clutch and solenoid arrangement to
prevent coasting. The step scanning arrangement w a s designed by D. L.
?9 Holcomb of the Engineering and Mechanical Division.

TFNFERATURE DIFFUSE SCATT'ERING FOR CUBIC POWDER PATTERNS

B. Borie

Since the appearance of Warren's theory' for temperature diffuse

scattering (TDS) for cubic powder patterns, there has been interest in
its experimental application, and there have been efforts to refine it

--- -
'B. E. Warren, Acta Cryst. -6, 803 (1953).
47
 /

theoretically. It w a s used t o determine independently t h e atomic scat-

t e r i n g f a c t o r f and t h e Debye-Waller f a c t o r 2M of copper,2 and Herbstein
and Averbach3 modified t h e o r i g i n a l theory t o obtain a form v a l i d f o r t e m -
p e r a t u r e s s i g n i f i c a n t l y lower than t h e Debye temperature 0. More recently,
P a ~ k i n proposed
~ ' ~ a refinement of t h e Warren theory, and Chipman and
Paskin6 used it t o i n t e r p r e t t h e powder p a t t e r n s of copper and l e a d . It
i s t h e purpose here t o show t h a t t h e r e a r e inaccuracies i n t h e Paskin
theory, and t h a t t h e o r i g i n a l Warren formulation remains a u s e f u l ex-
pression f o r cubic powder p a t t e r n s .
I n general t h e TDS i n e l e c t r o n u n i t s may be w r i t t e n

R = 1

i s t h e Rth order TDS, o r t h a t p a r t of t h e d i f f u s e s c a t t e r i n g

where ITDa
e
a s s o c i a t e d with R-phonon processes. A t small values of s i n @/A t h e dom-
i n a n t term i s I but a t g r e a t e r distances from t h e o r i g i n i n recipro-
TD~'
c a l space, t h e higher order terms of Eq. (1)make i n c r e a s i n g l y important
contributions. Paskin's r e s u l t i s t h a t f o r a cubic powder p a t t e r n ,
ITDR
may be w r i t t e n

N f 2e-2M(2%)R

The Debye model of a l a t t i c e i s used, and it i s assumed t h a t only one-

and two-phonon processes make s i g n i f i c a n t c o n t r i b u t i o n s t o Eq. (l), s o
t h a t it may be w r i t t e n
i

The quantity 2% i s s i m i l a r b u t not i d e n t i c a l t o 2M i n t h e Paskin theory,

and C 1 and C 2 a r e functions of s i n @/A and t h e c e l l s i z e . Chipman and

2B. Borie, Acta Cryst. -

- 9, 617 (1956).
-
3F. H. Herbstein and B. L . Averbach, ---- 8, 843 (1955).
Acta C r y s t . -
-
'A. Paskin, Acta Cryst. -
11, 165 (1958).
-
--
5A. Paskin, Acta Cryst. 12, 290 (1959).
J. Appl. Phys. -
6D. R. Chipman and A. P a z i n , - 30, 1992 (1959).
I
3

Paskin6 assert t h a t C1 has an average value of approximately 1, and C 2 of

0 approximately 5 .

must be i d e n t i c a l l y equal, and t h a t

supposed t h a t C
e,)
It w i l l be shown here t h a t w i t h tlne Debye l a t t i c e model 2
= 1for a l l R.
may be w e l l approxima-ted by C1 f o r a l l a,
MD and
I f it i s t h e n
Eq. (1)be-
2M

R
c ome s
- Nf2e-2M(e2b! -
ITD-
which i s t h e o r i g i n a l Warren expression.

D i f f r a c t i o n Theory

We begin w i t h t h e well-known resu:Lt t h a t f o r a c r y s t a l w i t h one atom

p e r u n i t c e l l , t h e i n t e n s i t y i n e l e c t r o n u n i t s may be w r i t t e n

The v e c t o r 2= 2n (5- 20)/A, where 50 and 5 a r e u n i t vec.tors i n t h e di-

r e c t i o n s of t h e i n c i d e n t and s c a t t e r e d r a d i a t i o n , r i s a l a t t i c e vector,
-m
and 6 i s t h e instantaneous displacement of t h e mth atom from i t s equi-
-m
l i b r i u m p o s i t i o n due t o thermal motion. The average i n d i c a t e d i n t h e
exponent i s a time average. If we l e t 2M =
((&-&) 2,
, Eq. ( 2 ) may be
written

I = f2e-2M cc exp [i&.(& - -nr ):I exp (k

N.6Nm N -n
k-6 )+ N f 2 , (31
m f n

where N i s t h e t o t a l number of atoms i n t h e c r y s t a l . I f we s u b t r a c t t h e

3 Laue-Bragg s c a t t e r i n g ,

t h e remaining d i f f u s e s c a t t e r i n g i s

+ Nf2e-2M exp [ i & * k a - -n

1- )I {exp (k-6 N
k.6N ) - 1) .
~ (4)

49
1

To o b t a i n Eq. ( 4 ) , t h e double sum of Eq. ( 3 ) has been r e p l a c e d by N times

a s i n g l e sum over a l l s i t e s except m, which i s v a l i d i f t h e c r y s t a l i s
large.
W e expand t h e exponents i n b o t h of t h e b r a c e s of Eq. ( 4 ) t o o b t a i n
t h e s e r i e s form of I given by Eq. (1). Then
TD

- N f 2e-2M(2M)a 1+ exp [ i 5 . k m - L,)I

ITD-~ a!
n
(n # m)
where
I

I It i s c l e a r t h a t Aln i s independent of t h e magnitude of &. From

Eqs. 5.22 and 5 . 2 7 of James7 i t may be seen t h a t for a cubic c r y s t a l t h e
angular dependence of Aln on 5 is contained i n t h e q u a n t i t y

Here it i s assumed t h a t t h e thermal motion i s a consequence of t h e super-

p o s i t i o n of 3 N e l a s t i c waves i n t h e l a t t i c e ; w
i s t h e c i r c u l a r frequency
@j
of t h e l a t t i c e wave of phase v e c t o r 2 , and t h e sum over j i s taken over
t h e t h r e e independent orthogonal d i r e c t i o n s of v i b r a t i o n a s s o c i a t e d w i t h
@.The Boltzmann
N
constant k i s not t o be confused w i t h t h e v e c t o r 5. The
angle between t h e d i f f r a c t i o n v e c t o r and one of t h e t h r e e v i b r a t i o n a l di-
i-
r e c t i o n s i s given byIf f o r a given L i t i s assumed t h a t w
Q! i s in-
aj' @j
dependent of j (which i s equivalent t o assuming t h a t t h e v e l o c i t y of t h e
e l a s t i c waves i s independent of j), t h e n t h e above expression becomes in-
dependent of a@ j *
Hence, f o r a cubic c r y s t a l w i t h t h e Debye l a t t i c e model Aan does not
depend on t h e d i f f r a c t i o n v e c t o r and t h e q u a n t i t y i n b r a c e s i n Eq. ( 5 ) i s
simply t h e F o u r i e r s e r i e s r e p r e s e n t a t i o n of a p e r i o d i c f u n c t i o n u (k-) i n
a
7R. W. James, The O p t i c a l P r i n c i p l e s of t h e D i f f r a c t i o n of X-Rays,
-I

p 200, G. B e l l and Sons, London, 1948.

Qc,
I 50
3

k3 r e c i p r o c a l space whose average value i s u n i t y .

t i v e s i n c e w e expect 6 and&
I n general, ARn i s posi-
t o tend. t o have common d i r e c t i o n s . It i s
wn
less t h a n 1 and approaches zero as t h e d i s t a n c e between s i t e s m and n be-
comes l a r g e enough f o r t h e thermal mot.ion of t h e occupants of t h e s i t e s t o

be uncoupled. Hence, u,(&) has d i f f u s e m a x i m a a t t h e r e c i p r o c a l l a t t i c e

p o i n t s , and from Eq. ( 6 ) t h e m a x i m a become broader and l e s s pronounced
for larger R .
If u ( k ) i s averaged over a sphere i n r e c i p r o c a l space t o o b t a i n t h e
a
r e s u l t for a cubic powder of c e l l s i z e a t h a t

where C R i s a f u n c t i o n of t h e v a r i a b l e x = 2 a s i n B/h and perhaps of 2B =

2M ( s i n @/A)-', then it i s obvious t h a t t h e average of C over x must be
a
unity.

First-Order TDS w i t h t h e Debye L a t t i c e Model

W e comment b r i e f l y on t h e various t r e a t m e n t s of f i r s t - o r d e r TDS for

close-packed cubic powder p a t t e r n s , i n . t h e l i g h t of t h e above r e s u l t .
Given t h a t t h e thermal motion of t h e atoms i n a c r y s t a l may be rep-
r e s e n t e d by t h e s u p e r p o s i t i o n of 3 N e l a s t i c waves, and t h e assumptions
t h a t a l l waves have t h e same v e l o c i t y and t h a t each B r i l l o u i n zone may
k

be r e p l a c e d by a sphere of equal volume of r a d i u s %, Warren' derived ex-

p r e s s i o n s f o r u l and C1 v a l i d i n t h e high-temperature l i m i t t h a t t h e av-
erage energy E of each e l a s t i c wave i s kT. Using t h e more g e n e r a l r e s u l t
that

E = -1 hv c o t h -hv
2 2kT '

Herbstein and Averbach3 o b t a i n e d an expression f o r u1 v a l i d a t any t e m -

perature :

where i s a p o s i t i o n v e c t o r i n r e c i p r o c a l space from t h e c e n t e r of a

B r i l l o u i n zone, and @(X) i s t h e well-known Debye f u n c t i o n of t h e v a r i a b l e

51
X = O/T. I n t h e l i m i t as X approaches zero, u1 t a k e s on t h e form given
by Warren, and i t s average value over a B r i l l o u i n zone i s u n i t y , as re-
quired by Eq. ( 5 ) . The form of C 1 given by Herbstein and Averbach f o r a
face-centered cubic element degenerates i n t o t h e Warren expression f o r
s m a l l X, and does not deviate s i g n i f i c a n t l y from it even f o r X as l a r g e
as 4 . Hence, except a t very low temperatures, f o r most m a t e r i a l s t h e
Warren C 1 i s adequate.

Second-Order TDS with t h e Debye L a t t i c e Model

W e compute C 2 with t h e Debye model f o r t h e case t h a t E = kT. The

general expression given by Olmer8 and Walkerg may then be w r i t t e n

6
L

where vb i s t h e volume of t h e r e c i p r o c a l u n i t c e l l . The i n t e n s i t y i s a

f u n c t i o n of t h e v e c t o r y extending from t h e p o i n t of measurement i n r e -
N

c i p r o c a l space t o a r e c i p r o c a l l a t t i c e p o i n t . The i n t e g r a l i s c a r r i e d
out over t h e volume comon t o two B r i l l o u i n zones whose c e n t e r s are sepa-
r a t e d by a d i s t a n c e y . Since y may b e as l a r g e as 2%) a t any p o i n t i n
.U

r e c i p r o c a l space one may c o n s t r u c t permissible v e c t o r s y t o e i g h t nearby

N

reciprocal l a t t i c e points f o r a primitive l a t t i c e . The summation over Q

accounts f o r t h e s e e i g h t c o n t r i b u t i o n s t o t h e second-order TDS a t any
point.
The i n t e g r a l of Eq. ( 7 ) may b e evaluated t o give

for 0 5 y 5 gm and

Y 2 Y
1% + ... + - 1
n2
(2) n-1 + ..I} (9)

8P. Olmer, B u l l . SOC. -

f r a n c . mine'ral. 71, 145 (1948).
-
'C. B. Walker, -
Phys. Rev. 103, 547 (1956).
-
52

t
for Iy 5 2%. After a p p r o p r i a t e averaging of E q s . (8) and ( 9 ) f o r a
face-centered cubic powder, C,(x) as shown i n Fig. 4.2 i s obtained. The
computation of t h i s curve i s t e d i o u s b u t not d i f f i c u l t , and t h e d e t a i l s
of t h e c a l c u l a t i o n w i l l not be reproduced here. Also shown i n Fig. 4 . 2
i s C l ( x ) as given by Warren.
UNCLASSIFIED
ORNL-LR-OWG50284
2.0 I I

Fig. 4.2. The Functions C , ( x ) and c,(x).

Except at t h e origin C , i s everywhere finite.

D i sc us s i on

Given t h e above r e s u l t , c e r t a i n discrepancies between theory and ex-

periment f o r copper and l e a d as r e p o r t e d by Chipman and Paskin6 may be
understood. I n both cases it w a s found that though there was agreement
a t high s c a t t e r i n g angles, a t small 28 t h e r e was apparently more d i f f u s e
s c a t t e r i n g than could be accounted f o r by theory, and it w a s concluded
t h a t t h e e x t r a s c a t t e r i n g w a s due t o some real b u t not understood e f f e c t .
We now see t h a t , because of t h e abnorma:lly l a r g e value of C2 used, Chipman
and Paskin were f o r c e d t o choose a sma1:L value of 2% t o f i t experiment a t
large 28. Hence, i n t h e low-angle region where second-order TDS contribu-
t i o n s a r e n e g l i g i b l e , t h e i r computed d i f f u s e s c a t t e r i n g i s t o o small by a
f a c t o r of approx 2%/2%, where 2% i s t h e value obtained with t h e Warren
theory. From t h e i r data, t h i s i s 68$ i n t h e case of copper. This cor-
r e c t i o n very n e a r l y accounts for t h e e x t r a d i f f u s e s c a t t e r i n g . For l e a d ,
s i n c e 2B i s very l a r g e , one may not neg:Lect I
TDR
for R > 2 as i s done i n

53
 t h e Paskin theory. I f we t a k e 2B t o b e 5 , a t t h e l i m i t i n g sphere f o r
copper r a d i a t i o n t h e average value of I i s approx 75% of t h a t of ITD1,
TD3
and t h e r e are s i g n i f i c a n t c o n t r i b u t i o n s from I and I
TD4 TD5 '
Though t h e Warren expression i s a good approximation, a t l a r g e val-
ues of 2M t h e assumption t h a t C = C i for a l l 4 introduces r a t h e r more
a
s t r u c t u r e i n t h e d i f f u s e s c a t t e r i n g than t h e r e s h o u l d b e . From Fig. 4.2
w e see t h a t t h e a c t u a l value of C2 over t h e range of x f o r which it w a s
computed i s approximately half'way between C2 = C 1 and C2 = 1 except a t
t h e Bragg m a x i m a , where t h e d i f f u s e s c a t t e r i n g i s not observable. If we
t a k e C2 = 1/2 (1+ C l ) , and Ca = 1 f o r R > 2, we o b t a i n

ITD
= Nf2(1 - e-2M) + N f 2 e - 2 M ( C 1 - 1)(2M + M 2 ) .
The above r e s u l t should be accurate f o r any 2M, and may be very e a s i l y
f i t t e d t o experimental measurements.
a
X-RAY DIFFRACTION STUDIES OF C U ~ OFILMS GROWN ON COPPER

B. Borie
C . J. Sparks J. V. Cathcart

I n a previous report" t h e r e has been described a method f o r t h e

i n t e r p r e t a t i o n of t h e shapes of t h e Bragg maxima of very t h i n oxide f i l m s
i n terms of t h e i r t h i c k n e s s and s t r a i n . There has a l s o been reported'' a
second independent x-ray d i f f r a c t i o n technique f o r t h e measurement of t h i n
f i l m thickness, based on i n t e g r a t e d i n t e n s i t y measurements i n a b s o l u t e
units. It has been shown t h a t film thicknesses as determined by t h e two
I
methods agree w i t h i n experimental e r r o r , s o t h a t one may have confidence
i n t h e s t r a i n determination r e s u l t i n g from t h e l i n e contour a n a l y s i s .
Included i n t h e l a s t report'' were t h e r e s u l t s of t h e l i n e shape i n t e r -
p r e t a t i o n s f o r f i v e f i l m s of CuzO grown on 110 f a c e s of f l a t copper sin-
g l e c r y s t a l s a t 250°C i n 1 a t m of oxygen. Figure 4.3 summarizes t h e s e
results: The i n t e r p l a n a r spacing d of t h e 110 planes (which a r e p a r a l l e l

'OB. S. Borie and J. V. Cathcart, Met. A n n . B o g . Rep. Oct. 10,

1958, ORNL-2632, p 34 ( c l a s s i f i e d ) .
"B. S. Borie, C . J. Sparks, and J. V. Cathcart, Met. Ann. prog.
-
Rep. Sept. 1, 1959, ORNL-2839, p 66.

54
 UNCLASSIFIED
ORNL-LR-DWG 42661
3.11

3.10

3.09

3.08

I
3.07
4
I

b
3.06

3.05

3.04

3.03

3.02
I
0 50 100 150 200 250 300 350 400 450
L(A)

Fig. 4.3. T h e Variation of the Interplanar Spacing of the (110)

Planes Through the F i l m Thickness for F i v e Films. T h e corresponding
spacing in bulk Cu,O i s 3.019 A.

t o t h e f i l m s u r f a c e ) v a r i e s e s s e n t i a l l y l i n e a r l y from one i n t e r f a c e t o
t h e o t h e r ; t h e r a t e of change of d through t h e f i l m decreases as t h e f i l m
grows and becomes t h i c k e r ; a t one i n t e r f a c e ( t h a t a t which d i s smallest)
a l l of t h e f i l m s have approximately t h e same d; and a t a l l p o i n t s i n a l l
of t h e f i l m s d i s g r e a t e r than t h a t found i n b u l k C u 2 0 .
It i s t h e i n t e n t i o n of t h i s r e p o r t t o discuss f u r t h e r experiments and
considerations which have helped us decide which i n t e r f a c e i s t h a t of t h e
oxide-gas, and which i s t h a t of t h e oxide-metal (information not a v a i l a b l e
from t h e d i f f r a c t i o n experiment d i r e c t l y ) , and which have helped us t o
understand t h e cause of t h e s t r a i n and t o devise a model f o r t h e d i s t o r t e d
oxide l a t t i c e c o n s i s t e n t with a l l of t h e experimental observations.
It i s known12 t h a t t h e mechanism of growth, a t l e a s t f o r t h i c k f i l m s
of Cu20, i s t h a t of c a t i o n vacancy d i f f u s i o n . We consider f i r s t t h e pos-
s i b i l i t y t h a t i n t h i n f i l m s such p o i n t d e f e c t s produce a general l a t t i c e

l2O. Kubashewski and B. E . Hopkins, Oxidation of Metals and Alloys,

p 26-36, Academic Press, I n c . , New York, 1953.

55
 expansion, and t h a t t h e l a t t i c e constant v a r i a t i o n through t h e f i l m i s due
t o a gradient i n t h e concentration of t h e defects, t h e r e being a l a r g e r
number near one i n t e r f a c e than t h e o t h e r . Two experiments were proposed
and performed t o t e s t t h i s p o s s i b i l i t y :
Annealing Experiment.
1. - - It w a s f e l t that i f the strain i n the
f i l m were due t o a nonuniform d i s t r i b u t i o n of point defects, a heat t r e a t -
ment would cause them t o become more uniformly d i s t r i b u t e d and thus reduce
the s t r a i n . Films of s e v e r a l hundred angstroms i n thickness were examined
before and a f t e r anneals a t a pressure of approx 1 x mm Hg a t 250°C
f o r 20 h r . Usually t h e r e s u l t of such an experiment w a s not c l e a r , be- .-.&

cause under such conditions t h e films grew i n thickness by 20 t o 30%. How-

ever, i n one case t h e thickness change w a s found t o b e s m a l l . For t h i s
f i l m no s i g n i f i c a n t change i n t h e s t r a i n w a s observed, though t h e r e w a s
6
a s m a l l change i n t h e average value of d. Though t h i s r e s u l t i s not en-
t i r e l y unambiguous, it tends t o c o n t r a d i c t t h e hypothesis of a nonuniform
d i s t r i b u t i o n of point defects.
2. -
L a t t i c e Constant Measurements. - For a cubic material such as
Cu20, a concentration of point defects should cause an i s o t r o p i c expan-
s i o n o r contraction of t h e l a t t i c e . To determine whether o r not t h i s s i t -
uation obtained, measurements of 28 f o r a number of planes hkR not paral-
l e l t o t h e f i l m surface were made. A c e r t a i n amount of defocusing of our
diffractometer r e s u l t s from the t i l t i n g of t h e specimen necessary f o r such
measurements; however, with a c a r e f u l l y aligned instrument, t h e r e should be
no e f f e c t on t h e l i n e p o s i t i o n s . Table 4.1 summarizes t h e r e s u l t s of t h e s e
I

measurements f o r a f i l m approx 200 A t h i c k . The orthorhombic axes used

f o r indexing t h e r e f l e c t i o n s from t h e f i l m are such t h a t a i s normal t o 6
t h e film, and b and c l i e i n t h e plane of t h e film. If t h e f i l m were un-
d i s t o r t e d compared t o bulk Cu20, then a and b would be face diagonals of
t h e cubic c e l l and c would be t h e cubic c e l l edge. Included i n t h e t a b l e
a r e t h e cubic indices and t h e values of s i n 2 8 c a l c u l a t e d from t h e bulk
l a t t i c e constant. It i s c l e a r from t h e s e data t h a t t h e average u n i t c e l l
i n t h e f i l m has been d i s t o r t e d , though i t s volume remains unchanged.
Hence, a nonuniform d i s t r i b u t i o n of point defects i s not t h e cause of t h e
observed s t r a i n i n t h e l a t t i c e .

56

CL
L
 Table 4.1. Indexing of Bragg Angle Measurements for a Film of Cu20

Cubic Indexing w i t h Bulk

Orthorhombic Indexing
L a t t i c e Constant
Observed
sin2 e C a l c u l a t ed
HKL Calculated
sin2 e hkl
sin2 e

0.0632 0.0632 200 0.0652 110

0.0660 0.0658 111 0.0652 101
0.0965 0.0968 201 0.0978 111
0.1281 0.1286 220 0.1304 200
0.1918 0.1922 311 0.1956 211
0.1967 0.1976 202 0.1956 112
0.2527 0.2527 400 0.2608 220
0.2626 0.2630 222 0.2608 202
0.3869 0.3871 402 0.3901 222
0.5144 0.5143 440 0.5205 400
0.6213 0.6205 423 0.6183 313
0.6492 0.6487 442 0.6509 402

Orthorhombic l a t t i c e c o n s t a n t s Tetragonal l a t t i c e c o n s t a n t s computed

f o r the film: from cubic c e l l s i z e of b u l k oxide:
a = 6.131 If: 0.002 A a = 6.038 A
b = 6.029 t 0.008 A c = 4.270 A
c = 4.206 f 0.006 A C e l l volume = 155.67 A3
C e l l volume = 155.47 t 0.5 A3

he now consider t h e p o s s i b i l i t y t h a t t h e observed l a t t i c e d i s t o r t i o n

arises from t h e e p i t a x i a l r e l a t i o n of t h e oxide and metal. Table 4.1
shows t h a t on t h e average t h e area of t h e bc f a c e of t h e oxide c e l l , which
i s p a r a l l e l t o t h e metal-oxide i n t e r f a c e , i s c o n t r a c t e d , while a i s ex-
panded, j u s t enough t o conserve t h e average c e l l volume. I f we suppose
t h a t t h e c o n t r a c t i o n i s t h e result of an e f f o r t on t h e p a r t of t h e oxide
' t o approach t h e smaller l a t t i c e c o n s t a n t s of copper a t t h e metal-oxide
i n t e r f a c e , t h e n a t t h i s i n t e r f a c e t h e c o n t r a c t i o n should b e g r e a t e s t and
a should t a k e on i t s l a r g e s t value. This allows us t o i d e n t i f y t h i s i n -
t e r f a c e t o be t o t h e r i g h t i n Fig. 4.3, while t h e gas i n t e r f a c e i s a t t h e

57
 e
Note from Table 4 . 1 t h a t almost a l l of t h e c o n t r a c t i o n i s ac-
origin.
counted f o r by a decrease i n c, while t h e b axis, which i s t h e d i r e c t i o n
Q
h

of c l o s e s t packing of metal atoms, b o t h i n t h e oxide and t h e metal, has

decreased very l i t t l e , i f any, compared t o t h e b u l k m a t e r i a l . I n t h e f o l -
lowing it w i l l be assumed t h a t b i s unchanged through t h e f i l m thickness
and i s s u b s t a n t i a l l y equal t o i t s b u l k value, while a i n c r e a s e s as t h e
metal i n t e r f a c e is approached and c decreases i n such a way t h a t t h e i r
product i s a constant, t h u s conserving t h e volume of each u n i t c e l l . Since
we know a as a f u n c t i o n of p o s i t i o n through t h e f i l m thickness (a i s s i m -
p l y twice d as p l o t t e d i n F i g . 4.3), we may compute c a t any point between
the interfaces. Figure 4.4 i s a p l o t of t h i s c e l l dimension a t t h e two
i n t e r f a c e s as a f u n c t i o n of f i l m t h i c k n e s s T, as computed from t h e d a t a of
Fig. 4.3. W e see t h a t a t t h e unconstrained oxide-gas i n t e r f a c e , t h e u n i t
c e l l dimensions a r e e s s e n t i a l l y independent of T and equal t o those of t h e c
bulk m a t e r i a l . A t t h e metal-oxide i n t e r f a c e , t h e c o n t r a c t i o n of t h e bc
f a c e of t h e u n i t c e l l decreases as t h e f i l m grows, l e a v i n g t h i c k e r f i l m s
l e s s strained.
If we assume t h a t t h e oxide f i l m i s continuous over t h e metal sur-
f a c e , t h e n t h e number of atomic planes p e r u n i t l e n g t h i n t h e c d i r e c t i o n
must be g r e a t e r a t t h e metal i n t e r f a c e than a t t h e gas i n t e r f a c e , t h u s
giving r i s e t o edge d i s l o c a t i o n s w i t h Burger's v e c t o r [OOl]. Figure 4.5
i s a p l o t of t h e density of such d i s l o c a t i o n s i n t h e f i l m as a f u n c t i o n
of i t s t h i c k n e s s , as determined from Fig. 4.4. The d e n s i t y i s seen t o be
high, on t h e order of t h a t observed i n cold-worked metals.

4301
4 . 2 5 H
I
1
I
= + -
\AT
I I

T H E GAS INTERFACE
UNCLASSIFIED
I I
1
ORNL-LR-DWG 50232
I

4.15

4.10
0 50 100 450 200 250 300 350 400 450
FILM THICKNESS ( A )

Fig. 4.4. T h e U n i t Cell Dimension c at t h e T w o Fig. 4.5. Dislocation Density as a Function o

Oxide Interfaces a s a Function of F i l m Thickness. F i l m Thickness.

58
 The above discussion must be confined t o f i l m s approx 140 A t h i c k
or thicker. Without changing temperature o r pressure, it i s very dif-
f i c u l t t o prepare f i l m s t h i n n e r t h a n t h i s , s i n c e i n t h i s range t h e growth
r a t e i s extremely r a p i d and it i s d i f f i c u l t t o s t o p t h e o x i d a t i o n reac-
t i o n s u f f i c i e n t l y quickly. Nevertheless, it appears p o s s i b l e t o consider
t h e o x i d a t i o n process as being divided i n t o two s t a g e s , s t a g e I covering
t h e development of oxide f i l m t o t h i c k n e s s e s l e s s t h a n 140 A and s t a g e
I1 involving t h i c k e r f i l m s . I n t h e following, apparent d i f f e r e n c e s i n
t h e two s t a g e s a r e discussed.
I n stage I (T < 140 A ) , t h e oxide f i l m s u f f e r s maximum d e v i a t i o n
Q from t h e b u l k l a t t i c e c o n s t a n t s because of i t s attachment t o t h e metal.
As T i n c r e a s e s , t h e two curves of Fig. 4.4 diverge from a common value
a t T = 0; t h u s t h e number of d i s l o c a t i o n s p e r u n i t l e n g t h i n t h e c d i -
rp
rection i n the film increases. The growth r a t e i s very r a p i d ; and t h e
l a t t i c e c o n s t a n t s a t t h e gas i n t e r f a c e a r e probably q u i t e d i f f e r e n t from
t h o s e of t h e b u l k m a t e r i a l . Probably t h e f i l m i s very nonuniform i n
thickness. The end of s t a g e I i s c h a r a c t e r i z e d by a maximum number of
d i s l o c a t i o n s per u n i t l e n g t h , and by t h e achievement of l a t t i c e c o n s t a n t s
n e a r l y equal t o those of t h e b u l k m a t e r i a l a t t h e gas i n t e r f a c e .
The onset of s t a g e I1 i s c h a r a c t e r i z e d b y a decrease i n d i s l o c a t i o n
d e n s i t y as t h e f i l m grows, accompanied.by changes i n t h e l a t t i c e c o n s t a n t s
a t t h e metal i n t e r f a c e toward t h a t of t h e b u l k m a t e r i a l . The f i l m i s now
s u f f i c i e n t l y t h i c k t h a t i t s atomic c o n f i g u r a t i o n i s determined p r i m a r i l y
by a need t o minimize t h e energy p e r u n i t volume a s s o c i a t e d w i t h t h e
s t r a i n , and t h e m i s f i t energy of t h e metal-oxide i n t e r f a c e becomes l e s s
important. The decrease i n t h e d i s l o c a t i o n d e n s i t y i s accomplished by
climb of d i s l o c a t i o n s toward t h e metal i n t e r f a c e , t h e d i s l o c a t i o n s d i s -
appearing upon reaching i t . A t r a n s f e r of mass i s r e q u i r e d i n t h i s proc-
ess, and one of t h e mechanisms f o r t h e t r a n s p o r t of copper i o n s through
t h e oxide f i l m may involve j u s t such d i s l o c a t i o n climb. Perhaps more i m -
p o r t a n t l y , t h e rate of d e f e c t diffusio:n i n t h e oxide may b e influenced by
t h e change i n t h e s t r e s s s t a t e i n t h e oxide a s s o c i a t e d w i t h t h e change i n
dislocation density. The above-discussed annealing experiment also shows
t h a t t h e s t r a i n , and, t h e r e f o r e , t h e d i s l o c a t i o n density, a r e u n a f f e c t e d
by h e a t treatment, suggesting t h a t t h e d i s l o c a t i o n s may climb out of t h e

59
 f i l m only when a copper atom s i n k i s present, f o r example, when an oxi-
dizing atmosphere i s a v a i l a b l e t o remove copper from t h e f i l m by t h e for-
mation of new oxide.
It i s necessary t o emphasize t h a t much of t h e above discussion, while
c o n s i s t e n t w i t h t h e a v a i l a b l e evidence, i s hypothesis, u s e f u l a t t h e mo-
ment mainly as a basis f o r t h e design of new experiments.
A v a r i e t y of such experiments suggest themselves. For example, i f
t h e a and c axes of t h e orthorhombic c e l l vary through t h e f i l m thickness
as described above, then one s e t of (111) planes (cubic i n d i c e s ) i n t h e
oxide should show very l i t t l e s t r a i n broadening. The x-ray d i f f r a c t i o n
l i n e contours of t h e 111 and 222 d i f f r a c t i o n m a x i m a should be i n t e r p r e t -
a b l e almost e n t i r e l y i n terms of p a r t i c l e s i z e l i n e broadening. If t h i s
i s indeed t h e case, it w i l l c o n s t i t u t e valuable evidence f o r t h e correct-
ness of t h e above-described oxidation model. Such an experiment w i l l soon k-
be attempted.

L i t t l e i s known about t h e very i n t e r e s t i n g s t a g e I. There e x i s t s

o p t i c a l evidence described elsewhere i n t h i s report13 t o i n d i c a t e t h a t
t h e termination of t h i s s t a g e corresponds t o maximum s t r a i n i n t h e film,
but there are no d i f f r a c t i o n data t o provide c l u e s t o i t s d e t a i l e d struc-
ture. E f f o r t s t o prepare f i l m s i n t h i s thickness range f o r x-ray d i f f r a c -
t i o n measurements are now under way.
F i n a l l y , t h e r e are no data t o i n d i c a t e t h e f a t e of t h e metal immedi-
a t e l y below t h e i n t e r f a c e during t h e formation of t h e film. The above dis-
cussion suggests t h a t t h e oxide accommodates i t s e l f t o t h e metal l a t t i c e
I by a c o n t r a c t i o n of i t s c a x i s , though i t s b a x i s remains unchanged. The

I [I101 d i r e c t i o n i n t h e metal i s p a r a l l e l t o b, and it may be t h a t an ex-

pansion i n t h e metal i n t h i s d i r e c t i o n , perhaps accommodated by edge dis-
l o c a t i o n s w i t h Burger's vector 1/2 [1101, develops to provide an improved
match w i t h t h e oxide l a t t i c e . The high p e n e t r a t i n g power of x rays causes
t h e d i f f r a c t i o n p a t t e r n from t h e metal t o be i n s e n s i t i v e t o t h e s t a t e of
i t s surface. It i s intended t o attempt t o perform oxidation experiments
w i t h very t h i n (about 300 A ) m e t a l s i n g l e - c r y s t a l films. It i s hoped t h a t
i n such a case t h e d i f f r a c t i o n p a t t e r n from t h e metal may contain informa-
t i o n about t h e condition of i t s surface.

13J. V. Cathcart, "Oxidation Studies on Copper," t h i s r e p o r t .

I '-.
 5. REACTIONS AT m!ru SURFACES

J . V. C a t h c a r t

OXIDATION STUDIES ON COPPER

J . V. C a t h c a r t G. F. P e t e r s e n

I n v e s t i g a t i o n s of t h e o p t i c a l a n i s o t r o p y of t h i n oxide f i l m s on copper
and t h e r e l a t i o n s h i p of t h e s e p r o p e r t i e s t o t h e s t a t e of s t r a i n i n t h e oxide
f i l m s have been c o n t i n u e d . The work i s c l o s e l y r e l a t e d t o an x - r a y d i f f r a c -
t i o n s t u d y of l a t t i c e d i s t o r t i o n s i n thi.n Cu20 films; t h i s l a t t e r r e s e a r c h
i s b e i n g performed i n c o o p e r a t i o n w i t h t h e M i c r o s t r e s s e s i n C r y s t a l s Group
@
of t h e M e t a l l u r g y D i v i s i o n and i s d e s c r i b e d i n Chap. 4 of t h i s r e p o r t .

Q Re s u l t E;

A p o l a r i z i n g s p e c t r o m e t e r l S 2 w a s w e d t o determine t h e t h i c k n e s s e s of
t h i n Cu20 f i l m s formed on v a r i o u s c r y s t a l l o g r a p h i c p l a n e s o f copper s i n g l e
crystals. I n t h e course of t h e measurements i t w a s observed t h a t , d e s p i t e
t h e f a c t t h a t t h e c r y s t a l l a t t i c e s f o r b o t h copper and b u l k Cu20 are c u b i c ,
t h e oxide f i l m s formed on t h e (311) and (110)p l a n e s of copper e x h i b i t e d
marked o p t i c a l a n i s o t r o p y . T h i s a n i s o t r o p y m a n i f e s t e d i t s e l f as a p e r i o d i c
v a r i a t i o n i n t h e a p p a r e n t t h i c k n e s s o f t h e oxide f i l m when a specimen w a s
r o t a t e d about, i t s s u r f a c e normal, on t h e s t a g e of t h e p o l a r i z i n g spectrom-
eter. Films formed on t h e (311) and (113) p l a n e s e x h i b i t e d very s i m i l a r
c h a r a c t e r i s t i c s , and a t y p i c a l s e t of d a t a f o r t h e oxide on t h e (311) p l a n e
of copper i s shown i n F i g . 5.1. The a p p a r e n t f i l m t h i c k n e s s i s p l o t t e d
a g a i n s t t h e a n g l e o f r o t a t i o n o f t h e specimen about i t s s u r f a c e normal.
Maxima and minima i n the t h i c k n e s s valueis o c c u r r e d a t 90' i n t e r v a l s d u r i n g
rotation. The maxima and minima were observed when t h e [110] and [loo]
d i r e c t i o n s , r e s p e c t i v e l y , i n t h e p l a n e of t h e oxide (see Table 5 . 1 ) l a y
i n t h e p l a n e of i n c i d e n c e o f t h e s p e c t r o m e t e r .

'0. Kubaschewski and B. E . Hopkins, O x i d a t i o n o f Metals and A l l o y s ,

p 106-10, Academic Press, New York, 1953.
2A. B. Winterbottom, " O p t i c a l S t u d i e s of Metal S u r f a c e s , Ql. Norske
Videnskab. S e l s k a b s , S k r i f t e r 1955, p 1-149.

61
 UNCLASSIFIED
ORNL-LR-DWG 50234

- 460
4
I

m
m
2 440
Y
0
I
I-
f 420
-
LL
I-
z
!$ 400
2
a
4
380
0 90 180 270 360
ANGLE OF ROTATION ABOUT SPECIMEN NORMAL (deg)

Fig. 5.1. Variation of Apparent Oxide Film Q

Thickness on the (311) and (100) Planes of Copper.

Table 5.1. E p i t a x i a l Relationship Between Cu2O and Cu Q

D i r e c t i o n i n Surface
Plane Plane of Oxide P a r a l l e l of Oxide P a r a l l e l t o
of Copper t o Cu Surface [110] i n Surface
of Metal

(100) ( 111) [ 1101

(111) ( 111) L1101
(110) (110) [1101
( 311 ) (110) [ 1101

No such v a r i a t i o n i n apparent f i l m t h i c k n e s s w a s observed f o r oxide

films formed on t h e (111) o r t h e (100) plane of copper. A t y p i c a l s e t of
d a t a f o r t h e (100) plane i s shown i n Fig. 5 . 1 .
e
An attempt w a s a l s o made t o determine t h e change i n t h e degree of
anisotropy of t h e oxide as a f'unction of f i l m t h i c k n e s s . The "degree of
anisotropy" f o r a given f i l m w a s defined i n terms of i t s apparent t h i c k -
ness values:

degree of anisotropy = (max t h i c k n e s s - min thickness)/max t h i c k n e s s .

P l o t s of degree of a n i s t r o p y vs t h e average f i l m t h i c k n e s s a r e shown i n
F i g s . 5 . 2 and 5 . 3 f o r oxide f i l m s formed on t h e (110) and t h e (311) plane,
r e s p e c t i v e l y , o f copper. The data f o r t h e (110) plane were obtained from

62

Q
a
UNCLASSIFIED
ORNL-LR- DWG 50235
0

-
UNCLASSIFIED
52 ORNL-LR-DWG 50236
X
48
T
L?64 11 40
'=z :- 0 N TEMPERATURE
z : p.
L=
I
:E
(3
2 32
2 48 L1? . t
L= :: > 24
iL
II =.+z
LL
0
16
h: W
& ::
I

8 32
E h..
b c3 w 8
E
z
a 0
16 0 200 400 600 800 1000
AVERAGE APPARENT FILM THICKNESS ( A )
1
w
0
n
0
0 ZOO 400 600 800 to00 1200 Fig. 5.3. Variation of Degree o f Anisotropy of
AVERAGE APPARENT FILM THICKNESS (A)
Oxide on the (311) Plane of Copper as a Function
Fig. 5.2. Variation of Degree of Anisotropy 01 o f F i l m Thickness.
Oxide on the (110) Plane of Copper as a Function
of F i l m Thickness.

specimens oxidized a t a s e r i e s of temperatures from 150 t o 300"C, although

most o f t h e p o i n t s shown on t h e curve were from o x i d a t i o n s a t 25OoC. Data
f o r t h e (311) plane were obtained from samples oxidized a t 250 and 30OoC.
A s may be seen from t h e curves, t h e range of oxide t h i c k n e s s e s covered a t
t h e various temperatures of oxidation overlapped considerably, t h e r e s u l t s
i n d i c a t i n g t h a t t h e degree of anisotropy o f t h e oxide w a s not a s e n s i t i v e
f i n e t i o n of o x i d a t i o n temperature.

D i scus s i on
B) Variation o f O p t i c a l Anisotropy w i t h C r y s t a l Plane

The occurrence of o p t i c a l anisotropy i n oxide f i l m s on t h e (110) and

(311) p l a n e s o f copper and i t s absence i n f i l m s on t h e (111) and (100)
p l a n e s appear t o be a t l e a s t p a r t i a l l y i n t e r p r e t a b l e i n terms of t h e e p i -
t a x i a l r e l a t i o n s h i p s between t h e oxide f i l m s nd t h e metal s u b s t r a t e and
t h e r e s u l t i n g s t r a i n s s e t up i n t h e oxide l a t i c e . A s i s well known, t h i n
oxide f i l m s on copper s i n g l e c r y s t a l s a r e h i g o r i e n t e d and may be r e -

garded as pseudo-single c r y s t a l s . The e p i t a r e l a t i o n s h i p between t h e

oxide and metal a r e summarized i n Table 5.1.

3K. R . Lawless and A. T. Gwathmey, 4, 1 5 3 6 3 (1956).

-

63
 When a cuprous oxide f i l m i s viewed symmetrically with r e s p e c t t o t h e
f i l m normal, as i s t h e case f o r t h e p o l a r i z i n g spectrometer measurements,
the observance o f o p t i c a l anisotropy r e q u i r e s t h a t t h e c r y s t a l l a t t i c e i n
t h e plane of t h e oxide f i l m be s t r a i n e d i n such a way as t o have l o s t t h e
elments of cubic symmetry.

It i s t o be expected t h a t t h e above c o n d i t i o n i s f i l f i l l e d i n t h e
case of t h e oxide formed on t h e (311) plane of copper, since t h e symmetry
of t h e s u b s t r a t e i s d i f f e r e n t from t h a t of t h e p a r a l l e l plane of t h e oxide.
Under such circumstances the m i s f i t between t h e oxide and t h e metal and,
t h e r e f o r e , t h e e p i t a x i a l l y induced s t r e s s e s i n t h e plane of t h e oxide should
be d i f f e r e n t i n d i f f e r e n t d i r e c t i o n s . Hence, t h e oxide f i l m s should e x h i b i t
o p t i c a l anisotropy.
The oxide forms on t h e (110) plane of copper with i t s l a t t i c e com-
p l e t e l y p a r a l l e l t o t h a t of t h e s u b s t r a t e ( s e e Table 5 . 1 ) . However, t h e
r a t i o of t h e e l a s t i c c o n s t a n t s f o r t h e oxide i n [110] and [loo] d i r e c t i o n s
i s d i f f e r e n t from t h a t of t h e metal; t h e r e f o r e , t h e oxide f i l m on t h e (110)
plane would i n g e n e r a l a l s o be d i s t o r t e d a n i s o t r o p i c a l l y .
This l i n e of reasoning i s n o t only c o n s i s t e n t with t h e o p t i c a l proper-
t i e s e x h i b i t e d by t h e oxide f i l m s on t h e (110) plane, it i s a l s o i n agree-
ment with t h e x-ray d i f f r a c t i o n data discussed i n Chap. 4 of t h i s r e p o r t .
That study revealed t h a t , compared with those of t h e bulk oxide, t h e l a t t i c e
parameters i n t h e f i l m remained unchanged i n t h e [110] d i r e c t i o n l y i n g i n
t h e plane of t h e f i l m b u t were abnormally s m a l l i n t h e [loo] d i r e c t i o n i n e
t h e plane of t h e f i l m .
The s i t u a t i o n on t h e (111)plane of copper, however, i s d i f f e r e n t Not
o n l y a r e t h e l a t t i c e s of t h e oxide and metal completely p a r a l l e l t o one 6
another, b u t t h e t h r e e f o l d symmetry e x h i b i t e d by both r e q u i r e s c i r c u l a r
symmetry f o r t h e s t r e s s e s developed i n t h e (111)p l a n e . Thus, any d i s -
t o r t i o n of t h e oxide l a t t i c e should be c i r c u l a r l y symmetrical about t h e
surface normal and t h e f i l m should e x h i b i t no o p t i c a l anisotropy.
O p t i c a l anisotropy w a s not observed i n oxide f i l m s formed on t h e (100)
plane, although t h e d i f f e r e n c e i n t h e symmetry o f t h e oxide and s u b s t r a t e
f o r t h e (100) plane of copper suggests t h a t t h e oxide on t h i s plane might
have o p t i c a l p r o p e r t i e s similar t o those of oxide on t h e (311) plane o f

64

0
 copper. Indeed, preliminary x-ray measurements of t h e oxide l a t t i c e param-
e t e r s showed t h a t r e l a t i v e t o bulk oxide t h e average l a t t i c e spacing normal
t o t h e s u r f a c e of t h e oxide i s expanded. I n t h e plane of t h e film, t h e
average spacing of t h e oxide i n t h e [110] d i r e c t i o n which p a r a l l e l s a [110]
d i r e c t i o n i n t h e metal remains almost unchanged, but t h e average spacing
i s c o n t r a c t e d i n t h e d i r e c t i o n p a r a l l e l t o t h e o t h e r s e t of [llO] d i r e c -
t i o n s i n t h e surface of t h e metal.
It i s believed t h a t t h e l a c k of o p t i c a l anisotropy on t h e (100) plane
i s a t t r i b u t a b l e t o t h e various twin r e l a t i o n s h i p s a v a i l a b l e t o t h e oxide
on t h a t plane. The general e p i t a x i a l r e l a t i o n s h i p of t h e oxide and metal
i s i l l u s t r a t e d schematically i n Fig. 5 . 4 . The e x i s t e n c e of t h r e e s e t s of

UNCLASSIFIED
ORNL-LR-DWG 5 0 2 3 7

p;[f 1 D I RECTI ONS

IN10Cu20

- [Of 01C"

Fig. 5.4. Schematic Representation o f Epitaxial

Relationship of Cu,O to Cu on the (100) Plane of
Copper. T h e four possible crystallographically
equivalent Orientations o f the oxide are indicated
by the triangles A , B , c,
and D.

[llO] d i r e c t i o n s i n t h e oxide and two s e t s of [llO] d i r e c t i o n s i n t h e metal

implies t h e p o s s i b i l i t y of four d i f f e r e n t , b u t c r y s t a l l o g r a p h i c a l l y equiva-
l e n t , o r i e n t a t i o n s f o r t h e oxide as represented by t h e t r i a n g l e s A, B, C,
and D . All four such o r i e n t a t i o n s have been observed3 i n x-ray d i f f r a c t i o n
s t u d i e s of Cu,O f i l m s . The d i r e c t i o n s i n t h e oxide i n which a c o n t r a c t i o n
of t h e average l a t t i c e spacing occurs a r e shown by t h e dashed arrows i n s i d e

65

a
 the t r i a n g l e s . The s o l i d arrows w i t h i n t h e t r i a n g l e s i n d i c a t e those d i r e c -
t i o n s i n which t h e average l a t t i c e spacing remains e s s e n t i a l l y unchanged.
It w i l l be noted t h a t A and B form a p a i r of o p t i c a l l y and c r y s t a l l o g r a p h i -
c a l l y equivalent o r i e n t a t i o n s a s do C and D. However, t h e A-B and C-D
p a i r s a r e not o p t i c a l l y equivalent b u t have s e t s of " o p t i c axes" d i f f e r i n g
i n o r i e n t a t i o n by a r o t a t i o n of 90" i n t h e plane of t h e f i l m . Thus, if it
i s imagined t h a t t h e oxide f i l m on t h e (100) of copper c o n s i s t s of many,
s m a l l , randomly d i s t r i b u t e d patches of oxide whose o r i e n t a t i o n s a r e d i s -
t r i b u t e d e q u a l l y among A, B, c, and D, t h e o p t i c a l e f f e c t s of t h e A-B and
C-D p a i r s would t e n d t o compensate each o t h e r , producing an apparently
o p t i c a l l y isotropic film.
The arguments j u s t presented t o j u s t i f y t h e e x i s t e n c e of a n i s o t r o p i c
s t r a i n s i n t h e oxide f i l m s imply t h a t t h e metal s u b s t r a t e likewise may be
strained anisotropically. However, no d a t a a r e a v a i l a b l e t o i n d i c a t e t h e
magnitude of such s t r a i n s o r t h e i r probable e f f e c t on t h e p o l a r i z i n g spec-
trometer measurements. It i s hoped t h a t planned x-ray d i f f r a c t i o n s t u d i e s
of t h e oxide on t h i n evaporated f i l m s of copper w i l l provide f u r t h e r i n f o r -
mation on t h i s s u b j e c t .

Variation of O p t i c a l Anisotropy with Oxide Thickness

The marked v a r i a t i o n i n t h e degree of anisotropy with f i l m t h i c k n e s s

for oxide formed on t h e (110) and (311) planes of copper has already been
noted. A s w a s i n d i c a t e d i n t h e d i s c u s s i o n of the x-ray d i f f r a c t i o n d a t a
("X-Ray D i f f r a c t i o n S t u d i e s of Cu20 Films Grown on Copper, 'I map. 4 ) , the
e x i s t e n c e of t h e pronounced peak i n t h e anisotropy curves i s c o n s i s t e n t
with t h e i d e a t h a t the p r o g r e s s of t h e oxidation process may be divided
i n t o two s t a g e s which d i f f e r p r i m a r i l y i n terms of t h e s t a t e of s t r a i n i n
t h e oxide and i n t h e manner i n which t h e s t r a i n changes with i n c r e a s i n g
f i l m thickness. Stage I may be taken t o include those t h i c k n e s s e s l y i n g
t o t h e l e f t of t h e c e n t e r of t h e a n i s t r o p y maxima i n F i g s . 5 . 2 and 5 . 3 ,
while s t a t e I1 i n c l u d e s a l l t h i c k e r f i l m s .
Such a choice y i e l d s a nominal t h i c k n e s s of approximately 250 A as t h e
d i v i d i n g l i n e between s t a g e s I and 11. The x-ray d i f f r a c t i o n d a t a i n d i -
c a t e d t h a t s t a g e I i s confined t o t h i c k n e s s e s l e s s than approximately 140 A.
This discrepancy between t h e x-ray d i f f r a c t i o n and p o l a r i z i n g spectrometer

66

a
r e s u l t s can be accounted f o r i n p a r t by t h e e r r o r s introduced i n t o t h e
spectrometer measurements on account of the a n i s t r o p y of t h e index of r e -
f r a c t i o n of t h e oxide, but t h e c o r r e l a t i o n between t h e x-ray and o p t i c a l
d a t a must s t i l l be regarded as q u a l i t a t i v e .
An e v a l u a t i o n of t h e causes of t h e v a r i a t i o n of o p t i c a l anisotropy as
a f u n c t i o n of f i l m t h i c k n e s s i s made d i f f i c u l t by t h e f a c t t h a t t h e oxide
f i l m i s not only a n i s o t r o p i c but i s s t r a i n e d inhomogeneously i n a t l e a s t
two d i r e c t i o n s . On t h i s account a l l attempts a t explaining t h i s phenomenon
must be regarded as h i g h l y s p e c u l a t i v e a t p r e s e n t .
One p o s s i b l e i n t e r p r e t a t i o n of t h e r e s u l t s involves t h e assumption
t h a t t h e c o n t r i b u t i o n s t o t h e o p t i c a l p r o p e r t i e s of t h e f i l m r e s u l t i n g
from t h e inhomogeneous s t r a i n i n t h e d i r e c t i o n of t h e f i l m normal a r e , t o
a f i r s t approximation, c i r c u l a r l y symmetrical with r e s p e c t t o t h e f i l m
normal. Then t h e marked reduction i n t h e degree of o p t i c a l a n i s t r o p y f o r
f i l m s approximately 100 A t h i c k ( s e e Fig. 5 . 2 ) suggests t h a t i n t h e plane
of t h e s e f i l m s t h e L a t t i c e i s s t r a i n e d uniformly. The peak i n t h e a n i s o t -
ropy curve might t h e n be r e l a t e d t o a more r a p i d approach t o bulk values
f o r t h e l a t t i c e parameter i n one d i r e c t i o n i n t h e oxide than i n another.
X-ray d i f f r a c t i o n d a t a show t h a t i n s t a s e I1 of t h e o x i d a t i o n process
t h e average values f o r a l l t h r e e l a t t i c e p a r , m e t e r s of t h e oxide a r e equal
t o o r approach the corresponding values f o r the bulk oxide as t h e f i l m s
t h i c k e n , t h e l a t t i c e of t h e oxide becoming, t h e r e f o r e , more n e a r l y cubic.
The observed decrease i n t h e o p t i c a l anisotropy of t h e oxide f i l m s i s t h u s
c o n s i s t e n t w i t h t h i s decrease in t h e degree of strain in t h e films.
However, t h e assumption t h a t t h e i n f l u e n c e of t h e s t r a i n i n t h e d i r e c -
t i o n of t h e film normal i s f e l t e q u i v a l e n t l y i n a l l d i r e c t i o n s about t h e
normal may not be v a l i d . I n such a case, changes i n t h e degree of a n i s o t -
ropy with f i l m t h i c k n e s s would probably be a complex f u n c t i o n of t h e cor-
responding changes i n a l l t h r e e l a t t i c e parameters of t h e oxide.
Evidently, f u r t h e r r e s e a r c h i s r e q u i r e d before t h e s e d i f f i c u l t i e s
can be resolved. E f f o r t s w i l l be made t o c h a r a c t e r i z e t h e s t r a i n i n t h e
f i l m more q u a n t i t a t i v e l y by measuring t h e index of r e f r a c t i o n of cuprous
oxide f i l m s grown on d i f f e r e n t f a c e s of copper as a f u n c t i o n of c r y s t a l -
lographic direction. It i s hoped t h a t t h e s e and s i m i l a r s t u d i e s of t h e
n a t u r e and d i s t r i b u t i o n of s t r a i n s i n t h e oxide w i l l a s s i s t i n demonstrat-
i n g t h e r o l e of s t r a i n i n t h e o x i d a t i o n process.

67
 1

n
"BREAK-AWAY I' PHENOMENA I N THE OXIDATION
OF NIOBIUM SINGU CRYSTALS

R. E . Pawel 5. V. Cathcart

A t temperatures i n t h e v i c i n i t y of 4OO0C, as has been demonstrated by

s e v e r a l previous i n v e s t i g a t o r s , the dominant f e a t u r e of the oxidation
of niobium i s t h e formation of an i n i t i a l l y p r o t e c t i v e oxide film which
becomes nonprotective as oxidation proceeds. It i s believed t h a t an un-
derstanding of the phenomena associated with t h i s t r a n s i t i o n t o the non-
p r o t e c t i v e stage of oxidation i s an important key t o t h e c l a r i f i c a t i o n of
t h e mechanism o f oxidation of niobium.
A s a p a r t of t h e continuing e f f o r t t o e s t a b l i s h t h e f a c t o r s which in-
fluence t h i s t r a n s i t i o n o r "break-away" process, as it i s frequently c a l l e d ,
an i n v e s t i g a t i o n of t h e oxidation c h a r a c t e r i s t i c s of both p o l y c r y s t a l l i n e
and s i n g l e - c r y s t a l niobium specimens w a s undertaken. The oxidation r a t e
and t h e oxide morphology were studied as a f'unction o f the c r y s t a l l o g r a p h i c
o r i e n t a t i o n of t h e s u b s t r a t e metal i n t h e temperature range 400-425°C, and
p a r t i c u l a r a t t e n t i o n w a s paid t o manifestations of s t r e s s generation i n the
oxide films during oxidation.

Specimen Preparation and Apparatus

P o l y c r y s t a l l i n e niobium specimens' i n t h e form of coupons 1 x 2 x 0.05

cm were cut from an annealed s h e e t . S i n g l e - c r y s t a l specimens were c u t from
a double-electron-beam-melted ingot containing extremely l a r g e g r a i n s . l o The

l a r g e s i n g l e c r y s t a l s t h u s obtained were machined i n t o specimens f o r both

'E. A. Gulbransen and K. F. Andrew, J. Electrochem. SOC. 96, 364

- -
( 1949) .
5E. A. Gulbransen and K. F. Andrew, J . Metals -2, 586 ( 1 9 5 0 ) .
6E. A. Gulbransen and K. F. Andrew, J . Electrochem. SOC. 105, 4 (1958).
7J. V. Cathcart, J . J . Campbell, and G. P. Smith, J . Electrochem.
,-c

-
-
SOC. --
105, 442 (1958).
8T. Hurlen -
et -
a l . , The Oxi,dation of Niobium, Technical Note No. 1
( A p r i l 1959), Central I n s t i t u t e f o r I n d u s t r i a l Research, Blindern, Oslo,
Norway.
'Fansteel nominal a n a l y s i s i n w t $: 0.007 C-0.10 Si-0.025 Ti-0.005
Fe-0.16 Ta-0.01 02-0.017 N 2 .
lowah Chang Corporation nominal a n a l y s i s i n w t $: 0.002 C4.01 Si-
0.015 Ti-O.01 Fe-4.10 Ta-O.01 02-0.01 N 2 .

I 68
microscopy and o x i d a t i o n - r a t e s t u d i e s . These specimens were i n t h e form of
spheres o r small coupons. The spheres were 1 . 2 5 cm i n diameter, and on
some of them f l a t s were cut p a r a l l e l t o major c r y s t a l l o g r a p h i c p l a n e s , The
coupons were a p p r o x l x l x 0.25 cm and were used f o r t h e r a t e measurements.
All specimens were hand-ground through 4/0 emery p a p e r , p o l i s h e d on t h e
m e t a l l u r g i c a l wheel with 0.3-p l e v i g a t e d alumina, and e l e c t r o l y t i c a l l y p o l -
i s h e d i n a 90% H2SO&-l0% HF s o l u t i o n . This procedurel1*l2 y i e l d e d b r i g h t ,
mirrorlike s u r f a c e s which upon o x i d a t i o n gave c o n s i s t e n t l y reproducible
r e s u l t s and w a s , t h e r e f o r e , adopted as a standard treatment.
Oxidation r a t e s f o r both p o l y c r y s t a l l i n e and s i n g l e - c r y s t a l specimens
were determined manometrically i n an apparatus similar t o t h a t de s c r i b e d
by Campbell and Thomas,13 i n which t h e p r e s s u r e change i n a closed system
w a s measured with a s e n s i t i v e d i f f e r e n t i a l manometer as o x i d a t i o n proceeded.
Most of t h e d a t a r e p o r t e d here were obtained with an Octoil-S manometer,
and t h e apprent s e n s i t i v i t y of t h e apparatus w a s about 5 x lo-' g-mole of
02*

Conventional l i g h t and e l e c t r o n microscopy techniques were used t o

study t h e t o p o l o g i c a l changes on t h e specimens oxidized f o r various times.
R e p l i c a t i o n d i f f i c u l t i e s encountered on specimens e x h b i t i n g t h i c k , porous
oxides were s a t i s f a c t o r i l y resolved by using an intermediate r e p l i c a c a s t
from a r e l a t i v e l y viscous s o l u t i o n ( 7 . 5 % ) of Parlodion i n amyl a c e t a t e .

Experimental Procedure and Results

Oxidation of P o l y c r y s t a l l i n e Niobium

Oxidation-rate measurements on p o l y c r y s t , a l l i n e niobium specimens were

made a t 400 and 425OC i n p u r i f i e d 0 2 a t 1 atm. A t 425"C, t h e oxidation-
r a t e curve i n d i c a t e d t h e occurrence of an i n i t i a l p r o t e c t i v e s t a g e of oxi-
d a t i o n l a s t i n g 25 min. The o x i d a t i o n r a t e t h e n g r a d u a l l y i n c r e a s e d f o r
about 250 min, by which time it became reasonably c o n s t a n t . A t 400"C,

llJ. V. Cathcart, R. Bakish, and D . R. Norton, J. Electrochem. SOC.

(in press).
12R. E . Pawel, J. V. Cathcart, and J . J. Campbell, J . Electrochem.
-
SOC. ( i n press).
I3W. E . Campbell and U. B. Thomas, Trans. Electrochem. SOC. 59 91,623
(194?).

69
t h e r a t e s of t h e two s t a g e s of o x i d a t i o n and t h e time a t which break-away
occurred were a l t e r e d ; however, t h e g e n e r a l form of t h e r a t e curve w a s
not changed. ?"ne amount of oxygen consumed before break-away was s l i g h t l y
g r e a t e r a t t h e lower temperature. Typical r e s u l t s f o r 425OC a r e shown i n
Fig. 5.5. The d a t a p l o t t e d i n t h i s f i g u r e were taken from runs using both
O c t o i l and mercury manometers. The high degree of s e l f - c o n s i s t e n c y of t h e
d a t a from a given run i s evident in Fig. 5.5, and t h e d a t a were reproducible

,
UNCLASSIFIED
ORNL-LR-DWG 48455
200
I I I lo I I I

475 --PA
a

-.
150 I- r- I o
A
0, PRESSURE. 1 atm
OCTOIL MANOMETER
MERCURY MANOMETER
PARTIALLY MASKED

I l a
(25
5
-
D

::400
5
m
z
u
0
5 75
W

0
X

50
0 io 20 30
I I I I

1
0 A&...
S O A 1
0 100 200 300 400 500 600 , 700 800
OXIDATION TIME (min)

Fig. 5.5. Oxidation-Rate Curve for Polycrystalline Niobium at 425%

t o +5$. The e f f e c t of p r e s s u r e changes during a normal o x i d a t i o n run (ap-

proximately 30 and 400 mm Hg f o r t h e O c t o i l and mercury manometers r e s p e c t -
i v e l y ) w a s found t o be n e g l i g i b l e in experiments where the p r e s s u r e w a s
purposely allowed t o decrease continuously t o low values. A t 425'C, a
p r e s s u r e dependence w a s observed only a t a b s o l u t e p r e s s u r e s below 200 mm
Hg. Since primary emphasis w a s placed on t h e study of t h e i n i t i a l s t a g e s
of oxidation, most of t h e rate measurements were made with an O c t o i l ma-
nometer.
In an e f f o r t t o f i n d a s u i t a b l e means f o r masking p o r t i o n s o f s i n g l e -
c r y s t a l specimens ( s e e below), o x i d a t i o n - r a t e measurements were a l s o made

70
 a t 4 2 5 O C on p o l y c r y s t a l l i n e niobium coupons p r o t e c t e d on one s i d e with a
vacuum-deposited gold f i l m . Although t h e method w a s e v e n t u a l l y a l t e r e d ,
t h i s procedure d i d not adversely a f f e c t t h e o x i d a t i o n c h a r a c t e r i s t i c s , as
may be seen i n Fig. 5.5. Specimens prepared. i n t h i s manner became curved
upon oxidation, i n d i c a t i n g t h e development cf s u b s t a n t i a l s t r e s s e s during
t h e process.
The e l e c t r o n miscrope showed abrupt changes i n t h e appearance of t h e
oxide as oxidation proceeded. I n the i n i t i a l , p r o t e c t i v e s t a g e s o f oxi-
d a t i o n the oxide developed a r i p p l e d t e x t u r e which could be observed a t
high magnifications. The t e x t u r e of the oxilfie v a r i e d from g r a i n t o g r a i n
as shown i n Fig. 5 . 6 . A s the o x i d a t i o n time w a s i n c r e a s e d i n t o t h e t r a n -
s i t i o n region of the r a t e curve, s m a l l b l i s t e r s and cracks s i m i l a r t o

Fig. 5.6. Electron Micrograph of Surface Texture of Oxide Film Formed on Polycrystalline Niobium
During Protective Stage of Oxidation. Oxidized 1 hr at 400OC. Indirect replica. 12,400X.

71
1

those r e p o r t e d by Cathcart7 were observed on t h e s u r f a c e . These a r e il-

l u s t r a t e d i n Fig. 5.7. Presumably t h e s e cracks permit easy access of
oxygen t o the r e a c t i o n zone, t h u s i n c r e a s i n g t h e oxidation r a t e .
Figure 5.8 i l l u s t r a t e s the oxide topography a s s o c i a t e d with the l a t e r
s t a g e s of oxidation. I n t h e case of t h i s specimen most of t h e surface w a s
covered with a t h i c k , cracked, porous l a y e r of oxide. It was Obvious,
however, t h a t t h e o x i d a t i o n r a t e v a r i e d g r e a t l y from g r a i n t o g r a i n , and
many g r a i n s s t i l l e x h i b i t e d t h i n oxide f i l m s c h a r a c t e r i s t i c of t h e pre-
t r a n s i t i o n range. Figure 5.9 i s a high-magnification micrograph o f t h e
boundary a r e a between t h e s e regions. The observed s t e p s t r u c t u r e suggested
t h a t t h e oxide tended t o grow o r form i n l a y e r s ; on t h e b a s i s of shadow e
l e n g t h s t h e average s t e p h e i g h t was estimated t o be approximately 5000 A.

Fig. 5.7. Electron Micrograph of Blister-Like Cracks in Oxide F i l m Observed Shortly After Break-
away. Oxidized 4 hr at 400°C. Indirect replica. 9600X.

72
 Fig. 5.8. Electron Micrograph of Oxidized Polycrystalline Niobium Specimen Just Prior to Constant-
Rate Stageof Oxidation. Oxidized 4 hr at 425T. Indirect replica. 6900X.

r
73
 Q

F i g . 5.9. Electron Micrograph of Boundary Between Grains of Different Orientation and Different
O x i d a t i o n Characteristics. Oxidized 2.25 hr a t 425T. Indirect replica. 33,OOOX.
a
Oxidation of Single-Crystal Niobium Specimens

From the r e s u l t s obtained on p o l y c r y s t a l l i n e specimens, it w a s ap-

parent t h a t the oxidation r a t e , a t l e a s t i n the i n i t i a l stages, w a s
6
g r e a t l y dependent upon t h e o r i e n t a t i o n of t h e s u b s t r a t e metal. Experi-
ments i n which s i n g l e - c r y s t a l spheres of niobium were oxidized i l l u s t r a t e d
t h e e x t e n t of t h i s e f f e c t . A p a t t e r n of oxide i n t e r f e r e n c e c o l o r s , which
w a s q u a l i t a t i v e l y r e l a t e d t o a v a r i a t i o n o f t h e o x i d a t i o n r a t e as a func-
t i o n of c r y s t a l l o g r a p h i c o r i e n t a t i o n , developed on t h e spheres as oxidation
proceeded. A c r y s t a l could be divided i n t o two g e n e r a l regions ( s e e Figs.
5.10 and 5 . 1 1 ) : (1)a r e a s centered around t h e (100) p o l e s where t h e r a t e s

74

e
 Fig. 5.10. Single-Crystal Niobium Sphere Oxidized 18 hr at 425oC.

9 of oxidation were r e l a t i v e l y low; and ( 2 ) a r e a s with r e l a t i v e l y high oxi-

dation r a t e s . Herein, t h e c r y s t a l l o g r a p h i c p l a n e s i n t h e s e two a r e a s w i l l
be r e f e r r e d t o a s "slow-rate" and " f a s t - r a t e , " respectively.

A s t h e more r a p i d l y oxidizing regions on t h e sphere e n t e r e d t h e non-

p r o t e c t i v e s t a g e of oxidation, t h e oxide appeared as a uniform t r a n s l u c e n t
l a y e r through which s u b t l e d i f f e r e n c e s i n t h e p a t t e r n could s t i l l be seen.
This c o n d i t i o n i s i l l u s t r a t e d i n Fig. 5.12. A t t h i s s t a g e of oxidation,

75
I

Fig. 5.11. Masked Single-Crystal Specimen of the Type Used for

Oxidation-Rate Measurements. Specimen No. 2 after oxidation for 16
hr at 425T.

t h e regions about t h e (100) plane e x h i b i t e d e s s e n t i a l l y a s i n g l e i n t e r -

ference c o l o r , and presumably t h e f i l m w a s s t i l l p r o t e c t i v e . Spheres oxi-
dized f o r much longer p e r i o d s showed d i s t i n c t d i f f e r e n c e s i n t h e manner
i n which t h e t h i c k l a y e r s of oxide grew on various o r i e n t a t i o n s . Figure
5.10 shows l a r g e nodular patches o f oxide which formed i n t h e (100) region;
t h e background s t i l l e x h i b i t e d f i r s t - o r d e r i n t e r f e r e n c e c o l o r s . Meanwhile, e
a very t h i c k oxide f i l m formed over t h e remainder of t h e specimen. The
dark areas i n t h i s f i g u r e between (110) and (111) a r e regions i n which t h e
oxide s p a l l e d during cooling of t h e specimen. The range of population 8
d e n s i t y of oxide nodules on t h e slow-rate regions suggested t h a t t h e oxide
f i l m formed on a p r e c i s e l y (100) face should be very r e s i s t a n t t o break-
down.
Odiation-rate measurements on s i n g l e - c r y s t a l specimens of various o r i -
e n t a t i o n s were made a t 425°C and 1 a t m 0 2 . To minimize c o n t r i b u t i o n s from
t h e unwanted s u r f a c e s and edges of t h e s i n g l e - c r y s t a l specimens, t h e s e a r e a s
were h e a v i l y coated i n vacuum with an aluminum-aluminum oxide l a y e r . The
t o t a l amount of oxygen consumed p e r square centimeter during blank runs on
t h i s m a t e r i a l w a s n e g l i g i b l e compared with t h e oxygen uptake f o r niobium.

76
 Fig. 5.12. Single-Crystal Niobium Sphere Oxidized 2 hr at 425OC.
Diffuse-light photograph.

T h i s technique proved g e n e r a l l y s a t i s f a c t o r y , e s p e c i a l l y f o r t h e more

r a p i d l y oxidizing faces; however, f o r t h e slow-rate f a c e s where long ex-
periments were required, small breakdowns i n t h e p r o t e c t i v e aluminum l a y e r
were observed. Figure 5.11 shows such a specimen a f t e r o x i d a t i o n .
It w a s impossible t o e s t i m a t e q u a n t i t a t i v e l y t h e e r r o r s t h i s l o s s of
p r o t e c t i o n introduced i n t h e r a t e measurements f o r t h e slow-rate f a c e s .
Thus t h e r a t e curves presented r e p r e s e n t an upper bound f o r the r a t e be-
havior. Nevertheless, it should be noted t h a t t h e shapes of t h e r a t e
curves, even f o r the slow-rate f a c e s , a r e c o n s i s t e n t with t h e observed
surface topography of t h e oxide f i l m s .
The o r i e n t a t i o n s o f the s i n g l e - c r y s t a l specimens under c o n s i d e r a t i o n
i n t h i s r e p o r t a r e shown i n t h e u n i t t r i a n g l e i n Fig. 5.13. Regions of

77
 e
"slow" and ''fast" o x i d a t i o n r a t e s as determined from t h e experiments w i t h
t'ne s i n g l e - c r y s t a l spheres are superimposed on t h e u n i t t r i a n g l e .
The r e s u l t s of t h e o x i d a t i o n - r a t e measurements a r e p r e s e n t e d i n F i g .
5.14. Specimens whose s u r f a c e s were approximately p a r a l l e l t o t h e (110)
UNCLASSIFIED
ORNL-LR-DWG 48151

Q
"321

0
a
320

Fig. 5.13. U n i t Triangle Showing Orientation of

Single-Crystal Specimens for Reported Oxidation-
R a t e Measurements.

UNCLASSIFIED
ORNL- LR- DWG 48154
200 I I / I

I75

N
I50
a
5
\

425
E
-a
9 100
I
m
9
0
0
z 75
0
0
X

50

25

0
0 IO0 200 300 400 500 600 700 800
OXIDATION TIME ( m i d

Fig. 5.14. Oxidation-Rate Curves for Single-Crystal Niobi um Spec-

imens.

78

e
and (111)p l a n e s of t h e metal oxidized p r o t e c t i v e l y f o r s h o r t times, and
t h e t r a n s i t i o n t o t h e s t e a d y - s t a t e s t a g e of oxidation w a s comparatively
abrupt, t h e r a t e curve becoming e s s e n t i a l l y l i n e a r a f t e r about 100 min.
The r a t e curves obtained from specimens o f d i f f e r e n t o r i e n t a t i o n w i t h i n
t h e f a s t - r a t e regions, ( 2 2 1 ) and (321), f o r example, were e s s e n t i a l l y
i d e n t i c a l t o t h a t observed f o r ( 1 1 0 ) . On t h e o t h e r hand, specimens of
approximately (100)o r i e n t a t i o n oxidized p r o t e c t i v e l y f o r much longer
p e r i o d s , and t h e t r a n s i t i o n w a s an extremely s l u g g i s h process. For
specimens with r e l a t i v e l y low o x i d a t i o n r a t e s whose o r i e n t a t i o n s were
n e a r t h e boundary of t h e slow-rate regions, t h e r e were considerable d i f -
f e r e n c e s i n t h e manner i n which a constant r a t e w a s approached. Specimen
No. 5 , f o r example ( s e e Fig. 5.13), oxidized p r o t e c t i v e l y f o r 100 min,
and t h e oxidation r a t e became constant a f t e r about 400 min, t h e steady-
s t a t e r a t e being equivalent t o t h a t observed f o r f a s t - r a t e o r i e n t a t i o n s .
More d e t a i l of t h e i n i t i a l s t a g e s of o x i d a t i o n f o r t h e s e specimens i s
given i n F i g s . 5.15 and 5.16.

..
OXIDATION TIME (min)

Fig. 5.15. Oxidation-Rate Curves for Single-Crystal Niobium Spec-

imens. I n i t i a l r a t e behavior.

79
 16

14

12
N
-
E
:
\
40
E
01
a
I

2 8
5
in
z
0

z 6
W

>
0
X

C
0 I00 200 300 400 500
OXIDATION TIME (mi")

Fig. 5.16. Oxidation-Rate Curves for Single-Crystal Niobium Spec-

imens. Specimens showing extended transition regions.

An important d i f f e r e n c e between t h e break-away process f o r t h e f a s t -

and slow-rate a r e a s of t h e c r y s t a l s concerned t h e frequency of crack f o r -
mation i n t h e oxide f i l m . The r a t e o f crack n u c l e a t i o n i n t h e oxide on
t h e f a s t - r a t e a r e a s w a s r e l a t i v e l y high, with t h e r e s u l t t h a t even a f t e r
extensive p e r i o d s o f o x i d a t i o n t h e s u r f a c e roughnesses were s m a l l r e l a t i v e
t o t h e t o t a l oxide t h i c k n e s s . On t h e slow-rate planes, on t h e o t h e r hand, a
break-away w a s a s s o c i a t e d with the formation and growth of i s o l a t e d patches
of t h i c k oxide (compare F i g s . 5.10 and 5 . 1 1 ) . The o x i d a t i o n r a t e f o r each
of t h e s e i s o l a t e d a r e a s w a s obviously q u i t e high, but t h e r a t e of nuclea-
8
t i o n and growth of such a r e a s w a s s m a l l . A s a r e s u l t the t r a n s i t i o n t o
t h e s t e a d y - s t a t e stage of o x i d a t i o n occurred much more slowly f o r the slow-
r a t e faces. E l e c t r o n microscopy i n d i c a t e d t h a t t h e formation of t h e s e
patches, as well a s t h e i n i t i a l breakdown of t h e p r o t e c t i v e f i l m on t h e
f a s t - r a t e f a c e s , w a s a s s o c i a t e d with t h e formation of s m a l l cracks i n t h e
oxide f i l m . Figure 5.17 shows such a crack i n an "embryonic" oxide patch
formed on an otherwise p r o t e c t i v e l y oxidizing s u r f a c e .
The f a c t t h a t l a r g e s t r e s s e s were generated i n t h e specimens during
oxidation has already been mentioned. Further evidence of t h e magnitude
 Fig. 5.17. Electron Micrograph of Oxide Nodule Formed on Single-Crystal Specimen Ori-
ented Approximately 6"from the (100) Plane. Oxidized 15 hr at 425°C. Indirect replica. 10,OOOX.

of t h e s e s t r e s s e s w a s furnished by t h e observation of deformation l i n e s

i n t h e metal surrounding t h e patches of porous oxide on t h e slow-rate
f a c e s , see Fig. 5.18. It i s p o s s i b l e t h a t some of t h i s deformation oc-
curred as a result of d i f f e r e n t i a l thermal c o n t r a c t i o n during cooling of
t h e specimens; however, t h e f a c t t h a t t h e deformation l i n e s were p r e f e r r e d
s i t e s for f u r t h e r n u c l e a t i o n of t h i c k oxide patches supports t h e contention
t h a t they were p r e s e n t a t t h e o x i d a t i o n temperature and occurred as a r e s u l t
of very high l o c a l s t r e s s e s generated during t h e o x i d a t i o n p r o c e s s .

81
 Fig. 5.18. Deformation L i n e s Adjacent to Large Nodular Oxide Patches Formed on Single-Crystal
Specimen Oriented Approximately 6 O from the (100) plane. Oxidized 15 hr at 425OC. 150X.

Discussion

The c o r r e l a t i o n between o x i d a t i o n - r a t e behavior and oxide topography

w a s reasonably c l e a r , a t l e a s t from a phenomenological p o i n t of view. Re-
g a r d l e s s of t h e o r i e n t a t i o n of a given specimen, t h e onset of break-away
could always be a s s o c i a t e d with the formation of cracks i n t h e oxide f i l m .
I n t h e f a s t - r a t e a r e a s t h e s e cracks formed r e l a t i v e l y e a r l y i n t h e o x i d a t i o n
process, covering t h e surface uniformly i n a s h o r t p e r i o d . On the slow-rate
f a c e s t h e period of p r o t e c t i v e o x i d a t i o n w a s considerably longer, and t h e
frequency of crack n u c l e a t i o n w a s much smaller. However, even on a slow-
r a t e f a c e , a crack i n the oxide produced a l o c a l i z e d region i n which t h e
o x i d a t i o n r a t e w a s obviously q u i t e high. The gradual i n c r e a s e of t h e meas-
ured o x i d a t i o n r a t e on t h e s e f a c e s w a s i n t e r p r e t e d as being p r i m a r i l y a r e -
s u l t of t h e very slow n u c l e a t i o n and propagation of t h e s e l o c a l i z e d high-
 r a t e regions. Perhaps a s a r e s u l t of the higher r e s i s t a n c e t o crack forma-
t i o n , t h e amount of oxygen consumed a t t h e i n i t i a t i o n o f break-away w a s
g r e a t e r on t h e slow-rate f a c e s .

The f a c t t h a t deformation l i n e s formed around growing oxide nodules

on an otherwise p r o t e c t i v e oxide film’was c o n s i s t e n t with t h e premise t h a t
considerable s t r e s s e s can a r i s e as a r e s u l t of t h e surface c o n f i g u r a t i o n
of a niobium specimen.14 The formation of a s m a l l imperfection o r c a v i t y
a t t h e oxide-metal i n t e r f a c e can l e a d t o t h e g e n e r a t i o n of s t r e s s e s which
c o n t i n u a l l y r u p t u r e the overlying oxide film, t h u s producing l o c a l i z e d ,
r a p i d l y oxidizing regions over t h e specimen s u r f a c e .

Regarding t h e o x i d a t i o n - r a t e curves f o r t h e p o l y c r y s t a l l i n e speci-

mens, it might be expected t h a t t h e o v e r - a l l r a t e of o x i d a t i o n f o r such
samples could be expressed as an average of t h e r a t e s f o r a l l t h e i n d i -
-
vidual g r a i n s i n t h e specimen s u r f a c e . Therefore, even t a k i n g i n t o account
t h e p o s s i b i l i t y of a high degree of p r e f e r r e d o r i e n t a t i o n i n t h e specimen,
it would be expected t h a t t h e o v e r - a l l r a t e f o r a p o l y c r y s t a l l i n e specimen
would always be l e s s t h a n t h a t f o r t h e most r a p i d l y oxidizing c r y s t a l l o -
graphic face of a niobium s i n g l e c r y s t a l . This l i n e of reasoning i s con-
s i s t e n t with t h e f a c t t h a t t h e break-away process occurs more gradually
on p o l y c r y s t a l l i n e specimens t h a n f o r f a s t - r a t e f a c e s on s i n g l e c r y s t a l s
(compare F i g s . 5.5 and 5.14). On t h e o t h e r hand, t h e s t e a d y - s t a t e r a t e
f o r t h e p o l y c r y s t a l l i n e specimens w a s , w i t h i n experimental e r r o r , t h e
same as t h a t f o r any o f t h e f a s t - r a t e s i n g l e - c r y s t a l specimens t e s t e d .
The cause of t h i s apparent anomalous a c c e l e r a t i o n of t h e o x i d a t i o n r a t e
of p o l y c r y s t a l l i n e specimens i s s t i l l not understood; t h i s behavior may
r e f l e c t t h e influence of g r a i n boundaries on t h e oxidation r a t e , o r , a l -
t e r n a t i v e l y , it may p o i n t t o s t r a i n s i n t h e oxide film a r i s i n g from t h e
i n t e r a c t i o n of t h e oxide films on a d j a c e n t g r a i n s i n t h e metal, where,
because of a d i f f e r e n c e i n t h e o r i e n t a t i o n of t h e g r a i n s , t h e two oxide
f i l m s have d i f f e r i n g t h i c k n e s s e s .

“J. V. Cathcart, J . J . Campbell, and G. P. Smith, J . Electrochem. SOC.

-
105, 442
- (1958).

83
 Conclusions

On t h e basis of research t h u s f a r completed, t h e s t e p s involved i n

t h e oxidation of niobium i n t h e v i c i n i t y of 425°C and 1 a t m i n oxygen
may be summarized as follows:

1. A p r o t e c t i v e f i l m forms on t h e surface of t h e metal, the r a t e of

formation and t h e maximum thickness a t t a i n e d being functions of t h e c r y s t a l -
lographic o r i e n t a t i o n of the metal.
2. A t some c r i t i c a l thickness, which v a r i e s as a function of o r i e n t a -
t i o n , cracks form i n t h e oxide f i l m , producing a marked increase i n t h e
oxidation r a t e . The r a t e of nucleation of such cracks i s a l s o a function
of o r i e n t a t i o n , being much higher f o r t h e f a s t - r a t e than f o r the slow-
r a t e faces.

3. The oxidatiori of a l l specimens eventually e n t e r s a steady-state

phase i n which t h e r a t e o f oxidation i s approximately constant.
4. Evidence of t h e development of severe s t r e s s e s within t h e oxide
f i l m w a s observed, and it i s believed t h a t these i n t e r n a l l y generated
s t r e s s e s play a dominant r o l e i n t h e "break-away" process.
 -.
_ .. .
. .....- . . .. . . . . . . . . . -

6. STRUCTURE OF IvETALS

C . J. McHargue

DEFORMATION STACKTNG FAULTS I N FACE-CENTERED CUBIC METALS

C . J. McHargue G. F. Boling' T. B. Massalski2

Close-packed c r y s t a l s t r u c t u r e s may b e produced by s t a c k i n g c l o s e -

packed l a y e r s of atoms. If each atom i s p l a c e d i n a s a d d l e of t h e p r e -
c e d i n g p l a n e , t h e r e a r e t h r e e d i f f e r e n t s e t s of p o s i t i o n s , which may b e
n o t e d A, B, and C . Obviously t h e r e e x i s t s an i n f i n i t e number of c l o s e -
packed s t r u c t u r e s having t h e common p r o p e r t y t h a t t h e number of n e a r e s t
n e i g h b o r s of atoms i s e q u a l t o 1 2 . However, only one s t r u c t u r e , t h e
f a c e - c e n t e r e d c u b i c l a t t i c e , i s a B r a v a i s l a t t i c e , and o n l y one o t h e r
s t r u c t u r e , t h e hexagonal close-packed s t r u c t u r e , i s commonly e n c o u n t e r e d
i n metals.
The s t a c k i n g sequence of close-packed p l a n e s i n t h e f a c e - c e n t e r e d
c u b i c l a t t i c e i s ABCABC; t h a t i s , each l a y e r must have a p o s i t i o n which
differs from t h a t of each of t h e two p r e c e d i n g l a y e r s . A stacking f a u l t
i s a b r e a k i n t h i s s t a c k i n g o r d e r which m a i n t a i n s t h e number and dis-
t a n c e of n e a r e s t n e i g h b o r s . T y p i c a l f a u l t e d arrangements i n c l u d e t h e
sequence ABCACABC, i n which each p l a n e above t h e f a u l t i s s h i f t e d by a
d i s t a n c e a / ! i n a [1121 d i r e c t i o n , and which i s c a l l e d a deformation
s t a c k i n g f a u l t , and ABCACBACBA, which i s a t w i n s t a c k i n g f a u l t .
It a p p e a r s t h a t i n some c a s e s a total d i s l o c a t i o n can split into
two p a r t i a l d i s l o c a t i o n s which move a p a r t . The r e g i o n between t h e two
p a r t i a l d i s l o c a t i o n s c o n t a i n s a deformation s t a c k i n g f a u l t . One param-
Q e t e r which determines t h e s e p a r a t i o n of t h e p a r t i c l e s i s t h e s t a c k i n g -
f a u l t energy, y , d e f i n e d as t h e s u r p l u s f r e e energy of a s t a c k i n g f a u l t
of u n i t area.
An experiment a1 o r der- of -magni t u d e estimate of t h e s t a c k i n g - f a u l t
energy of f a c e - c e n t e r e d c u b i c metals can b e o b t a i n e d from measurements
of t h e energy of c o h e r e n t t w i n b o u n d a r i e s . From such measurements, t h e
f a c e - c e n t e r e d c u b i c metals have been d i v i d e d i n t o two groups: those with

'Westinghouse Research L a b o r a t o r i e s , P i t t s b u r g h , Pennsylvania.

2Mellon I n s t i t u t e , P i t t s b u r g h , Pennsylvania.

85
low s t a c k i n g - f a u l t energies, 4C-60 e r g s (Cu, N i , Au, Ag), f o r exam-
p l e , and those with high e n e r g i e s , 200 e r g s cm-2 ( A l ) , f o r example. One
of t h e important f e a t u r e s of f a u l t s i s t h e i r r e l a t i o n s h i p t o extended dis-
l o c a t i o n s ; t h i s may provide t h e explanation f o r d i f f e r e n c e s i n p l a s t i c de-
formation behavior of metals having t h e same c r y s t a l s t r u c t u r e and s l i p
systems.
The s t a c k i n g - f a u l t frequency i s u s u a l l y r e p r e s e n t e d by t h e symbol
a-’, which gives t h e average number of c o r r e c t l y stacked close-packed
planes between deformation f a u l t s . Typical values of 6’f o r t h e mono-
v a l e n t metals (Cu, Ag, Au) a r e i n t h e range 6G80 f o r deformation by f i l i n g
a t l i q u i d - n i t r o g e n temperatures; 3-5 no such deformation f a u l t s have been
observed i n aluminum.‘
A q u a l i t a t i v e theory f o r t h e dependence of s t a c k i n g - f a u l t energy on
e l e c t r o n i c s t r u c t u r e has been proposed by Seeger. The argument begins
w i t h t h e observation t h a t a s t a c k i n g f a u l t l e a v e s t h e number and distance
of n e a r e s t neighbors unchanged. This i s i n t e r p r e t e d f o r n o n t r a n s i t i o n
metals as meaning t h a t t h e c o n t r i b u t i o n of t h e core e l e c t r o n s t o t h e co-
hesive energy remains e s s e n t i a l l y unchanged. Since t h e volume of t h e
atomic c e l l s i n t h e f a u l t i s t h e same as t h a t i n t h e p e r f e c t s t r u c t u r e ,
t h e r e i s no change i n t h e i n t e r a c t i o n between t h e conduction e l e c t r o n s and
t h e ion core. The number and d i s t a n c e of second n e a r e s t neighbors i s
changed by a f a u l t . Since t h e s t r u c t u r e of a c r y s t a l a f f e c t s t h e conduc-
t i o n e l e c t r o n s mainly through t h e e x i s t e n c e of t h e B r i l l o u i n zone bound-
a r i e s , t h e main change i n t h e Fermi energy comes from e l e c t r o n s whose wave
v e c t o r s a r e near t o a zone boundary. The d i r e c t i o n o f t h e change must be
such t h a t t h e i n t r o d u c t i o n of a s t a c k i n g f a u l t r e s u l t s i n an i n c r e a s e i n
energy. I n monovalent metals, t h e region of t h e wave-number space occu-
p i e d by conduction e l e c t r o n s does not overlap and i s u n l i k e l y t o even
touch t h e boundaries of t h e f i r s t B r i l l o u i n zone; t h u s , t h i s i n c r e a s e i n

3 C . N. J. Wagner, Acta Met. 5, 427 (1957).--

‘C. N. J. Wagner, Acta Met. - 5, 477 (1957).
5B. E . Warren, Progr. i n MetGl Phys. -
8, 147 (1959).
-
6A. Seeger, Rept. Conf. on Defects i n C r y s t a l l i n e S o l i d s , London,
-
1954, p 328.
 energy, and t h e r e f o r e t h e s t a c k i n g - f a u l t energy, i s s m a l l . I n a l l multi-
v a l e n t metals, t h e r e i s some o v e r l a p of t h e occupied r e g i o n i n t o t h e sec-
ond B r i l l o u i n zone. I n t h i s c a s e , a l a r g e i n c r e a s e i n energy of t h e con-
d u c t i o n e l e c t r o n s can b e expected; t h i s i s r e f l e c t e d as a l a r g e s t a c k i n g -
f a u l t energy.
The above t h e o r y i s e x p e r i m e n t a l l y b a s e d on t h e d i f f e r e n c e between
t h e behavior of aluminum and t h a t of t h e monovalent f a c e - c e n t e r e d metals,
Cu, Au, and Ag. Another m u l t i v a l e n t f a c e - c e n t e r e d cubic metal i s l e a d .
According t o S e e g e r ' s t h e o r y v e r y few f a u l t s should b e found i n l e a d , as
i n aluminum. On t h e o t h e r hand, important d i f f e r e n c e s i n t h e occurrence
of s t a c k i n g f a u l t s i n t h e s e two metals might b e i n t e r p r e t e d as showing
changes i n t h e c o n t r i b u t i o n of c o r e e l e c t r o n s t o cohesive energy o r i n
i n t e r a c t i o n of c o r e and conduction e l e c t r o n s . The c u r r e n t s t u d i e s a r e
concerned w i t h t h e f a u l t i n g behavior of l e a d , t h e e f f e c t s of a l l o y i n g on
t h i s b e h a v i o r , and an e x t e n s i o n of t h e deformation temperature range
downward i n t h e c a s e of aluminum.
A l i q u i d - h e l i u m c r y o s t a t mounted on a General E l e c t r i c XRD-5 spec-
trogoniometer w i t h p r o v i s i o n s f o r deforming t h e specimen s u r f a c e w a s used
i n t h i s study. The deformation w a s produced by s c r a t c h i n g t h e s u r f a c e ,
and i n o r d e r t o compare t h e s e r e s u l t s w i t h o t h e r s where t h e deformation
w a s by f i l i n g , a sample of 70-30 & b r a s s w a s used.
It has been shown7 t h a t t h e i n t r o d u c t i o n of deformation s t a c k i n g
f a u l t s i n t o a f a c e - c e n t e r e d cubic l a t t i c e causes c h a r a c t e r i s t i c s h i f t s i n
t h e x-ray l i n e s . T h e (111)r e f l e c t i o n i s s h i f t e d t o a h i g h e r 28 and t h e
(200) r e f l e c t i o n t o a lower 2 8 . The change i n t h e s e p a r a t i o n of t h e peak
p o s i t i o n s can b e r e l a t e d t o t h e deformation s t a c k i n g - f a u l t p r o b a b i l i t y by
Q

where

H = (<G>j t a n e o )h k l - (<G>j t a n 8.)

h'k'l' '
i n which j i s t h e f r a c t i o n of ( h k l ) p l a n e s a f f e c t e d by s t a c k i n g f a u l t s ,
and <G>j i s e q u a l t o +3.95 f o r (111)and -7.90 f o r (200) r e f l e c t i o n s . 3 - 5

7M. S . Paterson, J. Appl. Phys. 23, 805 (1952).

-

87
 The procedure included recording of the (111)and (200) reflections n

for a sample at some temperature before and after deformation. Because

of the purity of the lead samples, it was necessary to deform at liquid-
nitrogen temperature and anneal at l ? O ° K in the cryostat in order to
produce a fine-grained specimen. Specimens of the following composition
were studied: 99.99999 w t % Pb (furnished by Westinghouse Research Labo-
ratories), Pb-o.1 at. % Ag, Pb-20 at. % In, 99.996 w t Al, and 70-30 C&
brass. The results are summarized in Table 6.1.

Table 6.1. Peak Shifts and Reciprocals of Deformation

Stacking-Fault Frobabilitie s 4p
Deformation
Peak Shift
Mater ia1 Temperature a-1
(28"1
(OK) e
1 pb 77 -0.025 148
Pb 4.2 -0.04? 80
-0.1 at. Ag 4.2 -0.041 93
pb-20 at. % In 4.2 0.ooo No faults
Al 4.2 -0.015 290
70-30 %brass 4.2 -0.170 36

The value of 6'for %brass is of the same order as that obtained

by Wagner3 by filing at liquid-nitrogen temperature (36 as compared to
m
25). However, since (2-l might be expected to increase with decreasing
temperature, this indicates that the samples in the present study were
not as extensively worked as those in other studies. Consequently, the
values of (2-l are probably relatively high, a fact which must be consid-
ered when comparisons are made with other studies.
A number of interesting observations can be made regarding the data
given in Table 6.1. There is a definite difference between the behavior
of high-purity lead and that of aluminum. The change in peak separation
of -0.015" for aluminum is near the limits of resolution of the apparatus
and may not be real. Thus, the stacking-fault probability is equal to or
less than that calculated, since a larger probability would have been

88
 clearly noted. The value of 07' in Table 6.1 represents, then, the mini-
mum possible separation between faults in aluminum under the conditions
of this experiment. It appears that the faulting behavior of lead is
similar to that of copper, silver, gold, and nickel. Thus, it is con-
cluded that Seeger's theory6 cannot be applied without some further ad hoc
--
assumptions.
The effects of the solute elements silver and indium on the faulting
of lead should be noted. Silver in the amount of maximum solubility had
no significant effect on the faulting frequency, whereas 20 at. % In com-
pletely suppressed the faulting ability. It was noted that silver did
49
have an appreciable effect on the thermal stability of deformation stack-
ing faults. In the pure lead samples, annealing at 225°K completely re-
moved all faults, whereas annealing at 298°K had no effect at all on the
Q)
concentration of the faults in the lead-silver alloys.
These studies are being continued in an attempt to formulate a gen-
eral theory for deformation fault formation.

ON A COMPLEX RECRYSTALLIZATION TEXTURE I N Fe-3% Si

C. J. McHargue C. G. m n 8
A multicomponent recrystallization texture, which is a matrix tex-
ture for secondary recrystallization to the Goss texture in commercial
iron-silicon alloys, has been investigated and discussed recently. The
pole figure data obtained were interpreted as giving only a partial de-
scription of the texture, because the results failed to account for the
observed magnetic anisotropy in the material. Koh and Dunn suggested
that additional information possibly could be obtained on this complex
recrystallization texture by the ORNL method of texture analysis . l o One
of the primary aims of this study was to demonstrate the superiority of
the ORNL technique over conventional pole figures in analyzing complex
sheet textures.

8General Electric Research Laboratory.

9P. K. Koh and C. G. Dunn, Trans. Met. SOC. AIME 218, 65 (1960).
-
-
'OL. K. Jetter, C. J. McHargue, and R. 0. Williams, J. Appl. Phys.
2
-'7, 368 (1956).
 Knowledge of the present primary recrystallization texture, or one
with similar properties, is important because such a texture may influ-
ence the secondary recrystallization texture and thus the magnetic prop-
erties of annealed silicon iron. An appropriate secondary recrystalli-
zation anneal should develop a strong Goss or (110) [001]texture with
its associated directional magnetic properties. The primary recrystal-
lization material also has directional magnetic properties, but much
weaker. A satisfactory description of the texture should account for the
observed magnetic anisotropy.9 sl1 Also, a better description undoubtedly
would help clarify the obscure nature of the observed growth selecti~ity,~
that is, the dependence of rate of growth of secondary recrystallization
a
grains on orientation.
Pieces of O.Ol4-in.-thick silicon-iron strip, which had been de-
carburized in a 3-min anneal at 800"C, were descaled chemically and then
a
I

bonded together with an adhesive to make a laminated structure. From

this a spherical diffraction specimen 0.200 in. in diameter was machined.
Highly strained surface layers of the spherical specimen were removed
chemically.
Filtered Mo-Ka radiation was used with each of the following kinds
of diffracting planes: 110, 200, 112, 130, 222, 123, and 240. The speci-
I

men was rotated rapidly about the normal direction, N.D., the rolling di-
rection, R.D., or the transverse direction, T.D., while being scanned
slowly through an angle @ that varied from 0 to 90". The chart recordings
obtained were corrected for background radiation and then analyzed as de-
scribed elsewhereg to give axis distribution charts, that is, axis den-
sity figures.
The axis density figures deduced from the chart recordings are given
8
in Fig. 6.1. At @ = 0 the values of density and averaged {hkl} pole den-
sity are equal. Thus there are a number of points in the figures (black
dots) where the axis densities have been measured directly. Other values
in the figures are assigned to provide agreement with pole distribution
data. The assigned values of the axis densities are summarized in the

"P. K. Koh, Trans. Met. SOC. AIME -

215, 1043 (1959).
-

90

a
 UNCLASSIFIED
ORNL-LR-DWG 50238

(001 (013) (012) (Oft)

2.15 1.1 0.9 0.6

B)

F i g . 6.1. A x i s Density Figures for ( a ) the Normal Direction, ( b ) the Rolling Direction, and (c) the
Transverse Direction a f Silicon-Iron Strip After Primary Recrystallization.

figures by contour lines of constant density. The density corresponding

to a random texture has the value of unity. Clearly resolved {hkl} pole
concentrations parallel to the three axes of the specimen are listed be-
low:

N.D. R.D. T.D.

91
 e
The components of the texture deduced from the figures are listed in
Table 6.2. Four components of the (556) [056] type and four components
of the (117) [near 1161 type are given to account for the twofold symme-
try of the texture, which is evident in, for example, a (110)pole figure
of the material. In addition to these there may be two fiber-type compo-
nents - <OOl>I 1R.D. and U11>1 1N.D. - and two components of the (112)
[1101 type. The <001> component should provide some (110) [OOl], but pos-
sibly not enough (100) [Dol] to be resolved from the neighboring (117)
[near 1161 components. Furthermore, it is important to note that the
(111)pole density in the rolling direction (Fig. 6 . l b ) is zero. This
6
permits us to conclude that there are no (hkl) U11> components in the
texture. Consequently there is no significant part of the texture which
is random, because a random part would include all orientations.
6
Table 6.2. Components o f the Recrystallization Texture

Rolling Plane Rolling Direction Transverse Direction

(5561 [ 063 [bi,25,301 or [near 2111

[0&1 [61,25,301 or [near 2irl

(5561 [ 9051 [25,9i,301 or [near 1211

[ 6051 [z3,61,301 or [near 7211

[Giil e
[61il

[ 16il

[ ibil

[ iiol [nil*
dol> fiber texture,
approx

(111)fiber
texture

"Couldbe part of the spread of (556) [065] component.

 Before comparing the above results with previous ones we should like
to consider the question of magnetic-torque data. Prior data have shown
that the torque curve is nearly that of a (110) [OOl] single crystal, but
with one-fifth the amplit~de.~To a first approximation it may be repre-
sented as follows:12

L
2 -
K1
= -0.10 sin 20 - 0.15 sin 4e ,
where L is the torque, K1 is the first anisotropy constant, and 8 is the
angle between the rolling direction and the direction of the applied mag-
netic field. In the same connection, Dunn and Walter13 have considered
the texture of a different material having a torque curve represented by
2L/Kl = - 0 . 1 2 sin 20 - 0.18 sin 4 Q , which is not far different from the
present curve. The material also had a multicomponent texture, similar
to the present texture in having a concentration of (001)poles in the
neighborhood of the rolling direction. More importantly, the (017)
[near 1161 components are close to the present (117) [near 1161 compo-
nents. Such a component has a large influence on the coefficient of the
sin 40 term. This and other pertinent information is given in Table 6 . 3 .
The former texture results are needed for a continuation of the dis-
cussion and a comparison with present results. Figure 6 . 2 shows a re-
production of a (110)pole figure. The interpretation given for the tex-
ture was four (112) <681> components and two (111)U 1 2 > components, which
alone could not explain the torque data. The present (556) 4 6 5 > compo-
nents are t h e nearest to (112) <681> but they also tend to have little ef-
fect on the torque curve, because the torque vanished for (111)<uvw>.
However, the (112) U 1 0 > edge of the spread-out (556) <065> orientations
o f the present texture could provide something toward the A1 coefficient,
while the (117)<near 116> components contribute heavily to the A2 coef-
ficient. If we should assign about 6 to ?% of the texture to a spread-out
(110)d o l > component, then 37% (112) U10> and 39% (117)<near 116> for
the remainder would explain the torque curve. However, 26% of (123) <210>
and 14% (117)<near 116> will make up the difference just as well, and the

l2L. P. Tarasor and F. Bitter, Phys. Rev. 52, 352 (1937).

-
l 3 C . G. Dunn and J. L. Walter, J. Appl. Phys. 30, 1067 (1959).
-

93
I

Table 6.3. C o e f f i c i e n t s A1 and A2 of s i n 28 and s i n 48, Respectively,

f o r E i t h e r S i n g l e C r y s t a l s o r Twofold Symmetrized O r i e n t a t i o n s

Orientation A1 A2

(110) [ O O l I -0.5 -0.75

(100) [ O O l I 0 -1

(111)<uw> 0 0
(556) 465> 0.03 -0.10

(112) 410> -0.17 0.58

(112) <681> -0.16 0.47

(123) <210> -0.25 0.067

(117)<near 116> -0.01 -0.82

(017<271> 0.025 -0.493

numerical v a l u e s seem more r e a s o n a b l e . A simple c a l c u l a t i o n shows t h a t

t h e f r a c t i o n of t h e sample w i t h i n 10' of t h e (123) p o l e 1 I N.D. p o s i t i o n ,
which i s n o t a l a r g e spread, i s about 30%. It i s concluded t h a t t h e
p r e s e n t t e x t u r e can e x p l a i n t h e t o r q u e c u r v e . The p r i n c i p a l new informa-
t i o n making t h i s p o s s i b l e i s t h e i d e n t i f i c a t i o n of t h e (117)<near 116>
components. It i s a l s o concluded t h a t t h e ORNL method more d i r e c t l y re-
s o l v e s components i n a multicomponent t e x t u r e t h a n does t h e u s u a l p o l e
f i g u r e method.
L i t t l e can be s a i d about t h e e f f e c t of t h e p r e s e n t t e x t u r e on growth
r a t e s of secondary r e c r y s t a l l i z a t i o n g r a i n s ; l i t t l e i s known even f o r t h e
more simple m a t r i x t e x t u r e s . As b e f o r e , ' it can b e s a i d t h a t t h e compo-
nent w i t h maximum r a t e of growth of secondary g r a i n s , (110) [OOl], i s i n
d e v i a t i n g o r i e n t a t i o n t o t h e main components of t h e t e x t u r e , The r e l a -
t i o n s h i p i s very roughly a 40" r o t a t i o n about a a O O > a x i s , b u t whether
t h i s r e l a t i o n s h i p i s b e t t e r f o r r a p i d growth t h a n o t h e r s i n v o l v i n g a h i g h
a n g l e of r o t a t i o n remains an important q u e s t i o n f o r f u r t h e r work. I n any
such work t h e t e x t u r e needs t o b e known.
e

d U N C L A SlFlED
ORNL-LR-DWG 50239

Fig. 6.2. A (110) P o l e Density Figure After Primary Recrystallization at 800°C. Solid and open
c i r c l e s and solid and open squares g i v e the ( 1 12) <112> orientations.

95
 TWINNING I N VANADIUM

C . J. McHargue

Recent s t u d i e s have shown t h a t n i o b i m 1 4 and deform by

f o r m a t i o n of mechanical t w i n s w i t h r e l a t i v e e a s e . Both metals were r e -
p o r t e d t o form t w i n s under impact l o a d i n g even a t room t e m p e r a t u r e i f t h e
p u r i t y w a s high. On t h e o t h e r hand, d a t a r e p o r t e d by Clough and Pavlovic17
show commercially pure vanadium t o form deformation t w i n s only f o r impact
l o a d i n g below -78°C and only w i t h i n one o r two g r a i n s o f a c l e a v e d s u r f a c e .
A t t h i s l a b o r a t o r y , t w i n n i n g of electron-beam-melted vanadium h a s been
observed a f t e r deformation by slow compression a t l i q u i d - n i t r o g e n tempera-
ture. S i n g l e c r y s t a l s were c u t from a n i n g o t having t h e f o l l o w i n g i n t e r -
stitials: 0.033% C , 0.0047% 02, 0.0005% N 2 , and 0.0012% H2. The oxygen
and n i t r o g e n c o n t e n t of t h i s material was an o r d e r of magnitude lower t h a n
i n t h a t studied by Clough and P a v l o v i c , 1 7 w h i l e t h e carbon and hydrogen
c o n t e n t s were o n l y s l i g h t l y l o w e r .
The t w i n s were q u i t e similar i n appearance t o t h o s e found i n t h e
o t h e r body-centered c u b i c metals - t h i n with s e r r a t e d boundaries. A two-
s u r f a c e a n a l y s i s of t h e t w i n t r a c e s e s t a b l i s h e d t h e t w i n p l a n e as {112},
as e x p e c t e d .
Thus it a p p e a r s t h a t a l l of t h e group V body-centered c u b i c m e t a l s
t w i n w i t h r e l a t i v e e a s e below room t e m p e r a t u r e i f t h e y a r e v e r y p u r e and
have a r e l a t i v e l y l a r g e g r a i n s i z e .

1 4 C . J. McHargue, M e t . Ann. B o g . Rep. S e p t . 1, 1959, ORNL-2839,

p 10-16.
"C. S. B a r r e t t and R . Bakish, T r a n s . Met. SOC. AIME -
212, 122 (1958). '

1 6 R . W. Anderson and S. E . B r o n i s z , Acta Met. -

7, 645 (1959). 9
-
17W. R. Clough and A. S . P a v l o v i c , T r a n s . Am. SOC. Metals -
52, 948
(1960). -

96

. ... . .. .. ~ -. ..... .. __ -
 7. THEORY OF ALLOYING

J. 0 . B e t t e r t o n , J r .

THE METmLIC VAIXNCE OF ZIRCONIUM

J . 0 . B e t t e r t o n , Jr.

For copper, s i l v e r , and g o l d a l l o y s no d i f f e r e n c e e x i s t s between t h e

chemical v a l e n c e , t h e number of b i n d i n g e l e c t r o n s , and t h e m e t a l l i c v a l e n c e
o r t h e number of e l e c t r o n s c o n t r i b u t e d t o a common e l e c t r o n i c band. In
t r a n s i t i o n m e t a l s , g r e a t e r c a r e i s needed s i n c e t h e e l e c t r i c a l and magnetic
p r o p e r t i e s sugges-#;t h a t t h e d e l e c t r o n s are i n a narrower band, which i s
e s s e n t i a l l y independent of t h e o t h e r e l e c t r o n s , b u t w i t h t h e same Fermi sur-
face.' I n t h e e a r l i e r work on zirconium a l l o y s 2 it w a s p o i n t e d o u t t h a t
t h e e l e c t r o n d e n s i t y of such d e l e c t r o n s would n o t p e n e t r a t e s i g n i f i c a n t l y
i n t o t h e Wigner-Seitz c e l l s of t h e o t h e r component of t h e t r a n s i t i o n - m e t a l
a l l o y , p r o v i d e d t h a t t h i s component a l r e a d y had a c o m p l e t e l y f i l l e d d s h e l l ,
as it does w i t h B--subgroup s o l u t e s . Under t h e s e c i r c u m s t a n c e s such a t r a n -
s i t i o n m e t a l does n o t c o n t r i b u t e a l l of i t s outermost e l e c t r o n s t o t h e com-
mon band, and t h e m e t a l l i c v a l e n c e and t h e number of b i n d i n g e l e c t r o n s are
d i s t i n c t and d i f f e r e n t numbers. To i l l u s t r a t e f u r t h e r , one may imagine t h e
removal of a t r a n s i t i o n - m e t a l atom from an a l l o y of t h i s t y p e and s u b s t i -
t u t i o n of a B-subgroup s o l u t e atom. The wave f u n c t i o n of t h e s o l v e n t d
e l e c t r o n , being confined t o t h e t r a n s i t i o n - m e t a l c e l l s , i s absent a f t e r t h e
substitution. The, d e l e c t r o n s are s u b t r a c t e d as p a r t o f t h e i o n and are
n o t p a r t of t h e m e t a l l i c v a l e n c e . A f i n a l p r o p e r t y of t h e m e t a l l i c v a l e n c e
i n t r a n s i t i o n metals i s i t s variable nature with alloying conditions. For
example, zirconium c o u l d be n e a r l y z e r o v a l e n t as a s o l v e n t f o r s i l v e r b u t
t e t r a v a l e n t as a s o l v e n t f o r t i t a n i u m o r as a s o l u t e i n a n e l e c t r o n e g a t i v e
metal. Support f o r t h e s e c o n c e p t s i s p r o v i d e d by t h e low and v a r i a b l e va-
l e n c i e s of t r a n s i t i o n metals i n e l e c t r o n compounds w i t h B-subgroup s o l v e n t s
and t h e n e a r l y c o n s t a n t magnetic moments on t h e i n d i v i d u a l atoms of some
ferromagnetic-type a l l o y s .3

I N . F . Mott and H . J o n e s , The Theory of t h e P r o p e r t i e s of Metals and

A l l o y s , Clarendon P r e s s , Oxford, 1936.
2J. 0 . B e t t e r t o n , Jr., and J . H. F r y e , Jr., Acta Met. 6, 205 ( 1 9 5 8 ) .
-
'C. G. S h u l l and M. K. Wilkinson, Phys. Rev. 97, ,304 (1955).
-
97
 When t h e a l l o y can be described by t h e rigid-band model, m e t a l l i c va-
lence manifests i t s e l f as t h e power t o s h i f t t h e Fermi s u r f a c e , and because
of t h i s , it i s a u s e f u l v a r i a b l e f o r c o r r e l a t i o n of p h y s i c a l p r o p e r t i e s
which depend upon t h e p o s i t i o n of t h e Fermi s u r f a c e . Let us assume t h a t
t h e r i g i d band a p p l i e s t o zirconium and examine t h e e f f e c t s of B-subgroup
s o l u t e s Ag, Cd, I n , Sn, and Sb on t h e f o u r of t h e p r o p e r t i e s which a r e r e -
p o r t e d i n t h e l a t e r s e c t i o n s of t h i s r e p o r t .
I n F i g . 7.1, p a r t s a, b , e , and d, t h e e f f e c t s of t h e s e s o l u t e s on
t h e a l l o t r o p i c boundaries, t h e low-temperature spec i f i c h e a t s , t h e a x i a l
r a t i o s , and t h e e l e c t r i c a l r e s i s t i v i t i e s a r e p l o t t e d as a f u n c t i o n of s o l -
u t e valence. Each of t h e s e p r o p e r t i e s depends upon s o l u t e valence, n, and 0
atomic f r a c t i o n s o l u t e , x , i n a s i m i l a r way, t h a t i s , i f p be t h e property,
t h e n bp/ax = a + bn. This expression can a l s o be w r i t t e n as
I)

where no i s an a r b i t r a r y m e t a l l i c valence f o r zirconium and where a, a ' ,

and b a r e c o n s t a n t s , independent of x and n. It may be concluded t h a t when

0.004

-
h

'E 0.003
-
2
z 0.002
0
u

a
0
0.020 30
-
I

0.015
lal
5
-
9
25 8
z
0,010 G 20
6
E
0.005 '0 15
a
I

0
0 1 2 3 4 5
SOLUTE VALENCE SOLUTE VALENCE

Fig. 7.1. ( a ) Effects on t h e R e l a t i v e F r e e Energy o f a - and p-

Zirconium (F = Fp - Fa); ( b ) Effects of Solutes on the A x i a l Ratios
o f a-Zirconium; (c) Changes i n Density of States w i t h Alloying; (d)
Changes i n Electrical R e s i s t i v i t y with Alloying.

e
I . . ~
a cons-tarit term i s a s s o c i a t e d w i t h an e l e c t r o n c o n c e n t r a t i o n r e l a t i o n s h i p
t h e valence of t h e s o l v e n t cannot be chosen without an independent e v a l u -
a t i o n of t h e c o n s t a n t term.
Divalence was based on t h e d a t a shown i n F i g . ? . l a . This graph shows
t h e r e l a t i o n between t h e r a t e of change of t h e r e l a t i v e f r e e energy of t h e
a and p phases and t h e s o l u t e v a l e n c e . It w i l l be seen t h a t t h e curve h a s
a z e r o ' p o i n t a t t h e s o l u t e valence of approximately 2 . The e f f e c t of t i -
t a n i u m from group IVA has been drawn as i f it were d i v a l e n t . Two h o r i -
z o n t a l l i n e s a r e shown on t h e f i g u r e t o show t h e e f f e c t s of t h e t r a n s i t i o n
elements, i r o n and molybdenum.
The v a l u e s of &!F/ax were o b t a i n e d from t h e a l l o t r o p i c phase bound-
a r i e s i n t h e manner d e s c r i b e d p r e v i o u s l y 2 w i t h two changes: (1)f r e e
energy h a s been s u b s t i t u t e d f o r energy i n o r d e r t o allow f o r t h e p o s s i -
b i l i t y of an e n t r o p y term, and ( 2 ) a s i z e f a c t o r term, determined by l e a s t
s q u a r e s i n t h e e a r l i e r work,2 h a s been s u b t r a c t e d from each r e s u l t . This
i s a crude c o r r e c t i o n f o r t h e s i z e f a c t o r , and many o t h e r f a c t o r s have not
been considered, b u t t h e s t r a i g h t l i n e of t h e form &?/ax = C(n - 2 ) drawn
through t h e p o i n t s i n d i c a t e s t h e t r e n d of t h e e f f e c t s . The s l o p e of t h e

l i n e w a s i n t e r p r e t e d i n t h e e a r l i e r work2 i n t e r m s of t h e r i g i d - b a n d model
as t h e d i f f e r e n c e i n Fermi s u r f a c e of 0.03-0.04 e v i n t h e two phases, t h e
a phase having t h e lower s u r f a c e .
The changes i n t h e a x i a l r a t i o of a - z i r c o n i u m f o r a given amount of
solute, d(c/a)/dx, are d i r e c t l y p r o p o r t i o n a l t o t h e number of s o l u t e s and
p e l e c t r o n s on t h e s e s o l u t e s , as shown i n F i g . 7 . l b . One i n t e r p r e t a t i o n
of t h i s curve i s t h e Jones t h e o r y 4 of hexagonal-phase a x i a l r a t i o s , where
t h e a x i a l r a t i o depends upon e l e c t r o n c o n c e n t r a t i o n and t h e p o s i t i o n of
t h e Fermi l e v e l . A similar argument t o t h a t made f o r t h e a l l o t r o p i c bound-
a r i e s can be made i n terms of t h i s t h e o r y . F r o m t h e z e r o p o i n t of t h e
curve i n t h i s p r o p e r t y , t h e m e t a l l i c valence of zirconium would be n e a r l y
zero.
The e f f e c t s of t h r e e of t h e s e s o l u t e s on t h e d e n s i t y of s t a t e s of a-
zirconium have now been determined from t h e e l e c t r o n i c s p e c i f i c h e a t co-
e f f i c i e n t and w i l l be d i s c u s s e d i n g r e a t e r d e t a i l l a t e r i n t h i s r e p o r t .

'H. Jones, Proc . Roy. Soc . (London) l4?A, 396 ( 1 9 3 4 ) .

99
These e f f e c t s a r e a l s o p r o p o r t i o n a l t o t h e number of s and p e l e c t r o n s on
t h e s o l u t e s and a r e p l o t t e d as change i n d e n s i t y of s t a t e s f o r 1 a t . %
s o l u t e , as shown i n F i g . 7 . 1 ~ . The zero p o i n t of t h i s curve would i n d i c a t e
t h a t t h e zirconium valence i s n e a r l y zero.
F i n a l l y , t h e e f f e c t s of t h e s o l u t e s on t h e e l e c t r i c a l r e s i s t i v i t y of
a-zirconium a t 4.2'K a r e shown i n Fig. 7 . l d . A l i n e a r i n c r e a s e with s o l u t e
valence i s observed i n c o n t r a d i c t i o n t o Norbury's r u l e t h a t such e f f e c t s
should be p r o p o r t i o n a l t o t h e square of t h e charge on t h e s o l u t e ion. If
t h i s curve were t o be e x t r a p o l a t e d t o zero, t h e value obtained would be a
l a r g e negative number.
I n each of t h e l a s t t h r e e f i g u r e s t h e d e r i v a t i v e s were obtained e i t h e r
from t h e s l o p e s of l i n e a r curves of t h e s e p r o p e r t i e s , p l o t t e d a g a i n s t sol-
u t e composition x, o r i n t h e case of nonlinear curves by t h e l i m i t i n g slope
f o r small x. The experimental s c a t t e r makes t h e d e r i v a t i v e uncertain, p a r - Q
ticularly i n t h e c a s e of t h e e f f e c t of silver on t h e axial ratio and t h e
d e n s i t y of s t a t e s . Thus t h e exact p o i n t of i n t e r s e c t i o n o f t h e s e curves
w i t h t h e zero axis should not be taken t o o l i t e r a l l y .
Since t h e valence f o r zirconium w i l l depend upon t h e p h y s i c a l s i g n i f -
icance of t h e a t c o e f f i c i e n t s , t h e s e c o e f f i c i e n t s a r e considered below f o r
two choices of valency.

Zirconium Valence of Nearly Two

The zirconium valence of two from t h e a l l o t r o p i c transformation r e -

q u i r e s c o n s t a n t terms i n t h e d e r i v a t i v e s of t h r e e o t h e r p r o p e r t i e s . The
a x i a l r a t i o s would have t o depend, f o r example, upon a t l e a s t two phe-
nomena, t h a t i s , i n t h e simplest way

-Ca = - a ' ( l - x ) -i-b ( n - 2)x -t- c , (1)

$.-(a) = a' + b ( n - 2) ,
where a ' , b, and c a r e p o s i t i v e c o n s t a n t s , x i s atomic f r a c t i o n s o l u t e , and
n i s t h e s o l u t e valency. The f i r s t term, - a ' ( l - x), i s assumed here t o be
a r e l a x a t i o n of t h e negative d e v i a t i o n from t h e i d e a l value f o r c l o s e pack-
i n g which occurs i n a-zirconium. This i s assumed p r o p o r t i o n a l t o t h e num-
b e r of zirconium atoms i n t h e a l l o y . The second term i s p r o p o r t i o n a l t o

100
 changes i n numbers of e l e c t r o n s common t o t h e whole a l l o y and h a s a r e a -
sonable i n t e r p r e t a t i o n i n terms of a (002) B r i l l o u i n - z o n e o v e r l a p i n a-
zirconium.
The experimental changes i n t h e e l e c t r o n i c s p e c i f i c h e a t s , assuming
t h i s zirconium v a l e n c e , would be of a similar form. On t h e o t h e r hand,
t h e r i g i d - b a n d model w i l l l e a d t o t h e o r e t i c a l changes of t h i s t y p e , b u t
t h e c o n s t a n t t e r m i s of t h e o p p o s i t e s i g n . I n a d d i t i o n , as n + 0, t h e
change i n t h e axial r a t i o becomes n e a r l y z e r o , s o t h a t t h e a x i a l r a t i o
w i l l have l i t t l e e f f e c t on t h e e l e c t r o n i c s p e c i f i c h e a t i n t h i s r e g i o n .
A t p r e s e n t , any r e c o n c i l i a t i o n of t h e s p e c i f i c - h e a t d a t a , t h e r i g i d - b a n d
model, and t h e d i v a l e n c y f o r zirconium w i l l i n v o l v e t h e assumption of an
unknown p o s i t i v e t e r m i n aN(e)/ax.
A l a r g e , p o s i t i v e c o n s t a n t a ' i n t h e d e r i v a t i v e of t h e e l e c t r i c a l re-
4p
s i s t i v i t i e s can be r e a d i l y i n t e r p r e t e d by t h e d i s c o n t i n u i t i e s which are
i n t r o d u c e d i n t h e a l l o y by t h e absence of u n f i l l e d d s t a t e s i n t h e s o l u t e
atoms. S c a t t e r i n g from t h e s e d i s c o n t i n u i t i e s would i n c r e a s e t h e r e s i s -
t i v i t y and would be p r o p o r t i o n a l t o t h e atomic c o n c e n t r a t i o n of s o l u t e .

Zirconium Valence Nearly Zero

An a l t e r n a t i v e p r o p o s a l i s t o p l a c e n e a r l y a l l t h e zirconium e l e c -
t r o n s i n 4-d-type s t a t e s and t o assume a m e t a l l i c valence f o r zirconium
c l o s e t o zero. The d e r i v a t i v e s of b o t h t h e d e n s i t y of s t a t e s and t h e
axial r a t i o s would be simply p r o p o r t i o n a l t o t h e number of s o l u t e e l e c -
t r o n s i n t h i s c a s e , whereas t h e e l e c t r i c a l r e s i s t i v i t y would have an
i n t e r p r e t a t i o n which i s similar t o t h a t given i n t h e d i v a l e n t c a s e . The
only s e r i o u s o b j e c t i o n would be i n t h e d e r i v a t i v e s of t h e r e l a t i v e f r e e
e n e r g i e s of t h e a and @ phases. These would r e q u i r e an unknown c o n s t a n t
t e r m , s t a b i l i z i n g t h e B phase. Since f r e e energy depends upon b o t h energy
and entropy, e n t r o p y d i f f e r e n c e s might provide t h e a p p r o p r i a t e @ - s t a b i -
l i z i n g f a c t o r , b u t , a c t u a l l y , a c o n t r i b u t i o n of t h e o p p o s i t e sense t o t h a t
r e q u i r e d i s observed i n t h e thermodynamic measurements on one of t h e s o l -
u t e s , cadmium, as d e s c r i b e d i n a l a t e r s e c t i o n . An a l t e r n a t i v e view might
be t h a t an e n t r o p y c o n t r i b u t i o n s t a b i l i z e s t h e a phase and i s proportional
t o s o l u t e valence, and t h a t a c o n s t a n t term f a v o r i n g t h e @ phase o c c u r s
i n t h e energy. There i s as y e t no independent evidence t h a t t h i s i s t h e

101
 c a s e , b u t it i s c l e a r t h a t t h e adoption of n e a r l y zero valence f o r z i r - n

conium w i l l r e q u i r e a r e v i s e d t h e o r y f o r t h e a/@phase boundaries.

I n summary, t h e f o u r p r o p e r t i e s d i s c u s s e d above a l l show t e r m s which
are p r o p o r t i o n a l t o t h e number of e l e c t r o n s from t h e s o l u t e atoms. This
s u p p o r t s t h e a p p l i c a t i o n of t h e r i g i d - b a n d concept t o t h e s e a l l o y s . Sim-
i l a r l y , t h e c o n t r i b u t i o n of e l e c t r o n s from t h e s o l u t e t o t h e a l l o y appears
t o be maintained up t o t h e number f i v e i n agreement w i t h another assump-
t i o n of t h i s model. I n t h e p r e s e n t s t a t e of t h e s e data, however, one can-
n o t choose a valence f o r zirconium which does n o t i n t r o d u c e a q u e s t i o n a b l e
i n t e r p r e t a t i o n f o r a t l e a s t one p r o p e r t y . The most l i k e l y choice i s a
near-zero v a l u e , s i n c e t h i s l e a v e s only t h e more complicated a l l o t r o p i c a
phase boundaries unexplained. The n e a r l y z e r o v a l e n t zirconium i s i n
b e t t e r agreement w i t h t h e o r e t i c a l work on s i m i l a r metals by Lehman and
B e r l i n c o u r t on t i t a n i u m 5 and by Manning and Chodorow on t u n g s t e n , 6 which
a
show t h a t t h e e l e c t r o n s a r e mainly i n d-type s t a t e s i n t h e s e m e t a l s . The
absence of an a p p r e c i a b l e number of s-type e l e c t r o n s i n zirconium might
be independently confirmed by a K n i g h t - s h i f t measurement which, i f t h e
measurement can be done on zirconium, should d e t e c t mainly s-type d e n s i t y
of s t a t e s a t t h e n u c l e u s . The measurement of t h e p r o p e r t i e s of Zr-Pd i s
under c o n s i d e r a t i o n s i n c e conceivably t h i s s o l u t e when added t o z i r c o n i m
may n o t c o n t r i b u t e e l e c t r o n s t o t h e a l l o y , only t h e d i s c o n t i n u i t i e s i n t h e
a l l o y from i t s f i l l e d d s h e l l .

SPECIFIC HEATS AT LOW TEMPERATURES OF ZIRCONIUM ALLOYS

G. D . Kneip, Jr. J . 0 . B e t t e r t o n , Jr.

The s p e c i f i c h e a t s of d i l u t e a l l o y s of indium and t i n i n zirconium

have been measured from 1 . 2 t o 4.5"K and r e p o r t e d e a r l i e r . 7 These measure
ments have been extended t o d i l u t e a l l o y s of s i l v e r i n zirconium i n o r d e r
t o i n v e s t i g a t e t h e e f f e c t of a u n i v a l e n t s o l u t e on t h e d e n s i t y of e l e c -
tronic states.

5G. W . Lehman and T. G. B e r l i n c o u r t , F i n a l Report on Research on E l e c -

t r o n Energy S t a t e s i n T r a n s i t i o n Metals, Atomics I n t e r n a t i o n a l , AI-1889
(Feb. 1, 1 9 5 7 ) .
6M. F . Manning and M. I . Chodorow, " E l e c t r o n i c Energy Bands i n M e t a l l i c
Tungsten," Phys. Rev. - 56, 787 (1939).
-
7 M e t . Ann. Prog. Rep. Sept. 1, 1959, ORNL-2839, p 21.

102
 Ekcept f o r t h e two higher-composition Zr-Sn a l l o y s which a p p a r e n t l y
undergo a superconducting t r a n s f o r m a t i o n a t about 1.25"K, t h e s p e c i f i c
h e a t s were found t o c o n s i s t of an e l e c t r o n i c t e r m p l u s a v i b r a t i o n a l term
and t o obey t h e f o l l o w i n g e q u a t i o n over t h i s temperature range w i t h i n t h e
experimental e r r o r :

C = yT + BT3 . (3)

Alloy i n g o t s approximately 1 mole i n s i z e were p r e p a r e d by e l e c t r i c -

a r c m e l t i n g of i o d i d e zirconium and 99.99% pure s o l u t e s . Because of t h e
l i m i t e d s o l u b i l i t y of t h e s e elements i n hexagonal zirconium, t h e hexagonal
s t r u c t u r e w a s a t t a i n e d i n t h e highest-composition a l l o y s by a d i f f u s i o n l e s s
t r a n s f o r m a t i o n d u r i n g quenching from t h e cubic phase. This yields a
s t r a i n e d hexagonal s t r u c t u r e similar t o t h e e q u i l i b r i u m s t r u c t u r e w i t h t h e
s o l u t e atoms randomly d i s t r i b u t e d . The remaining a l l o y s were annealed i n
t h e e q u i l i b r i u m hexagonal-phase r e g i o n . The two types of a l l o y s are d e s -
i g n a t e d by open and f i l l e d symbols, r e s p e c t i v e l y , i n F i g s . '7.2 and '7.3,
which show t h e c o e f f i c i e n t s of t h e e l e c t r o n i c t e r m of t h e s p e c i f i c h e a t
and t h e Debye t e m p e r a t u r e s of t h e a l l o y s as f u n c t i o n s of composition.
E l e c t r o n i c energy bands a r i s i n g from b o t h t h e s and d atomic l e v e l s
are expected t o c o n t r i b u t e t o t h e e l e c t r o n i c s p e c i f i c h e a t of zirconium,

UNCLASSIFIED UNCLASSIFIED
ORNL-LR-DWG 48464 ORNL-LR-OWG 48160
295 292 I
B) I

290

-
8 -
Y
0 285
ull

280
2.81

SOLUTE CONCENTRATION

2.4 275
0 2 4 6 8 (0 42 0 2 4 6 8 40 12
SOLUTE CONCENTRATION (at 70) SOLUTE CONCENTRATION ( a t 7%)

Fig. 7.2. The Electronic Specific Heats of Fig. 7.3. The Debye Temperature of Hexagonal

& Hexagonal Zirconium Alloys. Zirconium Alloys.

103
 a
and, as i n o t h e r t r a n s i t i o n m e t a l s w i t h u n f i l l e d d s h e l l s , t h e d band
should e x i s t only over a narrow energy range and have a h i g h d e n s i t y of
Q
s t a t e s i n o r d e r t o accommodate t h e t e n e l e c t r o n s which can go i n t o d s t a t e s .
If it i s assumed t h a t t h e s and d bands c a n be t r e a t e d independently, t h e n
t h e c o e f f i c i e n t o f t h e e l e c t r o n i c t e r m of t h e s p e c i f i c h e a t s i s

where N ( e o ) and N (c0) are t h e d e n s i t i e s of s t a t e s a t t h e Fermi s u r f a c e

S d
i n t h e s and d bands, r e s p e c t i v e l y . T h i s band s t r u c t u r e i s shown schemat-
i c a l l y i n F i g . ?.4, and i f t h e bands are assumed t o be r i g i d and n o t t o
s h i f t i n energy w i t h r e s p e c t t o each o t h e r d u r i n g a l l o y i n g , t h e n i f e l e c -
t r o n s are added t o t h e bands, t h e Fermi energy s h i f t s from t o (cO + A€).

UNCLASSIFIED
ORNL-LR-DWG 50241
I

Fig. 7.4. Schematic Diagram o f the Zirconium

Band Structure.

Furthermore, i f t h e s band i s assumed t o be continuous throughout t h e a l l o y

and t h e d band assumed n o t t o p e n e t r a t e i n t o t h e Wigner-Seitz c e l l s of t h e
9
s o l u t e atoms, s i n c e t h e s e a l r e a d y c o n t a i n f u l l d s h e l l s , t h e n t h e change
i n t h e c o e f f i c i e n t of t h e e l e c t r o n i c s p e c i f i c h e a t d u r i n g a l l o y i n g f o r
s m a l l changes i n t h e Fermi l e v e l i s

where x i s t h e s o l u t e c o n c e n t r a t i o n . The change i n t h e Fermi energy LIE

104
Q

can be evaluated, s i n c e t h e change i n t h e number of e l e c t r o n s i n t h e a l l o y s

63 is

where n i s t h e number of e l e c t r o n s o u t s i d e c l o s e d s h e l l s i n t h e s o l u t e and

n and n a r e t h e number of e l e c t r o n s i n t h e s and d bands of zirconium,
S d
r e s p e c t i v e l y . The change i n t h e Fermi l e v e l t h u s i s

Equation ( 7 ) c l e a r l y shows t h a t t h e change i n t h e Fermi l e v e l during a l l o y -

i n g does not depend on t h e number of t h e d e l e c t r o n s i n t h e pure solvent
b u t i s determined by t h e number of s e l e c t r o n s and t h e d e n s i t y of s t a t e s .
Combining Eqs. ( 5 ) and ( 7 ) we have f o r t h e change i n t h e e l e c t r o n i c spe-
c i f i c h e a t during a l l o y i n g :

where

A simple two-band model for zirconium t h e n p r e d i c t s a l i n e a r v a r i a t i o n be-

9 tween Ay and n w i t h t h e slope a N ( ~ ) / d ~ , / N ( t o ) f o r small x . Figure 7.5 shows
t h a t t h i s r e l a t i o n s h i p i s v a l i d when n i s assumed t o be 1, 3, and 4 f o r
Ag, I n , and Sn, r e s p e c t i v e l y . From t h e slope of t h e l i n e , a N ( ~ ) / a c i s
found t o be l a r g e and p o s i t i v e , implying t h e e x i s t e n c e of an overlapped
band s t r u c t u r e . Equation (8) also shows t h a t ns, t h e number of e l e c t r o n s
i n t h e band shared by t h e s o l u t e and s o l v e n t , cannot be uniquely e s t a b -
l i s h e d without an independent e v a l u a t i o n of N ( e o ) or NS(cO). It i s ap-
d
p a r e n t from Eq. (8) t h a t when n = n Ay/x should equal -y f o r pure solvent
S'
and t h a t t h e p r e s e n t d a t a i n d i c a t e s t h a t n must be l e s s t h a n zero if t h e
S

105
 UNCLASSIFIED
ORNL-LR-DWG 5 0 2 4 2
8

1 Q
0
0 1 2 3 4 5
n (SOLUTE V A L E N C E )

Fig. 7.5. Rate of Change of the Coefficient of

the Electronic Specific Heat for Zirconium A l l o y s
as a Function of Solute Valence.

c o e f f i c i e n t of t h e e l e c t r o n i c s p e c i f i c h e a t i s determined l a r g e l y by t h e
d e n s i t y of d s t a t e s . It can be seen from F i g . 7.5 t h a t t h e i n t e r c e p t of t h e
l i n e i s determined l a r g e l y by t h e observed Ar/x f o r t h e s i l v e r a l l o y s and
t h a t a small change i n t h e value of Q / x f o r t h e s i l v e r a l l o y s would make
p o s s i b l e an agreement of t h e i n t e r c e p t of t h e l i n e w i t h a small p o s i t i v e
number of s e l e c t r o n s . Because of t h e l i m i t e d s o l u b i l i t y of s i l v e r (W 1
a t . $ ) i n zirconium and s m a l l change i n y w i t h s i l v e r a d d i t i o n s , t h e s i l v e r
a l l o y measurements a r e being repeated w i t h refinements i n t h e apparatus
and experimental techniques which should make p o s s i b l e a more r e l i a b l e e s -
timate of Ay/x for s i l v e r a d d i t i o n s t o zirconium.
The Debye temperatures for t h e same a l l o y s a r e shown i n Fig. 7.3.
Unfortunately, t h e s c a t t e r i s much l a r g e r than f o r t h e d e n s i t y of states,,
but t h e experimental values show a similar dependency on t h e s o l u t e va-
lence, %he decrease i n 8 f o r a f i x e d c o n c e n t r a t i o n i n c r e a s i n g i n magni-
D
tude throughout t h e s e r i e s s i l v e r , indium, t i n . Presumably, t h e dependence
of t h e e l e c t r o n i c energy on t h e e l e c t r o n concentration as shown i n t h e
e

d e l e c t r o n i c s p e c i f i c h e a t s i s important i n determining t h e e l a s t i c prop-

e r t i e s and hence t h e v i b r a t i o n a l s p e c i f i c h e a t s of t h e s e a l l o y s .

THE LATTICE SPACINGS AND AXIAL RATIOS OF a-ZIRCONIUM ALLOYS

J . 0. B e t t e r t o n , Jr. D. S. Easton

The l a t t i c e spacings of a-zirconium a l l o y s w i t h Ag, Cd, I n , Sn, and

Sb have been i n v e s t i g a t e d . Previous work8, had shown t h a t zirconium f i l -
i n g s were u n s a t i s f a c t o r y because of impurity contaminations b u t t h a t w i r e
specimens could be used with reasonable success. The Zr-Ag specimens were
prepared by wrapping t h e w i r e s i n degassed zirconium f o i l and annealing
i n a vacuum a t 800°C f o r 30 rnin. For t h e remaining a l l o y s an improved
technique w a s used. A hollow zirconium c y l i n d e r w a s heated t o 1100°C i n
an a l l - g l a s s , trapped system and t h e n cooled t o 800°C. The wire specimen
and a l i g h t tantalum suspension were lowered w i t h a magnet i n t o t h e c e n t e r
of t h i s hot c y l i n d e r and annealed f o r 1 t o 2 rnin. A p r e s s u r e p u l s e occurs
from about 1 x to 5 x mm Hg on t h e e x t e r n a l gage. This system
seems t o overcome t h e main d i f f i c u l t y i n annealing s m a l l zirconium s p e c i -
mens. This i s t h e tendency of t h e specimen t o r e a c t chemically w i t h t h e
r e s i d u a l i m p u r i t i e s i n o r d i n a r y vacuum systems, i n c l u d i n g t h e hydrogen
sorbed on t h e s u r f a c e of t h e w i r e . It i s thought t h a t most of t h e hydrogen
b u r s t from t h e surface w i l l not r e t u r n t o t h e specimen w i t h t h i s p r e s e n t
method.
A l l t h e w i r e s were f i n a l l y chemically polished i n a 46% HN03-46% H~C-
6% HE' s o l u t i o n , causing a removal of 0.1-0.3 mm of s u r f a c e m a t e r i a l , p r i o r
t o mounting i n an 11.43-cm North American P h i l l i p s Debye-Scherrer camera.
The d e t a i l s of t h e p r e c i s i o n determinations of l a t t i c e spacings have been
discussed earlier8-'' w i t h t h e only r e c e n t change being t h e adoption of
t h e Nelson-Riley'' extrapolation function. The average temperature of t h e
x-ray measurement w a s 23 k 4°C.

8Met. Semiann. Prog. Rep. Oct. 10, 1955, ORNL-1988, p 173.

'Met. Semiann. Prog. Rep. Apr. 10, 1956, ORNL-2080, p 218.
"Met. Ann. Prog. Rep. Oct. 10, 1957, ORNL-2422, p 229 ( c l a s s i f i e d ) .
"J. B. Nelson and D . P. R i l e y , Proc. Phys. SOC. (London) -
57, 16&77
(1945).
-

107
 The lump a l l o y s were arc-cast from WAPD i o d i d e zirconium (1436c),
thoroughly outgassed, homogenized i n t h e f3 region, and a-annealed p r i o r
t o c o l d swaging t o 1-mm wire. The composition o f t h e s e a l l o y s i s e s t i -
mated t o be a c c u r a t e t o w i t h i n 5% of t h e value used. I n the p a r t i c u l a r
case of t h e Cd-Zr a l l o y s , t h e a l l o y s cannot be made by a r c - c a s t i n g , b u t
must be made by a d i f f u s i o n t r e a t m e n t . This i s not so r e l i a b l e , and i n one
of t h e w i r e s (12.3 a t . % cadmium), a compositional g r a d i e n t w a s d e t e c t e d .
Nevertheless, t h e average analyses as determined by d i s s o l v i n g t h e whole
wire a r e used on t h e graph. Due t o a s c a r c i t y of m a t e r i a l , some p r e l i m i -
nary w i r e s c o n t a i n i n g more t h a n 1% cadmium were formed by hammering i n -
a
s t e a d of swaging, with consequent l o s s of q u a l i t y i n t h e d i f f r a c t i o n p a t -
t e r n because of p r e f e r r e d o r i e n t a t i o n and s p o t t i n e s s . These f a c t o r s
introduced g r e a t e r e r r o r s i n t h e Cd-Zr specimens, which w i l l be noted as a
increased s c a t t e r on t h e graphs.
The e f f e c t s of Ag, Cd, I n , Sn, and Sb on t h e l a t t i c e spacing and a x i a l
r a t i o of a-zirconium a r e p l o t t e d i n F i g . 7.6. It w i l l be observed t h a t
t h e experimental a spacings with a l l of t h e s e s o l u t e s very n e a r l y f i t t h e
same curve. With t h e c spacing, on t h e o t h e r hand, s i g n i f i c a n t valency
e f f e c t s a r e observed. These curves r o t a t e upwards w i t h i n c r e a s i n g numbers
of valency e l e c t r o n s i n t h e s o l u t e . Jones12 has developed a t h e o r y of
a x i a l r a t i o s f o r t h e close-packed hexagonal phases which have a few over-
lapping e l e c t r o n s on a p a r t i c u l a r f a c e of t h e B r i l l o u i n zone. The c r y s t a l
would a d j u s t i n a x i a l r a t i o s o as t o minimize t h e t o t a l e l e c t r o n i c energy
by reducing t h e d i s t a n c e i n K space of t h e s e e l e c t r o n s from t h e o r i g i n .
If t h e overlap phase i s a (002) plane, t h e r e s u l t i n g change would i n c r e a s e
c distances i n the c r y s t a l s t r u c t u r e . Goodenough13 has modified Jones'
treatment t o include a similar e f f e c t when t h e Fermi s u r f a c e approaches,
tangency w i t h a B r i l l o u i n zone f a c e , s i n c e a l e s s e n i n g of t h e e l e c t r o n
e n e r g i e s and an i n c r e a s e i n t h e d e n s i t y of s o l u t e s g e n e r a l l y occurs i n
t h i s vicinity. I n order t o account f o r t h e changes i n t h e c spacing i n
t h e zirconium a l l o y s , t h e t h e o r y would have t o be extended t o d e l e c t r o n s .

147A, 396 (1934) and P h i l . Mag.

l2H. Jones, Proc. Roy. SOC. (London) -
4
-.1,663 (1950).
l3J. Goodenough, Phys. Rev. -
89, 282 (1953).
-
I 108

0
a
UNCLASSIFIED
ORNL-LR-DWG 5 0 2 4 3
1.610

6iJ
1.606

1.602

j.598

1.594

1.590

-
I
5.16

t-

2
a v)
2
0
V
5.15

W 5.14
v
c
5.13

0 3.24

3.23

3.22

3.21

3.20

3.1 9
0 5 10 1E
S O L U T E CONCENTRATION ( a t % )

F i g . 7.6. The E f f e c t s o f Ag, Cd, In, Sn, and Sb

on L a t t i c e Spacings of a-Zirconium.

This would seem reasonable enough s i n c e such e l e c t r o n s a r e described by

N ( E ) curves, e x i s t i n B r i l l o u i n zones, and would have overlaps. However,
they a r e b e s t represented by t h e t i g h t l y bound e l e c t r o n approximation, and
some complications undoubtedly e x i s t which a r e not being considered h e r e .
A s p r e v i o u s l y discussed, it i s l i k e l y t h a t most o f t h e zirconium e l e c t r o n s
a r e of t h e d t y p e . Assuming t h a t t h e Jones theory of axial r a t i o s does
apply t o d e l e c t r o n s , t h e r e l a t i o n s h i p between t h e number of e l e c t r o n s i n
t h e s o l u t e and t h e slope of t h e c spacings curve can be understood i n terms
of an increased number of overlapped e l e c t r o n s . F u r t h e r , t h e band s t r u c -
t u r e of zirconium would appear t o be overlapped i n t h e c d i r e c t i o n .

109
 A

S l i g h t e f f e c t s of t h e s i z e s of t h e atoms (Ag -?$,, C d -l$, I n +l$, Sn

+3%, and Sb -7%, r e l a t i v e t o zirconium) appear t o be much l e s s important
t h a n t h e above p r o c e s s , and t h e y can be reasonably assumed i s o t r o p i c w i t h
r e s p e c t t o t h e a and c dimensions. By study of t h e above p r o c e s s i n t e r m s
of axial r a t i o s , t h e s i z e e f f e c t s would be l a r g e l y removed. The a x i a l
r a t i o s are shown i n t h e upper graph of F i g . 7.6. The axial r a t i o s are i n -
c r e a s e d b y a l l t h e s o l u t e s , w i t h t h e r a t e of i n c r e a s e p r o p o r t i o n a l t o t h e
number of e l e c t r o n s c o n t r i b u t e d by t h e s o l u t e . The e f f e c t of t h e s o l u t e
valence on t h e s l o p e of t h e c/a-vs-composition graphs have been p l o t t e d
previously i n Fig. 7.lb. Much t h e same c o n c l u s i o n s would be drawn on t h e
b a s i s of axial r a t i o s as would be drawn from t h e c dimensions. The i m -
e
p l i c a t i o n t h a t each s o l u t e i s adding e l e c t r o n s t o zirconium has been d i s -
cussed i n a p r e v i o u s s e c t i o n . e
THE Zr-Ga PHASE DIAGRAM I N THE V I C I N I T Y O F THE ALLOTROPIC
TRclNSITION OF ZIRCONIUM

D. S. Easton J. 0. B e t t e r t o n , Jr.

The experiments on Z r - G a a l l o y s a r e an e x t e n s i o n of t h e work on I n -

Z r t o a n o t h e r group I I I B s o l u t e which i s c o n s i d e r a b l y s m a l l e r t h a n z i r -
conium. The r e s u l t i n g s i z e m i s f i t h a s t h e e f f e c t 1 4 s 1 5 of g r e a t l y i n c r e a s -
i n g t h e r a t e of hardening i n t h e zirconium-rich phases, of r e s t r i c t i n g t h e
s o l i d s o l u b i l i t y , and of r o t a t i n g t h e normally r i s i n g a/f3 boundaries ( w i t h
group I I I B s o l u t e ) t o a downward i n c l i n a t i o n i n t h e phase diagram. New
experiments i n t h e p a s t y e a r have confirmed t h e e u t e c t o i d r e a c t i o n i n t h i s
system. These r e s u l t s a r e shown i n F i g . 7.7, which d e p i c t s t h e phase d i a -
gram between 8OC-9?O0C and (2-2.4 a t . $ Ga. The a l l o y s were made from spec-
t r o s c o p i c a l l y pure g a l l i u m and degassed Westinghouse i o d i d e zirconium ( 0 . 6
Cu, 2'7 F e , 14 N i , 4 C r , 1.3 Mo, 4 S i , 0.2 W , 80 T a , 20 02,5 N 2 , 2 H2, a l l
ppm), b u t because of t h e r a p i d changes i n a-phase boundaries w i t h minor
i m p u r i t i e s t h e e x p e r i m e n t a l diagram i s a d i s t o r t i o n of a b i n a r y system.
T h i s d i s t o r t i o n r e s u l t s i n an (a+ f3 + y ) r e g i o n below t h e e u t e c t o i d r e -
a c t i o n and an (a+ @ ) r e g i o n below t h e a l l o t r o p i c t r a n s i t i o n of pure z i r -
conium, The i d e a l phase diagram can be v i s u a l i z e d by moving t h e lower two

14Met. Ann. Prog. Rep. Oct. 10, 1958, ORNL-2632, p 17 ( c l a s s i f i e d ) .

I5Met. Ann. Prog. Rep. Nov. 16, 1959, OWL-2839, p 33.

110

a
 UNCLASSIFIED
ORNL-LR-DWG 50244
980

0 2-PHASE
960 0 3-PHASE
A SINGLE PHASE + TRACE SECOND PHASE
FILLED SYMBOLS INDICATE ANALYZED
940 SAMPLES

920
I

Y
I

w
5 900
tu
w
g 880
W
c

860

840

820

800
0 0.4 0.8 1.2 1.6 2.0 2.4 2.8
GALLIUM ( a t % )

Fig. 7.7. Eutectoid Region of t h e Zr-Ga Phase

Diagram.

boundaries of the ( a , +f3) and (a + f3 + y) regions upwards until the ( a +

B + y ) region disappears. The symbol y refers to the first intermetallic
phase, which is probably Zr3Ga.
The microstructures shown in Figs. 7.8, 7.9, 7.10, and 7.11 reveal
0 the rapid changes in constitution which occur at 8 4 3 O C between 0.5% and
1.3% gallium. Figure 7.8 is a photograph of the 0.5% gallium alloy in the
homogeneous a structure, followed by structures in the (a + @ ) region (Fig,
7.9), the (a + p + y ) region (Fig. ".lo), and the (a + y ) region (Fig.
7.11). The amount of p phase shown in the alloys of Figs. 7.9 and 7.10
is small, indicating that the maximum solubility of the a phase is in the
vicinity of these compositions and this temperature, as shown on Fig. 7.7.
In order to compare the position of a / ( a + p ) and @ / ( a+ @ ) boundaries
with other zirconium systems, the @ / ( a+ p ) boundary was extrapolated as
a straight line to 840°C, and the mean of this boundary and the a / ( a + /3)

111
 0

Fig. 7.8. Zirconium-0.5% Gallium Alloy i n the Homogeneous

a-Phase Region After Annealing at 843°C. Etchant: HN0,-H,O-HF.
500x.

Fig. 7.9. Zirconium-0.8% Gallium Alloy Showing Two Grains of

Transformed /3 in an a-Phase Grain Boundary After Annealing a t 843°C.
Etchant: HN0,-H,O-HF. 500X.

112
 Fig. 7.10. Zirconium-1.1% Gallium Alloy with a Matrix of a Phase
Containing Small, Dark y Crystals (Probably Zr,Ga) and Transformed
p (Gray Areas in Grain Boundary). Annealed a t 843°C. Etchant: HN0,-
H,O-HF. SOOX.

Fig. 7.11. Zirconium-1.3% Gallium Alloy in the (a + y) Region

After Annealing at 843%. The large dark areas in the center are over-
etched y phase, not pores. Etchant: HNO,-H,O-HF. SOOX.

113
boundary w a s used t o evaluate16 (a/ax) LY? = 4 . 0 3 3 ev/atom. The average
of t h e seven n e a r e s t neighbors i n t h e gallium s t r u c t u r e i s 2.702 A, which
i s equivalent t o an atomic s i z e f a c t o r f o r t h i s system of -13$1, and a
m i s f i t c o r r e c t i o n L 6 of 0.000327 X (-13)2 = 0.055 ev/atom. The c o r r e c t e d
value f o r t h e r e l a t i v e f r e e energy change +0.022 ev/atom i s p l o t t e d on Fig.
7 . l a , where it may be seen t o correspond w e l l w i t h t h e average behavior of
t h e o t h e r zirconium systems.
Figure 7.12 shows a t y p i c a l microstructure i n t h e upper p a r t of t h e
(a+ f3) region. The l i g h t l y shaded, oval-shaped g r a i n i n t h e c e n t e r of
t h e photograph i s an isothermal a grain. The absence of appreciable c o l o r

Fig. 7.12. Zirconium-1.0% Gallium Alloy in the (a + p) Region

After Annealing 24 Days at 866%. Etchant: HN0,-H,O-HF; polarized
light illumination. 250X.

d i f f e r e n c e s i n r o t a t i o n of t h e specimen i n p o l a r i z e d l i g h t and t h e constant

d i r e c t i o n of twins suggest t h a t t h e transformed f3 region immediately sur-
rounding t h e a g r a i n has n e a r l y t h e same o r i e n t a t i o n . It would appear t h a t
t h e transformed f3 grew outwards from t h e a g r a i n during t h e quench and
adopted t h e o r i e n t a t i o n of t h e p a r e n t c r y s t a l i n t h i s region. A t distances
f u r t h e r from t h e a grain, a t y p i c a l serrated a' s t r u c t u r e i s observed.

16J. 0. B e t t e r t o n , Jr., and J. H. Frye, Jr.; Acta Met. -

6 , 205 (1958).

114

0
-
- __ __ - - - . _ _ _ _ _ _ _ - - -
_ _ _
 E L E C T R I C A L RESISTIVITIES OF ZIRCONIUM AND ZIRCONIUM ALLOYS

J. 0. B e t t e r t o n , Jr. D . S. Easton

An i n v e s t i g a t i o n of r e s i s t i v i t i e s of zirconium a l l o y s w a s undertaken
t o determine whether valence e f f e c t s , such as i n Norbury's r u l e , were ob-
served i n zirconium a l l o y s , and t o make use of t h e c l o s e s i m i l a r i t y of p . / T
1
and s p e c i f i c - h e a t curves t o i n v e s t i g a t e t h e o r i g i n of entropy d e v i a t i o n s
i n the Z r - C d alloys. These o b j e c t i v e s were not f u l l y a t t a i n e d f o r reasons
which w i l l be discussed below, b u t o t h e r i n t e r e s t i n g e f f e c t s were found.

The r e s i s t i v i t i e s were measured by t h e potentiometric method, r e v e r s -

i n g t h e c u r r e n t and p o t e n t i a l l e a d s t o e l i m i n a t e spurious thermal e f f e c t s .
The specimen clamp and p o t e n t i a l c o n t a c t s a r e i l l u s t r a t e d i n Fig. 7.13.
The apparatus w a s kept s m a l l enough t o i n s e r t e a s i l y i n a liquid-helium-
s t o r a g e Dewar and i n various constant-temperature b a t h s . Gage l e n g t h w a s
determined with a t r a v e l i n g microscope, while t h e wire diameter w a s meas-
ured w i t h a micrometer i n many p l a c e s t o determine an average value. The
estimated accuracy of t h e r e s i s t i v i t i e s i s 1% or 0.1 ohm-em, whichever i s
larger. The w i r e s were prepared i n t h e same way as t h e wire specimens for
t h e l a t t i c e - p a r a m e t e r measurements, except t h a t t h e f i n a l anneal w a s f o r
30 min a t 8 0 0 ° C .

The numerical values of t h e r e s i s t i v i t i e s and t h e u n c e r t a i n t i e s of t h e

a l l o y composition a r e given i n Table 7.1. The same r e s u l t s a r e p l o t t e d i n
F i g . '7.14,the curve at t h e bottom of t h e graph being t h e e l e c t r i c a l r e s i s -
t i v i t y of pure zirconium. This curve i s l i n e a r at t h e higher temperatures

UNCLASSIFIED
Y-34964

Fig. 7.13. Arrangement of Potential Leads and the Specimen Holder in the Electrical Resistivity
Measurements.

d
115

e
r
I

Table 7.1. E l e c t r i c a l R e s i s t i v i t i e s of Zirconium and Binary Zirconium

Alloys i n Units of pohm-cm

Solute ( a t . $ )

Ag Ag Ag Cd In In In Sn Sb Sb
Temp
(OK)
Pure
Zr
0.26 k 0.44 ? 0.82 i 3.23 ? 2.08 i 3.89 i 6.4 t 1.34 0.095 If: 0.44 *
0.02 0.02 0.04 0.2 0.1 0.2 0.3 0.1 0.01 0.04

4.2 0.3 4.8 7.6 14.2 61.3 43.9 81.5 126.4 29.8 2.4 9.2
!

77.4 6.4 12.1 15.0 21.7 69.2 50.9 87.6 130.4 37.3 8.7 16.2

194.7 25.7 31.9 34.5 41.6 87.4 68.7 102.5 139.6 56.3 27.8 35.1

273.2 39.4 45.4 47.9 54.5 98.2 80.0 111.4 144.4 68.9 40.9 48.1

304.7 44.8 50.7 53.0 59.6 102.5 84.3 114.5 146.0 73.7 46.1 53.2
 UNCLASSIFIED
ORNL-LR-DWG 50245

X (436-5Zr A3.23 %Cd 0 1.34 Yo Sn

V 0.26 YoAg 0 6.4 %In 0.10 Yo Sb
+ 0.44 %Ag 3.89 Yo I n 0 0.44 YO Sb
0.82 Yo Ag A 2.08 YoI n
(€0
I

(D 400
I
0
x
E 80
Y
E
r
60

40

20

00 40 80 120 (60 200 240 280 300

1 7 G . K . White and S . B. Woods, P h i l . Trans. Roy. SOC. (London) 25L4

-'
273 (1959). The Z r 3 and Z r 4 samples i n t h i s r e f e r e n c e are t h e same wires
as used i n t h i s r e p o r t .
l 8 T . S. Smith and J. G. Daunt, Phys. Rev. 88, 1172 (1952).
-
"H. Jones, Handbuch der Physik 1 9 , 260-65 ( 1 9 5 6 ) .
-
117
 UNCLASSIFIED
ORNL- LR- DWG 4 a a g a ~

0 50 I00 150 200 250 300 350

TEMPERATURE (OK)

Fig. 7.15. Ideal R e s i s t i v i t i e s of Zirconium and Some Zirconium

AI loys.

M a t t h i e s s e n ' s r u l e might be obeyed and makes it c l e a r t h a t w i t h a d u a l

band s t r u c t u r e involving d e l e c t r o n s and w i t h a l l o y s c o n t a i n i n g a v a r i a b l e
number of e l e c t r o n s , t h e c o n d i t i o n s a r e unfavorable f o r Matthiessen's r u l e .
F u r t h e r , it i s w e l l known t h a t more concentrated a l l o y s almost never obey
this rule. Thus, i n t h e zirconium a l l o y s , i n t e r f e r e n c e occurs between t h e
impurity and thermal s c a t t e r i n g , and it i s not p o s s i b l e t o decide whether
t h e impurity s c a t t e r i n g i s temperature dependent o r whether t h e l a t t i c e
s c a t t e r i n g i s compositional dependent.
118
 P l o t t i n g t h e data i n t h e form ( p . / T ) v s l o g T does i n d i c a t e some s y s -
1
tematic trends. I n t h e Bloch-Gruneisen model, v a r i o u s m e t a l s are u n i v e r -
s a l l y of t h e form p . / T = c o n s t a n t G ( @ / T ) , where t h e Gruneisen2' f u n c t i o n
1
G(x) i s v e r y s i m i l a r t o Debye s p e c i f i c h e a t , "v/"v( c l a s s i c a1 ) .
Lewis and
R a n d a l l 2 l have p o i n t e d o u t t h a t i f a p r o p e r t y i s a u n i v e r s a l f u n c t i o n of
@/T, it i s also a u n i v e r s a l f u n c t i o n of l o g ( @ / T ) . A graph of t h i s t y p e
f o r t h e i d e a l r e s i s t i v i t i e s of zirconium and zirconium a l l o y s i s given i n
F i g . 7.16. A displacement of t h e curve t o t h e l e f t i s e q u i v a l e n t t o low-
e r i n g t h e Debye temperature. Assuming t h a t t h e a l l o y i n g e f f e c t s on p near
i
77°K r e a l l y are changes i n t h e thermal o s c i l l a t i o n s of t h e atoms, t h e spe-
c i f i c h e a t would be h i g h e r t h a n i n pure zirconium and t h e thermal e n t r o p y
of a l l t h e a l l o y s except t h e two h i g h e s t indium a l l o y s would be i n c r e a s i n g
more r a p i d l y i n t h i s r e g i o n t h a n i n pure zirconium. A t higher temperatures
and c o n c e n t r a t i o n s of a l l o y i n g element, it i s known from t h e i n c r e a s e i n
t h e axial r a t i o of a-zirconium w i t h t e m p e r a t u r e 2 2 and from o t h e r d a t a 2 3
t h a t an o v e r l a p i s probable i n t h e e l e c t r o n i c s t r u c t u r e , which i n c r e a s e s
w i t h b o t h temperature and s o l u t e element c o n c e n t r a t i o n . The r e s i s t i v i t i e s
determined b y Cook, Castleman, and Johnson24 f o r t h e temperature i n t e r v a l
373-1123°K are a l s o shown i n F i g . 7.16. Above 600"K, p /T f o r zirconium
i
shows a s i g n i f i c a n t downward c u r v a t u r e which, according t o Smoluchowski, 25

i s probably due t o t h e i n c r e a s i n g a v a i l a b i l i t y of e l e c t r o n s of h i g h mo-

b i l i t y caused by t h e i n c r e a s i n g o v e r l a p a t h i g h t e m p e r a t u r e s . The shape
of t h e c u r v e s f o r t h e alloys, p a r t i c u l a r l y t h e more c o n c e n t r a t e d cadmium
and indium a l l o y s , s u g g e s t s t h a t t h e s t r o n g d e v i a t i o n s from M a t t h i e s s e n ' s

16, 530 (1933).

2oE. Gruneisen, Ann. Physik -
21G. N. Lewis and M. R a n d a l l , Thermodynamics, p 7 5 (1923).
2 2 R . B. R u s s e l l , The C o e f f i c i e n t s of Thermal Expansion f o r Zirconium,
MIT-1073 (Oct. 1 9 , 1951).
23G. D . Kneip, Jr., and J. 0. B e t t e r t o n , Jr., " S p e c i f i c Heats a t Low
Temperatures of Zirconium Alloys," and J. 0. B e t t e r t o n , Jr., and D. S.
Easton, "The L a t t i c e Spacings and Axial R a t i o s of Alpha-Zirconium Alloys,"
i n t h i s report.
24L. A. Cook, L. S. Castleman, and W. E. Johnson, WAPD-25 (December
20, 1950).
25R. Smoluchowski, Metallurgy of Zirconium ( B . Lustman and N. F . Kerze,
Jr., e d s . ) p 434 (1955).

119
 UNCLASSIFIED
ORNL-LR-DWG 50247

o PURE Z I R C O N I U M
0.15 5 G ( 2 5 0 / T )
0.155G ( 2 8 7 / T )
0.15
0.155 G ( 3 0 0 / T )
0 Zr + 0.0026 A g
El Z r + 0.0044 Ag
IZ r + 0.0082 A g
- + Zr + 0.0323 Cd
0 Z r + 0.0208 In
X Z r + 0.0389 In
v Zr+ 0.0640 I n
0.10 v Z r + 0.0134 Sn
A Z r t 0.00095 Sb
A Z r t 0.00440 Sb
f
- 0 Z r COOK, C A S T L E M A N , J O H N S O N
T

0.05

a
I I
0
0 1 2 3
log,o T ( " K ) 4
Fig. 7.16. Ratios o f Ideal Resistivity and Temperature, Showing the Possible Effect of Increased
Numbers of Overlapping Electrons at Higher Temperature.

r u l e may be due t o t h e above phenomenon o c c u r r i n g a t lower temperatures i n

t h e a l l o y s , due t o t h e reinforcement of both t h e a l l o y i n g and temperature
effects. This second e f f e c t would be c l a s s i f i e d as a temperature e f f e c t
on impurity s c a t t e r i n g , and r e f e r e n c e t o F i g . 7.14 w i l l show t h a t i f such
d e v i a t i o n s a r e due t o impurity s c a t t e r i n g , t h e y a r e much more modest e f -
f e c t s t h a n t h e y appear t o be as shown on F i g . 7.16. From t h e standpoint

120
 of t h e thermodynamic p r o p e r t i e s of t h e a-phase a l l o y s one would expect t h e
overlap t o i n c r e a s e t h e e l e c t r o n i c s p e c i f i c h e a t and entropy, and through
e f f e c t s on t h e e l a s t i c p r o p e r t i e s , t o change t h e l a t t i c e s p e c i f i c h e a t as
well.
The e f f e c t s of t h e v a r i o u s s o l u t e s on t h e impurity s c a t t e r i n g a t 4.2'K
a r e shown by t h e r e s i s t i v i t y - c o m p o s i t i o n graphs i n F i g . 7.17. These curves
for t h e various s o l u t e s should be n e a r l y l i n e a r i n t h e d i l u t e composition
range. This w a s found t o be t r u e for t h e Z r - A g a l l o y s , and n e a r l y so f o r

UNCLASSIFIED

13(

12c

1IC

10c

-
E 9c
k
f

-i BC
>
k
E 70
v,
W
ul
60
J
a
u
E 50
0
W
W
_I
40

30

Q 20

10

n
0 0.02 0.04 0.06
SOLUTE (atomic fraction)

Fig. 7.17. R e s i s t i v i t y Composition Curves a t

4.2OK.

t h e Zr-Sb and t h e Zr-In a l l o y s , as shown on t h i s f i g u r e .

It w a s neces-
s a r y t o assume t h a t t h e curves for Zr-Cd and Zr-Sn were l i n e a r , s i n c e only
one a l l o y of each w a s a v a i l a b l e . The slopes of t h e s e graphs, apo/ax evalu-
a t e d f o r s m a l l x , a r e p l o t t e d i n F i g . 7 . l d as a f u n c t i o n of t h e s o l u t e
valence.

121
 Norbury's r u l e s t a t e s t h a t 3po/ax = a + b(n - where a and b are
I

c o n s t a n t s and n - no i s t h e d i f f e r e n c e i n t h e e l e c t r i c a l charge on t h e
s o l u t e and s o l v e n t i o n s . The v a l u e s of dpo/dx f o r t h e s o l u t e s Ag, C d , I n ,
Sn, and Sb do n o t r e v e a l t h e e f f e c t s of p o s i t i v e charges on t h e s o l u t e
i o n s i n a manner which would be expected from t h i s r u l e . Rather, as can
be seen on F i g s . 7 . l d and 7.17, l a r g e e f f e c t s a r e observed which i n c r e a s e d
i n an almost l i n e a r manner w i t h t h e number of valence e l e c t r o n s . The s i z e
of t h e e f f e c t i s of t h e same o r d e r of magnitude as t h e e f f e c t of t i t a n i u m
i n gold.26 One f a c t o r a l l of t h e s e s o l u t e s have i n common i s t h e i r com-
p l e t e 4-d s h e l l i n c o n t r a s t t o t h e u n f i l l e d d band i n zirconium. The l a r g e 0
e f f e c t s may t h e r e f o r e be a s s o c i a t e d w i t h t h e d i s c o n t i n u i t i e s i n t h e d
band of zirconium i n t h i s t y p e of a l l o y . I n support of t h i s , t i t a n i u m
and hafnium,which have u n f i l l e d d b a n d s , h a v e much smaller [l-2 pohrn- 0
cm*(at. I'-)% e f f e c t s i n zirconium. It i s of i n t e r e s t t o compare t h e
l i n e a r i n c r e a s e i n a p o / a x w i t h s o l u t e v a l e n c y from one t o four w i t h a
s i m i l a r i n c r e a s e i n t h e d e n s i t y of s t a t e s w i t h t h e s o l u t e v a l e n c y i n
these alloys. An i n v e r s e r e l a t i o n s h i p between t h e e f f e c t i v e r e l a x a t i o n
t i m e i n t h e s band and t h e d e n s i t y of s t a t e s i n t h e d band h a s been d i s -
cussed by Mott and Jones27 and b y Jones'' f o r n i c k e l , and i n view of t h e
above c o r r e l a t i o n of r e s i s t i v i t y and d e n s i t y of s t a t e s , t h e argument may
I
a l s o a p p l y t o t h e zirconium a l l o y s .

VAPOR PRESSURES I N THE Zr-Cd SYSTEM

J. 0. B e t t e r t o n , Jr. J. H. Frye, Jr. D . S. Easton

The vapor p r e s s u r e s of Z r - C d a l l o y s have been i n v e s t i g a t e d i n o r d e r

t o t e s t t h e v a l i d i t y of e a r l i e r assumptions28 about t h e s p e c i f i c h e a t s
and e n e r g i e s i n a t y p i c a l phase diagram. The zirconium-rich p o r t i o n of
t h e Zr-Cd system i s shown i n F i g . 7.18. The p r i n c i p a l f e a t u r e s of t h e
diagram are hexagonal a and cubic f3 phases w i t h a g r a d u a l l y r i s i n g (a + p)

I
26J. 0. Linde, Ann. Physik -
15, 219 ( 1 9 3 2 ) .
27N. F. Mott and H. Jones, The Theory of t h e P r o p e r t i e s of Metals and
Alloys, Clarendon P r e s s , Oxford, 1936.
28J. -
0. B e t t e r t o n , Jr., and J. H. Frye, Jr., Acta Met. -
6 , 205 (1958). a
122
0
.
 UNCLASSIFIED
ORNL-LR- DWG 50249

1100
r

1000
, R i -i ,:I
A A 4
fit Cd

A
A '1
VAPOR

I **/I I

V S I N G L E PHASE +TRACE
SECOND PHASE
I DEW-POINT METHOD

600 F I L L E D SYMBOLS

!/ ! INDICATE ANALYZED

0 5 40 15 20
CADMIUM lot.%)

Fig. 7.18. The Zirconium-Rich Portion of the

Phase Diagram Zi rconi urn-Cadrni urn.

region between them. I n p r i o r vapor p r e s s u r e t h e @ a l l o y s obeyed

Henry's l a w and were exothermic. I n a d d i t i o n t h e s e a l l o y s have a l a r g e
negative d e v i a t i o n from random-mixing entropy. The a a l l o y s were similar
i n t h e l a t t e r two a s p e c t s , b u t t h e slower d i f f u s i o n r a t e s i n t h i s phase
made t h e r e s u l t s much l e s s c e r t a i n .
The cadmium vapor p r e s s u r e s were determined by theHargreavesmethod,32
modified3' by p l a c i n g t h e observation window i n a n i c k e l conductor block
and reducing i t s diameter t o 1 mm. The cadmium p r e s s u r e s over t h e a l l o y
B, a r e known from t h e dew-point temperatures and from t h e following r e l a t i o n
between p r e s s u r e and temperature f o r l i q u i d cadmium, according t o Lumsden.33

Loglo P1 ( m Hg) = 11.775 - -- 1.1283 loglo Tw . (9)

TW

29Met. Ann. Prog. Rep. Oct. 10, 1957, ORNL-2422, p 229 ( c l a s s i f i e d ) .

30Met. Ann. Prog. Rep. Oct. 10, 1958, ORNL-2632, p 17 ( c l a s s i f i e d ) .
31Met. Ann'. Prog. Rep. Sept. 1, 1959, ORNL-2839, p 33.

32R. Hargreaves, J. I n s t . Metals -

64, 115 (1939).
33J. Lumsden, Thermodynamics o f Alloys, p 134, I n s t i t u t e of Metals
(London) 1952.

123
 The p r i n c i p a l c o r r e c t i o n t o be made i s f o r t h e l . W . O ° C / i n . temper-
a t u r e g r a d i e n t a c r o s s t h e observation window. This c a l i b r a t i o n w a s de-
termined i n t h e same apparatus, w i t h a pure cadmium b a t h i n t h e normal
p o s i t i o n of t h e a l l o y , and t h e c o r r e c t i o n has t h e form shown i n F i g . 7.19.

UNCLASSIFIED
ORNL-LR-DWG 5025(

z "0
0 1 2
1 I
3
I
4
1
5
I
6
I
7 I
WINDOW TEMPERATURE GRADIENT (deg/ln)

Fig. 7.19. Correction Curve for Window Gradient

(for 0 . 8 W m i n Rates).

The f r e e e n e r g i e s of t h e a l l o y s a r e based on t h e e q u a l i t y of t h e p a r -
t i a l f r e e e n e r g i e s of cadmium i n t h e a l l o y and i n t h e e q u i l i b r i u m gas
phase. It i s hoped b e f o r e t h e conclusion of t h i s work t o be a b l e t o c a l -
c u l a t e a more a c c u r a t e equation of s t a t e f o r t h e cadmium gas from s p e c t r a l
d a t a . 3 4 n 3 5 Meanwhile, an e v a l u a t i o n of t h e f r e e e n e r g i e s of t h e a l l o y s
w i l l be made by n e g l e c t i n g t h e d e v i a t i o n s of t h e a c t u a l cadmium gas phase
from t h e i d e a l monatomic gas. A t a temperature T t h e Gibbs f r e e energy
S
of t h e cadmium component of t h e a l l o y i s given i n terms of t h e r e f e r e n c e 8
s t a t e , pure s o l i d cadmium, as follows:

4
m
where F1 i s a r e l a t i v e q u a n t i t y 3 6 equal t o aF/an, - FY ( t h e p a r t i a l molar

34G. Herzberg, Molecular S p e c t r a and Molecular S t r u c t u r e 1. S p e c t r a

of Diatomic Molecules, p 516 (2d ed., t r a n s l a t e d by J. W. T . Spinks), V a n
Nostrand, Princeton, 1950.
35J. H i l s e n r a t h , M. Klein, and D . V. Sumida, Thermodynamic and Trans-
p o r t P r o p e r t i e s of Gases, Liquids, and S o l i d s , p 4-16-37'. Symposium held
at Purdue University, Lafayette, I n d . , Feb. 23-26, 1959, published by ASME,
New York, 1959.
3 6 C . Wagner, Thermodynamics of Alloys, p 10, 17, Addison-Wesley, Cam-
bridge, Mass., 1952.

124

a
f r e e energy of cadmium i n t h e a l l o y l e s s t h e molar f r e e energy of s o l i d
cadmium), and where p1 and pf are t h e e q u i l i b r i u m cadmium p r e s s u r e s over
t h e a l l o y and t h e r e f e r e n c e s t a t e , r e s p e c t i v e l y . The s u b s c r i p t 1 r e f e r s
t o t h e cadmium component of t h e a l l o y . Since i n d i l u t e a l l o y s p1 becomes
very s m a l l , t h e above q u a n t i t y has a s i n g u l a r i t y a t x = 0 where x i s t h e
atomic f r a c t i o n cadmium. It i s convenient t o s u b t r a c t t h e f r e e energy
c o n t r i b u t i o n of p e r f e c t l y random mixing entropy, and thereby o b t a i n a more
slowly varying f u n c t i o n . This i s t h e n known as t h e thermodynamic devia-
t i ~ or
n t~h e ~excess p a r t i a l f r e e energy of cadmium:36

E
F1 = RTs I n p1 - RT& I n p! - R T ~I n x .
The p r e s s u r e s assumed f o r t h e s o l i d cadmium a r e given by

5 915
l o g l o pf (KUII H g ) = 9.7828 - - -
TS

- 0.2214 l o g l o Ts - 0.0003212Ts . (12)

I n t h e p a s t year new experiments have been completed which permit a

t e n t a t i v e account t o be given of t h e p r o p e r t i e s of t h e a phase. Contrary
t o what w a s thought i n t h e e a r l i e r work, it has been found t h a t consid-
e r a b l e time can be saved i n reaching e q u i l i b r i u m a-phase p r o p e r t i e s by
cooling c a r e f u l l y t o t h e lowest temperature of t h e (a+ p ) r e g i o n before
entering the a region. Thus, t h e maintenance of a f a s t - d i f f u s i n g network
of @ grains d u r i n g t h e p r e s s u r e drop of t h e (a + p) r e g i o n i s m o r e impor-

t a n t t h a n avoiding p o s s i b l e segregation i n t h e a l l o y . A s a r e s u l t of t h e
above, considerable confidence can be placed on t h e thermodynamic devia-
t i o n s determined along t h e upper temperature r e g i o n of t h e a phase. The
thermodynamic d e v i a t i o n s of cadmium a r e shown f o r t h e a and f5 alloys i n
F i g . 7.20. The values f o r t h e a phase l i e below t h e e x t r a p o l a t i o n of t h e
@-phase values. This agrees w i t h t h e upward r i s e of t h e a/@phase bound-
a r i e s i n t h i s system.
A s discussed above, t h e most r e l i a b l e d a t a i s i n t h e upper temperature
region of t h e a phase. Values of t h i s type f o r t h e temperature 1150°K a r e
p l o t t e d as a f u n c t i o n of cadmium composition i n F i g . 7.21. The expression
E = 11055Rx2 - 352R r e p r e s e n t s t h e experimental p o i n t s approximately.
Fla

125
 UNCLASSIFIED
ORNL-LR-DWG 5 0 2 5

I
:ADMIUM ( a t % )
0
0
0

A
v
A
1.1
2.0
2.2
3.2
5.0
5.2
-1-
7.8
0 11.1

.--:I
- 9...
00 u
1050 1100 11 50 1200 1250 1300 1350

TEMPERATURE ( O K )

Fig. 7.20. Thermodynamic D e v i a t i o n s o f Cadmium i n the Zirconium-Rich P h a s e s of the Z r - C d

System.

A p a r a b o l a w a s s e l e c t e d t o meet t h e c o n d i t i o n t h a t FE should become con-

1CX
s t a n t f o r t h e most d i l u t e a l l o y s . Reference t o F i g . 7.20 w i l l show t h a t
t h e thermodynamic d e v i a t i o n of t h e B-phase a l l o y s , on t h e o t h e r hand, does
n o t have a s i g n i f i c a n t dependence upon composition, b u t may be r e p r e s e n t e d
by t h e e x p r e s s i o n , FE = -2705R + 2.16RT. The s c a t t e r i n t h e s e d a t a ap-
1B
p e a r s l a r g e because of t h e expanded s c a l e , b u t t h e u n c e r t a i n t i e s i n t h e
p a r t i a l f r e e e n e r g i e s , +lo0 cal/mole, are a c t u a l l y q u i t e s m a l l , when com-
pared t o o t h e r thermodynamic data. The e x t r a p o l a t e d v a l u e f o r t h e p phase

126
 -* -200
UNCLASSIFIED
OANL-LR-DWG 5 0 2 5 2

E
\
-
-8 -300

lu
C
I' -400
z
-500
5
>
W
n -600
uI
Q
2
-700
>
n
g -800
n
w
2 -900
0 2 4 6 8 40 12 44 16 48

CADMIUM ( a t . % )

Fig. 7.21. Thermodynamic D e v i a t i o n of Cadmium

i n the a P h a s e at 1150'K.

a t 1150'K h a s been shown on F i g . '7.21 f o r comparison t o t h e v a l u e s of t h e

CX phase.
The s l o p e s of t h e c u r v e s i n F i g . 7.20 r e p r e s e n t t h e e x c e s s p a r t i a l
e n t r o p i e s of cadmium i n t h e a l l o y s 3 7 and have been p l o t t e d i n F i g . 7.22
as a f u n c t i o n of composition. The v a l u e s f o r t h e f3 phase show a s m a l l
s y s t e m a t i c t r e n d ( s o l i d c u r v e ) , b u t t h i s i s based mainly on t h e one a l l o y
w i t h 7.8 a t . $ Cd. The c o n s t a n t v a l u e of (-4.3 2 0.4) cal.mole-l*deg-l
i s p r o b a b l y a more r e a l i s t i c i n t e r p r e t a t i o n of t h e d a t a , and w i l l be used.
The upper l i n e r e p r e s e n t s t h e d a t a which are now a v a i l a b l e f o r t h e CX phase.
With f o u r of t h e a l l o y s , 1.1, 2, 5, and 7.8 a t . '$ Cd, t h e e n t r o p y i n v e s t i -
g a t i o n i s incomplete, as t h e s e a l l o y s a r e e i t h e r a t t h e beginning s t a g e s
of t h e c r i t i c a l low t e m p e r a t u r e (1093'K) p o i n t , o r i n t h e c a s e of 1.1 a t . '$
Cd, a new experiment a t 1093'K i s needed because r e c y c l i n g slowly t h r o u g h
9 the ( a + f3) r e g i o n h a s shown e a r l i e r incomplete e q u i l i b r i u m . Because t h e
a l l o y s a r e made i n t h e f3 r e g i o n and t h e n c o o l e d i n t o t h e a r e g i o n , t h e most
p r o b a b l e e r r o r i s a n accumulative cadmium enrichment o f t h e s u r f a c e of t h e

E
37Measurements are made of F1 under c o n d i t i o n s i n which t h e p r e s s u r e
E
and t e m p e r a t u r e v a r y : dFl/dT E
E (dFl/dp), dp/dT + (dF:/dT)
P
. The e x p e r i -
E
mental r e s u l t s c l o s e l y approximate (dFF/dT) o r -S1, however, because t h e
P
t e r m (aFF/ap) dp/dT i s n e g l i g i b l e f o r a condensed phase w i t h t h e s m a l l
change i n p r e s s u r e i n v o l v e d .

127
 UNCLASSIEIED
ORNL-LR-DWG 50253
0

-1

-I -2
0
U
W

--
IW
-3

E -4
-
- 0

-5
lu
%-
-6

-7
0 2 4 6 8 10 12 14 16 18

C A D M I U M (at."/.)

Fig. 7.22. Excess Partial Entropies of Cadmium

in the a Phase (1090-1170%) and i n the 0 Phase
( 1 170-13259().

foil and t h e entropy value, i f i n e r r o r , w i l l t e n d t o be a l g e b r a i c a l l y

t o o high. The c o n s t a n t value -2.7 cal.mole-l*deg-l has been s e l e c t e d by
drawing a l i n e through t h e two lowest p o i n t s , and t h e purpose of t h i s p r e -
l i m i n a r y s e l e c t i o n i s t o i l l u s t r a t e t h e type of c a l c u l a t i o n s which w i l l
be p o s s i b l e with t h e s e d a t a . The higher entropy i n t h e a phase than i n
t h e B phase should be i n t h e meantime considered w i t h some c a u t i o n , as t h e
i m p l i c a t i o n s a r e far-reaching. This i s i l l u s t r a t e d schematically i n F i g .
7.23, where a s m a l l change i n slope of t h e FE d a t a produces upon e x t r a p -
la
o l a t i o n an e n t i r e l y d i f f e r e n t i n t e r p r e t a t i o n of t h e a/B phase boundaries
t h a n t h e previously3 E! assumed dependence upon t h e d i f f e r e n c e
as shown by t h e d o t t e d curves. E x t r a p o l a t i o n of t h e experimental curves
if:@ Hk,-

E
( s o l i d l i n e s ) would show a r e v e r s a l of t h e s i g n of (FE - F ) a t lower
q3 la
temperatures.
the a/@phase
A s discussed e a r l i e r t h e r e a r e o t h e r reasons t o t h i n k t h a t
boundaries may a r i s e from s o l u t e valence dependent e f f e c t s
e
on t h e entropy which s t a b i l i z e t h e a phase, while a p - s t a b i l i z i n g f a c t o r
of an unknown o r i g i n e x i s t s i n each type of a l l o y . It i s c l e a r t h a t t h e
l i m i t e d temperature range of t h e p r e s s u r e measurements on t h e a phase
makes a d d i t i o n a l information on t h i s p o i n t d e s i r a b l e . For example, t h e
e l e c t r i c a l r e s i s t i v i t i e s have shown a p o s s i b l e e f f e c t of t h e €3 subgroup

38J. 0 . B e t t e r t o n , J r . , and J. H . Frye, Jr., Acta Met. -

6 , 205 (1958).
-

128

0
 UNCLASSIFIED
ORNL-LR-DWG 50254

0 500 1000
TEMPERATURE (OK)

o Fig. 7.23. Schematic Drawing I l l u s t r a t i n g t h e

L a r g e E f f e c t s o f Small Changes i n t h e Slope o f
F y a . Dotted l i n e s represent t h e assumption that
r e l a t i v e s p e c i f i c heat effects in a l l o y i n g are
small and that the excess entropy i s o f thermal
type.

s o l u t e s on t h e overlap of t h e zirconium band s t r u c t u r e a t higher temper-

a t u r e s , and s i n c e such a phenomenon would a f f e c t t h e energy and entropy,
s p e c i f i c h e a t measurements on a-phase a l l o y s over t h e whole temperature
i n t e r v a l would be informative. The d o t t e d curves i n F i g . 7.23 a r e drawn
w i t h t h e assumption t h a t t h e excess p a r t i a l entropy of cadmium i n each
phase i s of thermal o r i g i n and disappears a t 0°K. The support f o r t h i s
i s t h e absence of an appreciable dependence of SE upon composition, as
1B
shown i n F i g . 7.22.

The phase boundaries a/(a + @ ) and @ / ( a+ f3) were previously38 ex-

pressed i n terms of t h e e n e r g i e s of 0°K and t h e s p e c i f i c h e a t s . The r e -
l a t i o n s i n t h i s form a r e most u s e f u l f o r c a l c u l a t i o n s of phase boundaries
where n e a r l y zero values of
..
ECCl’ Eog, @,
Ca,
.. .. and OC can be assumed. The
single-dot symbol r e f e r s t o d i f f e r e n t i a t i o n w i t h r e s p e c t t o s o l u t e compo-
s i t i o n ; t h e double dot means d i f f e r e n t i a t i o n twice; and E a r e en-
OB
e r g i e s of t h e a and B phases a t 0°K; C and Ca a r e s p e c i f i c heats; and AC
B
i s the r e l a t i v e specific heat. The f i r s t f o u r of t h e s e approximations
a r e equivalent t o Henry’s l a w i n both phases over a range of temperatures,
and A6 implies a l s o t h a t t h e thermal c o n t r i b u t i o n s t o e n t r o p i e s of f o r -
mation a r e equal i n both phases. Henry’s l a w w a s found t o hold e x p e r i -
mentally f o r t h e f3 phase of Cd-Zr, b u t t h e r e c e n t a-phase measurements

129
d i s c u s s e d above suggest t h a t Henry's l a w i s obeyed f o r o n l y d i l u t e a l l o y s .
Entropy of f o r m a t i o n i s n o t e q u a l i n two p h a s e s . I n view of t h i s it i s
more u s e f u l now t o r e w r i t e t h e a/B r e l a t i o n s i n terms of f r e e e n e r g i e s .
The e q u a t i o n s f o r t h e phase boundaries xa and x B are i n v a r i a n t t o changes
of t h e r e f e r e n c e s t a t e s 3 ' and can be r e w r i t t e n i n terms of excess quan-
t i t i e s as f o l l o w s :

where
1 .E E
L = -
RT
( x $'E - x Z a
P B
- FB +):F ,

- E - Fa
N = 1 (FB 'E) .

I n t h i s form, t h e e q u a t i o n s should apply t o g e n e r a l phase boundaries of

b i n a r y systems, and experimental e v a l u a t i o n s of t h e excess f r e e e n e r g i e s
can be transformed t o t h e phase boundaries i n t h i s way. T h i s w i l l be il-
lustrated for the all3 boundaries of t h e Cd-Zr system. It i s f i r s t neces-
s a r y t o change t h e thermodynamic d e v i a t i o n s i n t o i n t e g r a l e x c e s s f r e e
energies. These p r o p e r t i e s a r e i n d i c a t e d by Wagner by t h e same symbol,
b u t w i t h o u t t h e component s u b s c r i p t , and t h e t r a n s f o r m a t i o n i s done by t h e
f o l l o w i n g Gibbs-Duhem i n t e g r a l :

39That i s , t h e a d d i t i o n of a t e r m ( e x + b ) t o b o t h f r e e e n e r g i e s ,
where c and b a r e c o n s t a n t s independent of mole f r a c t i o n s o l u t e x , does
* *
n o t a f f e c t t h e phase b o u n d a r i e s , Let F = F + ( e x + b ) and Fa = Fa +
B B B
(exa + b). Then i f aFB /ax = dFa/ax,
* *
dFB /ax i s e q u a l t o aFa/dx, and i f
* *
B + b ) - Fa + (exa + b ) ] / ( x g -
(F
B
- Fa)/(xB - = aF /ax,
B B -
[F (CX

* * * *
xa) = aFB/bx - e , w i t h t h e r e s u l t t h a t (FB - Fa)/(xB - x,) = dFB/ax.

130

a
 For p u r p o s e s of i n t e g r a t i o n , t h e thermodynamic d e v i a t i o n s of t h e Zr-
Cd a l l o y s are assumed t o be of t h e p a r a b o l i c form g i v e n below:

E
= a + b x + e x 2
a aa aa '
E = aB + bBXB + c B x i
FIB ,

where a b , and c a r e a r b i t r a r y f u n c t i o n s of T which do n o t depend upon x ,

and t h e s u b s c r i p t s a, B are phase d e s i g n a t i o n s o n l y . I n t e g r a t i o n by E q .
(16) gives t h e following: "

E
Fa = aaxa + b a [ xa -+ (1 - xu) Rn (1 - x a ) l +

E*
FB
= aBxB + b [x + (1 - x ) Rn (1- x )I + 2c
B B B B

S u b s t i t u t i o n of t h e s e e x p r e s s i o n s i n t o E q s . (14) and (15) y i e l d s

L=- --
R

4oAn a s t e r i s k h a s been added t o t h e f r e e - e n e r g y symbol wk-n t h e e x c e s s

f r e e energy of t h e B phase r e f e r s t o a - z i r c o n i u m as a r e f e r e n c e s t a t e . The
number (1 - x,) (F$ ) h a s been approximated by -Aso (T - T~ ) (1- x )
- F2a c B
and added t o t h e l e f t s i d e of t h e e q u a t i o n f o r t h e i3' a l l o y . S u b s c r i p t 2
r e f e r s t o t h e zirconium component, and S o and T a r e t h e e n t r o p y change and
C C
t h e t e m p e r a t u r e of t h e a/B t r a n s f o r m a t i o n of p u r e zirconium w i t h t h e v a l u e s
0.405R and 1143'K, r e s p e c t i v e l y .

131
( .='
AS'
R
T - Tc
T )
a
+ - -B-
RT
b
RT
B [Rn (1 - x
B
)I - Q

2c
+- a
RT [xu + Rn (1- x u ) ] . (19)

A t p r e s e n t , t e n t a t i v e numerical values f o r t h e above c o e f f i c i e n t s

from t h e vapor p r e s s u r e measurements a r e as follows: aa = -1898R + 1.34RTY
c = 11055R, a = -2705R + 2.16RT, w i t h ba, b B ' and c B zero. The i n t e g r a l
a B
excess f r e e e n e r g i e s obtained when t h e s e numbers a r e s u b s t i t u t e d i n E q .
(17) a r e as follows:
X2
E
Fa = (-1898 + l.34T)Rxa + 22110R xa - 9+ (1 - x,) Rn (I - xa) Y

(20)
FE = (-2705 + 2.16T)Rx B - 0.405R(T - T c ) ( l - x,) ,
B
and numerical r e s u l t s f r o m t h e s e expressions are p l o t t e d i n F i g . 7 24.
From t h e i n t e r s e c t i o n s of t h e s e curves one may o b t a i n a p o i n t w i t h i n t h e
UNCLASSIFIED
OR N L- L R- DWG 5 0 2 5 5

I I '1100°K 1

C A D M I U M (otornlc fraction)

Fig. 7.24. The Integral Excess F r e e Energies

as Functions o f Composition and Temperature.
 HM" and $
M
t h e curves
the a/@phase
B
and S*'
transformation.
B and S r e p r e s e n t t h e h e a t and entropy of
a
Both d i f f e r e n c e s diminish with increased
Q
cadmium content i n t h e a l l o y . The i d e a l entropy of formation f o r t h e a
phase has been shown by means of t h e dashed curve f o r comparison t o t h e
smaller experimental v a l u e s .
Numerical c a l c u l a t i o n s of t h e phase boundaries a r e p o s s i b l e by sub-
s t i t u t i n g t h e experimental c o e f f i c i e n t s i n t o Eqs. (18)and ( 1 9 ) . The r e -
s u l t i s shown below:

L = 0.405
T - Tc
T T
X2
a a
T - Tc
N = 0.405 - -807 i- 0.82 i-
22110
- [xa + an (1- x,) 1 . 8
T T
Equation (13) t h e n may be solved numerically for t h e phase boundaries x a

and xB'
The r e s u l t s of t h i s c a l c u l a t i o n f o r t h e region between 0 and 15 a t . $I
Cd a r e i n d i c a t e d on F i g . 7.18 by t h e d o t t e d l i n e s . The phase boundaries
c a l c u l a t e d from t h e above r e l a t i o n s agree f a i r l y w e l l w i t h t h e phase d i a -
gram determined by quenching i s o t h e r m a l l y annealed a l l o y s . The p r i n c i p a l
d i f f e r e n c e i s t h a t a much narrower ( a + p) region i s i n d i c a t e d . This i s
due p a r t l y t o t h e f a c t t h a t t i e l i n e s i n t h e phase diagram may be r o t a t e d
i n a l l these alloys. Rotation of t h e t i e l i n e s by t h e small i m p u r i t i e s
8
occurs t o a g r e a t e r e x t e n t i n t h e a/@type of e q u i l i b r i u m t h a n normally
encountered i n o t h e r phase diagrams. No account w a s taken of p o s s i b l e
c u r v a t u r e s i n t h e thermodynamic d e v i a t i o n s near t h e phase boundaries when
t h e a n a l y t i c a l expressions were chosen. Metallographic examination of
e
i s o t h e r m a l l y annealed specimens has not y e t revealed t h e m a x i m u m i n t h e
a/@b o m d a r i e s shown by t h e c a l c u l a t i o n s from t h e p r e s s u r e measurements.

134

__ --
 8. X-RAY DIFFFWTION
H. L. Yakel, Jr.

ROUTINE ANALYSES

H. L. Yakel, Jr. R. M. Steele 0. B. Cavin

Over 500 samples of a routine nature have been submitted to the Me-
tallurgy X-Ray Diffraction Laboratory for examination during the reporting
period. The bulk of these samples originated within the Metallurgy Divi-
sion and pertinent results are described in the appropriate sections of
BD this report. Some routine problems of more than passing interest which
originated outside the Metallurgy Division will be mentioned briefly.
In cooperation with the Metallurgical Development Department at Y-12,
e, a stress analysis program is being carried out in order to evaluate rela-
tive stress levels in metal parts after a forming process, and after various
stress-relief treatments. This x-ray diffraction examination utilizes a
back-reflection technique with polycrystalline material. Results are ob-
tained from an accurate measurement of one or more of the high-angle dif-
fraction lines and comparison of the spacings of these lines from a series
of specimens. With the use of a silver powder standard lightly dusted
onto the sample of interest, it has proved possible to measure the spacings
of a chosen reflection to an accuracy approaching one or two parts in one
hundred thousand.
A low-temperature (liquid nitrogen) diffractometer attachment' was
used to study the structure of the crystalline phases formed when concen-
trated (7-M) aqueous solutions of LiNO3 and NaN03 were frozen rapidly.
This experiment was performed at the request of H. A. Mahlman of the
Chemistry Division. While the CUXa(h = 1.5418 A) diffraction pattern of
the frozen LiN03 solution showed reflections from a crystalline hydrate
of LiNO3, that of the frozen NaN03 solution showed only reflections at-
tributable to one of the forms of ice. In the latter case, it seems evi-
dent that the salt is present in an amorphous or glassy state, a not un-
expected result in view of other crystallization studies.

IL. K. Jetter - al., Rev. Sei. Instr. 28, 1087 (1957).

et -
-
 The Physics Division submitted several heretofore unreported phos-
phides, arsenides , and antimonides of the heavy lanthanide elements (9%-Lu)
for structural studies. These materials have the rock-salt structure.
Their lattice parameters, listed below, are in reasonable agreement with
C ompound ao@) (ref 2)
TbP 5.685 2 0.001
TbAs 5.800 i 0.001
TbSb 6.183 f. 0.001
HoSb 6.133 5 0.001
extrapolations of previously reported data on similar compounds of the
lighter lanthanides (La-Sm).3--5
Structural analyses of representatives of a new class of AB03 com-
pounds are in progress, with the cooperation of W. C. Koehler, Physics
Division, ORNL, and E. F. Bertaut, University of Grenoble. The unit cell
and lattice symmetry of ErMn03, the first member of this class to be d i s -
covered, was described in a previous report.6 It has recently been deter-
mined that LuMn03, YbMnO3, TmMnO3, HoMnO3, and k’MnO3 also crystallize with
the new structure, although a perovskite polymorph of YMn03 exists. Unit
cell parameters of several of these hexagonal materials are given in Table
8.1.

2Extrapolated against a Nelson-Riley function; C u K a (A = 1.54123 A)

data from Debye-Scherrer photographs.
3A. Iandelli and E. Botti, Atti reale accad. nazl. Lincei 24, 459
=
(1936).
4A. Iandelli and E. Botti, Atti reale accad. nazl. Lincei = 25, 498
(193’7). a
5A. Iandelli, Z. anorg. Chem. -
288, 81 (1956).
-
6H. L. Yakei, Met. Ann. Prog. Rep. Oct. lo, 1957, ORML-2422, p 226
(classified).
Table 8.1. Lattice Parameters of Rare-Earth Orthomanganites
e

LUMnO 3 6.043 f. 0.001 11.39 2 0.01

TmMnO3 6.062 i 0.001 11.40 -i- 0.01
ErMnO3 6.115 2 0.001 11.41 * 0.01
Hoi’hO3 6.136 F 0.001 11.42 ? 0.01

*Hexagonal lattice parameters determined by least squares fit to

high-angle CrKa (A‘= 2.2909 A) Debye-Scherrer diffraction data.

136

0
 Large s i n g l e c r y s t a l s of L W 0 3 were grown from a m i x t u r e o f Lu203
and MnO2 h e a t e d w i t h a Biz03 f l u x . The c r y s t a l s were opaque and were red-
dish-brown i n c o l o r . They had t h e form of hexagonal bipyramids t r u n c a t e d
by b a s a l p l a n e s . Goniometry showed t h e pxramid f a c e s t o be of t h e (10i1)
family. A crude t e s t f o r p y r o e l e c t r i c i t y was performed, i n which a den-
d r i t i c f o r m a t i o n of i c e c r y s t a l s w a s n o t e d on a L W O 3 c r y s t a l c o o l e d i n
l i q u i d n i t r o g e n , t h e n exposed t o room atmosphere. This p o s i t i v e r e s u l t
t o g e t h e r w i t h t h e p o s i t i v e r e s u l t s of t e s t s f o r p i e z o e l e c t r i c i t y performed
a t Grenoble, w a s t a k e n as proof of t h e absence of a c e n t e r of symmetry i n
the crystals.

S i n g l e c r y s t a l d i f f r a c t i o n d a t a were c o l l e c t e d from a c r y s t a l r o t a t e d
about i t s c a x i s , w i t h t h e u s e of C"Ka ( A = 1.5418 A ) and MoKa ( A = 0.7107
A) x-radiation. R o t a t i o n photographs and h k . 0 t h r o u g h h k - 7 Weissenberg
photographs were r e c o r d e d w i t h C u K
a r a d i a t i o n , w h i l e complete three-dimen-
s i o n a l i n t e n s i t y d a t a on l a y e r s hk.0 through hk.20 were o b t a i n e d w i t h a
An hO-R MoK
K r - f i l l e d Geiger c o u n t e r and MoKa r a d i a t i o n . a p r e c e s s i o n pho-
tograph w a s a l s o recorded.
The o n l y s y s t e m a t i c absences which c o u l d b e a t t r i b u t e d t o s p a c e group
symmetry were observed f o r khOR r e f l e c t i o n s w i t h R f 2n. P o s s i b l e space
groups a r e t h u s : P6c2, P63cm, and P 3 c l . Two a d d i t i o n a l s e t s of r e f l e c -
t i o n s were found t o be s u b j e c t t o p s e u d o e x t i n c t i o n s which must a r i s e from
t h e p a r t i c u l a r v a l u e s of atomic p a r a m e t e r s . These a b s e n t r e f l e c t i o n s a r e :
hk.0 w i t h h - k = 3n, and hk*R w i t h R f 2n and e i t h e r h and/or k and/or
i = 3n.
A s t r u c t u r e h a s been proposed, b a s e d on t h e space group P63cm, and
i s now b e i n g r e f i n e d by s t a n d a r d p r o c e d u r e s .

L. A. Harris H . L. Yakel

During t h e p e r i o d of t h i s r e p o r t , t h e e f f o r t s of t h e Ceramic X-Ray

Laboratory have been d i v i d e d e q u a l l y between r o u t i n e s e r v i c e and r e s e a r c h
applications. T h i s r e s e a r c h h a s i n c l u d e d phase e q u i l i b r i a s t u d i e s and
c r y s t a l s t r u c t u r e d e t e r m i n a t i o n s f o r s e v e r a l m a t e r i a l s of i n t e r e s t . Sev-
e r a l c o o p e r a t i v e programs have a l s o been c a r r i e d o u t d u r i n g t h e p a s t y e a r
w i t h members of t h e R e a c t o r Chemistry D i v i s i o n .

137
 Phase Studies

Phase equilibrium investigations in the system CaO-Be0 and SrO-Be0

have been pursued and are included elsewhere (see R. A. Potter and L. A.
Harris, "Ceramics Laboratory," Part 111, this report). As an outcome of
these studies, single crystals of the compound 2Sr0~3BeOwere obtained.
A cursory optical examination of the crystals showed them to be biaxial
with parallel extinction and needle-like habit.

Data from rotation and Weissenberg photographs (CuKa radiation, A =

1.5418 A) indicate orthorhombic crystal symmetry. Parameters perpendicular

to the needle axis are a0 = 8.98 A and bo = 7.12 A. Iayer-line spacings
observed on needle-axis (e-axis) rotation photographs of any Sr2Be305
crystal show no simple integral relationship between all lines. Further
study of this unusual observation is now in progress.

C a i c ination Studies

The high-temperature x-ray diffractometer was employed as an aid in

following the phase changes observed in the calcination of beryllium oxa-
late trihydrate (BeC204.3H20). Figure 8.1 summarizes the diffraction re-
sults obtained.
A product obtained at an intermediate stage of dissociation of
BeC204-3H20 (weight loss - 56s) was reacted with hydrochloric acid. Evo-
lution of C02 was observed, together with eventual formation of needle-
like crystals from the solution. The crystals are biaxial, with parallel
extinction, but produce x-ray diffraction patterns appreciably different
from that of the known compound, BeC12. They are presumably a new hydrate
of beryllium chloride.

Strueture Determinations

Single crystals of the phase LizZrF6 were obtained from the Reactor
Chemistry Division for the purpose of structure analysis. Data from Weis-
senberg and rotation photographs (CuKa radiatihn, A = 1.5418 A) were in-
dexed on the basis of a hexagonal unit cell with parameters a0 = 4.97 A

7R. L. Hamner and L. A. Harris, "The Calcination in Air of Beryl-

lium Oxalate Trihydrate to Beryllium Oxide," paper presented at the Apr.
24-28, 1960, convention of the American Ceramic Society.

138

a
 UNCLASSI FlED
ORNL-LR-DWG 43498

100
90
IT' ' "1
80

70
60

50

40

30
T
23

IO

- 0
38 36 34 32 30 28 26 24 22 20 38 36 34 32 30 28 26 24 22 20 I
8 16 14 12 IO
28 VALUES 28 VALUES
IO0

:MUu<
60 -

50

40
M

230
IO
0
O - (C)
- U J 1 1 I I 1 I I '
28 MLUES

70

loo
I I I I I I I
90 - -

80 ~ -

70 - B -
T BeC204 3 H p

M &Cp4 H20

BBeo

Fig. 8.1. X-Ray Diffraction Patterns Obtained on a High-Temperature X-Ray Diffractometer Showing
Phase Changes Observed on Heating BeC2O,.3H,O at( a ) Room Temperature, ( b ) 74OC, (c) 142T,
(d) 181°C, ( e ) 200"c, (f) 242"c, and ( g ) 336OC.

139
 a
and co = 4.62 A. The calculated density is 3.56 g/cm3, based on one for-
mula weight per unit cell. A survey of the diffracted intensities strongly
suggests that this structure is isotypic with K2GeFg (ref 8).
Papers dealing with the structure of phases in the LiF-ThF4, RbF-ThFr,,
and Na.F-BeF2-U(Th)Fg systems have been published, or have been submitted
for publication.'-11

AGING TRANSFORMATIONS OF METASTABLE ALLOYS

H. L. Yakel 0. B. Cavin

Single crystal x-ray diffraction studies of aging transformations in

p-quenched zirconium-niobium alloys have demonstrated that the net reac-
tion pr Zr + @Nb
+ CX ,
whereby the metastable retained-beta (@r ) alloy
reaches an equilibrium a (hcp, zirconium-rich) + @Nb (bcc, niobium-rich)
Zr
configuration, may involve an intermediate reaction in which another meta-
stable phase, the so-called w phase, is produced.12 It was also shown
that the lattice symmetry of the w phase is a function of the aging treat-
ment, changing from trigonal in as-quenched alloys to hexagonal in alloys
aged for short periods at 400°C. A further description of the w structure
was not possible, since the almost equal x-ray scattering powers of zir-
conium and niobium precluded any observation of the effects of atom or-
dering.
During the period of this report, a program has been initiated with
the twofold objective of investigating the possible occurrence of stable e
or metastable w-type phases in other alloy systems, and of obtaining more
precise structural data for these phases. The binary systems proposed
for study are: U-Nb, Ti-Nb, Zr-Ta, and Ti-Ta.
Q
To date, alloys of composition U-7.5 wt $ Nb, -15 wt $ Nb, U-20 wt
$I Nb, Ti-50 wt $I Nb, Zr-10 wt $ Ta, Zr-20 wt $I Ta, and Ti-70 wt $ Ta have

8J. L. Hoard and W. B. Vincent, J. Am. Chem. SOC. -

61, 2849 (1939).
-
'L. A. Harris, G. D. White, and R. E. Thoma, J. Phys. Chem. -
63, 1974
(1959).
l o L . A. Harris, Acta Cryst. -
13, 502 (1960).
-
"R.E. Thoma -
et -
al., "The Compounds NaFoBeF2 -3ThF4and NaF.BeF2 *UF4,"
submitted for publication in J. Am. Ceram. S O ~ .
12H. L. Yakel, Met. Ann. Prog. Rep. Sept. I, 1959, ORNL-2839, p 51.

140

a
been c a s t , homogenized, and h o t r o l l e d t o 80-mil s h e e t a f t e r soaking a t
850-950°C i n argon. The x - r a y d i f f r a c t i o n d a t a from p o l i s h e d and e t c h e d
coupons c u t from t h e r o l l e d s h e e t show t h a t m e t a s t a b l e body-centered cubic
A2-type s t r u c t u r e s a r e r e t a i n e d i n a l l c a s e s except t h e two Z r - T a a l l o y s .
T h i s r e s u l t i s a n t i c i p a t e d i n view of p r e v i o u s l y r e p o r t e d d a t a f o r U-Nb
( r e f 13) and Z r - T a (ref 1 4 ) a l l o y s .
E f f o r t s w i l l now be made t o induce growth of l a r g e g r a i n s of t h e body-
c e n t e r e d cubic phases through v a r i o u s h e a t t r e a t m e n t s and/or s t r a i n - a n n e a l -
ing techniques. Low-temperature (250-500°C) a g i n g t r e a t m e n t s w i l l t h e n
b e made i n o r d e r t o s t u d y t h e d i s s o c i a t i o n of t h e m e t a s t a b l e s t r u c t u r e .

ORDERING OF COPPER-GOLD ALLOYS

B. S . B o r i e C . J. Sparks H . L. Yakel R . M. S t e e l e

Observations of x-ray d i f f r a c t i o n p a t t e r n s of Cu-31.6 a t . $ Au samples

have i n d i c a t e d t h e presence of a new, s t a b l e o r d e r e d s t r u c t u r e which e x i s t s
a t t e m p e r a t u r e s j u s t below t h e expected o r d e r - d i s o r d e r t r a n s i t i o n tempera-
ture. T h i s phase has been observed i n quenched samples15 and i n samples
s t u d i e d a t e l e v a t e d temperatures .17 A proposed c r y s t a l s t r u c t u r e f o r t h e
phase has been given, based on s i n g l e c r y s t a l and powder d i f f r a c t i o n d a t a . 1 7
During t h e p e r i o d of t h i s r e p o r t , t h e i n v e s t i g a t i o n s d e s c r i b e d above
have been extended by high-temperature x - r a y d i f f r a c t i o n s t u d i e s of samples
of Cu-25 a t . $ Au and Cu-3'7.5 a t . $ Au composition, t o g e t h e r w i t h a r e -
examination of the Cu-31.6 a t . $ A u a l l o y .
P o l y c r y s t a l l i n e d i f f r a c t i o n specimens were p r e p a r e d i n a r o u t i n e man-
ner,17 and a l l experiments were c a r r i e d o u t i n a Unicam S.150 high-tem-
p e r a t u r e camera u s i n g CuK ( A = 1.5418 A ) r a d i a t i o n . The r e s u l t s o b t a i n e d
a
"P. C . L. P f e i l , J. D. Brown, and G . K . Williamson, The Uranium-
Niobium Alloy System i n t h e S o l i d S t a t e , AERE-MR-2498 (February 1 9 5 8 ) .
l 4 W . L. Larsen and D . E. W i l l i a m s , Annual Summary Research Report i n
Metallurgy f o r J u l y 1958-June 1959, IS-17, p '75 (November 1 9 5 9 ) .
15P. S. Rudman, S.B. t h e s i s , Physics Department, Massachusetts I n -
s t i t u t e of Technology.
16R. E . S c o t t , Ph.D. t h e s i s , Physics Department, Massachusetts I n -
s t i t u t e of Technology (1958).
1 7 B . S. Borie, C . J. Sparks, and H . L. Yakel, Met. Ann. Prog. Rep.
S e p t . 1, 1959, ORNL-2839, p 58.

141
 n
to date may be summarized as follows:
1. Cu-25 at. $ Au. - The behavior of this material was normal, in
that good agreement with previously reported data was found. The order-
disorder transition temperature was observed to be 386°C * 3" on the basis
of heating and cooling cycles. Linear thermal expansion coefficients in
the ordered and disordered phases were computed from measured lattice param-
eters. These results are recorded in Table 8.2. There was no indication of
an intermediate ordered structure at temperatures just below the order-dis-
order transition, in contrast to a recent brief report.18

Table 8.2. Thermal Expansion of a Cu-25 at. p Au Alloy

a = aol(T - To)/(a - ao)
~~

Interval a

340-3 80 C (18.5 k 0.5) X 10-6/"C

39c-420 " C (18.3 * 0.5) X 10-6/oC

T (order-disorder) = 386°C L 3"

a0 (ordered phase at 386°C) = 3.7734 A i 0.0002
a0 (disordered phase at 386°C) = 3.7776 A I0.0003

2. Cu-37.5 at. $ Au. - This composition lies just to the gold-rich

side (-2 at. $ ) of a eutectoid (T = 285"C), at which the reaction

a (disordered fcc) F= a' (Cu3Au type) + a" (CuAu I1 type)

occurs, according to a widely accepted equilibrium diagram for the Cu-Au
systemlg (see Fig. 8.2). Difficulty in establishment of thermodynamic
equilibrium in the high-temperature diffraction experiment was anticipated
and found. It is primarily due to the sluggishness of transformations at
the relatively low temperatures involved.
Annealing of a sample, furnace-quenched from the disordered state,
at temperatures below 285°C produces a transformation from a disordered

18A. Pianelli and R. Faivre, Bull. SOC. Chim. France (I), 8 (1959).
19F. N. Rhines, W. E. Bond, and R. A. Rummel, Trans. Am. Soc. Metals
-
47, 578
- (1955).

142
 UNCLASSIFIED
ORNL-LR-DWG 50257
425
I I I l

400

375

- 350
Y
I

325

300

275
\

250
25 30 35 40 45 50
GOLD ( a t . % 1

Fig. 8.2. A Portion of the Cu-Au Binary Equi-

librium Diagram Proposed by Rhines, Bond, and
Rummel. l 9

fcc a structure to an ordered CuAu 11-type lattice.20 The lattice param-

eters of this orthorhombic phase were measured to be:

ao = 3.871 A , bo = 12ao = 46.45 A ,

= 3.738 A , ao/co = 1.036 , 3 J -az -c = 3.826 A .
The accuracy of this measurement was not greater than 0.05$ due to a dif-
fuseness o'f the diffraction lines which could be ascribed to lattice strains
or to the presence of a second phase. The latter explanation would agree
with the accepted phase diagram if the second phase were assumed to be
a'.
It seems more likely, however, that the CuAu 11-type phase described
above is actually a metastable phase with composition near 37.5 at. $ Au.

'OC. H. Johansson and J. 0. Linde, Ann. Physik 28 1 ( 1 9 3 6 ) . = J

143
 This assumption i s supported b y two o b s e r v a t i o n s . F i r s t , t h e measured
parameters a g r e e w e l l w i t h e x t r a p o l a t i o n s of e x i s t i n g d a t a f o r CuAu II-
t y p e phases t o 37.5 a t . Au ( r e f 2 1 ) . Second, as t h e specimen i s h e a t e d
a t s u c c e s s i v e l y h i g h e r temperatures up t o 295"C, a second Cu4u 11-type
phase a p p e a r s . This phase, although p r e s e n t i n minor amounts c l e a r l y h a s
a g r e a t e r ao/co r a t i o , and t h e r e f o r e g r e a t e r g o l d c o n t e n t , t h a n t h e p a r e n t
CuAu 11-type s t r u c t u r e . One may assume t h a t t h e system i s endeavoring t o
approach t r u e e q u i l i b r i u m by means of a p r e c i p i t a t i o n of t h e e q u i l i b r i u m
CuAu 11-type phase f r o m i t s m e t a s t a b l e p r e c u r s o r . The f a i l u r e t o p o s i -
t i v e l y i d e n t i f y d i f f r a c t i o n s from t h e e q u i l i b r i u m CusAu-type a' s t r u c t u r e
a t any s t a g e of t h i s s t u d y may be t a k e n as an i n d i c a t i o n o f t h e nearness
of t h e a"/a' + Ct'I boundary t o t h e composition s t u d i e d , o r as an i n d i c a t i o n
of a s t i l l s i g n i f i c a n t d e p a r t u r e of t h e system from thermodynamic equi-
librium. The l a t t e r p o s s i b i l i t y i s g i v e n added weight by t h e d i f f e r e n c e
between t h e 295'C p s e u d o e u t e c t o i d c i t e d above and t h e t r u e 285°C e u t e c t o i d .
F u r t h e r h e a t i n g above 295°C results i n ( a ) t h e g r a d u a l disappearance
of t h e d i f f r a c t i o n p a t t e r n of t h e "equilibrium" CuAu 11-type phase, (b)
t h e g r a d u a l appearance of t h e d i f f r a c t i o n l i n e s of a d i s o r d e r e d a phase,
and ( e ) t h e broadening of t h e d i f f r a c t i o n l i n e s of t h e "metastable" CUAu
11-type phase and t h e g r a d u a l i n c r e a s e i n t h e ao/co r a t i o of t h i s phase.
This b e h a v i o r may b e understood i n terms of a continuous p r e c i p i t a -
t i o n of t h e d i s o r d e r e d a phase from t h e "metastable" CuAu 11-type phase,
w i t h t h e e n t i r e system approaching t h e e q u i l i b r i u m a + phase configura-
t i o n which t h e diagram of F i g . 8.2 s u g g e s t s should be s t a b l e from 285 t o
(2"
a
325°C a t 37.5 a t . $ Au. F i n a l l y , t h e r e i s some i n d i c a t i o n t h a t t h e upper
l i m i t of t h e a + (2'' r e g i o n should b e n e a r 337°C i n s t e a d of 325"C, although
h e r e t o o t h e s l u g g i s h n e s s of t h e t r a n s f o r m a t i o n s p r e c l u d e s any d e f i n i t e
statement .
3. Cu-31.6 a t . $ Au. - I n t e r e s t i n a re-examination of a sample w i t h
31.6 a t . $ Au composition i s based on a c o n f l i c t between p r e v i o u s l y r e -
p o r t e d data from t h i s Laboratory17 and data o b t a i c e d by S c o t t . 1 6 This
c o n f l i c t a r i s e s from S c o t t ' s o b s e r v a t i o n of a two-phase f i e l a s e p a r a t i n g

21W. B . Pearson, A Handbook of L a t t i c e Spacings and S t r u c t u r e s of

Metals and Alloys, p 413, Pergamon P r e s s , New York, 1958.
I

144
\ the low-temperature Cu3Au-type ordered structure and the new intermediate
ordered structure at Cu-31.6 at. $I Au. No such two-phase field was found
at any of the temperatures studied and reported here. Since the presence
or absence of such a field has some direct bearing on the structure of
the intermediate ordered structure, a second high-temperature diffraction
experiment with a polycrystalline Cu-31.6 at. $ Au sample has been ini-
tiated.

145
 P a r t I1

LONG-RANGE APPLIED METALLURGY

 9. PHYSICAL PROPERTIES

D. L. McElroy T. G. Kollie

The purpose of the Physical Properties program is to investigate the

temperature dependence of the thermal conductivity of refractory materials
of nuclear interest and to determine the effect of physical and chemical
variations in these materials upon this property. To accomplish this ob-
jective, measurements must be made at temperatures where physical property
data are conflicting or nonexistent. The initial research work has been
directed toward program orientation, laboratory construction, equipment
0
design and construction, and studies on specific problems related to the
investigation of the thermal conductivity of U02.
A literature survey of thermal conductivity was conducted to ascer-
0
tain the details and relative merits of existing steady-state and nonsteady-
state measurement techniques and to become acquainted with current concepts
of heat transport mechanisms in solids. From this study, five methods were
selected which collectively span and overlap the range of -100 to 2400"C,
allowing critical intercomparison of the methods. These methods allow
environmental control of the specimen, a high degree of accuracy, and the
utilization of small, simple specimens.
The Powell ball apparatus,lS2 by which the first measurements will be
attempted, has been constructed and is currently being placed in operation.
Requisite to this method are two sensing spheres, which are positioned
above the specimen, and held at a temperature different than that of the
specimen. The specimen is brought into contact with one of the spheres,
and the other noncontacting sphere corrects f o r heat transfer by radia-
tion. The time-temperature response of the two spheres is measured and
this is proportional to the specimen thermal conductivity. This apparatus
is expected to cover the temperature range -100 to 600°C with an accuracy
of 115% or better. The specimen is a 1-in.-dia disk and can be from l/8
to 3 / 4 in. thick. The apparatus will operate in a vacuum or a selected
atmosphere and will require standards for calibration.

-
'R. W. Powell, J. Sci. Instr. -
34, 485 (1957).
2A. I. Dahl, private communication Aug. 17, 1959.

149
1

A second method3 involves the quenching of a cylinder from TI to Tz

and observing the time-temperature response of the body center which yields
thermal diffusivity data. Apparatus is currently being designed to span
the range -40 to 1600°C. The thermal conductivity can be calculated from
a knowledge of the thermal diffusivity, density, and specific heat. Three
other high-temperature methods yet to be designed are: a direct heating
method, an arc-image periodic method, and an adiabatic calorimeter method.
Concurrent with the above, the group has devoted time to equipping
the laboratory and constructing several apparatuses. This auxiliary equip-
ment will be used to study the effects of physical and chemical variables
in the materials under thermal-conductivity study. Specific items con-
@
structed include: an 18OO0C, controlled-atmosphere, rhodium-wound fur-
nace; an 18OO"C, controlled-atmosphere, thermal expansion device; an ex-
perimental vacuum chamber for high-temperature U02-metal oxide thermoelec-
e
tric studies; a gas purification system; and an apparatus for growth of
U02 crystals from fluoride melts.
This crystal growth equipment is being used in an attempt to produce
stoichiometric U02 for Debye temperature determinations. The U02 crystals
are formed from a melt of LiF-NaF-UF' when water-saturated argon is passed
over it at 850°C. The U02 crystals formed after 10 days of reaction are
crushed and washed in a saturated ammonium oxalate solution at 75°C to
remove unreacted fluorides. Work is proceeding on these crystals.
The reason for the interest in the Debye temperature is that the ther-
mal conductivity of ionic bonded materials is classically a maximum at ap-
I
proximately 0.28 0 , where 8 is the Debye temperature. Debye temperatures
reported for UO;! vary from 160 to 870°K (ref 4,5). The literature indi-
cates that the thermal conductivity of U02 has not been measured below
300°K. A maximum has not yet been observed, but the values do increase
sharply with decreasing temperature, indicating a Debye temperature less
than 1070°K.

3E. S. Fitzsimmons, J. Am. Ceram. SOC. -

33, 327 (1950).
-
'W. M. Jones, J. Gordon, and E. A. Long, J. Chem. Phys. -
20, 695 (1952).
5 V . 5. Tennery, Review of Thermal Conductivity and Heat Transfer in
Uranium Dioxide, ORNL-2656, p 4 (April 9, 1959).

150
 Diffuse x-ray scattering offers a means of obtaining the Debye tem-
perature and, hence, a means of predicting the temperature for the maximum
thermal conductivity. The maximum is expected to be slightly below 300°K
for U 0 2 , and if this proves correct, the existing data spread in thermal
conductivity near 300°K would be explained. Low-temperature thermal-con-
ductivity data on other refractories, such as A 1 2 0 3 , are particularly in-
fluenced by specimen grain size, and this effect persists to temperatures
above the maximum. Thus a high Debye temperature for U02 and inherent
specimen differences among investigators could explain a part of the +20$
spread in thermal-conductivity data for U02.
Studies have been initiated on the effects of composition and cooling
rates on the microstructures of fused UO (0 < X < 0.25) using materials
2+x '
having O/U ratios of 2.05, 2.09, and 2.14. In this composition range at
room temperature, two phases are expected, U02 and U40g. The U02 phase
exhibits an increasing solubility for oxygen as the temperature is in-
creased such that above 900°C all three compositions are single phase

u02+x
. Samples of each composition were heated at 1000°C for 100 hr in
a helium atmosphere. After this treatment samples of each were furnace
cooled, air cooled, oil quenched, and water quenched. Microstructures of
the U02.0g samples are shown elsewhere (see Fig. 1 9 . 6 ) . The expected
Widmanstgtten precipitate of U409 was found in all furnace-cooled samples,'
and the amount increased with increasing oxygen content. In all of the
air-cooled specimens, the U409 precipitate w a s fine but definitely present.
Supersaturated single phase UO was produced in the oil- and water-
2+x
quenched samples for UO2.05 and U02.09. These samples cracked on quench-
4 ing. The oil- and water-quenched U02.14 samples still contained a fine
precipitate of U40g in the U02 matrix. These results lend support to the
phase equilibrium between U02 and U Q O ~proposed by G r o n ~ o l d ,and
~ further
indicate that supersaturated single phase material can be formed by
quenching compositions up to an O/U ratio of 2.09. The possibility of
using lattice parameter shifts on the supersaturated single phase products
to determine the O/U ratio is now being studied.

6 R . H. Tuxworth and W. Evans, J. Nuclear Materials - 3, 302 (1959).

7F. Gronvold, J. Inorg. & Nuclear Chem. - 1, 357 ( 1 9 5 5 ) .

151
 The thermal c o n d u c t i v i t y of r e f r a c t o r i e s a t low temperatures i s a f -
f e c t e d by g r a i n s i z e . A t h i g h temperatures t h e e f f e c t i s l e s s pronounced,
b u t h a s n o t been thoroughly s t u d i e d . Recent d a t a 8 on U02 i n d i c a t e d a
g r a i n s i z e e f f e c t up t o 600°C. I n p r e p a r a t i o n f o r a study of g r a i n s i z e
e f f e c t s on t h e thermal c o n d u c t i v i t y of U02, a l i t e r a t u r e survey w a s made.
I n many systems, g r a i n boundaries a c t as s i n k s f o r vacancies by absorbing
pores and permit g r a i n growth t o occur. The g r a i n growth behavior of UOz,
however, appears t o be unusual i n t h a t pores c o n c e n t r a t e i n U02 g r a i n
boundaries and i n h i b i t growth. Thus uniform g r a i n growth i n UOz should
occur only when it i s r e l a t i v e l y pore f r e e . Therefore, i n i t i a l g r a i n
growth d e t e r m i n a t i o n s s h a l l b e conducted i n t h e range of 1400 t o 2400°C
u s i n g h i g h - d e n s i t y compacts. Grain s i z e s w i l l b e determined by t h e i n t e r -
c e p t method.
C r i t i c a l t o any p h y s i c a l measurement i s t h e e s t i m a t i o n and determina-
t i o n o f measurement e r r o r s . I n p r e p a r a t i o n f o r f u t u r e c o n s i d e r a t i o n s of
t h i s important phase of measurement work, an e r r o r a n a l y s i s was made of
t h e e x i s t i n g r a d i a l h e a t flow t h e r m a l - c o n d u c t i v i t y equipment of t h e Ce-
ramics Laboratory. This a n a l y s l s d e f i n e d t h e p r e s e n t a p p a r a t u s e r r o r and
suggested a number of a p p a r a t u s changes t o reduce t h e measurement e r r o r .

8H. W . Newkirk, HW-59235, p 5.15 ( J a n u a r y 1959).

 10. SINTERING STUDIES

C. S. Morgan

An investigation of the mechanism of material transport during sin-

tering of oxides having the CaF2 structure has been initiated. The in-
fluence of the surface properties of the oxides on sintering character-
istics is being evaluated first. Particle size and size distribution,
particle shape, particle substructure, that is, porosity, crystallites,
and subgrains, and surface area will be considered. Subsequently the in-
fluence of additives on the oxide surface and homogeneously distributed,
e hot-pressing characteristics, and sintering rate will be studied.
Preliminary results of Tho2 sintering are summarized in Table 10.1.

Bp Table 10.1. Tho2 Sintering as a Function of Digestion Time

Density (g/cc )
Digestion
- Mean Surface
Time Particle Area
Green 1200°C 1800°C
(hr) Size 01) (m2/g) 15,300 psi 2 hr 2 hr

0 0.85 28.2 4.35 6.01 9.76

48 1.4 20.0 4.96 6.31 9.13
100 3.5 20.8 5.19 6.96 8.76
~~

Thoria batches prepared by similar oxalate precipitation and calcining

procedures [concentrated solutions of Th (NO3)4 and HzC2O4 cooled to 10°C
and poured together, filtered, and fired stepwise to 650°C] were varied
by different digestion times in the supernatant liquid. Complete data

8 have not been gathered on these samples; however, results suggest that,
while the larger, less porous particles press to a substantially higher
density, they are less sinterable. An explanation of this phenomenon may
be the greater resistance to plastic flow of the less porous digested oxide
particles. Also, voids after pressing are presumably larger with the di-
gested oxide.
Table 10.2 demonstrates that the influence of particle size on sin-
tering characteristics of Tho2 is interlocked with particle substructure
determined by the method of preparation.

153
 n
Table 10.2. Tho2 S i n t e r i n g as a Function of P r e p a r a t i o n

Powder Density (g/cc )

Mean
Calcination Particle
Preparation Temperature Green 1200°C 1800°C
("c) Size (') 15,300 p s i 2 hr 2 hr

Hydrothermal 300 0 .? 4.29 6.12 9.69

decomposition
of Th(C204)2
Th (C204)2 p r e - 650 1.3 4.15 6.08 9 .?O
cipitation i n
ultrasonic
bath
Special pre- 1600 2.7 5.45 5 SO 6.73
cipitation t o
give p l a t e l e t s
Th(C20412 p r e - 800 3.6 4.70 6.47' 8.86
cipitation
Th(C204,)2 p r e - 1600 3 .? 5.90 7.17
cipitation
Th(OH)4 p r e - 650 > 50.0 6.39 6.95 6.35
cipitation

154
 11. SOLID FC3ACTION STUDIES

T. S. Lundy

DIFFUSION STUDIES

T . S. Lundy
J . I . Federer J . F. Murdock

A l a b o r a t o r y t o be used i n connection with t h e i n v e s t i g a t i o n of v a r i -

ous s o l i d s t a t e d i f f u s i o n phenomena has been designed and s e t up. A metal
evaporator, a pressure-temperature welder, a 9 - i n . p r e c i s i o n l a t h e , a semi-
a micro balance, a measuring microscope, a single-channel gamma spectrometer,
and various h e a t - t r e a t i n g furnaces and c o n t r o l l e r s were procured. Appro-
p r i a t e s h i e l d i n g and o t h e r precautions f o r handling r a d i o a c t i v e i s o t o p e s
Bp have a l s o been provided.
S e l f - d i f f u s i o n measurements i n pure s i l v e r have been made by o t h e r i n -
vestigat0rs.l The r e s u l t s of t h e i r experiments a r e i n close agreement. As
a check of experimental techniques a determination of t h e s e l f - d i f f u s i o n
c o e f f i c i e n t of pure p o l y c r y s t a l l i n e s i l v e r a t temperatures of 750, 850, and
925°C i s being made. The value of t h e d i f f u s i o n c o e f f i c i e n t a t 925°C a g r e e s
w i t h i n 5% of t h e value c a l c u l a t e d from t h e equation'

D = 0.724 exp (-45,50O/RT) . (1)

S o l i d F i s s i o n Product Diffusion

The problem of r e l e a s e of fission product gases from f u e l t o r e a c t o r

coolant i s being e x t e n s i v e l y s t u d i e d . A program t o study t h e d i f f u s i o n
of s o l i d f i s s i o n products, such as Ea, La, Nd, Ru, Sr, Y , and Zr, i n f u e l
and cladding m a t e r i a l s has been i n i t i a t e d . These p a r t i c u l a r elements a r e
of i n t e r e s t because of t h e i r r e l a t i v e l y high f i s s i o n y i e l d s , long h a l f -
l i v e s , high decay e n e r g i e s , or combinations of the,se c h a r a c t e r i s t i c s . The
immediate o b j e c t i v e s a r e t o determine t h e d i f f u s i o n c o e f f i c i e n t s of S r and
Z r i n fused UO2 and i n Z r by use of r a d i o a c t i v e t r a c e r s . Variables of ex-
perimental i n t e r e s t include f a b r i c a t i o n techniques, g r a i n s i z e e f f e c t s ,
stoichiometry, and mechanisms of mass t r a n s p o r t . Preliminary experiments

'L. M. S l i f k i n , D. Lazarus, and T. Tomizuka, J . Appl. Phys. -

23, 1032
(1952) .
-

155
 A
have been d i r e c t e d toward development o f sample p r e p a r a t i o n and h a n d l i n g
techniques.

S e l f - D i f f u s i o n o f Aluminum

Several investigator^^-^ have s u g g e s t e d o r i n d i r e c t l y measured t h e

s e l f - d i f f u s i o n of aluminum. T h e i r v a l u e s f o r Do and Q i n t h e A r r h e n i u s
equation
D = D o e-Q/RT

vary from 0.001 t o 0.72 cm2/sec and from 21,000 t o 42,600 cal/mole, r e -
spectively. The purpose of t h e p r e s e n t s t u d y i s t o determine t h e s e l f -
d i f f u s i o n of aluminum by t h e d i r e c t method o f o b s e r v i n g i s o t o p e movement
i n t h e m e t a l as a f u n c t i o n o f t i m e and t e m p e r a t u r e . T h i s w i l l be accom-
26
p l i s h e d by use of t h e i s o t o p e A 1 which can be produced i n s u f f i c i e n t
q u a n t i t i e s i n t h e 8 6 - i n . ORNL c y c l o t r o n by a ( p , p n ) r e a c t i o n w i t h a h i g h -
p u r i t y aluminum t a r g e t .
The s p e c i f i c a c t i v i t y of t h e A126 formed on t h e aluminum t a r g e t w i l l
be q u i t e low. T h e r e f o r e , t h e u s u a l t y p e of d i f f u s i o n specimen, which con-
s i s t s of a v e r y t h i n l a y e r o f i s o t o p e on a f l a t f a c e o f an i n a c t i v e s e c t i o n ,
cannot be u s e d . I n s t e a d , a d i f f u s i o n couple having a n a c t i v e aluminum
l a y e r o f t h i c k n e s s , 2h, sandwiched between l o n g c y l i n d e r s of t h e i n a c t i v e
m a t e r i a l w i l l be used. The a p p l i c a b l e d i f f u s i o n e q u a t i o n f o r t h i s system
is

where

A ( x ) i s t h e a c t i v i t y a t a d i s t a n c e x from t h e c e n t e r of t h e a c t i v e
portion,
A0 i s t h e o r i g i n a l a c t i v i t y o f t h e a c t i v e p o r t i o n ,
D i s t h e d i f f u s i o n c o e f f i c i e n t , and
t i s t h e e f f e c t i v e time o f a n n e a l i n g a t temperature T .

2T. F e d e r i g h i , P h i l . Mag. -
4 , 502-10 (1959).
-
3J. W. H. C l a r e , M e t a l l u r g i a 57,
- 2 7 3 7 8 (1958).
‘J. Spokas, U n i v e r s i t y of I l l i n o i s t h e s i s , 1958.
5W. DeSorbo and D . T u r n b i l l , Phys. Rev. 115, - 560-63 ( 1 9 5 9 ) .

c - .. .~
.
The experimental d a t a l o r any one specimen w i l l give A(x) as a f'unction
of x f o r given h, t , and T values. S u i t a b l e hand o r computer techniques
w i l l be used f o r determining t h e b e s t D f o r a f i t of t h e experimental d a t a
with t h e t h e o r e t i c a l equation. P l o t s of I n D vs 1/T w i l l then be used t o
determine Q and Do i n t h e Arrhenius equation.

FUEL IRRADIATION PROGRAMS

T. S. Lundy J. I . Federer
The ORR f i e 1 i r r a d i a t i o n program,6 which had as i t s o b j e c t i v e t o i n -
v e s t i g a t e t h e e f f e c t s of exposure temperature and f i s s i o n burnup on tho-
rium-base m a t e r i a l s , w a s terminated a f t e r completion of an experiment t o
determine t h e gamma h e a t i n g . P a r t i c i p a t i o n i n t h e ORNL F a s t Breeder A s -
s i s t a n c e Program, however, was continued. The o b j e c t i v e of Phase I i r -
r a d i a t i o n s i n t h e l a t t e r program i s t o study t h e e f f e c t s o f v a r i a b l e burnup
of U235 a t about 1200'F on specimens of 25 vol % U02 d i s p e r s e d i n type 347
s t a i n l e s s s t e e l ( s e e J . H . Cherubini, "Fuel Element Development, i n Part
I11 of t h i s r e p o r t ) .
E s s e n t i a l f e a t u r e s of t h e gamma h e a t i n g capsule a r e shown i n Fig. 11.1.
Chromel-Alumel thermocouples were a c c u r a t e l y placed a t r a d i a l p o s i t i o n s on
the s t a i n l e s s s t e e l discs. The h e a t i n g of t h e s e d i s c s w a s c a l c u l a t e d from
t h e i r s t e a d y - s t a t e temperature d i s t r i b u t i o n by use of t h e equation

L-

where

Q i s t h e h e a t production r a t e ,
k i s a mean thermal c o n d u c t i v i t y of t h e d i s c m a t e r i a l over t h e tem-
m
p e r a t u r e range involved,
r i s t h e r a d i u s t o t h e placed thermocouple, and
To - Tr i s t h e temperature d i f f e r e n c e between r = 0 and r = r .
Figure 1 1 . 2 shows t h e g m a h e a t i n g a t a r e a c t o r power of 20 Mw as
a f u n c t i o n of v e r t i c a l d i s t a n c e from t h e c e n t e r l i n e of l a t t i c e p o s i t i o n

6T. S. Lundy - a l . , Met. A n n . Prog. Rep. Sept. 1, 1959, ORNL-2839,

et -
p 274.

157
 UNCLASSIFIED
ORNL-LR-DWG 50216

1 5 27/32
0.060 in. OD x 0 020 in.
WALL x 2 in. LONG TUBE, l f
2 000 in. OD X 1.875 in. ID TUBE

FLEXIBLE METAL HOSE NICKEL ROD, in.

SPHERICAL RADIUS
f'/8 in. OD X 0.065 in. WALL, 304 SS TUBE

SAUEREISEN CEMENT / GLASS INSULATED THERMOCOUPLE WIRE, 30-go

CHROMEL-ALUMEL WITH CERAMIC SPAGHETTI
ENDS. LENGHS TO SUIT. TYPICAL PLACES

A L L DIMENSIONS ARE
in DIA. x '/32 in 0 0 IN INCHES
THICK PLATE-

VIEW A-A

SECTION 6-B SECTION C-C

Fig. 11.1. Gamma-Heating Capsule.

e
 DISTANCE ABOVE REACTOR CENTERLINE ( i n )

Fig. 11.2. Gamma Heating in Position F-1 o f

the Oak Ridge Research Reactor.
QD
F-1 of t h e O M . These d a t a were obtained on September 14, 1959. Subse-
quent runs were made, b u t a r e a c t i o n between t h e thermocouples and Sauer-
Q
e i s e n cement i n t h e l e a d tube caused e r r a t i c r e s u l t s l e a d i n g t o t e r m i n a t i o n
of t h e experiment.

The capsule design f o r t h e Phase I i r r a d i a t i o n s was described e l s e -

where. B r i e f l y , t h e capsule c o n s i s t s of two concentric p r e s s u r e v e s s e l s
separated by a 0.005-in.-thick annulus containing helium. The i n n e r v3s-
s e l c o n t a i n s two f u e l e d specimens immersed i n sodium. The temperature
of each specimen w i l l be measured by a thermocouple on i t s s u r f a c e , and
temperature c o n t r o l w i l l be maintained by two e l e c t r i c a l h e a t e r s immersed
i n t h e sodium and surrounding t h e specimens. The capsule i s constructed
o f s t a i n l e s s s t e e l components j o i n e d t o g e t h e r by welding o r brazing. The
r e s u l t s of c a l c u l a t i o n s on which t h e capsule w a s designed a r e summarized
i n Table 11.1.

Four i d e n t i c a l capsules were constructed and a r e now a t t h e MTR a w a i t -

ing i r r a d i a t i o n . The design and f a b r i c a t i o n of instrumented i r r a d i a t i o n
capsules completes t h e group p a r t i c i p a t i o n i n t h i s program.

7J. I . Federer, T. S. Lundy, and M. C. Ziemke, Fast Breeder Reactor

Assistance Program - Phase I I r r a d i a t i o n of UO2-Stainless S t e e l Fuel Speci-
mens (ORNL-MTR-46), ORNL CF-60-1-14, p 2 ( J a n . 7, 1960).

159
 Table 11.1. Capsule Design Data

F i s s i o n a b l e m a t e r i a l ( U2 3 5 )
Q
1.350 g / i n . of core l e n g t h
Thermal neutron p e r t u r b a t i o n f a c t o r 0.37
Unperturbed n e u t r o n f l u x 7.5 x 1013 n e u t r o n s . emd2 see-'
e

Specimen h e a t i n g value 1 . 4 1 kw/in. o f core l e n g t h

Capsule s u r f a c e h e a t f l u x 1.96 x lo5 Btu.hr-1.ft-2
Capsule s u r f a c e temperature -136°F
Specimen c e n t e r l i n e temperature 1260°F
-
N

Specimen s u r f a c e temperature 1017°F

Hot-spot f a c t o r 2.6
Hot -channel f a c t o r 1.9

URANIUM DIOXIDE-ALUMINUM IiEACTION

J . F. Murdock

The r e s u l t s of experiments on t h e uranium dioxide-aluminum reaction8-''

are being e v a l u a t e d as a guide t o f u t u r e s t u d i e s on t h e d e t e r m i n a t i o n of t h e
cause and n a t u r e of t h e r e a c t i o n . These experiments i n c l u d e d t h e e v a l u a t i o n
of i n d i v i d u a l m a t e r i a l s - aluminum powders and argon and hydrogen f i r e d
U02 (A-UO2, U02 reduced from U03-H.7-0 i n h i g h - p u r i t y argon; H-UO2, U02 re-
duced from U03.Hz0 i n hydrogen), and of Al-50 w t $ UO;! compacts.
To e v a l u a t e i n d i v i d u a l powders, samples of each powder were vacuum
a
annealed and a l l g a s e s released were analyzed by mass s p e c t r o g r a p h . F i g u r e s
11.3 and 1 1 . 4 show t h e compositlons of g a s e s evolved d u r i n g 600°C h e a t
t r e a t m e n t s of aluminum powder and p r e s s e d aluminum compacts, r e s p e c t i v e l y .
Figure 1 1 . 5 i s a s i m i l a r p l o t f o r A-UOz and H-UO2 powders a l s o h e a t t r e a t e d
a t 600°C. The primary c o n s t i t u e n t s of t h e g a s e s r e l e a s e d a t 600°C from t h e
aluminum and t h e U02 are H2 and C02, r e s p e c t i v e l y . A t temperatures above

8R. C . Waugh, The Reaction and Growth o f Uranium Dioxide-Aluminum Fuel

P l a t e s and Compacts, O m - 2 7 0 1 (Mar. 9, 1 9 5 9 ) .
9R. C . Waugh, Met. Ann. Prog. Rep. Oct. lo, 1958, O m - 2 6 3 2 , p 1 5 5 5 6
(classified) .
'OR. C . Waugh, unpublished work.

160
 UNCLASSIFIED
OANL-LR-OWG 33484

T O T A L HEAT T R E A T M E N T (hr)
0 0.67 4.83 2.83 3.83 4.83 6.08 22.08
400

90

80
i
70

60

-.\"
z
0
!Z 50
V)
0
a
I
0
V

40

30

20
I

10

4 00 200 300 4 00 500 600 600 6 00

TEMPERATURE ('C)

I 1 I I I I I
0 0.25 47.25
H E A T TREEITMENT
AT 60OoC ( h r )

Fig. 11.3. Mass-Spectrometer A n a l y s i s of Vacuum Annealed Aluminum Powder During Heat

Treatment; Run No. 6.

161
 Fig. 11.4. Gas Formation During Vacuum Heat
Treatment of 0.40-g Aluminum Compact a t 600OC.
O R NULN- C
L LRA- D
SSWI F
GI3E4D9 5 9

TEMPERATURE ('C)

0.!6

0.09

0.08

-a 0.07
$I

20.06
I

w
32 0.05
>

0.04

0.02

0.02

0.01

C
( 10 0.25 0.32 0.50
HE r TREATMENT TO 600°C l h r )
1 1 1 1 1 1 1
0 5 10 15 20 25 30 35
HEAT TREATMENT AT 600°C l h r l

Fig. 11.5. Gas Formation During Vacuum Heat

Treatment of 0.40 g A-UO, and 0.40 g H-UO,
Powder a t 600°C.
162
 800°C, s u b s t a n t i a l amounts of H2 were r e l e a s e d from H-UO2 b u t n o t from A-
U02 as shown i n F i g s . 1 1 . 6 and 11.7.

Compacts of Al-50 w t % UO2 c o n t a i n i n g 0.4 g UO2 were c o l d p r e s s e d a t

33 t s i . S t u d i e s o f t h e amount and composition o f g a s e s r e l e a s e d d u r i n g

UNCLASSIFIED
ORNL-LR-OWG 33486

TOTAL HEAT TREATMENT (hr)

0 0.75 1.75 2.75 3.75 5 6 23.5 25 27.25 28.5
1oc

90

00

70

60
-8
I

z
9
50
0
a
H
0
C)

40

30

Q
20

10

0
100 200 300 400 500 600 700 800 900 1 000 1000
TEMPERATURE ("C)

Fig. 11.6. Mass-Spectrometer Analysis o f A-UO, During Heat Treatment; Run No. 8.

163
 UNCLASSIFIED
ORNL- L R - D W G 3 3 4 8 5

TOTAL HEAT TREATMENT ( h r )

0 0.75 1.25 2.25 3.25 4.25 5.25 6.25 23.75 27.25 29
400
I
-400 + 325 MESH UO2 REDUCED
FROM U 0 3 . H Z O IN HYDROGEN
90

80

70

N2+CO

i
60

50

4
40 N2 + CO

30

20

10

02
&
0
400 200 300 400 500 600 700 800 0 4000 4000
TEMPER AT U RE ("C )

F i g . 11.7. Mass-Spectrometer Analysis of H-UO, During H e a t Treatment; Run No. 7.

164
 r e a c t i o n a t 600°C were made by use of a c a l i b r a t e d break-seal c o l l e c t i o n
apparatus and a mass spectrograph. Figures 11.8 and 1 1 . 9 summarize t h e
d a t a f o r compacts containing both A-UO2 and H-UO2. The primary gas con-
s t i t u e n t w a s hydrogen f o r both cases.
It has been noted'' i n t h e break-seal experiments t h a t the UO2-A1 r e -
a c t i o n appeared t o depend upon t h e volume i n which t h e compacts were h e a t
treated. This would i n d i c a t e some dependence of t h e degree of r e a c t i o n
upon t h e p r e s s u r e of gases generated i n t h e capsules. A s e r i e s of break-
s e a l specimens i s now being h e a t t r e a t e d t o determine the p r e s s u r e a t
which t h e r e a c t i o n i s a c c e l e r a t e d .

UNCLASSIFIED
ORNL-LR-DWG 34962
0 50

0 45

s
0 5 (0 (5 20 25 30 35
HEAT TREATMENT AT 600T (hrl

Fig. 11.8. Gas Formation During Vacuum H e a t

Treatment of 0.40 g A-UO, +
0.40 g Aluminum
Compact a t 600'C.

165
 e
n

UNCLdSSIFlEO
ORNL-LR-DWG3496
0 55

050

0 45

0 40

0 35

-a
g- 0 3 0
-
w
I
3 025
>

0 20

OI5

0 IC

0 0:

CH

(
IO 15
ILIl 25

H E A T TREATMENT AT 600°C ( h i )
30 35

F i g . 11.9. G a s Formation During Vacuum H e a t

Treatment of 0.40 g H-UO, + 0.40 g Aluminum
Compact a t 600OC.

166
 12. ZIRCONIUM ALLOYS

M. L. P i c k l e s i m e r

ZIRCONIUM ALLOY DEVELOPMENT

M. L. P i c k l e s i m e r
P. L. Rittenhouse R . L. Stephenson

Zirconium-niobium-X a l l o y s have shown c o n s i d e r a b l e promise i n having

an i n - p i l e c o r r o s i o n r e s i s t a n c e s u p e r i o r t o t h a t of Z i r c a l o y - 2 i n aqueous
uranyl s u l f a t e solutions. An a l l o y development s t u d y has been under way
f o r t h e p a s t s e v e r a l y e a r s w i t h t h e major o b j e c t i v e of developing such a
zirconium-base a l l o y as an e n g i n e e r i n g m a t e r i a l f o r t h e c o n s t r u c t i o n o f
t h e c o r e t a n k of t h e r e a c t o r v e s s e l of t h e Aqueous Homogeneous R e a c t o r .
The s t u d y has r e q u i r e d t h e d e t e r m i n a t i o n of t h e p h y s i c a l m e t a l l u r g y of
t h e a l l o y systems. The p r i o r work has been r e p o r t e d i n HRP Q u a r t e r l y
P r o g r e s s Reports as w e l l as p r e v i o u s Metallurgy D i v i s i o n P r o g r e s s Reports.
Zirconium-base a l l o y s a r e of i n t e r e s t f o r o t h e r r e a c t o r systems as
p o t e n t i a l s t r u c t u r a l m a t e r i a l s , s i n c e t h e i r use i n r e a c t o r s u s i n g low-
enrichment f u e l s can r e s u l t i n c o n s i d e r a b l e economy o f n e u t r o n s .' Thus,
t h e a l l o y development study o r i g i n a l l y confined t o a l l o y s of i n t e r e s t t o
t h e Homogeneous Reactor has been broadened t o i n c l u d e zirconium-base a l l o y s
o f p o t e n t i a l i n t e r e s t t o o t h e r r e a c t o r systems.

Zirconium-Niobium Alloys

P r i o r s t u d i e s of t h e @-quench and r e h e a t t r a n s f o r m a t i o n s of t h e Z r -
Nb and Zr-Nb-X a l l o y s have shown t h a t t h e r e t a i n e d @ phase t r a n s f o r m s t o
a f3 phase e n r i c h e d i n niobium and a m e t a s t a b l e t r a n s i t i o n phase, poor i n
niobium, c a l l e d w phase. The w phase has been found t o be hexagonal i n
c r y s t a l s t r u c t u r e and n o t d e t e c t a b l e by o p t i c a l o r e l e c t r o n microscopy.
The p r i n c i p a l means of s t u d y of t h e t r a n s f o r m a t i o n have been by x-ray d i f -
f r a c t i o n t e c h n i q u e s u s i n g s i n g l e c r y s t a l s , and by hardness measurements
on p o l y c r y s t a l l i n e specimens. The completion of t h e s t u d y r e q u i r e d t h e

'M. Benedict, "An Economic A p p r a i s a l of S t a i n l e s s S t e e l s and Z i r c o -

nium i n Nuclear Power Reactors," Metal Progr. -- 75(2), 76-81 (February 1959).
-

167

A
I

use of a l l o y s made from a new l o t of i o d i d e zirconium. Rechecks of t h e

p r e v i o u s d a t a , u s i n g t h e new a l l o y s , d i d n o t confirm t h e p r i o r r a t e s of
t r a n s f o r m a t i o n found, p r i m a r i l y due t o an i n c r e a s e d i n c u b a t i o n time f o r
t h e s t a r t of t h e reaction. A c a r e f u l check of t h e e x p e r i m e n t a l procedures
d i s c l o s e d t h a t a d i f f e r e n c e i n t h e e x a c t homogenization and p-quenching
p r o c e d u r e s had o c c u r r e d . For t h e e a r l i e r s t u d i e s , t h e a l l o y i n g o t s and
r o l l e d s t r i p s had been e n c l o s e d i n a r g o n - f i l l e d q u a r t z c a p s u l e s , homoge-
n i z e d , and t h e m a t e r i a l s quenched by b r e a k i n g t h e c a p s u l e s under w a t e r .
The l a t e r m a t e r i a l s were n o t c a p s u l a t e d b u t were homogenized i n an argon-
atmosphere f u r n a c e and quenched d i r e c t l y i n t o w a t e r by r a p i d l y removing
t h e specimen b o a t from t h e f u r n a c e and dropping t h e specimens d i r e c t l y
i n t o t h e w a t e r quench. This o b s e r v a t i o n l e d t o a s t u d y of t h e e f f e c t s of
quenching t e m p e r a t u r e and quenching r a t e on t h e i n c u b a t i o n t i m e f o r w-
phase f o r m a t i o n on subsequent a g i n g .
The a g i n g t e m p e r a t u r e s e l e c t e d f o r t h e s t u d y was 4OO0C, based on t h e
r e s u l t s of t h e e a r l i e r s t u d y which showed t h a t t h e s h o r t e s t i n c u b a t i o n
time f o r w-phase f o r m a t i o n o c c u r r e d a t t h i s t e m p e r a t u r e . Specimens from
f o u r i n g o t s of Zr-15 Nb, made from d i f f e r e n t l o t s of i o d i d e zirconium,
were quenched from 850 o r 950°C a f t e r homogenization t i m e s of 30, 60, and
120 min i n t o w a t e r - c o o l e d mercury w i t h d e l a y t i m e s of l e s s t h a n I, 5, 15,
and 30 s e c from t h e time of removal from t h e f u r n a c e t o t h e i n s t a n t of
e n t r a n c e i n t o t h e quenching b a t h . The specimens t h u s c o o l e d t o d i f f e r e n t
and unknown t e m p e r a t u r e s i n a p u r i f i e d argon atmosphere b e f o r e e n t e r i n g
t h e quench. S i n c e t h e s t u d y was i n t e n d e d t o be only a rough determina-
t i o n of some of t h e v a r i a b l e s t h a t could be i m p o r t a n t , it w a s i m p o r t a n t
o n l y t h a t t h e t e m p e r a t u r e s j u s t b e f o r e quenching be a p p r e c i a b l y d i f f e r e n t
and t h a t a l l specimens f o r a g i v e n quenching t e m p e r a t u r e and d e l a y r e c e i v e
e x a c t l y t h e same t r e a t m e n t by h e a t - t r e a t i n g them t o g e t h e r . Considerably
more work on t h e s t u d y i s i n t e n d e d , w i t h t h e v a l u e s of t h e v a r i a b l e s b e t t e r
c o n t r o l l e d and b e t t e r known. D e s p i t e t h e roughness of c o n t r o l of some of
t h e v a r i a b l e s , it i s b e l i e v e d t h a t t h e d a t a c o l l e c t e d t o d a t e p r o v i d e an
e x p l a n a t i o n of t h e b e h a v i o r .
The p r i n c i p a l r e s u l t s of t h e s t u d y a r e shown i n F i g . 1 2 . 1 and Table
1 2 . 1 f o r one i n g o t of Zr-15 Nb. The r e s u l t s f o r t h e o t h e r i n g o t s f o l l o w
t h e same p a t t e r n a l t h o u g h t h e e x a c t r e s u l t s vary t o some e x t e n t .

168

e
a
UNCLASSIFIED

c) 420
ORNL-LR-OWG 502t8

380

o < I-sec QUENCH DELAY __

- 3 40
0
5-sec QUENCH DELAY
1 A 15-sec QUENCH DELAY

2 60

220

4 80
1 2 5 10 20 50 (00
AGING TIME AT 4 0 0 T (min)

Fig. 12.1. T h e Effect of Time of Quench Delay

on Hardening at 400T for P-Heat-Treated Zr-15
Nb Alloy.

Table 12.1. E f f e c t of p Temperature and Quench Delay on

Hardness of Zr-15 N'c Alloy A f t e r Aging a t 400°C

B Quench
DPH (10 kg)
Treatment Time Aging T i m e a t 400°C (min)
Delay
Temperature (min)
( see)
( "c) 0 5 15 60

850 30 <1 198 225

15 195 214

850 60 <1 201 256

15 207 218

850 120 <I 217 229 288 410

5 209 246 240 393
15 212 234 256 362
30 208 232 232 284

950 60 <1 221 321

15 217 25 8

169
 Higher homogenization temperatures, longer homogenization times (maxi-
mum studied, 2 hr), and higher temperatures when entering the quenching
bath consistently resulted in shorter incubation times and in higher hard-
nesses at the maximum aging time of 60 min.
The results of an incomplete study on the effects of room-temperature
aging after f3 quenching show that longer times cause increased incubation
times for the formation of w phase at 400°C. Data reported previously have
shown that small amounts of cold work decrease the incubation time;2 that
the concentration of w phase is homogeneous throughout a specimen, being
essentially the same in a grain boundary and in the center of a neighboring
grain;3 that w-phase particles very rapidly reach their maximum size;3 and
that oxygen is known to decrease the incubation time.4
The only explanation which can be postulated at the present time,
which is consistent with all of the observations, is that the vacancy con-
centration in the specimen strongly influences the nucleation and concen-
tration of w phase, an increased number of vacancies increasing the rate
of nucleation of w phase and thereby the volume of w phase present after
any given time interval. Vacancy concentration should be affected by al-
loying element, homogenization temperature, homogenization time, quenching
temperature, quenching rate, cold work, and aging at room temperature after
f3 quenching, in a manner consistent with the data determined to date for
the change in the incubation period for w-phase formation.

Zireonium-Molybdenum Alloys
Molybdenum additions to a Z r - 1 5 m-base alloy have been found to
strongly affect and delay the formation of w phase on aging of retained
p (ref 5), to improve slightly the corrosion resistance of the binary al-
loy to fissioning uranyl sulfate,6 and to increase the oxidation resist-
ance of the binary alloy to air.7 Molybdenum additions have also been
2M. L. Picklesimer -et -
al., Met. Div. Ann. Prog. Rep. Sept. 1, 1959,
ORNL-2839, p 114.
3H. L. Yakel, unreported data, 1959.
' G . M. Adamson et al., HRP Quar. Prog. Rep. Jan. 31, 1958, ORNL-2493,
L -

p 141.
'G. M. Adamson -et -
al., HRP Quar. Prog. Rep. Jan. 31, 1958, ORNL-2493,
p 142.
6G. H. Jenks - et -
al., E P Quar. Prog. Rep. Oct. 31, 1958, ORNL-2654,
p 159+60.
7 G . M. Adamson -
et -
al., HRP Quar. Prog. Rep. Jan. 31, 1958, O m - 2 4 9 3 ,
p 143.
170
shown to increase the yield, tensile, and creep strengths of a-zirconium
quite appreciably.8

Other in~estigators,~
using spor-"e zirconium (high iron and oxygen
impurity levels) as the alloy base, have studied the isothermal transfor-
mation kinetics of the Zr-Mo system, using metallography, x-ray diffrac-
tion powder techniques, and room-temperature electrical-resistivity meas-
urements for determining tlie data. They have shown that on isothermal

sequence is f3
sequence is @
+

-+
a + f3
@ + u
-+

--+
-
transformation at temperatures above approx 500"C, the transformation
a + f3 + ZrMo2 a + ZrMo2. Below 500"C, the
@ + u + a. The decomposition below 500°C to
form only a p lu s ZrMoz was not completed in one week. They did not study
the @-quench and reheat-type of transformation nor were any alloys using
iodide zirconium as the alloy base studied. Hardness data were not used
to study the transformation kinetics. The electrical-resistivity meas-
urements were made at room temperature after quenching the specimen from
the transformation temperature. Mechanical property tests showed appreci-
able increases in strength levels and decreases in ductility, particularly
for the specimens transformed at temperatures below 500°C.
Physical metallurgy studies of the Zr-Mo alloy system have been
started using iodide zirconiwbase alloys containing 4 and 7.5 w t % Mo.
Both @-quench and reheat and true isothermal transformation studies are
being conducted. Metallography and hardness measurements have been the
techniques of study. Determinations of electrical resistivity at temper-
ature will be included shortly. X-ray diffraction examinations will be
conducted as found appropriate.
Specimens of both alloys have been transformed at 400, 500, 600, and
700°C for times up to 60 min by both the isothermal and the @-quench and
reheat techniques.
Metallographic examination has shown that little difference can be
found between the microstructures for any of the transformed specimens,
regardless of transformation time, temperature, or type, for either alloy.

8R. K. Wagner and H. E. Kline, H i g h Strength Zirconium Alloys, NAA-

SR-3481 (July 15, 1959).
9R. F. Domagala et &., "Transformation Kinetics and Mechanical Prop-
erties of Zr-Mo Alloys," J. Metals -
9, 1191-96 (October 1957).
-

171
The d i f f e r e n c e s found i n t h e m i c r o s t r u c t u r e s f o r v a r i a t i o n i n composition
are discrete but not definitive. M i c r o s t r u c t u r a l examination has been of
l i t t l e a i d t o d a t e i n f o l l o w i n g t h e t r a n s f o r m a t i o n k i n e t i c s of t h e Zr-Mo
system b u t may be of more v a l u e f o r l o n g e r t r a n s f o r m a t i o n t i m e s .
The m i c r o s t r u c t u r e s of t h e B-quenched specimens of b o t h a l l o y s show
a Widmanststten p l a t e l e t s t r u c t u r e i n a r e t a i n e d p matrix s i m i l a r t o t h a t
r e p o r t e d f o r t h e Zr-Nk a l l o y s . Transformed specimens show changes i n
s t r u c t u r e ranging from no d e t e c t a b l e change f o r t h e 400°C specimens t o a
completely c l e a r m i c r o s t r u c t u r e w i t h only f a i n t g r a i n boundaries f o r t h e
700°C, 1 - h r , 7.5 w t % Mo specimens.
Hardness data show t h a t small b u t reasonably c o n s i s t e n t changes oc-
c u r r e d d u r i n g b o t h t y p e s of t r a n s f o r m a t i o n f o r t h e 7.5 w t % Mo a l l o y and
t h a t somewhat l a r g e r changes occurred f o r t h e 4 wt % Mo a l l o y . The d a t a
are p r e s e n t e d i n Figs. 1 2 . 2 and 1 2 . 3 and i n Table 12.2. The d a t a i n d i -
c a t e t h a t t h e times of t r a n s f o r m a t i o n were t o o s h o r t f o r more t h a n a s m a l l
amount of t r a n s f o r m a t i o n t o have t a k e n p l a c e o t h e r t h a n on t h e o r i g i n a l
@-quench f o r t h e Zr4 Mo a l l o y , a r e s u l t c o n s i s t e n t w i t h t h e d i f f e r e n c e s
i n oxygen l e v e l s f r o m t h e a l l o y s s t u d i e d by Domagala -
et -
ai.’ The d a t a
f o r t h e Zr-4 Mo a l l o y f o r t h e @-quench and r e h e a t t r a n s f o r m a t i o n suggest
t h a t an age-hardening r e a c t i o n had occurred a f t e r 20-30 min, and t h a t t h e
r e a c t i o n concerned i s probably a formation of w phase followed by a p r e -
c i p i t a t i o n of a-zirconium.
Specimens of b o t h a l l o y s a r e p r e s e n t l y b e i n g transformed f o r l o n g e r
t i m e s a t t h e same s e t of t e m p e r a t u r e s . Specimens f o r e l e c t r i c a l - r e s i s -
t i v i t y measurements a t temperature have been made f o r s t u d y i n t h e n e a r
future.
UNCLASSIFIED
ORNL-LR-DWG 50219
360

- 320
LTI
1

-
0
I
280
a
n

240

200
I 2 5 10 20 50 100 200
AGING T I M E ( m l n )

Fig. 12.2. Hardnesses for Zr-7.5 wt % Mo

Alloy Aged After /3 Quenching.
 1 2 5 to 20 50 100 200
AGING TIME (rnin)

Fig. 12.3. Hardnesses for Zr-4 wt % Mo Alloy

Aged After /3 Quenching.

Table 1 2 . 2 . Hardnesses of Isothermally Transformed

Zirconium-Molybdenum Alloys*

Transformation
DPH (10 kg), Time at Trans-
formation Temperature (min)
Alloy Temperature
("c> 15 30 60

Zr-4 Mo** 400 450 436 447

500 362 343 35 3
600 306 323 299
700 341 337 339
Q, Z r 7 . 5 Mo 400 267 299 382
500 298 262 25 9
600 293 291 289
700 293 281 293

*Specimens quenched to transformation temperature from 950°C.

**Weight per cent.

173
 Zirconium-Copper Alloys

Copper additions to a 21-15 Nb-base alloy have been found to improve

Q
the corrosion resistance of the binary alloy to fissioning uranyl sulfate6
and the oxidation resistance to air.' The additions affect, rather dras-
tically, the rate of formation of w phase in retained p in the Zr-Nb alloy
system, decreasing slightly the rate of reaction at temperatures below
45OoC, and essentially eliminating the reaction at temperatures of 450°C
and above.
Zirconium-copper alloys have been found to be more resistant than
Zircaloy-2 to atmospheric oxidation at temperatures as high as 700"C,10
and to steam at 500°C and below.
Some datahavebeen determined by other investigators'' on the me-
chanical properties of zirconium-copper alloys, but the alloys used were
melted in graphite crucibles using sponge zirconium, or, if arc-melting
was used, the data collected were restricted to tensile properties in the
as-rolled and as-rolled and annealed at 700°C condition. The data indi-
cated that no significant strengthening occurred.
Since copper would likely be used as a ternary addition to a number
of binary alloy systems, it was felt necessary that some information be
determined on the transformation kinetics and products of zirconium-copper
binary alloys. Contents of 1.0 and 1.6 w t '$ copper were selected for the
initial study.
Rolled strip for both alloys was homogenized for 48 hr in purified
argon at 1000°C and water-quenched, the quartz capsule bejng broken under
water. The specimens cut from the strips were betatized for 15 min at
950°C before transformation. Specimens were isothermally transformed at
400, 500, 600, and 700°C for times up to 1 hr in a transformation machine
using lead baths for the betatizing and transformation furnaces. Beta-
quench and reheat transformation specimens were aged in the same machine
for the same times and temperatures. Metallographic examination of the

1°J. A. Burka -
et -
al., Scaling of Zirconium and Zirconium Alloys, AEC
Research and Development Report. Second Progress Report, March 1958, Dept.
of Mining and Metallurgical Engineering, University of Kentucky.
"F. B. Litton, "Ten Zirconim Alloys Evaluated," Part I, Iron Age
95-99 (Apr. 5, 1951) and Part 11, 112-14 (Apr. 12, 1951).

174

0
 transformed specimens showed only minor differences in the microstruc-
tures, regardless of time, temperature, transformation type, or composi-
tion. The microstructures of the @-quenched specimen of each alloy dif-
fered from the transfomed specimens but not from each other. Both p-
quenched specimens showed large amounts of a fine rectangular block pre-
cipitate, faintly anisotropic under polarized light and occurring in a
Widmanstgtten pattern, existing in a matrix showing an acicular needle
structure which was also faintly anisotropic under polarized light. All
of the transformed specimens showed the same matrix as the @-quenched
specimens but the block precipitate was present in only small amounts.
e What little precipitate was detectable at 600X was not resolvable and did
not appear to occupy as much volume of the specimen as in the @-quenched
microstructure.
a Hardness data were determined for each of the transformation and
alloy series. The data are presented in Table 12.3 and Figs. 12.4 and
12.5. The hardness data for the isothermal transformations indicate that
an age-hardening transformation occurs at 500°C and below, and that, if
it occurs at temperatures above 500"C, the alloys overage in less than

Table 12.3. Hardnesses of Isothermally Transformed

Zirconium-Copper Alloys*

Transformation
DPH (10 kg), Time at Trans-
formation Temperature (min)
Alloy Temperature
("c) 15 30 60

zr-1 cu** 400 263 250 294

500 254 210 224
600 183 177 177
700 153 155 146

Z r 1 . 6 Cu 400 364 321 360

500 227 254 261
600 203 200 191
700 161 145 147

*Specimens quenched to transformation temperature from 950°C.

**Weight per cent.

175
 UNCLASSIFIED
ORNL-LR-DWG 50221

AGING TIME (min)

F i g . 12.4. Hardnesses for Zr-1 wt '3 C u Alloy

Aged After p Quenching.

UNCLASSIFIED
ORNL-LR-DWG 50222
380

340

300
I

2 260
a
I
n
220

480

440 1 2 5 10 20 50 400 200

AGING TIME ( m i n )

Fig. 12.5. Hardnesses for Zr-1.6 wt ?' 4 C u

Alloy Aged After /3 Quenching.

1 5 min. I s o t h e r m a l t r a n s f o r m a t i o n s a t s h o r t e r t i m e s are p r e s e n t l y b e i n g
run.
The h a r d n e s s d a t a f o r t h e @-quench and r e h e a t t r a n s f o r m a t i o n s , F i g s .
12.4 and 12.5, a r e t o o f e w t o p e r m i t t h e i n t e r p r e t a t i o n s t h a t might be
i n d i c a t e d from t h e d e c r e a s e and t h e n i n c r e a s e i n h a r d n e s s w i t h i n c r e a s i n g
a g i n g t i m e a t 400°C. Specimens a r e b e i n g t r a n s f o r m e d f o r t i m e s r a n g i n g
from 1 min t o 24 h r a t a l l f o u r t e m p e r a t u r e s .

Z i r c a l o y - 2 F a b r i c a t i o n Study

The e f f e c t s of t h e f a b r i c a t i o n v a r i a b l e s on t h e p r e f e r r e d o r i e n t a -
t i o n and t h e a n i s o t r o p y of mechanical p r o p e r t i e s of Z i r c a l o y - 2 have been
i n v e s t i g a t e d i n o r d e r t o b e t t e r u n d e r s t a n d t h e p r o p e r t i e s and t e x t u r e s

176
observed, t o o b t a i n t h e background i n f o r m a t i o n n e c e s s a r y f o r t h e p r e d i c -
t i o n and c o n t r o l of t e x t u r e , and t o p r e p a r e a s t a r t i n g b a s i s f o r t h e study
n e c e s s a r y t o provide t h e i n f o r m a t i o n t h a t must b e o b t a i n e d b e f o r e a - z i r -
conium a l l o y s can b e used as g e n e r a l e n g i n e e r i n g s t r u c t u r a l m a t e r i a l s f o r
c o n s t r u c t i o n of r e a c t o r systems.
A c o n s i d e r a b l e p o r t i o n of t h e data c o l l e c t e d and t h e conclusions drawn
were r e p o r t e d i n t h e l a s t r e p o r t . 1 2 A new method f o r determining t h e a n i s o -
t r o p y of s t r a i n behavior i n an a n i s o t r o p i c material w a s a l s o r e p o r t e d . The
s t u d y has been t e r m i n a t e d and a l l of t h e d a t a determined and t h e conclu-
s i o n s drawn have been r e p o r t e d i n two t o p i c a l reports.13'14 I n summary,
it w a s concluded t h a t s m a l l v a r i a t i o n s i n t h e e x a c t d e t a i l s of t h e f a b r i -
c a t i o n procedure can a f f e c t r a t h e r s t r o n g l y t h e p r e f e r r e d o r i e n t a t i o n de-
veloped and t h e r e s u l t i n g a n i s o t r o p y of mechanical p r o p e r t i e s , t h a t t h e
i n g o t axis o r i e n t a t i o n and t h e p o i n t i n t h e f a b r i c a t i o n schedule a t which
c r o s s r o l l i n g i s i n t r o d u c e d can a f f e c t t h e t e x t u r e and a n i s o t r o p y d r a s t i -
c a l l y , t h a t t h e ORNL-HRP f a b r i c a t i o n schedule15 which has been i n use f o r
s e v e r a l y e a r s i s t h e b e s t y e t found f o r t h e p r o d u c t i o n of t h e most i s o -
t r o p i c material, and t h a t s i m i l a r s t u d i e s should be conducted f o r t h e f a b -
r i c a t i o n of p i p e and t u b i n g .
The p r e f e r r e d o r i e n t a t i o n d e t e r m i n a t i o n s of t h e study14 have shown
t h a t t h e u s u a l commercial f a b r i c a t i o n schedule (which d i f f e r s from t h e
O m - K R P ~ c h e d u l e l i~n? t~h a~ t most of t h e r e d u c t i o n i s performed from a
temperature of 1550°F and no i n t e r m e d i a t e f3 h e a t t r e a t m e n t i s performed)
r e s u l t s i n t h e production of a v e r y s t r o n g t e x t u r e whose p r i n c i p a l f e a -
t u r e i s an alignment of t h e p o l e s of t h e basal p l a n e s of t h e close-packed-
hexagonal u n i t c e l l t o w i t h i n a f e w degrees of t h e normal t o t h e r o l l i n g
plane. Such a t e x t u r e shows l i t t l e a n i s o t r o p y of mechanical p r o p e r t i e s
"M. L. P i c k l e s i m e r - a l . , Met. Div. Ann. Prog. Rep. S e p t . 1, 1959,
et -
ORNL-2839, p 11527.
13P. L. Rittenhouse and M. L. P i c k l e s i m e r , M e t a l l u r w of Z i r c a l o y - 2 :
P a r t I - The E f f e c t s of F a b r i c a t i o n V a r i a b l e s on t h e Anisotropy of Mechani-
c a l P r o p e r t i e s , OFNL-2944 (i-n p r e s s ) .
"P. L. Rittenhouse and M. L. P i c k l e s i m e r , Metallurgy of Z i r c a l o y - 2 :
P a r t I1 - The E f f e c t s of F a b r i c a t i o n V a r i a b l e s on t h e P r e f e r r e d O r i e n t a -
t i o n and Anisotropy of S t r a i n Behavior, ORNL-2948 ( i n press).
I 5 M . L. P i c k l e s i m e r and G. M. Adamson, Development of a F a b r i c a t i o n
Procedure f o r Zircaloy-2, ORNL CF-56-11-115 (Nov. 21, 1956).

177
of tensile specimens whose axes lie in the rolling plane but does show a
very marked anisotropy of strain behavior in each specimen. While the
elongation and reduction of area are relatively large (approx 27 and 428,
respectively), the cross sections of the fractured round tensile speci-
mens became elliptical, showing that little contractile strain had oc-
curred in the normal direction of the rolled plate from which the speci-
mens were made.
The material of one of the schedules studied13 (schedule J) showed
a very strong alignment of the poles of the basal planes in the transverse
direction of the rolled plate .14 The transverse-direction tensile speci-
mens of this material showed no significant differences in tensile proper-
ties other than an increased yield strength, indicating that tensile stress
along the c axis of the close-packed-hexagonal unit cell did result in
considerable ductility. The resolved shear stress for slip in both ten-
sion and compression in the transverse direction for this material was de-
termined for stress before and after twinning. The data are presented in
Table 12.4 and Fig. 12.6. The twin system operating for tensile stress
UNCLASSIFIED
ORNL- L R - DWG 5 0 2 2 3
POLES OF THE S L I P PLANES
A S L I P DIRECTIONS
0 POLE OF THE TWIN P L A N E ACTIVE IN TENSION-(4OT21
A POLE OF THE TWIN P L A N E ACTIVE IN COMPRESSION-(11?11
POSITION OF THE TRANSVERSE DIRECTION
TD-BEFORE TWINNING
T D ' - A F T E R (10121 TWINNING
TD"-AFTER ( I I ? 4 ) TWINNING
1010

I OTO

Fig. 12.6. Reorientation o f Slip Systems After

Twinning i n T e n s i o n or Compression for Transverse
Direction Specimens o f Schedule J Zircaloy-2.

178
 Table 12.4. Resolved Shear Stress in the Transverse
Direction Before and After Twinning

Angle (deg) Resolved

Slip System Shear Stress
X A T cos x cos A

Before Twinning

(ioio) [i2io] 88 84 0.002 T

(1100) [ 11201 88 97 0.002 T
(0110) [2110] 89 90 0
4)
After Twinning in Tension - (1012)

(ioio) [i2io] 4 86 0.070 T

Q (iioo) [ 11201 56 34 0.444 T
(olio) [2110] 64 26 0.394 T

After Twinning in Compression - (1121)

(ioio) [ i 2 i o] 59 70 0.176 T
(1100) [ 1120] 88 52 0.022 T
(olio) [2110] 57 74 0.150 T

T - Applied stress.
x - Angle between stress axis and normal to slip plane.
A - Angle between stress axis and slip direction.

along the c axis is the (1012) family.16 The data show that, before twin-
ning, no deformation by slip can occur but that twinning does result in
Q, --
the realignment of the slip systems of the {lOTO} <1210> type so that slip
can occur. However, if the stress applied is that of compression, produc-
ing twinning on the (1121) twin system,16 little realignment of slip sys-
tems to produce deformation by slip can occur. Thus, most of the compres-
sive deformation must occur by twinning, a method which does not produce
much strain, and which can lead to cleavage and early fracture if forced

1 6 E . J. Rapperport, Room-Temperature Deformation Processes in Zirco-

nium, NMI-1199 (Feb. 24, 1958).

179
to occur. Such is the case for multiaxial stressing of engineering struc-
tures made from plate material as normally produced by the present com-
mercial practice. The data also explain the ellipticity of cross section
observed in the fractured test specimens, allowing an experimental deter-
mination and analysis, by the contractile strain-axial strain method,17
of the strain available in each principal stress direction.

OXIDATION OF ZIRCONIUM-BASE ALLOYS

J. C. Banter S. Peterson

A program of study of the effects of alloying elements and oxidizing

environment on the oxidation rates and mechanisms for zirconium-base alloys
has been initiated. The study will encompass many of the zirconium-base
alloys of potential interest in reactor systems and the environments en-
countered in those systems. The early portion of the study will be re-
stricted to oxidation in pure oxygen and in water. U r a n y l sulfate fuel
solutions, steam, C02, impure helium, and radiation fields will be included
at a later stage of the study.
The techniques of study planned are high-precision oxidation-rate
measurements over a range of temperatures and pressures in pure oxygen,
electron microscopy of replicas of oxidized specimens, x-ray diffraction
studies of thin oxide films on single crystals to determine the oxide
structure, strain, and phases present, and ultraviolet, visible, and infra-
red light spectrophotometric studies of the optical constants of the thin
films and of adsorbed layers of ions in aqueous solutions, such as uranyl
sulfate and uranyl nitrate.

Oxidation Rate Determinations

Oxidation equipment for the determination of the oxidation rates of

zirconium alloys to a high degree of precision during the thin film stage
of oxidation has been built and is undergoing tests for accuracy, sensi-
tivity, and reproducibility. The equipment uses a small oxidation cham-
ber for the specimen which is separated from a large oqgen storage system
by a small ball-and-socket glass valve. A thermostatted differential oil

I7R. C. Waugh, Met. Ann. Prog. Rep. Oct. 10, 1958, ORNL-2632, p 155-
56 (classified).

180

a
 manometer between t h e two oxygen chambers senses a p r e s e t p r e s s u r e change
as small as 0.1 mm of o i l by a p h o t o c e l l - r e l a y system t o operate t h e g l a s s
valve t o rebalance t h e p r e s s u r e s of t h e two oxygen chambers. Thus, a con-
s t a n t weight of oxygen i s added t o t h e specimen chamber a t each valve op-
eration. The oxygen p r e s s u r e i n t h e system can range from 10 mm Hg t o
atmospheric p r e s s u r e without appreciably a f f e c t i n g t h e weight of oxygen
added p e r valve operation. Each o p e r a t i o n of t h e valve, t h e time p e r i o d
it i s open, and a time t r a c e a r e recorded on a m u l t i p l e pen r e c o r d e r . Du-
p l i c a t e runs made on Zircaloy-2 a t 1 0 mm Hg oxygen p r e s s u r e , 4OO0C, and
1 mm o i l d i f f e r e n t i a l p r e s s u r e have shown an average of 33.9 and 34.1 pg
e of oxygen a d d i t i o n p e r valve opening f o r runs 48 h r long. A p l o t of time
p e r valve opening vs t o t a l time has shown considerable s c a t t e r i n t h e
values i n a p a t t e r n which can only p a r t i a l l y be c o r r e l a t e d t o f l u c t u a -
6 t i o n s i n room temperature and l i n e voltage, and not a t a l l t o o p e r a t i o n
of t h e h e a t e r f o r t h e d i f f e r e n t i a l manometer thermostat. It i s b e l i e v e d
t h a t t h e dry g l a s s ball-and-socket valve does not s e a t reproducibly a f t e r
every operation, causing an undetected and unpredictable l e a k a c r o s s t h e
valve. The g l a s s valve i s being replaced with a p o s i t i v e - s e a t i n g metal
valve. The equipment i s a l s o being modified t o i n c o r p o r a t e an apparatus
f o r maintaining a constant p r e s s u r e i n t h e oxygen s t o r a g e system which
w i l l , by measuring t h e volume change necessary t o maintain t h e d e s i r e d
p r e s s u r e , measure p e r i o d i c a l l y t h e t o t a l volume of oxygen consumed by t h e
specimen t o t h a t time. The accuracy of t h e measurement cannot be as g r e a t
as t h a t m a d e by t h e d i f f e r e n t i a l oil manometer, b u t w i l l provide a second
system of measurements made e s s e n t i a l l y simultaneously and continuously
during each o x i d a t i o n r u n . A constant c r o s s check of t h e accuracy of t h e
d a t a obtained can t h u s be made, one method providing d i r e c t l y t h e d i f f e r -
e n t i a l o f t h e o x i d a t i o n r a t e curve and t h e o t h e r t h e i n t e g r a l r a t e curve.

PRODUCTION OF SINGU CRYSTALS OF ZIRCONIUM-BASE ALLOYS

R. L. Stephenson

Single c r y s t a l s (approx 1/8 x 1 x 1 i n . i n s i z e ) of a number of z i r -

conium-base a l l o y s a r e needed i n t h e determination of t h e d a t a f o r t h e
o x i d a t i o n study. Attempts by o t h e r i n v e s t i g a t o r s t o produce good q u a l i t y

r. s i n g l e c r y s t a l s of iodide zirconium, f r e e of s u b s t r u c t u r e , l a r g e r t h a n

18 1

B)
approx 1/4-i n . r i g h t c y l i n d e r s , have i n v a r i a b l y f a i l e d whatever technique
was used. It has been shown by s e v e r a l i n v e s t i g a t o r s t h a t l a r g e s i n g l e
c r y s t a l s of s e v e r a l metals could be produced by s t r a i n i n g annealed s h e e t
a c r i t i c a l amount and t h e n annealing by passing t h e m a t e r i a l through a
thermal g r a d i e n t . Others have shown t h a t g r a i n boundaries can be forced
t o move by applying a s m a l l s t r e s s t o a specimen h e l d a t an annealing
temperature. It w a s thought t h a t it might be p o s s i b l e t o produce t h e de-
s i r e d s i n g l e c r y s t a l s of t h e zirconium a l l o y s as l a r g e g r a i n s i n s t r i p
m a t e r i a l by passing a sharp thermal g r a d i e n t slowly along a sheet-type
specimen which w a s s t r e s s e d by t h e a p p l i c a t i o n of a constant load.
A high-vacuum zone-melting furnace has been obtained and modified t o
permit s t r e s s i n g of a rod- or sheet-type specimen by a c o n s t a n t l y a p p l i e d
load. The thermal g r a d i e n t zone i s produced by a high-frequency induc-
t i o n h e a t i n g c o i l , e x t e r n a l t o t h e high-vacuum specimen chamber, which i s
slowly moved along t h e specimen by a d r i v e mechanism.
Two sheet-type specimens (1/8 x 1 x 10 i n . ) have been run t o d a t e .
The f i r s t specimen ruptured e a r l y i n t h e experimental run due t o t h e ap-
p l i c a t i o n of t o o g r e a t a s t r e s s b u t d i d show t h a t considerable g r a i n growth
had occurred, The second specimen run i s s t i l l i n progress. A f t e r approx
150 passes of t h e thermal g r a d i e n t zone, t h e g r a i n s i z e o f t h e specimen
has i n c r e a s e d from l e s s t h a n 0.01-mm d i a t o an average of approx 3-mm d i a
with many g r a i n s having a diameter of more t h a n 5 mm. The l a r g e g r a i n s
show no twinning or s u b s t r u c t u r e by m i c r o s t r u c t u r a l examination a t 600X
i n polarized l i g h t . A very rough determination of t h e r a t e of growth of
t h e l a r g e g r a i n s i n d i c a t e s t h a t t h e r a t e i s e s s e n t i a l l y c o n s t a n t p e r pass
and i s independent of t h e r a t e of p a s s i n g of t h e thermal g r a d i e n t zone
w i t h i n t h e l i m i t s of t h e machine (from l e s s t h a n 1 i n . / h r t o 18 i n . / h r ) .
Only one s t r e s s l e v e l has been i n v e s t i g a t e d , 1600 p s i , and t h a t has pro-
duced enough necking of t h e specimen t o probably terminate t h e run a t
about 250 p a s s e s .
A one-turn induction c o i l has been constructed t o permit a steepening
of t h e thermal g r a d i e n t . The next t e s t w i l l be made using 3/4-in. dia,
as-deposited, c r y s t a l - b a r zirconium, t h e one-turn induction c o i l , and a
s t r e s s of approx 1200 p s i .

182

0
 P a r t 111

FZACTOR METALLURGY
a
13. CERAMICS LABORATORY
4id
L. M. Doney

URANIUM DIOXIDE TECHNOLOGY STUDIES

F a b r i c a t i o n of GCR P e l l e t s

A. J. Taylor J. M. Robbins

I n t h e i n t e r e s t of reducing f u e l f a b r i c a t i o n c o s t s , a s i m p l i f i e d cold-
p r e s s i n g and s i n t e r i n g technique has been developed by which U02 p e l l e t s
can be made t o t h e s p e c i f i e d s i z e and d e n s i t y without t h e need f o r machin-
i n g following s i n t e r i n g . This f a b r i c a t i o n technique depends on a source
of powder of reproducible q u a l i t y . Development of a reproducible process
f o r making a h i g h l y s i n t e r a b l e UO2 powder (from uF6) i s e s s e n t i a l l y com-
plete. When made i n q u a n t i t i e s of 10 kg or more, t h e powder from t h i s
process e x h i b i t s c o n s i s t e n t forming and s i n t e r i n g c h a r a c t e r i s t i c s .
Completion of t h e work r e q u i r e s t h e development of a r e c y c l e process
for converting both hard and s o f t f a b r i c a t i o n s c r a p back t o a usable and
f a b r i c a b l e form o f U02 powder. From t h e standpoint of f a b r i c a t i o n it would
be p r e f e r a b l e t o have r e c y c l e powder i n d i s t i n g u i s h a b l e i n i t s c h a r a c t e r -
i s t i c s from t h e o r i g i n a l U02 powder; however, it would not be economically
f e a s i b l e t o convert s c r a p back t o L T 6 . I n i t s p r e s e n t form t h e r e c y c l e
process i s based on p r e c i p i t a t i o n of ammonium d i u r a n a t e (ADU) from a n i -
t r a t e solution. The o b j e c t i v e i s t o a d j u s t t h e p r e c i p i t a t i o n conditions
s o t h a t t h e kDU p r e c i p i t a t e i s i d e n t i c a l i n i t s c h a r a c t e r i s t i c s t o t h e ADU
p r e c i p i t a t e d from t h e f l u o r i d e s o l u t i o n of t h e process f o r which t h e s t a r t -
i n g m a t e r i a l i s m6. When t h e r e c y c l e process has been developed t o t h e
p o i n t t h a t t h e U02 i s reproducibly i d e n t i c a l i n i t s forming and s i n t e r i n g
c h a r a c t e r i s t i c s t o t h e powder from t h e f l u o r i d e process, ADU f i l t e r cake
from e i t h e r process, i n d i v i d u a l l y o r as a mixture, can t h e n be brought
through t h e same c a l c i n i n g , reduction, and s t a b i l i z a t i o n s t e p s .
A f t e r an i n v e s t i g a t i o n of t h e p r e c i p i t a t i o n c h a r a c t e r i s t i c s of t h e
u r a n y l n i t r a t e s o l u t i o n s , seven batches of powder were prepared and t e s t e d .
Three of t h e s e batches y i e l d e d e x c e l l e n t oxides which were i d e n t i c a l t o
t h e s t a n d a r d oxide i n forming and s i n t e r i n g c h a r a c t e r i s t i c s ; however, o t h e r

185
characteristics of these powders were different, as evidenced by their ab-
normally high oxygen/uranium ratio. The extent to which this or other Q
differences are related directly to the ADU precipitate is being investi-
gated.

Development of U02 Particles for Fast

Breeder Assistance Program
J. M. Robbins A. J. Taylor

In support of the Fast Breeder Assistance Program (FBAP), a study is

being made to evaluate the characteristics of -100 +140 mesh U02 spheres
B)
so as to aid in the specification of the quality of powder required to
provide uniform distribution and resistance to crushing and stringering
during rolling of UO2-stainless steel dispersion-type fuel elements. The B)
lack of uniformity in the UO2 particles investigated to date was attri-
buted mainly to processing techniques.
The properties which appear to be most useful in characterizing these
UO;! particles are bulk density, grain size, and crushing strength. At
present a mercury pycnometer technique is being used to measure bulk den-
sity, but in order to obtain the precision which is needed an embedding-
'
and-immersion technique, as described elsewhere, is being developed. Prop-
erty measurements will be correlated with observations made on the dispersed
particles after rolling of the fuel elements.
Uranium dioxide particles have been obtained or ordered from several
outside vendors. Particles produced at Y-12 which are known to have good
quality will be used as standard.

UO2-Graphite Compatibility Studies

T. G. Godfrey
The rate of reaction between U02 and graphite to form UC and UC2 was
studied as a function of U02 particle size and temperature. The purpose
of this study is to determine the limiting operating temperature of a fuel
element consisting of U02 or other oxide-type fuels dispersed in graphite.
Preliminary work has been reported in detail.
'Cf . "Density Determinations, I' this chapter.
;!GCR Quar. Prog. Rep. Mar. 31, 1960, ORNL-2929, p 98-100.
 .. . . . -. . . ..

A t temperatures above 1200°C i n vacuum t h e r e a c t i o n proceeded a t a

measurable r a t e and followed a p a r a b o l i c r a t e l a w . The r e a c t i o n w a s e s -
s e n t i a l l y complete w i t h i n 1 h r a t 1450°C. A s t h e temperature of t h e r e -
a c t i o n w a s increased, t h e q u a n t i t y of UC;! formed a p p a r e n t l y i n c r e a s e d r e l a -
t i v e t o UC.
A comparison of r a t e s observed f o r -60 +80 mesh U02 and -325 mesh UO;!
i n d i c a t e d t h a t t h e r e a c t i o n r a t e w a s s e n s i t i v e t o p a r t i c l e s i z e below about
1325"C, t h e smaller p a r t i c l e s having t h e f a s t e r r a t e , and r e l a t i v e l y i n -
s e n s i t i v e above t h i s temperature.
F u r t h e r d e t a i l s on t h e s e s t u d i e s have been r e p o r t e d elsewhere.

P r e p a r a t i o n of U02 P a r t i c l e s by Hydrothermal Process

R . E. Meadows A. J. Taylor T . S. Shevlin4

C r y s t a l s of U O 3 * H z O which a r e approximately equiaxed orthorhombic b i -

pyramids can be grown by a hydrothermal process using moderately e l e v a t e d
temperatures and p r e s s u r e s . On subsequent reduction t o UO;! a t high tem-
p e r a t u r e , a dense s i n g l e p a r t i c l e of U02 i s made which r e t a i n s t h e shape
of t h e p a r e n t U O ~ D H ~c rOy s t a l . This type of U02 p a r t i c l e has proven q u i t e
u s e f u l as t h e f u e l i n s e v e r a l dispersion-type f u e l elements.
A t p r e s e n t , t h e process for growing t h e s e p a r t i c l e s i s i n e f f i c i e n t
due t o t h e f a c t t h a t some o f t h e v a r i a b l e s involved a r e not recognized,
while some o t h e r s t h a t a r e recognized a r e not under c o n t r o l . Material
balances and pressure-volume-temperature d a t a were used t o study t h e r e -
a c t i o n s occurring i n t h e autoclave. The l a c k of good c o r r e l a t i o n between
experiments w a s a t t r i b u t e d t o t h e v a r i a b i l i t y i n t h e c r y s t a l form and com-
p o s i t i o n of t h e s t a r t i n g uranium peroxide cake.
I n o r d e r t o e l i m i n a t e t h i s v a r i a b l e such source m a t e r i a l s as U02,
U3O8, and u r a n y l n i t r a t e s o l u t i o n were t r i e d . C r y s t a l s were grown from
both t h e U02 and U3O8, b u t not from t h e u r a n y l n i t r a t e s o l u t i o n ; however,
t h e s e m a t e r i a l s a r e proving t o be u n s a t i s f a c t o r y from s t a n d p o i n t s o t h e r
than v a r i a b i l i t y . The U308 and U02 have very l i m i t e d s o l u b i l i t i e s u n l e s s
t h e a c i d concentration of t h e s t a r t i n g mixture i s q u i t e high. Consequently,

3GCR Quar. Prog. Rep. June 30, 1960, OWL-2964 ( i n p r e s s ) .

'Consultant from Ohio S t a t e University.

187
some p r o p o r t i o n of t h e s e materials remains as a n unwanted i m p u r i t y i n t h e
f i n i s h e d product. With t h e r a t e of c r y s t a l growth b e i n g d i r e c t l y r e l a t e d Q
t o t h e rate a t which m a t e r i a l becomes a v a i l a b l e from t h e s o l u t i o n , t h e
l i m i t e d s o l u b i l i t y of t h e U02 and U3O, r e s u l t s i n an extended p e r i o d of
n u c l e a t i o n and growth, w i t h a consequent unwanted wide range of c r y s t a l
s i z e s and shapes i n t h e f i n i s h e d p r o d u c t .

BERYLLIUM OXIDE TECHNOIDGY STUDIES

F a c t o r s A f f e c t i n g S i n t e r a b i l i t y of Be0

R . L. Hamner

S t u d i e s i n support of t h e GE-ANPD e f f o r t were made t o d e f i n e and con-

t r o l t h e v a r i a b l e s a f f e c t i n g s i n t e r a b i l i t y of h i g h - p u r i t y Be0 powders ob-
t a i n e d by c a l c i n i n g BeC204-3H20. V a r i a t i o n s i n s i n t e r a b i l i t y occurred
which could n o t be a t t r i b u t e d t o d i f f e r e n c e s i n p u r i t y , s u r f a c e a r e a , p a r -
t i c l e shape, o r f a b r i c a t i o n p r o c e s s e s . This o b s e r v a t i o n l e d t o an i n v e s -
t i g a t i o n of t h e c a l c i n a t i o n p r o c e s s w i t h p a r t i c u l a r r e g a r d t o phase changes
o c c u r r i n g d u r i n g t h e decomposition of BeC204*3H20 t o BeO.
A s t u d y of t h e c a l c i n a t i o n p r o c e s s w a s made5 under dynamic and equi-
l i b r i u m h e a t i n g c o n d i t i o n s b y means of d i f f e r e n t i a l t h e r m a l a n a l y s i s , t h e r -
mogravimetric measurement, and x - r a y a n a l y s i s , i n c l u d i n g high-temperature
x-ray a n a l y s i s .
Beryllium o x a l a t e t r i h y d r a t e was shown t o b e r e l a t i v e l y u n s t a b l e i n
a i r a t low t e m p e r a t u r e s , decomposing t o BeC204-H20 a t temperatures as low @
as 5OoC, g i v e n s u f f i c i e n t t i m e . During decomposition of t h e t r i h y d r a t e
t o t h e monohydrate under r a p i d h e a t i n g c o n d i t i o n s ( 3 t o 7"C/min) a l i q u i d
phase w a s formed which w a s n o t observed when t h e t r i h y d r a t e w a s allowed t o e
decompose slowly under e q u i l i b r i u m h e a t i n g c o n d i t i o n s a t 100°C o r below.
The monohydrate w a s found t o b e s t a b l e i n a i r a t 225°C b u t decomposed
slowly a t 250°C t o Be0 which produced s u b s t a n t i a l l i n e broadening i n x - r a y
d i f f r a c t o m e t e r p a t t e r n s . W e l l - c r y s t a l l i z e d Be0 d i d n o t appear u n t i l a tem-
p e r a t u r e of approx 400°C w a s reached. There w a s no evidence of t h e f o r -
mation of any s t a b l e i n t e r m e d i a t e compound during decomposition o t h e r t h a n
BeC204 *HzO.

50RNL-2942 ( i n p r e s s ) ( c l a s s i f i e d ) .

188
 S t u d i e s were begun t o r e l a t e t h e programming of t h e c a l c i n i n g cycle
t o s i n t e r a b i l i t y of Be0 powders derived from BeC204-3H20. Preliminary
r e s u l t s i n d i c a t e d t h a t s i n t e r a b i l i t y w a s i n h i b i t e d by r a p i d decomposition
t o t h e monohydrate. This i n h i b i t i o n w a s b e l i e v e d t o be r e l a t e d t o t h e
l i q u i d phase which occurred under dynamic h e a t i n g c o n d i t i o n s .
I n t h e i n t e r e s t of s p e c i f y i n g l i m i t a t i o n s of t h e l i t h i u m content i n
Be0 powders t o be f a b r i c a t e d for r e a c t o r a p p l i c a t i o n s , experiments were
conducted t o determine t o what e x t e n t l i t h i u m would be r e t a i n e d i n a be-
r y l l i u m oxide body a t various s i n t e r i n g temperatures. With an i n i t i a l
l i t h i u m content of 100 ppm, r e s u l t s showed removal t o proceed almost l i n e -
a r l y from 65$ removal a t 1000°C t o 90% a t 1650°C i n 1 h r .

F a b r i c a t i o n of Fueled Be0

R . L. Hamner

Fueled Be0 s t u d i e s a r e p a r t of a long-range r e s e a r c h and development

program f o r advanced gas-cooled power r e a c t o r concepts. The development
o f f a b r i c a t i o n procedures f o r bodies containing high volume p e r c e n t s of
f u e l s d i s p e r s e d i n a high-density Be0 matrix i s i n progress . 2 '
Development work has been d i r e c t e d p r i n c i p a l l y toward t h e f a b r i c a t i o n
of i r r a d i a t i o n specimens containing 30 v o l $ f u e l as U02 o r as a U02-Th02
mixture i n t h e form of a fine-grained d i s p e r s i o n . Bodies of t h i s t y p e
were f a b r i c a t e d t o bulk d e n s i t i e s of approx 95% by e x t r u s i o n and by cold-
p r e s s i n g techniques, followed by s i n t e r i n g i n H2 a t 1750°C. Bodies i n
which t h e f u e l w a s added i n t h e form of U02 were s u p e r i o r t o t h o s e i n which
U308 w a s used, t h e l a t t e r e x h i b i t i n g cracking around t h e f u e l p a r t i c l e s .
Cold-pressing w a s s e l e c t e d as t h e technique f o r forming i r r a d i a t i o n s p e c i -
mens i n view of t h e warpage problem encountered with extruded specimens.
Shrinkage c h a r a c t e r i s t i c s and f i r e d d e n s i t i e s were s t u d i e d as a f u n c t i o n
o f green d e n s i t i e s i n an e f f o r t t o e s t a b l i s h a technique f o r f a b r i c a t i n g
specimens of t h e r e q u i r e d d e n s i t i e s and dimensions.
Development work w a s also undertaken t o f a b r i c a t e Tho2 thermal insu-
l a t o r s t o r i g i d dimensional s p e c i f i c a t i o n s f o r use w i t h BeO-UO2 and BeO-
U02-Th02 specimens scheduled f o r i r r a d i a t i o n s a t 1100 t o 137OOC. A com-
p a t i b i l i t y study of an i n s u l a t o r i n c l o s e c o n t a c t w i t h a f u e l e d Be0 specimen

189
a t 1750°C showed no s i g n i f i c a n t change i n dimensions o r i n t e g r i t y of t h e
i n s u l a t o r although t h e formation of a s o l i d s o l u t i o n of U02 and Tho2 w a s
apparent a t t h e p o i n t of c o n t a c t .
A study w a s undertaken t o determine simultaneously t h e shrinkage
c h a r a c t e r i s t i c s of coarse-grained U02 p a r t i c l e s (100 t o 500 1-1) produced
by h e a t i n g U03-H20 i n H2 a t i n c r e a s i n g temperature l e v e l s t o 1750°C and
Be0 bodies of various green d e n s i t i e s over t h e same temperature range.
The purpose of t h i s study i s t o develop f u e l and matrix of s i m i l a r shrink-
age c h a r a c t e r i s t i c s s o t h a t cracks o r l a r g e voids w i l l not occur around
t h e U02 p a r t i c l e s i n t h e f u e l e d b o d i e s , Up t o 1000°C, t h e l i n e a r shrink-
age of Be0 w a s found t o vary between 0.13 and 0.31$, depending upon green
d e n s i t y , and t h e average l i n e a r shrinkage a s s o c i a t e d w i t h t h e formation
of UO;! from UO3*H20 w a s approx 185.

Phase Relationships i n B e W e t a l Oxide Systems

R. A. P o t t e r

I n v e s t i g a t i o n s of t h e phase r e l a t i o n s h i p s e x i s t i n g i n s e v e r a l Be&
m e t a l oxide systems were ~ n d e r t a k e n . ~E i t h e r o p t i c a l o r x-ray d a t a , o r
both, were obtained f o r t h e following systems: CaO-BeO, La2O3-BeO, SrO-
BeO, Y203-Be0, and MgO-BeO. I n a d d i t i o n , thermal a n a l y s i s techniques were
employed i n studying t h e system CaO-Be0 and a r e p r e s e n t l y being u t i l i z e d
i n t h e preliminary i n v e s t i g a t i o n of t h e system La203-BeO. With t h e ex-
c e p t i o n of t h e MgO-Be0 system, compound formation w a s observed i n each of
t h e systems.
I n t h e CaO-Be0 s t u d i e s , specimens were prepared a t composition i n -
crements of 10 mole $. Thermal analyses on cooling slowly from 15OO0C
i n d i c a t e d t h e e x i s t e n c e of a s o l i d u s i n t h e v i c i n i t y of 1365°C. Quenched
samples examined o p t i c a l l y and w i t h t h e x-ray d i f f r a c t o m e t e r i n d i c a t e d
t h e e x i s t e n c e of a e u t e c t i c composition a t about 60 BeO-40 C a O (mole 8).
Upon quenching l i q u i d of t h e e u t e c t i c composition, a metastable, i s o -
t r o p i c phase w a s formed. The x-ray d i f f r a c t i o n p a t t e r n f o r t h i s phase was
indexed on t h e b a s i s of a face-centered cubic u n i t c e l l with a l a t t i c e
parameter of 14.06 A. Slow cooling showed only t h e two t e r m i n a l phases,
C a O and BeO. On h e a t i n g samples a t 1000°C f o r 150 h r , a new phase ap-
peared, t h e x - r a y d i f f r a c t i o n p a t t e r n f o r t h i s phase being s t r o n g e s t a t

190

0
a composition of 90 Be0-10 CaO (mole $ ) . Powder x-ray diffraction data
for this phase were indexed on the basis of a simple cubic cell with a
lattice parameter of 7.02 A.
Cooling curves obtained for mixtures of La203 and Be0 cooled from
1500°C indicated the existence of a eutectic reaction at about 1350°C and
at a composition of 85 La203--15 Be0 (wt 5).
Evolution of Lithium from Be0

R. A. Potter
In the consideration of beryllium oxide as a moderator material, it
is necessary to obtain information concerning the buildup of Li6 due to
fast-neutron reactions of the (n,a) type. One factor under investigation
is the rate of evolution of Li6 from the Be0 due to the in-service thermal
environment.
Four beryllia tiles, 4 X 4 X 1 in., which contained initially 100 to
300 ppm lithium, were prepared and the cross section for absorption of
thermal neutrons of these tiles was determined in a critical assembly.
Two of the tiles were then heat-treated in a dynamic C02 atmosphere at
850°C for 14 weeks and have been returned for redetermination of the cross
section. A decrease in the cross section would indicate the extent to
which lithium was evolved on heating.

ADVANCED FUEL ELEMEW DEVELOPMErJT

Uranium Carbide Studies

J. M. Kerr
The purpose of the research program on uranium carbide is twofold:
(1)to provide a better understanding of the phenomena which occur in this
material during high-temperature, high-vacuum sintering, and (2) to deter-
mine the effects of irradiation on uranium carbide shapes made by various
laboratories.
Preliminary sintering studies have included an investigation of the
nature of the atmosphere above uranium carbide at the high temperatures
and low pressures by means of mass spectrometer analyses. This study has
required careful metallographic examinations of the starting material and

191
1

of t h e mass spectrometer f i l a m e n t s a f t e r each run. The r e s u l t s a r e not

complete.
I n connection w i t h t h e i r r a d i a t i o n s t u d i e s , it w a s necessary t o d e t e r -
mine t h e r a t e of o x i d a t i o n of uranium carbide i n a i r i n t h e event o f r u p t u r e
of t h e capsule. The equipment used f o r t h i s determination was a s t a n d a r d
thermogravimetric balance w i t h a constant h e a t i n g r a t e i n t h e furnace used.
The o x i d a t i o n w a s found t o t a k e place over a p e r i o d of 20 t o 30 min r a t h e r
t h a n n e a r l y i n s t a n t a n e o u s l y as w a s expected. While t h e conditions used
I

d i d not simulate capsule r u p t u r e a t high temperature, an i n d i c a t i o n of t h e

approximate length of time a v a i l a b l e f o r h e a t removal t o prevent a melt-
d
down of t h e adjacent a r e a s around t h e capsule w a s obtained. The volume
change and weight change f o r complete o x i d a t i o n of uranium carbide were
Y
a l s o c a l c u l a t e d and found t o be s m a l l enough s o t h a t r e a c t i o n products
d
could be r e t a i n e d i n t h e capsule.

Ceramic-Clad F u e l Elements

J. M. Kerr

The development of ceramic-clad f u e l elements includes s e v e r a l ma-

t e r i a l s of i n t e r e s t . Among t h e s e a r e Cr-Al203 cermet, M g O , BeO, Si-Si02
cermet, and some of t h e s p i n e l s . The u l t i m a t e t e s t of t h e body i n question
i s i t s behavior when i r r a d i a t e d i n c o n t a c t w i t h t h e ceramic f u e l . The
f a b r i c a t i o n of 1 2 c y l i n d e r s f u e l e d w i t h 0.5 g of f u l l y enriched UOz c l a d
w i t h Cr-Al203 w a s s u c c e s s f u l l y completed f o r use i n ORR i r r a d i a t i o n ex- e
periments.

Graphite F a b r i c a t i o n
0
A. W . S e i f e r t

The purpose of t h i s program w a s t o develop high bulk density, low-

p o r o s i t y g r a p h i t e bodies which could be e v e n t u a l l y f u e l e d w i t h uranium
compounds f o r use i n high-temperature gas-cooled r e a c t o r s . D e t a i l s of
t h e development procedures have been r e p o r t e d elsewhere . 2 ’
More t h a n 400 p i e c e s were formed from 27 bodies of varying cornposi-
t i o n s and f a b r i c a t i o n h i s t o r i e s . S i g n i f i c a n t r e s u l t s of t h e study can be
summarized as follows : (1)Bodies containing n a t u r a l g r a p h i t e were higher

192
i n bulk d e n s i t y t h a n t h o s e i n which a r t i f i c i a l g r a p h i t e w a s used; (2) i n
general, only s l i g h t i n c r e a s e s i n d e n s i t y were noted w i t h l a r g e i n c r e a s e s
i n cold-pressing p r e s s u r e s ; ( 3 ) h i g h e s t bulk d e n s i t i e s without impregnating
were obtained w i t h f u r f u r y l a l c o h o l b i n d e r s (highest value, 2.05 g / c c ) ;
( 4 ) bulk d e n s i t i e s of 1.90 t o 2.00 g/cc were e a s i l y obtained by use of
various o t h e r thermosetting, high-carbon-forming b i n d e r s procured from
d i f f e r e n t manufacturers without impregnating; ( 5 ) d e n s i t y w a s found t o
i n c r e a s e w i t h decreasing amounts of binder; ( 6 ) impregnating with f u r -
furyl. a l c o h o l s o l u t i o n increased t h e bulk d e n s i t y by as much as 5.65 and
i n c r e a s e d compressive s t r e n g t h by 24 t o 54%; and ( 7 ) compressive s t r e n g t h s
ranged from 860 t o 7400 p s i , with t h e s t r o n g e s t bodies being those f a b r i -
c a t e d using D u r i t e b i n d e r s .

Fueled Graphite F a b r i c a t i o n

A. W. S e i f e r t

The o b j e c t i v e of t h i s program i s t o develop a f u e l e d g r a p h i t e body

t h a t w i l l b e s u i t a b l e f o r r e a c t o r use. To date, bodies have only been
f a b r i c a t e d by t h e admixture method, i n which g r a p h i t e , a b i n d e r , and ura-
nium carbide a r e used. Upon f i r i n g i n argon, t h e s e specimens showed t h e
formation of a UO2 c o a t i n g on t h e s u r f a c e of t h e uranium carbide, presum-
a b l y due t o a r e a c t i o n between t h e uranium carbide and t h e b i n d e r . At-
tempts t o e l i m i n a t e t h i s e f f e c t by f i r i n g i n H2 a r e under way.

Vibratory Compaction o f Oxide Fuels

W. S. Ernst, Jr.

A study of v i b r a t o r y compaction of g r a n u l a r oxide i n t o cladding tubes

was i n i t i a t e d f o r t h e ORNL Fuel-Cycle Development Program and has been per-
formed on a cooperative b a s i s w i t h t h e Unit Operations Section of t h e Chem-
i c a l Technology Division.
Bulk d e n s i t i e s of 8.5 t o 8.7 g/cc were e a s i l y obtained f o r g r a n u l a r
f u s e d Th02-3.4 w t $ UO, i n s i n g l e s t a i n l e s s s t e e l t u b e s . Particle size
d i s t r i b u t i o n appeared t o be t h e primary c o n t r o l l i n g f a c t o r , with t h e char-
a c t e r i s t i c s of t h e v i b r a t o r y energy being of secondary importance. Length,
diameter, and m a t e r i a l of t h e tube d i d not appear t o be important.

193
 Some cursory experiments using multitube assemblies i n d i c a t e d t h a t
bulk d e n s i t i e s of a t l e a s t 8.5 g/cc can be obtained f o r Th02-3.4 w t $ U02.
D e t a i l s of t h i s work have been r e p o r t e d . 6 ’ 7 8 8

TiIORIUM DIOXIDE TECHNOLQGY STUDIES

Slip-Casting of Thorium Oxide

C. E. C u r t i s

Thorium oxide i s of value i n r e f r a c t o r y a p p l i c a t i o n s as w e l l as i n

breeder r e a c t o r uses because it i s t h e h i g h e s t melting oxide (330OOC) and
one of t h e b e s t thermal i n s u l a t o r s (0.008 cgs u n i t a t 1000°C). For c e r -
t a i n a p p l i c a t i o n s , s l i p - c a s t i n g of Tho2 i s t h e s i m p l e s t f a b r i c a t i o n method.
I n producing t h e well-deflocculated Tho2 suspensions e s s e n t i a l for. success-
f u l slip-casting, t h e advantages of b a s i c d e f l o c c u l a n t s over t h e a c i d type
normally used a r e : (1)t h e i r a c t i o n i s immediate and does not e n t a i l t h e
b a l l - m i l l i n g and leaching operations necessary i n a c i d d e f l o c c u l a t i o n ;
( 2 ) b a s i c d e f l o c c u l a n t s do n o t a t t a c k t h e p l a s t e r of P a r i s molds used i n
slip-casting; and ( 3 ) t h e y a r e not unpleasant t o t h e worker.
Heretofore, t h e c h a r a c t e r i s t i c s necessary f o r b a s i s s l i p - c a s t i n g of
t h o r i a powders have not been explored. Therefore, a study of 25 samples
w a s made and two were found amenable t o b a s i c d e f l o c c u l a t i o n . The main
requirement a p p a r e n t l y i s t h a t t h e p a r t i c l e s i z e s be l e s s t h a n 2 t o 3 p,
w i t h about 50 vol $ below 1 p.
The t h o r i a powders which were c a s t a b l e r e q u i r e d 20 ml of water and
a
approx 7 m l of a 2s s o l u t i o n of tetrasodium pyrophosphate p e r 100 g of
Tho2 t o form a good c a s t i n g s l i p .
Th02-Al203 Studies
8
C . E. C u r t i s

I n s t u d i e s f o r a homogeneous r e a c t o r b l a n k e t , A120, w a s mixed with

Tho2 i n proportions of 3 t o 5 v o l $, formed i n t o dry-pressed p e l l e t s , and

6D. E . Ferguson -et -a l . , P r e p a r a t i o n of High-Density Oxides and V i -

b r a t o r y Compaction i n F u e l Tubes, ORNL-2965 ( i n p r e s s ) .
7D. E. Ferguson, F u e l Cycle Development: Semiann. Prog. Rep. Mar.
30, 1960, ORNL CF-60-5-41, p 1-8.
8D. E. Ferguson, ORNL F u e l Cycle Prog, Rep. Mar. 1 5 t o May 15, 1960,
ORNL CF-60-6-72, p 2-3.

194
cs f i r e d a t 1700°C i n a i r .
t o 5 vol
i n porosity;
5
The r e s u l t s showed t h a t (1)t h e a d d i t i o n s of 3
of A1203 caused a s l i g h t i n c r e a s e i n bulk d e n s i t y and a decrease
( 2 ) with f u r t h e r a d d i t i o n s t h e bulk d e n s i t y decreased slowly
while t h e p o r o s i t y remained low; (3) t h e A1203 w a s a p p a r e n t l y concentrated
i n t h e bonding m a t e r i a l between t h e Tho2 agglomerates; and ( 4 ) compounds
o r formation of s o l i d s o l u t i o n s were not d e t e c t a b l e by o r d i n a r y x-ray o r
petrographic means.
The r e s u l t s were a t t r i b u t e d t o t h e formation of a e u t e c t i c l i q u i d
high i n A1203 and of low v i s c o s i t y , which a p p a r e n t l y wetted and u l t i m a t e l y
coated t h e Tho2 p a r t i c l e s . The A1203 c o a t i n g s (Mohs hardness, 9 ) were
observed t o i n c r e a s e t h e r e s i s t a n c e of t h e Tho2 (Mohs hardness, 6.5) t o
a b r a s i o n and t o e r o s i o n by h o t water i n autoclave t e s t s .

B) PHYSICAL PROPERTY STUDIES

Thermal Conductivity

S . D. Fulkerson

An apparatus f o r measuring thermal c o n d u c t i v i t y c o e f f i c i e n t s as a

f u n c t i o n of temperature w a s designed, b u i l t , and p u t i n t o o p e r a t i o n . P r i -
m a r i l y t h i s apparatus w a s designed f o r UO;! thermal c o n d u c t i v i t i e s d e t e r -
minations a t temperatures from 200 t o 135OOC. For t h e purpose of evalu-
a t i n g t h e performance of t h e apparatus, i n g o t i r o n samples were used.
Although t h e apparatus w a s not designed f o r metals o r o t h e r e q u a l l y good
t h e r m a l conductors, t h e r e i s a range between 600 and 1000°C where t h e
d a t a c o l l e c t e d f o r i r o n were c o n s i s t e n t and agreed w e l l w i t h t h o s e of o t h e r
investigators.

Information Center f o r Thermal P r o p e r t i e s

M. P. Haydon

The information c e n t e r f o r thermal p r o p e r t i e s of r e f r a c t o r y r e a c t o r

f u e l m a t e r i a l s of p o s s i b l e concern f o r gas-cooled r e a c t o r s comprises more
t h a n 1000 r e f e r e n c e s t o r e p o r t s and a r t i c l e s i n t h e l i t e r a t u r e . These
r e f e r e n c e s a r e arranged as a c a r d f i l e , c h r o n o l o g i c a l l y w i t h i n t h e alpha-
b e t i c a l order of t h e o r i g i n a t i n g i n s t a l l a t i o n s and i n s t i t u t i o n s . Approxi-
mately one-half of t h e r e f e r e n c e s have been a b s t r a c t e d and one-third have

195
 been categorized into 93 subject headings in an attempt to make the ac-
cumulatedmaterialmore useful to design engineers and others who need Q
this information. The preparation of an author file, cross-referenced
to the report numbers, is in progress.

Density Determinations

M. P. Haydon
It is desirable to find a simple, fast, reliable, and accurate method
for obtaining bulk density measurements on small (approx 2 cc) samples of
low-porosity ceramic bodies to an accuracy of +0.5$. The methods presently
used involve the physical measurement of the small hollow cylinders, but
the slight warpage which frequently occurs is difficult to determine ac-
curately. Immersion techniques also introduce errors since accurate weights
on surface-dried samples are unreliable. Several designs of volumeters and
pycnometers have been developed specifically for small pellets of UOz, but
I
none of these have produced the desired degree of precision. A mercury-
vacuum system of potentially high accuracy has been designed and is under
construction.
Bulk density determinations for the small spherical particles of fuel
being considered for dispersion-type fuel element cores in the Fast Breeder
Assistance Program are an important phase of the study of the physical
properties of the various particulate materials available. These properties
are of interest for purposes of specifications in procurement procedures.
Ordinary approaches to bulk density determinations are difficult for
these fuel materials because of the small particle sizes involved. There-
fore, a modified immersion-and-suspended-weighttechnique was examined which
involved the embedding of known weights of granular material in a resin of
known density and, by difference in volumes obtained by suspended weight
measurements, arriving at a bulk volume for the grains and thence a bulk
density.
Preliminary experiments indicated that with improved embedding tech-
niques the resin method holds promise of being a reliably accurate means
of obtaining bulk density values for granulated materials. A continuing
effort in improved embedding methods is under way.

196
 14. CORROSION ENGINEERING

J. H. DeVan

MOLTEN-SAU REACTOR PROGRAM

J. H. DeVan R. C . Schulze
The three-phase test program' to evaluate the corrosion resistance
of Inconel and I N O R - 8 when in contact with fused fluoride mixtures has
been continued. Test results of eight INOR-8 and six Inconelthermal-
convection loops, which circulated fluoride mixtures for one year at maxi-
mum temperatures of 1250 and 1350°F, marked the completion of all phases
of the molten-fluoride corrosion program dealing with thermal-convection
experiments. Also, results were obtained for seven tests (four utilizing
INOR-8 and three utilizing Inconel) operated under phase 3 of the test
program, which incorporates forced flow to simulate flow rates and tem-
perature conditions representative of reactor operation. Three additional
INOR-8 tests were started under the phase 3 program. Metallographic and
chemical examinations were also carried out to determine the nature of
corrosion films which formed on long-term INOR-8 loops.

Inconel Thermal-Convection Loops

Metallographic results obtained on the six Inconel forced-convection

loops, which operated for one year, are smarized in Table 14.1. In gen-
eral, as shown in Table 14.1, the attack incurred in all six l o o p s w a s
in the form of intergranular and general subsurface void formation. In
loops which operated at 1250°F, the attack in hot-leg regions ranged from
depths of 4 to 7 mils. In the loops operated at 1350°F, the attack ranged
from depths of 7-1/2 to 15 mils. Attack in the form of surface roughening
and pitting to a maximum depth of l m i l w a s found in the cold-leg regions
of the loops. No evidence of mass transfer deposits was found in the cold-
leg regions.

'Met. Ann. Prog. Rep. Oct. 10, 1958, ORNL-2632, p 89-92 (classified).
2MSR Quar. Prog. Rep. Jan. 3 1 and Apr. 30, 1960, ORNL2973 (in press).

197
 Table 14.1. Results o f Metallographic Examination of Inconel Thermal-Convection Loops

Maximum
Test Fluid-Metal Salt Metallographic Examination

No. Period
(hr) Interface
Temperature No.* Hot -Leg Appearance Cold-Leg Appearance

1236 8760 1250 134 Light s u r f a c e roughening and p i t - Light s u r f a c e roughen-

t i n g t o 1 m i l . Moderate i n t e r - i n g and p i t t i n g t o
granular voids t o max depth of 1 mil
5 mils
1237 8760 1350 134 Light s u r f a c e roughening and p i t - Light surface roughen-
t i n g t o 1 m i l . Heavy i n t e r - ing
granular voids t o m a x depth of
12 m i l s
1245 $760 1250 135 Moderate surface roughening and Light s u r f a c e p i t s
p i t t i n g t o 1 m i l . Moderate i n -
t e r g r a n u l a r voids t o max depth
of 6 m i l s
1247 8760 1350 135 Moderate s u r f a c e roughening, heavy Iiight s u r f a c e roughen-
g e n e r a l voids t o max depth of ing and p i t t i n g t o
15 m i l s 1-12m i l
1235 '7789 1250 133 Light surface roughening and p i t - A few p i t s t o 1m i l
t i n g t o l m i l . A few i n t e r g r a n -
u l a r voids t o rnax depth of 4
m i Is
1239 8760 1350 133 Moderate s u r f a c e roughening. Mod- Moderate s u r f a c e
e r a t e i n t e r g r a n u l a r voids t o max roughening and p i t -
depth of '7-1/2m i l s t i n g t o 1m i l

*Compositions : 133, LiF-BeF2-ThF4 ('71-16-13 mole $); 134, LW-BeF2-ThF4-UF4 (62-36.5-1-0.5 mole
$); 135, NaF-BeF:-Th.F4-W4 (53-45.5-1-0.5 mole $).

e
cp

ea INOR-8 Thermal-Convection Loops2'

As seen in Table 14.2, attack in all but three INOR-8 thermal-con-

vection-loop experiments which operated for one year was limited to sur-
face roughening and pitting to a maximum depth of 1/2 mil. Figure 14.1
is representative of the attack found in these loops. Three loops, 1216,
1226, and 1244, exhibited attack in the form of shallow subsurface voids.
The maximum depth of attack in loop 1216 was 1-1/2 mils, whereas in 1226
and 1244 the maximum depth of attack was limited to 1/2 mil. No attack,
except for light roughening of the surfaces, was found in the cold legs
B) of the loops. Also, examination of the cold regions revealed no deposits
or other evidenee of mass transfer.
An extremely thin corrosion film was found on the surfaces of several
B) of these loops. As previously disc~ssed,~
this film has occurred in a
majority of the thermal-convectiontests which have exceeded 3000-hr op-
eration. Attempts are being made to identify this film, and a discussion
of the results obtained is included in a subsequent section of this report.

Forced Convection L00ps~-~

Chemical and metallographic examinations have been completed on three

Inconel and three INOR-8 forced-convection loops, all of which operated
for one year or longer. Also, two hot-leg specimens in the form of care-
fully weighed inserts were examined after being removed from I N O R - 8 forced-
convection loop 9354-4 following 10,000 and 15,000 hr of operation. Oper-
ating conditions and metallographic results for the six loops are shown
in Table 14.3.
Inconel loop 9344-2, which circulated the coolant salt NaF-LiF-KF'
(11.5-46.5-42.0 mole $ ) for 8735 hr at a maximum temperature of 1200°F,

3Met. Ann. Prog. Rep. Sept. 1, 1959, ORNL-2839, p 15G53,

'!+MSRQuar. Prog. Rep. Oct. 31, 1959, ORNL-2890, p 41-42.
5R. C. Schulze and J. H. DeVan, Examination of Inconel Forced Con-
vection Loops 9377-1, 9377-2, 9377-3, and 9377-4, ORNL CF-60-4-54 (Apr .
6, 1960).
'J. H. DeVan and R. C. Schulze, Examination of First INOR-8 Insert,
ORNL CF-59-6-53 (June 5, 1959).

199
 Table 14.2. R e s u l t s of Metallographic Examination of INOR-8 Thermal-Convection Loops

Maximum
T e st Fl u i d- Met a 1 Metallographic Examination
Salt
Period Interface No.++
No. (hr) Temperature Hot-Leg Appearance Cold-Leg Appearance
(OF)

1226 8760 1250 131 Moderate s u r f a c e roughening, i r - Light s u r f a c e roughen-

regular corrosion film varying ing, w i t h 1/2 m i l
I
from 1 / 2 t o 1 m i l t h i c k . There corrosion film
a r e s c a t t e r e d voids within t h i s
zone
1231 8760 1250 134 Light s u r f a c e roughening and p i t - No a t t a c k
t i n g t o 1/2 m i l , c o r r o s i o n f i l m
t o 1/2 m i l
1238 8760 1350 134 Light s u r f a c e roughening No a t t a c k , v e r y s h a l -
low c o r r o s i o n f i l m
present
1244 8760 1250 135 Light s u r f a c e roughening, moderate No a t t a c k
v o i d s and p i t s t o 1 m i l
1246 8760 1350 135 Light s u r f a c e roughening No a t t a c k
1233 8760 1250 133 No a t t a c k , v e r y shallow c o r r o s i o n No a t t a c k
film present
1240 8760 1350 133 Light s u r f a c e roughening No a t t a c k
1216 8760 1350 127 Moderat e s u r f a c e roughening and No a t t a c k
I p i t t i n g t o 1/2 m i l , l i g h t s c a t -
t e r e d intergranular voids t o
2 mils

*Compositions : 12’7, LiF-BeF2-ThF4 (58-35-7 mole $); 133, LiF-BeF2-ThFq (71-16-13 mole $); 134,
LiF-BeF2-ThF4-UF4 (62-36.5-1-0.5 mole $); 135, NaF-BeF2-ThF4-w~ (53-45.5-1-0.5 mole $1

0 e
 F i g . 14.1. Specimen Taken from Hot L e g of INOR-8 Thermal-Convection Loop 1231 at Point
of Maximum Loop Temperature (125OOF). Loop was operated for one year with salt mixture
L i F-B e F 2-Th F ,-U F, (62-36.5- 1 -0.5 mole %). Etchant: 3 parts HCI, 2 parts H20, 1 part 10%
chromic acid. 250X.

w a s a t t a c k e d a l o n g b o t h h e a t e r - l e g s e c t i o n s t o a m a x i m u m depth of 8 mils.
I n c o n t r a s t , I n c o n e l loops 9377-3 and 9377-4, which c i r c u l a t e d f u e l s a l t s
of t h e system LiF-BeFz-UF4 (60-36-4 and 62-37-1 mole $, r e s p e c t i v e l y )
showed s u b s t a n t i a l l y h i g h e r r a t e s of a t t a c k f o l l o w i n g o p e r a t i o n f o r 8,746
and 10,205 h r , r e s p e c t i v e l y , a t a m a x i m u m t e m p e r a t u r e of 1300'F. Loop
9377-3 w a s a t t a c k e d a l o n g b o t h h e a t e r l e g s t o a m a x i m u m depth of 14 mils;
t h e m a x i m u m a t t a c k i n loop 9377-4 w a s found t o b e 15 m i l s . The c o l d - l e g
s e c t i o n s of a l l t h r e e loops r e v e a l e d l i g h t a t t a c k i n t h e form of s u r f a c e
roughening and p i t t i n g t o a m a x i m u m depth of l e s s t h a n l m i l .No evidence
of m a s s t r a n s f e r d e p o s i t s was found i n any of t h e loops examined.
INOR-8 forced-convection loops MSRP-8 and MSRP-9, which c i r c u l a t e d
f l u o r i d e mixtures f o r 9633 and 9687 h r , r e s p e c t i v e l y , appeared u n a t t a c k e d
except f o r t h e development of a t h i n s u r f a c e l a y e r . The e x t e n t of t h i s
l a y e r can be s e e n i n F i g . 14.2, which shows t h e m e t a l l o g r a p h i c appearance
of t h e h o t - l e g s e c t i o n of loop E R P - 8 . R e s u l t s of chemical a n a l y s e s of
t h e s e l a y e r s a r e d i s c u s s e d i n t h e next s e c t i o n .

20 1
 Table 14.3. Operating Conditions and Results of MSRP Forced-Convection Tests

Salt-Metal Time Flow

Interface Operated Reynolds
No. Rate Metallographic Results
No. No '* Temperature (OF ) (hr) (am
(OF)

Inconel
9344-2 12 1200 100 8,735 8200 2.5 Moderate intergranular voids
ranging from 2-3 mils in
first heater leg, 4-8 mils
in the second
9377-3 131 1300 200 8,746 3400 2 Moderate intergranular voids
ranging from 2-8 mils in
first heater leg, 6-14 mils
in the second
9377-4 130 1300 200 9,574 2600 1.8 Heavy intergranular voids rang-
ing from 1/2-11 mils in first
heater leg, 7-15 m i l s in the
second

INOR-8
9354-1 126 1300 200 14,563 2000 1.8 Heavy surface roughening and
pitting to m a x depth of 1-1/2
mils along both heater legs
9354-4 130 1300 200 15,150 3000 2.5 No attack
MSRP-8 124 1300 200 9,633 4000 2 No attack
MSRP-9 134 1300 200 9,687 2300 1.8 No attack

*Salt compositions: 12, NaF-LiF-KF (11.5-46.5-42mole $); 124, NaF-LiF-ThFh (58-35-7mole $1;
126, UF-BeFz-UF4 (53-46-1mole $); 130, L ~ F - B ~ F ~ - U(62-37-1
FL, mole '$1; 131, LiF-BeF2-UF4 (60-36-4
mole $1; 134, LiF-BeFz-UF4-ThF4 (62-36.5-0.5-1mole 5).

e a
 Fig. 14.2. Appearance of Specimen Removed from Point of Maximum Salt-Metal Interface
Temperature (130OOF) of INOR-8 Forced-Convection Loop MSRP-8. Loop was operated for 9633
hr with a salt mixture NaF-BeF,-ThF, (58-35-7 mole '7%). Etchant: 3 parts HCI, 2 partsH20,
1 part 10% chromic acid.

INOR-8 loop 9354-1, which w a s terminated a f t e r 14,563 h r because of

a l e a k i n t h e second h e a t e r leg, showed a considerably h e a v i e r concentra-
t i o n of a t t a c k i n t h e form of g e n e r a l s u r f a c e roughening and p i t t i n g t o
a m a x i m u m depth of 1-1/2 m i l s (Fig. 1 4 . 3 ) . Examination of t h e cold-leg
B) regions a l s o revealed t h e presence o f m e t a l c r y s t a l s which were magnetic
and l o o s e l y adherent t o t h e cold-leg w a l l . Analysis of t h i s deposit, as
shown i n Table 14.4, showed it t o be composed predominantly of n i c k e l
along w i t h minor amounts of i r o n snd chromium.
The abnormally high r a t e of , a t t a c k and m a s s t r a n s p o r t of n i c k e l i n
t h i s loop w a s t r a c e d t o t h e i n t r o d u c t i o n of o x i d i z i n g i m p u r i t i e s during
test. A f t e r - t e s t s a l t analyses i.ndicated a r e l a t i v e l y l a r g e percentage
of UF4 t o have been converted t o 'U02 during t h e t e s t , a p p a r e n t l y as a
r e s u l t of H 2 0 contamination which e n t e r e d t h e loop during one of t h r e e
t u b i n g f a i l u r e s encountered during o p e r a t i o n . Oxidation of n i c k e l as
w e l l as o t h e r c o n s t i t u e n t s of INOR-8 can be e f f e c t e d by HF, which i s a
product of HzO r e a c t i o n with components of t h e s a l t .

203
 B

014 1
F i g . 14.3. Specimen Removed from INOR-8 Forced-Convection Loop 9354-1 at Point of Max-
imum Salt-Metal Interface Temperature ( 13OO0F), Showing Maximum Attack Found. Loop operated
for 14,563 hr with solt mixture L i F - B e F , - U F , (53-46-1 mole %). Etchant: 3 parts HCI, 2 parts
H,O, 1 part 10% chromic acid. 250X.

Table 14.4. Analysis of Deposit from INOR-8 Loop 9354-1*

Composition o f Deposit
Length of Weight of
Specimen Tubing Deposit
(in.) (g)
Ni
(wt k )
Cr
(wt k )
. Fe
( w t $1
Mo
(ppd
a
1 11-118 1.9000 88.2 7.33 0.23 7035
2 42-118 4.4994 94.3 1.22 1.34 6380 0
3 18 4.4134 92.5 1.26 1.37 6215
4 32-7/8 4.0994 92.5 1.95 1.39 7850
5 24- 5 1 8 7.1898 94.3 0.68 0.81 5690

*Deposit contained s m a l l m o u n t s o f s a l t r e s i d u e .

204

(D
 Two hot-leg specimens i n t h e form of c a r e f u l l y weighed i n s e r t s were
removed i n o r d e r t o measure a c c u r a t e l y t h e weight l o s s a f t e r 10,000 and
15,000 h r a t s u r f a c e s operating a t t h e m a x i m u m loop temperature. These
two i n s e r t s were t h e l a s t two of t h r e e i n s e r t s incorporated a t t h e end
of t h e second h e a t e r l e g , t h e f i r s t i n s e r t being removed a f t e r 5000 h r
of o p e r a t i o n .
The second of t h e i n s e r t s , which w a s removed a f t e r 10,000 h r , showed
an average weight l o s s of 2 . 1 (i3$) %/em2 along i t s 4-in. l e n g t h . If
uniform removal of s u r f a c e metal i s assumed, t h i s weight loss corresponds
t o a l o s s i n w a l l t h i c k n e s s of 0.09 m i l .
Examination of t h e t h i r d i n s e r t i n d i c a t e d an average weight l o s s of
1.7 (+6$)%/em2 along a 4-in. l e n g t h . Again assuming uniform removal of
t h e s u r f a c e metal, t h i s weight l o s s corresponds t o a l o s s i n w a l l t h i c k -
ness of 0.08 (+6$)mil.
A s p r e v i o u s l y reported, t h e f i r s t of t h e i n s e r t s , which was removed
a f t e r 5000 h r , showed a weight l o s s of 1.8 ( + 2 $ ) , o r a l o s s i n w a l l t h i c k -
ness of 0.08 m i l . The s i m i l a r i t y of t h e s e values t o t h e values obtained
a f t e r 10,000 and 15,000 h r i n d i c a t e s t h a t no s i g n i f i c a n t weight loss oc-
c u r r e d a f t e r t h e f i r s t 5000 h r of o p e r a t i o n . On a l l t h r e e i n s e r t s , no
d e t e c t a b l e l o s s i n w a l l t h i c k n e s s w a s noted i n comparing measurements of
t h e i n s e r t s taken b e f o r e o r a f t e r t e s t .
A s p r e v i o u s l y reported, metallographic examination of t h e 5,000- and
10,000-hr i n s e r t s revealed no a t t a c k o t h e r t h a n t h e formation of a t h i n
c o r r o s i o n f i l m on t h e s u r f a c e exposed t o t h e s a l t s . However, a band be-
tween l and 2 m i l s t h i c k , which appeared t o be extremely fine-grained,
w a s found on both i n s e r t s .
Metallographic examination of a t r a n s v e r s e s e c t i o n of t h e 15,000-hr
i n s e r t revealed l i g h t s u r f a c e roughening, as shown i n F i g . 14.4. As i n
the case of both t h e 5,000- and 10,000-hr i n s e r t s , t h e f i l m and t h e band
of f i n e - g r a i n e d m a t e r i a l were again found. The c o r r o s i o n f i l m w a s t h e same
t h i c k n e s s as found on t h e 10,000-hr i n s e r t ; however, t h e band of f i n e -
grained m a t e r i a l had i n c r e a s e d i n s i z e compared with t h e 10,000-hr i n s e r t .
The band of fine-grained m a t e r i a l i s a t t r i b u t e d t o r e c r y s t a l l i z a t i o n
of t h e matrix n e a r t h e i n s i d e s u r f a c e s of t h e i n s e r t . This assumption i s
supported by t h e f a c t t h a t g r a i n growth has occurred i n t h i s band during

205
 Fig. 14.4. Transverse Section of 15,000-hr Insert Removed from INOR-8 Forced-Convection
Loop 9354-4. Etchant: 3 parts HCI, 2 parts H,O, 1 part 10% chromic acid. 250X.

t h e 15,000 h r of o p e r a t i o n and t h a t a reaming o p e r a t i o n v a s performed on

t h e i n s e r t s p r i o r t o s e r v i c e which undoubtedly induced some c o l d work
along t h e i n s i d e surfaces.
The s t a t u s of two I n c o n e l and n i n e INOR-8 forced-convection loops
which are p r e s e n t l y i n o p e r a t i o n w i t h v a r i o u s f l u o r i d e mixtures i s swn-
marized i n Table 14.5.
e
A n a l y s i s of Corrosion Film7’

Chemical and m e t a l l u r g i c a l s t u d i e s have been under way t o i n v e s t i g a t e

t h e n a t u r e and cause of t h e t h i n c o r r o s i o n f i l m s observed on t h e s u r f a c e s
of long-term INOR-8 c o r r o s i o n loops, as d i s c u s s e d above. The f i l m appears
as a continuous second phase which extends below t h e exposed s u r f a c e s t o
a t h i c k n e s s of 1 / 2 m i l o r l e s s . No t r a n s i t i o n o r d i f f u s i o n zone h a s been
e v i d e n t between t h e f i l m and t h e b a s e m e t a l ( F i g s . 14.1, 14.2, and 14.4).
I n thermal-convection loops t h i s f i l m has been observed b o t h i n h o t - and

7MSR Quar. Prog. Rep. J u l y 31, 1959, ORNL-2799, p 55.

8MSR Quar. Prog. Rep. J a n . 31 and Apr. 30, 1960, ORNL-2973 ( i n p r e s s ) .
" t 8 Q
c e

Table 14.5. Status of MSRP Forced-Convection Loops

Maximum
Time** Salt-Metal Minimum Flow
Loop No. Salt No.* Operated Interface Fluid Reynolds Rate
Remarks
(hr) Temperature Temperature No. (gpm1
(OF) (OF)

Inconel

9377-5 134 13,096 1300 1100 200 2300 1.8 Operating

9377-6 133 10,579 1300 1100 200 3100 1.8 Operating

INOR- 8

9354-3 84 17,330 1200 1050 150 3000 2 Operating

MSRP-6 134 ,
15 380 1300 1100 200 2300 1.5 Operating
MSRP-7 133 15,457 1300 1100 200 3100 1.8 Operating
MSRP-10 135 14,623 1300 1100 200 3400 2 Operating
MSRP-11 123 14,351 1300 1103 200 3230 2 Operating
MRSP-12 134 13,096 1300 1100 230 3900 2 Operating
MSW-13 136 8,085 1300 1100 200 3900 2 Terminated
(no re-
sults )
MEISP-14 BuLT-14 + 0.5U 5,999 1300 1100 200 Operating
MSRF - 15 Bum-14 + 0.5U 5,236 1400 1200 200 Operating
MSRP-16 Bum-14 + 0.5U 2,081 1500 1300 200 Operating

*Salt compositions : 84, NaF-LiF-BeF2 (27-35-38mole $); 123, NaP-BeF2-UF4 (53-46-1mole $); 133,
LLF-BeFz-UFr, (71-16-13mole $); 134, LiF-BeFz-UF4-ThF4 (62-36.5-0.5-1mole $I); 135, NaF-BeFz-UF4-ThF4
h)
0
v
(53-45.5-0.5-1mole 8 ) ; 136, LiF-BeFz-UFk (70-10-20mole $I); Bum-14 + 0.5U, LiF-BeF2-UF4-ThF4 (67-
18.5-0.5-14 mole $ ) .
+*Operational time up to May 31, 1960.

I
 cold-leg specimens, whereas i n forced-convection t e s t s it has been found n
only along t h e t u b i n g between t h e pump e x i t and end of t h e second h e a t e r
leg.
Comparative hardnesses of t h e f i l m and p a r e n t metal of a specimen
removed from t h e p o i n t of m a x i m u m s a l t - m e t a l i n t e r f a c e temperature o f
INOR-8 forced-convection loop 9354-5 were determined using a Bergman m i -
crohardness t e s t e r with a l - g l o a d . On t h e basis of t h i s load, t h e f i l m
w a s found t o have a diamond pyramid hardness (DPH) of 518, while t h e DPH
f o r the parent metal w a s 269. A check of t h e base metal using t h e Tukon
hardness t e s t e r with a 200-g l o a d i n d i c a t e d a DPH of 218. Thus, t h e num-
b e r s based on t h e Bergman t e s t e r would appear t o be s l i g h t l y high; never-
t h e l e s s , t h e values obtained demonstrate t h a t t h e f i l m i s approximately
twice as hard as t h e p a r e n t metal.
Q u a l i t a t i v e chemical analyses obtained f o r s e v e r a l d i f f e r e n t s p e c i -
mens of t h i s s u r f a c e f i l m are l i s t e d i n Table 14.6. A s can be seen, t h e s e
f i l m s a r e p r i m a r i l y composed o f n i c k e l along with smaller amounts of chro-
m i u m , i r o n , and molybdenum. Analysis o f t h e f i l m from loop 9354-5 showed
it t o have a composil;ion approximately t h e same as t h e p-phase (Ni4Mo) of
t h e Ni-Mo system.

Table 14.6. Spectrographic Analyses Made of Surface Films

Approx Spectrographic Analysis

Specimen
Removed from Location Temperature of Salt (wt %I
Specimen C irculated
Loop No. (OF) Hi Cr Fe MO

1226 C o l d leg 1078 131 62 4.3 29 4.7

9354-5 End of first 1269 130 80 1.5 14.5 4.0
heater leg
9354-5 End of second 1296 130 70.6* 29.4*
heater leg
MSRP - 7 End of second 1300 133 67.9" 32.I*
heater leg

*These analyses assume Ni + Mo = 100%.

 GCR MATERIALS COMPATIBILITY TESTS

J. H . DeVan A. J. Rosenberg

During t h e p a s t y e a r t h e materials c o m p a t i b i l i t y t e s t s i n p r o g r e s s
i n support of t h e Gas-Cooled Reactor Program have been d i r e c t e d toward
problems i n t h e EGCR. T e s t s have been continued i n f o u r t y p e s of t e s t
f a c i l i t i e s i n an e f f o r t t o e s t a b l i s h t h e n a t u r e of t h e EGCR c o r e environ-
ment and i t s e f f e c t on t y p e 304 s t a i n l e s s s t e e l , t h e proposed f u e l e l o -
ment c l a d d i n g m a t e r i a l , and carbon- and low-alloy s t e e l s t o b e used i n
v a r i o u s s t r u c t u r a l a p p l i c a t i o n s . '-17

S t a t i c Pot T e s t s

I s o t h e r m a l s t a t i c p o t t e s t s o p e r a t e d a t 1100 and 1400°F have demon-

s t r a t e d t h e importance of metal-gas r e a c t i o n s i n c o n t r o l l i n g t h e g r a p h i t e -
induced i m p u r i t y b u i l d u p i n heliwn.16 I n o r d e r t o determine t h e e f f e c t s
of b o t h t h e a r e a and temperature s t r u c t u r e of m e t a l surfaces;a s e r i e s of
polythermal s t a t i c p o t t e s t s have been c a r r i e d o u t i n which t h e tempera-
t u r e and s u r f a c e a r e a of m e t a l r e l a t i v e t o t h a t of g r a p h i t e were made t o
c o i n c i d e w i t h EGCR c o n d i t i o n s . 1 7 I n t h e s e t e s t s , t u b u l a r specimens of
type 304 s t a i n l e s s s t e e l , corresponding t o f u e l element cladding, have
been h e l d a t temperatures ranging from 1500 t o 1800°F w h i l e t h e tempera-
t u r e of t h e g r a p h i t e and m e t a l surroundings w a s maintained a t 1100°F. Two
g e n e r a l t e s t arrangements were employed, one having 5 t i m e s more s u r f a c e
a r e a of exposed m e t a l a t 1100°F t h a n t h e o t h e r .
A f t e r a t t a i n i n g t h e same i n i t i a l c o n c e n t r a t i o n s , t h e l e v e l s o f oxy-
gen-bearing i m p u r i t i e s , CO and C02, d e c l i n e d much e a r l i e r and f a s t e r i n

'The ORNL Gas-Cooled Reactor - Materials and Hazards, ORNL-2505, p

1333 (May 22, 1 9 5 8 ) .
"Met. Ann. Prog. Rep. Oct. 10, 1958, ORNL-2632, p 89 ( c l a s s i f i e d )
"GCR Semiann. Prog. Rep. Dee. 31, 1958, ORNL-2676, p 13&46.
1 2 G C R Semiann. Prog. Rep. June 30, 1959, ORNL-2'76'7, p 188-90.
.
13Met. Ann. Prog. Rep. Sept 1, 1959, ORNL-2839, p 15&62.
14GCR Quar. Prog. Rep. S e p t . 30, 1959, ORNL-2835, p 125-32.
15GCR Q u a r . Prog. Rep. Dee. 31, 1959, ORNL-2888, p 141-53.
16GCR Quar. Prog. Rep. Mar. 31, 1960, ORNL-2929, p 187-96.
17GCR Quar. Prog. Rep. June 30, 1960, ORNL-2964 ( i n p r e s s ) .

209
t h e h i g h e r surface-area t e s t s t h a n i n t h e lower. I n c o n t r a s t , no d i f f e r -
ence w a s apparent i n t h e l e v e l s of non-oxygen-bearing i m p u r i t i e s , CH4 and
H2, between t h e two types of t e s t s , and r a t i o s of t h e s e l a t t e r contami-
nants remained s t r o n g l y c a r b u r i z i n g throughout t h e t e s t s . The d i f f e r e n c e s
i n oxidizing impurity concentrations between t h e high- and low-surface-
a r e a t e s t s were manifested i n c h a r a c t e r i s t i c d i f f e r e n c e s i n t h e surfaces
and t h e m i c r o s t r u c t u r e s of t h e type 304 s t a i n l e s s s t e e l heated elements.
The surfaces of t h e tubes exposed i n t h e h i g h e r metal-surface-area tests
were s i l v e r i n c o l o r and were i d e n t i f i e d as Fe3O4 and C r 2 O 3 . The surfaces
of t h e tubes exposed i n t h e lower metal-surface-area t e s t s were dark green
t o b l a c k i n c o l o r and were i d e n t i f i e d as p r i m a r i l y 2Cr203*Fe203. Carbu-
r i z a t i o n of t h e h e a t e d elements w a s d e t e c t e d i n a l l t e s t s , b u t t h e amount
of carbon pickup i n c r e a s e d with i n c r e a s i n g element temperature and was
g r e a t e r f o r specimens exposed i n t e s t s having t h e higher metal-surface
area.
Low-Pressure Thermal-Convection Loops

A s r e p o r t e d e a r l i e r , excessive s c a l i n g of carbon- and low-alloy s t e e l s

w a s experienced i n s e v e r a l loops which have operated with h o t - l e g tempera-
t u r e s of 1100, 1200, and 1400°F.12-17 To f u r t h e r i n v e s t i g a t e t h i s problem,
t h r e e low-pressure thermal-convection loops were operated w i t h continuously
c o n t r o l l e d impurity l e v e l s equivalent t o maximum l e v e l s which had been
s p e c i f i e d f o r t h e EGCR.
Two of t h e s e loops operated with helium containing c o n t r o l l e d l e v e l s
of approx 0.18 v o l $ CO. The helium w a s e s s e n t i a l l y f r e e of a l l o t h e r im-
p u r i t i e s except f o r approx 0.15 v o l $ COz, which w a s p r e s e n t by v i r t u e of
t h e CO-graphite equilibrium. The t h i r d loop w a s operated w i t h helium con-
t a i n i n g H20 c o n t r o l l e d t o a l e v e l of approx 0.12 v o l $. The maximum l e v e l s
of a l l i m p u r i t i e s i n t h e s e t e s t s a r e shown i n Table 14.7.
The e x t e n t of o x i d a t i o n which occurred f o r T-1 s t e e l , Croloy 2-1/4,
Croloy 3M, and Croloy 5 specimens i n t h e s e t e s t s i s i n d i c a t e d i n Table
14.8. Representative r e s u l t s published f o r plain-carbon and low-chromium
s t e e l s t e s t e d i n a i r a t 1100°F a r e also shown i n Table 14.8 f o r comparison
purposes. 18 t 19

1 8 H . H. u h l i g , The Corrosion Handbook, p 644-46, Wiley, New York,

1948.
I g S t e e l s f o r Elevated Temperature Service, p 21-23, United S t a t e s
S t e e l Co., 1949.

210
 Table 14.7. Maximum I m p u r i t y h v e l s Observed i n C o n t r o l l e d
Environment Low-Pressure Thermal-Convection Loops

I m p u r i t y (vol $ )

T e s t No. 10 0.132 0.185 3.0010 0.0012 0.0020 0.0090

T e s t No. 11 0.040 0.060 0.0009 0.010 0.14 0.16
T e s t No. 12 0.15 0.18 0.0005 0.0005 0.002 0.003
EGCR s p e c i - 0.2 0.1 0.1
f i c a t i ons
@

Table 14.8. Data f o r S c a l i n g of Low A l l o y S t e e l s Exposed

a- f o r 1000 h r a t 1100°F

W t of Metal
W t Gain
Alloy Wt Of Film Reacting
(mg/cm2 ) (mg/cm2 1 (mg/cm2)

T e s t No. 10 T-1 s t e e l 3.9 14.1 10.2

T e s t No. 10 Croloy 3 M 2.4 8.6 6.2
T e s t No. 11 T-1 s t e e l 7.4 26 .7 19.3
T e s t No. 11 Croloy 2-114 4*4 15.8 11.4
T e s t No. 12 T-1 s t e e l 2 .o 7.3 5.3
T.est No. 12 Croloy 2-114 1.5 5.5 4.0
T e s t No. 12 Croloy 3 M 1.3 4.9 3.5
T e s t No. 12 Croloy 5 1.6 5 .7 4.1
Oxidized i n Carbon s t e e l 27 98 71
air
Oxidized i n 2.255 Cr-l$ 15 54 39
air Mo s t e e l
Oxidized i n 5% cr-o.576 5 .O 18 13
air Mo s t e e l

&
211

e
 n
High-pressure Thermal-Convection Loops

Thermal-convection loops operating with helium at 325 psig have been

completed with hot-leg temperatures of 1100, 1225, and 1400°F.12-17 Three
loops were operated at 1100°F for periods of 500, 1000, and 5000 hr, re-
spectively, and single-loop experiments of 1000-hi- duration were completed
at 1200 and 1400°F. No changes in react'ion rate or corrosion products were
detected as a consequence of the high pressure of the circulating gas.

Forced-Convection Loop

A small-scale version of the gas-purification system proposed for

the EGCR has been added to the forced-convection-loopassembly. Evalua-
tion of reactor materials in this system is under way in conjunction with
an evaluation of the purification system itself which is being conducted
by the Experimental Engineering Group of the Reactor Projects Division. 16?17

Graphite-Metal Contact Studies

A project has been initiated to determine the effect of temperature,

contact pressure, and environment on the rate of solid state diffusion of
carbon into various iron-base alloys. The design of the test apparatus
has been completed, and assembly of the rig is in progress.

212

(D
 15. FUELS EVALUATION
J. L. S c o t t

THE RELEASE OF FISSION PRODUCTS FROM U02

J. L. S c o t t D. F. Toner R . E. A W s

One of t h e most important f a c t o r s which determine t h e o p e r a t i n g l i f e

of a metal-clad ceramic f u e l element i s t h e r e l e a s e of v o l a t i l e f i s s i o n
products, such as xenon and krypton, out of t h e ceramic f u e l . These vol-
a t i l e f i s s i o n products c r e a t e an i n t e r n a l p r e s s u r e w i t h i n t h e f u e l capsule
which might exceed t h e e x t e r n a l p r e s s u r e and l e a d t o r u p t u r e of t h e f u e l
capsule, i f p r o v i s i o n s a r e not made i n t h e design f o r t h e r e l e a s e . The
release of v o l a t i l e f i s s i o n products i s p a r t i c u l a r l y troublesome i n a gas-
cooled r e a c t o r , such as t h e EGCR, because t h e temperature of t h e cladding
i s high and t h e e x t e r n a l p r e s s u r e i s low compared with a pressurized-water
reactor. Since t h e f u e l f o r t h e EGCR i s U02 c l a d with type 304 s t a i n l e s s
s t e e l , and s i n c e t h e r e i s a marked v a r i a t i o n i n r e p o r t e d values of t h e
r a t e s of r e l e a s e of f i s s i o n products from U02, a study w a s i n i t i a t e d t o
determine t h e mechanisms and r a t e s of r e l e a s e of f i s s i o n products from
u02.
P r i o r work on t h e r e l e a s e of f i s s i o n products from U02 a t B e t t i s l S 2
and Chalk River3 showed t h a t t h e r e l e a s e of f i s s i o n products occurs p r i -
m a r i l y by a d i f f u s i o n mechanism above 1000°C, and t h a t t h e r a t e of r e -
l e a s e i s markedly a f f e c t e d by p r o p e r t i e s of t h e U 0 2 , such as d e n s i t y ,
O/U r a t i o , r a t i o of open t o c l o s e d p o r o s i t y , and t o t a l s u r f a c e a r e a .
A
model w a s proposed by Lustman' t o account f o r t h e experimental observa-
tions. According t o t h i s model a p r e s s e d and s i n t e r e d p e l l e t i s equiva-
l e n t t o spheres of t h e o r e t i c a l d e n s i t y w i t h t h e same s u r f a c e a r e a p e r u n i t
weight. Thus t h e r a d i u s , a, of t h e sphere equivalent t o a p e l l e t w i t h a
-

'B. Lustman, Release of F i s s i o n Gases from UO2, WAPD-173 (March 1957).

2J. D. Eichenberg - a l . , E f f e c t s of I r r a d i a t i o n on Bulk U02, WAPD-183
et -
(October 1957).
'A. H. Booth and G. T . Rvmer. -" Determination
I -
-~~ . _~- of t h e Diffusion Constant
of F i s s i o n Xenon i n U02 C r y s t a l s and S i n t e r e d Compacts, CRDC-720 (August
1958).

213
s u r f a c e a r e a per u n i t weight, S, is

a = -3
SPO '
where po i s t h e t h e o r e t i c a l d e n s i t y of t h e U02. From t h i s model t h e f r a c -
t i o n of a p a r t i c u l a r element r e l e a s e d , f , i n time, t , f o r a sample irradi-
a t e d i n - p i l e a t low temperatures and then given a high-temperature out-of-
p i l e h e a t treatment i s given by t h e equation

I n t h i s expression t h e q u a n t i t y , D, i s t h e d i f f u s i o n c o e f f i c i e n t f o r t h e
p a r t i c u l a r element i n U02. For values of f l e s s than 0.1, Eq. ( 2 ) may be
approximated by t h e expression

The r e l e a s e r a t e parameter, D', i s o f t e n used t o describe a p a r t i c u l a r

b a t c h of U02 i n t h e absence of a p r e c i s e knowledge of t h e values of t h e
d i f f u s i o n c o e f f i c i e n t , D, and t h e equivalent r a d i u s , a. Solutions t o t h e
d i f f u s i o n equation f o r o t h e r boundary conditions and methods o f using val-
ues of D' i n t h e design of a f u e l element have r e c e n t l y been summarized
elsewhere. 4
The method adopted f o r t h e study of t h e r a t e s of r e l e a s e of f i s s i o n
products from U02 w a s t h e neutron a c t i v a t i o n , out-of-pile anneal tech-
nique. The procedure c o n s i s t s of an i r r a d i a t i o n t o 4 X nvt of 100-
500 mg samples of U02 i n t h e ORR a t t h e pool water temperature. This ir-
r a d i a t i o n i s followed by a heat treatment i n t h e apparatus shown i n Fig.
15.1. I n t h i s apparatus samples a r e h e l d for varying l e n g t h s of time a t
temperatures up t o 200o0C, and t h e Xe133 o r Kr8* r e l e a s e d from t h e f u e l
i s c o l l e c t e d i n one of a s e r i e s of charcoal t r a p s . The amount of gas i n
a given bulb i s determined q u a n t i t a t i v e l y by means of g m a spectrometry.
From t h e s e d a t a and a knowledge of t h e number of f i s s i o n s which had oc-
c u r r e d i n t h e sample, t h e f r a c t i o n of t h e f i s s i o n gas r e l e a s e d i n a given

'W. B . C o t t r e l l e t al., The Release of Fission Products from UOz,

ORML-2935 ( t o be issua).-

214

e
 UNCLASSIFIED
ORNL-LR-DWG 47680

f BALL AND SOCKET ,+GROUND G L A S S JOINT @ VALVE

OPTICAL
PYROMETER ION GAGE\

r/ 4fl ,/
Ll QU I D - N ITROG E N
COLD T R A P

TO EXHAUST
4
i,7 - 11
To B U C K E T

i
COIL
5
nlCr

3 To RADIATION

LAVITE BASE H E AT ED \LIQUID-NITROGEN

CHARCOAL T R A P CHARCOAL BULBS

LIQUID-NITROGEN)
CHARCOAL T R A P '

Fig. 15.1. Fi ssion-Gas Collection Apparatus (Revision).

time i n t e r v a l a t a given temperature i s determined. Burnups a r e d e t e r -

mined by means of a c o b a l t f l u x monitor and have been confirmed on a num-
b e r of samples by an a n a l y s i s of t h e Cs137 and Z r g 5 c o n t e n t s .
Since a knowledge of t h e r a t e s of r e l e a s e of f i s s i o n gases from U02
p e l l e t s t y p i f y i n g those t o be used i n t h e f u e l elements f o r t h e EGCR w a s
t h e most p r e s s i n g concern, s t u d i e s completed t o d a t e have been concerned
with these p e l l e t s . Samples f o r study were taken from p i l o t runs of pel-
l e t s produced by a number of vendors ( s e e Tsble 1 5 . 1 ) and span t h e range
Q of s p e c i f i c a t i o n s f o r UOz p e l l e t s t o be used i n t h e EGCR.
A compilation of t h e r e s u l t s obtained t o d a t e i s shown i n Table 15.1.
The f i r s t samples of U02 s t u d i e d , designated 2-1 and GE-H-4,had decayed
f o r long periods and it w a s necessary t o count t h e K r B 5 . Since t h e count-
i n g of K r 8 5 i s not e f f i c i e n t and t h e rates of r e l e a s e from t h e s e samples
were low, t h e counting e r r o r s were high and t h e amounts of gas c o l l e c t e d
i n i n d i v i d u a l t e s t s were b a r e l y above t h e l i m i t s of d e t e c t i o n . I n order
t o e l i m i n a t e counting e r r o r s , t e s t s on subsequent samples were conducted
s h o r t l y a f t e r i r r a d i a t i o n (1-4 weeks) and t h e Xe133 i s o t o p e w a s counted.

215
 Table 15.1. Results of Fission-Gas-Release Rate Measurements on UOp Pellets

Release Rate
Extrapolated
No. Designation ., . Parameter (D' Temperature
neieasea to Zero Time ("C)

2 2-1 ORNL 94.8 11.2 4.5 2.1 x 6.0 x 1400

3 2-1 ORNL 94.8 11.2 16 7.1 x 0 7.8 x 10-'3 1400
4 2-1 ORNL 94.8 11.2 3 5.0 x 2.0 x 10-l2 1600
5 GE-H-4 GE-VAL 93.6 8.11 3 2.7 x 10-4 8.4 10-13 1600
6 GE-H-4 GE- VAL 93.6 8.11 3 3.4 x 9 . 7 x 1.0-l~ 1700
7 GE- E-4 GE-VAL 93.6 8.11 3 2.5 x lo-'* 5.0 x 10-l3 1700
8 1173 ORNL 95.5 89.3 2 2.0 x 10-2 5 .o x 10-9 1600
9 1173 ORNL 95.5 89.3 3 1.39 x lo-' 1.56 10-9 1400
10 1173 ORNL 95.5 89.3 16 2.43 x lo-' 1.95 x lou2 7.68 x l
o
-
'' 1400
11 1173 ORNL 95.5 89.3 3 8.6 x 5.97 x 10-10 1200
12 1173 ORNL 95.5 89.3 3 1.28 x 1.32 x 10-l~ 1000
17 34-30 NUMEC 94.4 28.6 6 1.63 x 1.03 x 2.51 x 10-l3 1400
18 34-30 NUMEC 94.4 28.6 6 1.22 x 7.1 x 7.75 x 10-l~ 1600
19 34-30 NLiMEC 94.4 28.6 6 9.2 K 7.0 x 6.66 x 1300
20 34-30 NUMEC 94.4 28.6 6 9 . 4 x 10-2 1.10 x 10-7 1800
21 GE-6 GE-VAL 95.5 7.7 6 4.6 x 4.0 x 3.28 x 1400
23 51- 5 B & W 91.5 18.9 1.5 1.24 x 6.0 x 6.98 x 1400
24 51- 5 B&W 91.5 18.9 6 6 . 5 X lo-' 4.95 x 10-8 1800
25 25-8 Mallinc k r o d t 94 2.94 6 3.1 1.92 x 4.72 10-l~ 1400
26 25-8 Mallinckrodt 94 2.94 6 6.7 x 1.39 x 10-9 1800
27 50-6 B&W 92 58 .O 6 5.6 X 2.2 x 2.82 x 1O-l' 1400
28 50-6 B&W 92 58 .o 6 1.47 X 10-1 1 . 5 x 10-7 1800
29 33-5 Davison 93.5 34.2 9 3.2 X 10-l 6.66 x
1 hr at -
1400
2000°C
31 GE- 5 GE-VAL 93.8 12.7 9 1.23 X lo-' 9 .o x 5.92 x 1400
32 GE- 5 GE-VAL 93.8 12.7 9 2.92 X 1.48 x 10-9 1600
33 GE-5 GE-VAL 93.8 12.7 9 9.93 x 10-2 8.23 x 1800
34 33-9 Davison 93.5 12.5 18 6.67 X 5.84 x lo-' 1.99 x 10-l' 1600
35 25-8 Mallinc krodt 94 2.94 9 5.15 x 10-4 1.60 x 2.23 x 10-l~ 1400
The t o t a l a c t i v i t i e s of gas samples c o l l e c t e d i n t h e l a t t e r t e s t s were
s e v e r a l o r d e r s of magnitude g r e a t e r t h a n i n e a r l y t e s t s , and more confi-
dence i s placed i n t h e r e s u l t s .
According t o t h e Lustman model, a p l o t of t h e f r a c t i o n r e l e a s e d , f ,
vs t h e square r o o t of time should y i e l d a s t r a i g h t l i n e passing through
the origin. I n most of t h e samples s t u d i e d t o date, however, a charac-
t e r i s t i c b u r s t of f i s s i o n gas i s observed a f t e r which t h e r e l e a s e i s l i n -
e a r with t h e square r o o t of time. This e f f e c t i s shown i n Fig. 15.2 f o r
U02 p e l l e t NUMEC 34-30 a t 1300, 1400, and 1600°C. It w a s observed f o r
NlJMEC 34-30 t h a t t h e amount of Xe133 r e l e a s e d i n t h e i n i t i a l b u r s t w a s
independent of temperature and t h a t t h e d i f f u s i o n - c o n t r o l l e d process w a s
predominant a f t e r 90 min. Since t h e r e l e a s e r a t e parameter, D ' , i s only
c h a r a c t e r i s t i c of t h e d i f f u s i o n process, t h e D' values i n Table 1 5 . 1 were
computed from t h e l i n e a r p o r t i o n s of t h e curves of f vs t1/2. I n runs
4-9 and 11 and 1 2 only one gas sample was taken. Thus, t h e D' values
f o r t h e s e runs are b e l i e v e d t o be higher than t h e t r u e v a l u e s .
It may be observed i n Fig. 15.2 t h a t t h e s l o p e of t h e curve f v s
t1/2 i n c r e a s e s as temperature i s i n c r e a s e d i n accordance with t h e d i f f u -
s i o n model over t h e temperature range 1300-1600°C. When a saqple from
t h e same p e l l e t w a s t e s t e d a t 18OO"C, however, an abrupt i n c r e a s e i n t h e
r a t e of r e l e a s e w a s observed. This e f f e c t i s shown i n Fig. 15.3. Not
only i s t h e amount r e l e a s e d i n 6 h r much higher t h a n one would p r e d i c t
from lower temperature data, b u t a l s o t h e shape of t h e curve of f vs t1/2
i s a l t e r e d considerably. These observations i n d i c a t e t h a t t h e mechanism
of f i s s i o n - g a s r e l e a s e i s a l t e r e d when t h e p e l l e t temperature exceeds t h e
normal s i n t e r i n g temperature of 1700°C.
Since U02 i s known t o have a high vapor p r e s s u r e above 2000"C,5 it
w a s p o s t u l a t e d t h a t t h e release w a s o c c u r r i n g as a r e s u l t of v a p o r i z a t i o n
of t h e U02 i n t h e vacuum. A s a check of t h i s mechanism a s e r i e s of m e a s -
urements were made of t h e weight l o s s of a sample of U02 as a f u n c t i o n of
time a t 1800°C. R e s u l t s showed t h a t t h e w e i g h t l o s s w a s l i n e a r with time
and t o t a l e d 2% i n 9 h r . Since t h e t o t a l r e l e a s e i n 6 h r w a s 9.1$, vapor-
i z a t i o n w a s , r u l e d out as a c o n t r o l l i n g mechanism of r e l e a s e .

5R. J. Ackermann, P. W. G i l l e s , and R . J. Thorn, -

J. -Chem.
- - Phys. -
25(6)
1089-1097 (December 1 9 5 6 ) .

217
 0.20

0.46

s-" 0.12
..
m
W
a
W
J
W
LL
c) 0.08
n
X

0.04

0
0 1 2 3 4 5 6 (xm)
SQUARE ROOT OF TIME (rnin'z I
SQUARE ROOT OF TIME ( rnin'"

Fig. 15.2. Release of X e ' 3 3 from Pellet NUMEC

34-30 a s a Function of Time at 1800, 1600, 1400, Fig. 15.3. Release of X e ' 3 3 from Pellet NUMEC
and 13OOOC. 34-30 as a Function of Time at 1600 and 1800°C.

A second explanation f o r t h e marked increase i n t h e r a t e of r e l e a s e

a t 1800°C i s t h a t g r a i n boundaries a c t as s h o r t - c i r c u i t d i f f u s i o n paths
f o r f i s s i o n gases. If t h i s i s t r u e , then as t h e g r a i n growth occurs all
of t h e gas i n t h e swept-out volume may be released. To check t h i s hy-
pothesis, u n i r r a d i a t e d samples of UO2 from batch NUMEC 34-30 were s i n t e r e d
a t 1800°C f o r varying lengths of time and t h e g r a i n s i z e s were measured.
Results showed t h a t t h e g r a i n s i z e increased from 32 t o 41 p i n 6 hr a t
1800OC .
The r e l a t i o n between t h e a f f e c t e d volume f r a c t i o n , Va, and t h e g r a i n
diameter, D, i s given by t h e expression

3
V a = l - ( % ) ,
where Do i s t h e i n i t i a l g r a i n diameter. Using t h e measured g r a i n s i z e s ,
t h e a f f e c t e d volume f r a c t i o n i s computed t o be 0.52. Since t h i s f r a c t i o n
i s much higher than t h e observed f r a c t i o n released, t h e r a t e of r e l e a s e
of Xe133 a t 1800°C cannot be explained on t h e basis of t h e assumption of
complete r e l e a s e from t h e swept-out volume.

218

a
 I n order t o determine i f t h e b u r s t of r e l e a s e occurred each time t h e
sample temperature w a s a l t e r e d , a sample o f U02 w a s h e a t t r e a t e d a t 1400°C
and subsequently heat t r e a t e d a t 1600°C. The f r a c t i o n of f i s s i o n gas r e -
l e a s e d f r o m t h i s sample as a f u n c t i o n o f t h e square r o o t of time i s shown
i n Fig. 15.4. It w a s observed t h a t t h e r a t e o f r e l e a s e i n c r e a s e d with in-
c r e a s i n g temperature, b u t no b u r s t of f i s s i o n gas w a s observed when t h e
temperature w a s r a i s e d from 1400 t o 1600°C. The b u r s t may be a result of
s u r f a c e o x i d a t i o n of t h e U02, high r e l e a s e r a t e s from sharp corners of t h e
p e l l e t , or r a p i d r e l e a s e from g r a i n boundaries.
A summary of D' values obtained t o date from runs i n which t h e f r a c -
t i o n r e l e a s e d w a s measured as a f u n c t i o n of time i s shown i n Fig. 15.5.
It may be observed t h a t t h e r e a r e b e t t e r t h a n t h r e e orders of magnitude of
s c a t t e r i n D' values f o r d i f f e r e n t batches of approximately 95% dense U02.
This s c a t t e r i s not reduced when "true" d i f f u s i o n c o e f f i c i e n t s .are com-
puted using equivalent sphere radii determined from BET s u r f a c e a r e a s .
There i s a l s o a d i f f e r e n c e i n a c t i v a t i o n energy between sample GE-5 and

oRr
O L
I

02

-
,\"
I
T
w
cn
a
Y o 2
w
LL
m
'0
X

01

0
4 6 8 fO(X'
SQUARE ROOT OF TIME (rnin(/z)

Fig. 15.4. Release of X e 1 3 3 from P e l l e t GE-5

as a Function o f Time at 1400 and 1600T.
c
219
 UN

‘ I
x 33-9

0 GE-H-4
04473
34-30
A GE-6
A 54-5
4 25-8
50-6
+ GE-5

5 6
‘ I T l’K1

F i g . 15.5. Relationship Between D ’ and the

Reciprocal of the Absolute Temperature.

NUMEC 34-30. The value of t h e a c t i v a t i o n energy f o r t h e former m a t e r i a l i s

100 kcal/mole whereas t h e value f o r t h e l a t t e r m a t e r i a l i s 47 kcal/mole. 0
Recent r e s u l t s from Chalk River‘ i n d i c a t e t h a t t h e a c t i v a t i o n energy i s
approximately 70 kcal. F u r t h e r work will be done t o c l a r i f y t h e mecha-
nisms and a c t i v a t i o n energy f o r t h e r e l e a s e of Xe133 from U02.

‘5. A. L. Robertson, personal communication t o J. L. S c o t t , May 2 5 ,

1960.
 - .

16. MATERIALS COMPATIBILITY

E. E . Hoffman

COMPATIBILITY OF GRAPHITE, FUSED SALTS, AND STRUCTURAL MATERIALS

W . H . Cook D . H. Jansen E . E . Hoffman

An u n c l a d g r a p h i t e moderator would b e a d e f i n i t e advantage i n t h e

I
Molten-Salt Power R e a c t o r . T h i s would r e q u i r e t h a t p o r t i o n s of t h e s t r u c -
t u r a l a l l o y s of t h e r e a c t o r b e exposed t o t h e molten s a l t i n c o n t a c t w i t h
t h e g r a p h i t e a t t h e r e a c t o r o p e r a t i n g t e m p e r a t u r e of approx 1200°F ( 6 4 9 " C ) . l
The c o m p a t i b i l i t y and p e r m e a b i l i t y of t h e u n c l a d g r a p h i t e w i t h t h e molten
s a l t p l u s t h e e f f e c t s of c a r b u r i z a t i o n , i f any, on t h e s t r u c t u r a l a l l o y s
a t t h e o p e r a t i n g c o n d i t i o n s must b e known b e f o r e t h e s e components can be
i n c o r p o r a t e d i n t o t h e d e s i g n of t h e r e a c t o r .
A t t h e b e g i n n i n g of t h e i n v e s t i g a t i o n of t h e p r e c e d i n g q u e s t i o n s ,
I n c o n e l and INOR-8 were c o n s i d e r e d p o t e n t i a l s t r u c t u r a l a l l o y s and LiF-
BeFZ-UF4 (62-37-1 mole $, f u e l 130) w a s t h e f u e l g e n e r a l l y c o n s i d e r e d f o r
use i n t h e Molten-Salt R e a c t o r . A t e s t t e m p e r a t u r e of 1300°F (7'04°C) w a s
chosen f o r most work t o p r o v i d e a s m a l l margin of s a f e t y and y e t be w i t h i n
t h e range of t h e o p e r a t i n g t e m p e r a t u r e proposed f o r t h e r e a c t o r .

Permeation of Various Grades of G r a p h i t e by Molten F l u o r i d e s

W . H . Cook

Screening Tests

It w a s s p e c i f i e d t h a t no more than 0.5$ of t h e b u l k volume of t h e

g r a p h i t e i n t h e r e a c t o r be f i l l e d w i t h f l u o r i d e s . Therefore, various grades
of g r a p h i t e were e v a c u a t e d and t h e n exposed f o r 100 h r t o L ~ F - B ~ F ~ - T ~ Y ~ - U F L ,
(67-18.5-14-0.5 mole $, BULT 14-.5U) a t 1300°F (704°C) under a p r e s s u r e of
150 p s i g t o s c r e e n them f o r t h e above s p e c i f i c a t i o n . This p r e s s u r e w a s a t
l e a s t twice t h a t expected i n t h e r e a c t o r .

'H. G . MacPherson e t a l . , ORNL CF-57-4-27 ( A p r i l 29, 1957) ( c l a s s i -

--
fied).

22 1
 Thirty-one grades of graphite have been tested under the conditions
described above. Twenty-four of them were manufactured as low-permea-
bility grades of graphite; and of these, four grades, B-1, S-4-L;B, GT-123-82,
and CS-112-S, met the permeation specification under the screening test con-
ditions. The apparent densities and permeation values for these and six of
the next best grades are listed in Table 16.1.

2MSR Quar. Prog. Rep. Jan. 31 and Apr. 30, 1960, ORNL-2973 (in press).

Table 16.1. Permeation of Various Grades of Graphite by

LiF-BeF2-ThF4-UF4 (67-18.5-14-0.5 Mole $, BULT 14-.5U)
Test Conditions : Temperature, 1300°F (704°C)
Pressure, 150 psig
Exposure Period, 100 hr

Apparent Density Bulk Volume of

Graphite Graphite Permeated
of Graphite
Grade with BULT 14-.5U
(g/cc )* (P )*
B-1 1.91 0.02

s-4-L;B 1.90(4) 0.2 (4)

GT-123-82 1.91(6) 0.3(6)

cs-112-s 1.89(4) 0.5 ( 4 )

RH-1 1.89(6) 0.6 a

CEY-1350 1.90 0.7
CEY-G 1.88 0.9

s-4-LA 1.89 (4) 1.0(4)

RIM-24 1.91(6) 1.0(6)

*All values are averages of three with the exception of those with
superscripts of numbers in parentheses; the numbers in parentheses are
the number of values averaged.
NOTE: The original shapes of some of the graphite grades and all of the
test specimens are given in MSR Quar. Prog. Rep. Jan. 31 and Apr. 30,
-
1960, ORNL-2973 (in press).

222

BD
E f f e c t of Time

F l u o r i d e permeation of g r a p h i t e as a f u n c t i o n of time h a s been i n i -

t i a t e d w i t h AGOT, S-4, and R - 4 g r a d e s of g r a p h i t e . A p a r t i a l l y completed
s e r i e s of t e s t s i n d i c a t e s t h a t a 1 - h r exposure of t h e s e g r a d e s of g r a p h i t e
t o BULT 14-.5U a t 1300°F (704°C) under a p r e s s u r e of 150 p s i g produced t h e
same d e g r e e of permeation as d i d 100-hr exposures under l i k e c o n d i t i o n s .

E f f e c t of P r e s s u r e

T e s t s were conducted t o determine t h e p e r m e a b i l i t i e s of t h e d i f f e r e n t

g r a d e s of g r a p h i t e t o molten f l u o r i d e s a t lower p r e s s u r e s t h a n 150 p s i g ,
t h e screening t e s t pressure. These d a t a would a s s i s t i n e v a l u a t i n g t h e
advantage, i f any, of d e s i g n i n g a r e a c t o r t o o p e r a t e a t lower f l u o r i d e -
salt pressures.
Twenty of t h e t h i r t y - o n e g r a d e s of g r a p h i t e t h a t a r e b e i n g i n v e s t i -
g a t e d were exposed s i m u l t a n e o u s l y f o r 100 h r t o BULT 14-.5U a t 1300°F
(704°C) and 95 p s i g . 2 The same specimens were t h e n permeated a second
time under t h e same c o n d i t i o n s except t h e p r e s s u r e w a s 150 ~ s i g .The
~
r e s u l t s of t h e s e t e s t s a r e compared i n Table 16.2. These e x p l o r a t o r y
t e s t s s u g g e s t t h a t i f t h e r e a c t o r p r e s s u r e were 95 p s i g , f o u r a d d i t i o n a l
g r a d e s , CT-150, CEY-1350, CT-158, and CEY-G, might b e brought w i t h i n t h e
MSRP s p e c i f i c a t i o n . It w a s also i n d i c a t e d t h a t t h e s t r u c t u r e of t h e graph-
i t e may be t h e p r i n c i p a l f a c t o r d e t e r m i n i n g t h e s e n s i t i v i t y of f l u o r i d e
permeation t o p r e s s u r e . Only t h e s m a l l - g r a i n e d and s m a l l shapes of graph-
i t e showed a permeation t h a t was s e n s i t i v e t o p r e s s u r e .
Grades AGOT and S - 4 g r a p h i t e specimens have been permeated w i t h BULT
14-.5U a t 1300°F (704°C) a t p r e s s u r e s of 25, 6 5 , and 150 p s i g i n 100-hr
exposure p e r i o d s . The purposes v e r e (1)t o f u r t h e r i n v e s t i g a t e t h e re-
d u c t i o n of m o l t e n - s a l t permeation w i t h lower p r e s s u r e s and ( 2 ) t o r o u g h l y
c o r r e l a t e m o l t e n - s a l t permeation v s mercury permeation a t room tempera-
ture. The a c t u a l m o l t e n - f l u o r i d e permeations of g r a d e s AGOT and s - 4 were
n o t s i g n i f i c a n t l y changed ( p e r c e n t b u l k volume permeation d i f f e r e d by
< 2 u n i t s ) by v a r y i n g t h e permeation p r e s s u r e . The agreement of t h e a c t u a l

3The o r i g i n a l weight of t h e un-permeated g r a p h i t e specimens w a s used

t o c a l c u l a t e t h e weight of BULT l4-.5U t a k e n up a f t e r each of t h e 95- and
150-psig t e s t s .

223
 Table 16.2. Permeation of Various Grades of Graphite by
LiF-BeFz-ThF4-UF4 (67-18.5-14-0.5 Mole $, BULT 14- .5U)
a t 95 and 150 p s i g
T e s t Conditions : Temperature, 1300°F (704°C)
P e r i o d o f T e s t s , 100 h r

Bulk Volume of G r a p h i t e Permeated

Graphite w i t h BULT 14-.5U ($)*
Grade A t 95 p s i g A t 150 p s i g P95 :P150**

CT-158 0.04 1.2 0.03

CT-150 0.3 1.2 0.2
-
CEY 1350 0.2 0.6 0.3
CEY -G 0.3 0.8 0.4
CEY - 82 1.0 1.8 0.6
GT - 123-82 0.25 0.4 0.6
CEY-B 3 .O 4.4 0.7
R-4 2.3 2.9 0.8
GT-123 6.6 8.0 0.8
R-0009 RG 2.6 2.9 0.9

S 4 4.4 4.9 0.9

CS-82 RG 5.3 5.8 0.9
R-0013 5.4 5.9 0.9
ATJ-82 RG 6.3 6.4 1.0
R-0009 2.2 2.2 1.0

186 4.2 4.0 1.0

MH4LM 8.9 8.4 1.1
SM- 1 12.2 11.5 1.1
AGOT 16.1 14.6 1.1
ATL- 82 10.6 9.6 1.1 8
*Each v a l u e i s an average of t h r e e o r more v a l u e s .
**P95:P150 i s t h e r a t i o of t h e p e r c e n t of t h e b u l k volume of t h e
g r a p h i t e permeated b y BULT l4-.5U a t 95 and 150 p s i g ; it i s t h e r a t i o of
v a l u e s i n column 2 t o t h o s e i n column 3 f o r each grade of g r a p h i t e .

m o l t e n - f l u o r i d e permeations w i t h p r e d i c t e d permeations (based on mercury

i n t r u s i o n ) were, i n g e n e r a l , good. However, more work i s n e c e s s a r y t o
a c c u r a t e l y determine t h e f a c t o r s a s s o c i a t e d w i t h such a c o r r e l a t i o n .

Uniformity i n Large P i e c e s of Graphite

Since grades R-0025 and MH4LM-82 were f a b r i c a t e d as l a r g e p i e c e s and

p i t c h impregnation t e c h n i q u e s were used t o decrease t h e i r p e r m e a b i l i t i e s ,

224

a
t h e s c r e e n i n g t e s t s i n c l u d e d specimens from d i f f e r e n t l o c a t i o n s and o r i -
e n t a t i o n s i n o r d e r t o determine t h e u n i f o r m i t y of t h e s e two p i e c e s . The
l o c a t i o n of t h e specimens, t h e i r o r i e n t a t i o n , and t h e t e s t r e s u l t s are
summarized i n Table 16.3. I n general, t h e results indicated t h a t t h e
l a r g e p i e c e s of g r a d e s R-0025 and MH4LM-82 were uniform.
Grade R-4 g r a p h i t e i s one i n which r e l a t i v e l y l a r g e , a c c e s s i b l e v o i d s
were p a r t i a l l y f i l l e d w i t h carbon t o d e c r e a s e t h e p e r m e a b i l i t y of t h e
graphite. The bulk volume of t h e g r a p h i t e permeated by BULT 14- .5U av-
eraged 1.4s (0.7 t o 2.?$) f o r f o u r specimens t h a t were l o c a t e d a t t h e sur-
f a c e and 3.0% (2.3 t o 4 . 2 $ ) f o r t h r e e specimens t a k e n from 1 / 2 t o 1 i n .

Table 16.3. Apparent D e n s i t i e s and Molten F l u o r i d e s Permeation

of G r a p h i t e Grades R-0025 and MH4tLM-82 i n R e l a t i o n
t o Specimen Location and O r i e n t a t i o n

Center** Midway A t Outside

on Radius** Diameter**
Grade*
1 1 1
R-0025 PA' g/cc 1.89 1.85 1.88 1.86 1.87 1.87
J' 5 4.4 6.4 5.5 6.7 5.2 5.7

MH4I.M-82 pAJ g/CC 1-82 1.82 1.81. 1.80

p, k 7.7 8.0 8.4 8.7

*Dimensions of original p i e c e s of:

Grade R-0025, 39 i n . i n d i a m e t e r X 11-1/2 i n . l o n g
Grade MH4LM-82, 4 9 i n . i n d i a m e t e r X 4 i n . long
**A11 v a l u e s a r e a v e r a g e s of s i x .
Legend :
11 - C y l i n d r i c a l
specimens were t a k e n w i t h axes p a r a l l e l
w i t h t h e forming f o r c e (specimen dimensions: 112 i n .
OD x 1-1/2 i n . l o n g )
1 - Specimens were t a k e n w i t h axes p e r p e n d i c u l a r t o t h e
forming f o r c e (specimen dimensions: 1 / 2 i n . OD X
1-1/2 i n . l o n g )
pA - Apparent (bulk) density
P - Bulk volume of g r a p h i t e permeated w i t h BULT 14-.5U
d u r i n g a 100-hr exposure a t 1300°F ( 7 0 4 O C ) and 150
Psig

225
 n
from the surface.2 More tests would be necessary to fully evaluate the
variations in the fluoride-salt permeability of grade R-4. However, these
data indicate that the maximum effectiveness of the carbon-impregnation
technique used was to a depth of 112 to 1 in. below the surface of the
graphite.

Bismuth-Impregnated Graphite

In precursory tests, grade AGOT graphite was impregnated with molten

bismuth prior to a standard fuel permeation test.2 The purpose of the
bismuth impregnation was twofold: (1)to determine if the bismuth would
occupy the pore spaces in the graphite and exclude fuel from these pores
and (2) to determine if the bismuth which had permeated the graphite pores
would be retained within them during reactor temperature and pressure
cycles.
The results showed that the bismuth pretreatment suppressed the f u e l
pickup (Table 16.4) but the bismuth was not completely retained in the
pores of the graphite during the fuel permeation test. Naturally, the

Table 16.4. Effect of Impregnation with Bismuth to

Inhibit Fuel Permeation of AGOT Graphite
_Pretreatment
_ ~ Conditions: Molten Bismuth at 1022°F (550°C),
200 hr, 125 psig
Fuel Permeation Conditions: Fuel 130 at 1300°F (704,"C),100
hr, 150 psig

Uranium Analyses (mg U/g graphite)

Location of
Successive Untreated Pretreated
Samples Graphite Graphite

0*-1/ 16 6.6 2.6

1/16-1/8 7.5 2.6
1/8-3/16 7.2 2.4
3/1&1/4 7.6 1.7
1/4-5116 7.4 1.3
5/16-3/8 7.3 0.9

*Surface of specimen.
I
Qo

unretained bismuth attacked the Inconel pressure container as it would

Gs any other nickel-base alloy such as 1N0R-8.4

Uranium Precipitation from Molten Fluorides

in Contact with Graphite

W. H. Cook

It has been reported that contamination of graphite causes part of

the uranium in LiF-BeF2-UF4 (62-37-1 mole $, fuel 130) to precipitate as
uranium dioxide when the fuel is exposed to the contaminated graphite at
1300°F (704°C) in a vacuum.5’6 Similar exposures for 4000 and 3000 hr of
NaF-ZrF4-UF4 (50-46-4mole $, fuel 30) and LiF-BeF2-ThF4-UF4 (67-18.5-14-
0.5 mole $, BULT 14-.5U), respectively, have not produced precipitates
that can be detected radiographically. Excluding other factors, these
results suggest that the uranium precipitation can be eliminated by the
choice of fuel components.

Removal of Oxygen Contamination from Graphite

W. H. Cook

The nuclear requirements of the Molten-Salt Reactor may be such that

it is undesirable or impractical to make fluoride component changes that
would eliminate the uranium precipitation problem. ,
Therefore efforts
have continued to develop and evaluate methods for removing oxygen con-
tamination from graphite as a means of eliminating precipitation of ura-
nium from the fuels.
T h e exposure of graphite to flowing hydrogen preheated to 1300°F
(704°C) did not significantly reduce the graphite oxygen contamination.
However, either purging the graphite with molten fuel 130 (ref 2) or ex-
posing it to thermally decomposing crystals of NH4F.D (ref 2 ) appears
to be a successful method for decontaminating graphite.

4R. N. b o n (ed.), Liquid Metals Handbook (rev. ed.), p 176, Office

of Naval Research, NAVEXOS P-733, June 1952.
’W. H. Cook, Met. Ann. Prog. Rep. Oct. 10, 1958, ORNL-2632, p 105
(classified).
6W. H. Cook, D. H. Jansen, and E. E. HofRnan, Met. Ann. Prog. Rep.
Sept. 1, 1959, ORNL-2839, p 162.
7MSR Quar. Prog. Rep. Oct. 31, 1959, ORNL-2890, p 44.

227
1

A
C o m p a t i b i l i t y of INOR-8 and I n c o n e l w i t h Graphite-Fluoride Systems

I n c o n e l and INOR-$ i n t h e F u e l 1 3 W r a p h i t e T e s t Systems ( D . H . Jansen

and W . H. Cook)

The use of unclad g r a p h i t e as moderator i n t h e Molten-Salt Reactor

w i l l make it n e c e s s a r y f o r t h e g r a p h i t e t o b e i n d i r e c t c o n t a c t w i t h t h e
f u e l and I N O R - 8 o r I n c o n e l . 8 Therefore, I N O R - 8 and I n c o n e l were s t a t i -
c a l l y t e s t e d i n f u e l 130 (LiF-BeF2-UF4, 6 2 - 3 7 - l m o l e $) which w a s i n con-
t a c t w i t h b a r e g r a p h i t e t o determine whether t h e s e a l l o y s would b e c a r -
burized. A t e s t c o n f i g u r a t i o n similar t o t h a t used i n p r e v i o u s l y r e p o r t e d
sodium-graphite t e s t s g w a s employed. T e s t s of 2000- through 12,000-hr
d u r a t i o n have been t e r m i n a t e d . A t e s t system scheduled f o r 14,000 h r and
one scheduled f o r a n extended p e r i o d a r e s t i l l i n o p e r a t i o n .
No evidence of c a r b u r i z a t i o n of I N O R - 8 was d e t e c t e d m e t a l l o g r a p h i -
c a l l y i n any of t h e completed t e s t s . Chemical r e s u l t s of m i l l i n g s from
t h e specimens i n t h e 6000-hr t e s t showed no s i g n i f i c a n t c a r b u r i z a t i o n .
The e f f e c t s of exposure time t o f u e l - g r a p h i t e systems on t h e mechani-
c a l p r o p e r t i e s of INOR-8 a r e shown i n Table 16.5. It can b e s e e n t h a t
t h e r e were no a p p r e c i a b l e d i f f e r e n c e s i n t h e mechanical p r o p e r t i e s of t h e
c o n t r o l and t e s t specimens i n t h e s e t e s t s .
I n c o n e l which had been exposed t o f u e l 130 i n t h e presence of g r a p h i t e
f o r only 4000 h r w a s a t t a c k e d t o such an e x t e n t t h a t any minor e f f e c t of
c a r b u r i z a t i o n on t h e t e n s i l e p r o p e r t i e s could n o t b e determined. Conse-
q u e n t l y , t e n s i l e t e s t s were o m i t t e d on t h e t e s t s o f l o n g e r d u r a t i o n . 0
G r a p h i t e i n D i r e c t Contact w i t h INOR-8 (D. H. J a n s e n )

The tendency f o r INOR-8 t o c a r b u r i z e when i n d i r e c t c o n t a c t w i t h graph- e

i t e under p r e s s u r e w a s i n v e s t i g a t e d . Grade TSF g r a p h i t e w a s h e l d i n con-
t a c t w i t h I N O R - 8 a t 1000 p s i f o r 3400 h r i n f u e l 30 a t 1300°F (704°C).
Metallographic examination i n d i c a t e d t h a t c a r b u r i z a t i o n had occurred t o
a depth of about 1 4 m i l s . Two s u c c e s s i v e s e t s of m i l l i n g s , each 7 m i l s

8Molten-Salt Reactor Program S t a t u s Report, ORNL CF-58-5-3, p 6 (May

1, 1 9 5 8 ) .
'E. E. Hoffman, W. H. Cook, and D . H . Jansen, MSR Quar. Prog. Rep.
June 30, 195$, ORNL-2551, p 59.
 Table 1 6 . 5 . T e n s i l e T e s t R e s u l t s on IMOR-8 Specimens Exposed
t o F u e l - G r a p h i t e Systems Compared w i t h C o n t r o l Specimens
Exposed t o Argon f o r Various Times

C o n t r o l Specimens* Test Specimens**

Time.
of T e s t
Tensile Elongat i o n Tensile Elongat i o n
(hr) Strength ( p s i ) ($ i n 2 i n . ) Strength ( p s i ) (5 i n2 in.)

Room Temperature T e n s i l e T e s t s
2,000 123,200 42.5 124,800 41.0
4,000 123,000 42.0 124,500 43.0
6,000 124,700 39.0 124,200 36.0
8,000 127,700 43.5 128,200 36.5
10,000 130,800 43 .O 130,300 41.0
12,000 130,600 36.5 126,700 36.3

1250°F T e n s i l e T e s t s
2,000 74,600 18.0 75,600 18.5
,
4 000 75,900; 76,000 19.0, 20.0 76,200; 74,300 1 8 . 5 , 18.5
6,000 72,800 . 16.5 74,500 16.0
8,000 76,700 17.5 76,600 19.0
10,000 78,900 1 5 .O 80,800 17.5
,
1 2 000 72,800 15.5 75,800 17.0

*Control specimens were exposed t o argon a t 1300°F (704°C) f o r t h e

times i n d i c a t e d .
**Test specimens were exposed t o f u e l 130 (LiF-BeFz-UF4, 62-37-1
mole $ ) - g r a p h i t e a t 1300°F (704°C) f o r t h e t i m e s i n d i c a t e d .

t h i c k , t a k e n from INOR-8 p l a t e n a t t h e m e t a l - g r a p h i t e c o n t a c t s u r f a c e ana-

l y z e d 0.38 and 0.12 w t $ C , r e s p e c t i v e l y . Nominal carbon c o n t e n t of t h e
INOR-8 i s 0.07 w t $. The s i d e of t h e p l a t e n n o t i n c o n t a c t w i t h t h e graph-
i t e and t h e s u r f a c e s of t h e female t h r e a d s i n t h e p l a t e n were examined
m e t a l l o g r a p h i c a l l y and no evidence of c a r b u r i z a t i o n was d e t e c t e d .
A t e s t i s c u r r e n t l y i n p r o g r e s s t o determine i f t h e r a t e of c a r b u r i -
z a t i o n of INOR-8 i s i n f l u e n c e d by t h e s t r e s s on t h e m a t e r i a l . An INOR-8
specimen i s b e i n g t e s t e d i n a s t r o n g l y c a r b u r i z i n g medium (sodium p l u s
g r a p h i t e ) while being subjected t o various s t r e s s l e v e l s .

229
 CORROSION STUDIES OF BRAZING ALLOYS

D . H . Jansen

Corrosion of Brazing Alloys i n Thermal-Convection Loops

Brazing m a t e r i a l s which e x h i b i t e d good r e s i s t a n c e t o t h e NdF-ZrFr,

b a s e f u e l s ( f u e l s 30 and 4 4 ) have been s u b j e c t e d t o r e l a t i v e l y long-term
t e s t s i n f u e l 130 (LiF-BeF2-UF4, 62-37-1 mole $ ) i n thermal-convection
loops. Such b r a z i n g a l l o y s have p o t e n t i a l a p p l i c a t i o n i n f a b r i c a t i n g
fuel-salt-to-barren-salt h e a t exchangers employed i n t h e Molten-Salt Re-
actor. The t e s t methods used'' and t h e r e s u l t s of a 1000-hr t e s t have
been reported." Subsequent t e s t s of 5000- and 10,000-hr d u r a t i o n have
been conducted and t h e r e s u l t s of t h e l a t t e r t e s t a r e o u t l i n e d i n Table
16.6. R e s u l t s of t h e s e long-term c o r r o s i o n t e s t s i n d i c a t e t h a t t h e Coast
Metals Nos. 52 and 53 and t h e General E l e c t r i c No. 8 1 n i c k e l - b a s e alloys,
t h e gold-base a l l o y , and copper when b r a z e d t o INOR-8 would have adequate
c o r r o s i o n r e s i s t a n c e i n f u e l 130 systems.
"MSR Quar. Prog. Rep. June 30, 1958, ORNL-2551, p 62.
"Met. Div. Ann. Prog. Rep. S e p t . 1, 1959, ORNL-2839, p 166.

Table 16.6. Metallographic R e s u l t s of Brazing Alloys A f t e r

10,000-hr Exposure t o F u e l 130 a t 1300°F (704OC)
i n an I n c o n e l Thermal-Convection Loop

Metallographic R e s u l t s
Brazing M a t e r i a l
(nominal w t $ Base Material e
compos it ion )
INOR- 8 Inconel

Coast Metals No. 52 No a t t a c k observed; D i f f u s i o n voids t o 3

(89Ni-4B-5Si-Ze ) no p o r o s i t y m i l s i n depth below
surface
Coast Metals No. 53 No a t t a c k o r po- Severe p o r o s i t y 15
( 81Ni-8Cr-4B-4Si-3Fe ) rosity m i l s deep
General E l e c t r i c No. 8 1 No a t t a c k observed Complete a t t a c k ;
( 7ONi-20C 1-10s i ) severe porosity
through f i l l e t
82Au-18Ni No a t t a c k No a t t a c k .

Pure copper No a t t a c k o r d i f - No a t t a c k ; s m a l l d i f -
fusion voids fusion voids a r e
present i n f i l l e t

230
a
e
Corrosion R e s i s t a n c e of Brazing Alloys i n S t a t i c T e s t Systems
c3 D . H . Jansen

Refractory-metal-base and gold-base b r a z i n g a l l o y s , developed by t h e

Welding and Brazing Group f o r p o t e n t i a l g r a p h i t e - t o - g r a p h i t e and g r a p h i t e -
t o - m e t a l j o i n i n g , were s c r e e n t e s t e d i n f u e l s 30 and 130.
Severe weight l o s s e s occurred on titanium-base and zirconium-base
a l l o y s i n fuel-130 t e s t s when n i c k e l o r n i c k e l - b a s e a l l o y c o n t a i n e r s were
used.12 These weight l o s s e s were a t t r i b u t e d t o d i s s i m i l a r - m e t a l mass t r a n s -
f e r t o t h e n i c k e l s i n c e s u r f a c e l a y e r s on t h e n i c k e l c a p s u l e s r e v e a l e d t h e
presence of t i t a n i u m and zirconium.
Corrosion t e s t s have been conducted on gold-base a l l o y s c o n t a i n i n g
v a r i o u s amounts of tantalum, n i c k e l , and o t h e r minor c o n s t i t u e n t s which
provide p r o p e r f l o w a b i l i t y and m e l t i n g p o i n t . The r e s u l t s of t h e t e s t s
on t h e s e gold-base experimental a l l o y s i n d i f f e r e n t f u e l s a r e t a b u l a t e d
i n Table 16.7. A moderate c o n c e n t r a t i o n of t a n t a l u m was d e t e c t e d s p e c t r o -
g r a p h i c a l l y on t h e i n s i d e w a l l s of t h e n i c k e l c o n t a i n e r from t h e 60s Au-
30$ Ta-lO$ N i test. The r e l a t i v e l y l a r g e weight g a i n on t h e g r a p h i t e - t o -
molybdenum j o i n t specimen i s due t o pickup of f u e l by t h e g r a p h i t e . The
two a l l o y s l i s t e d l a s t i n t h e t a b l e showed good r e s i s t a n c e t o f u e l 30.

COMPATIBILITY OF A BERYLLXUM-NaK-STAINLESS STEEL SYSTEM

D . H . Jansen

Since N a K (56% K-44$ N a ) i s t o be used as t h e t h e r m a l bonding a g e n t

in beryllium-UO2 c a p s u l e i r r a d i a t i o n t e s t s , experiments have been conducted
t o determine t h e e x t e n t of t h e t r a n s f e r of b e r y l l i u m t o t h e s u r f a c e of t y p e
304 s t a i n l e s s s t e e l as a f u n c t i o n o f t h e spacing d i s t a n c e between t h e be-
r y l l i u m and t h e s t a i n l e s s s t e e l . Experimental assemblies as shown i n F i g .
1 6 . 1 w e r e exposed t o p u r i f i e d NaK f o r 500 and 1000 h r a t 1112, 1292, and
1472°F (600,700, and 800°C).
A s shown i n Table 16.8, t h e weight change r e s u l t s from t h e 1000-hr
t e s t s p a r a l l e l t h o s e of t h e 500-hr t e s t b u t were, i n g e n e r a l , of g r e a t e r

12MSR Quar. Prog. Rep, Oct. 31, 1959, ORNL-2890, p 46-48.

1
23 1

Q
r I

Table 16.7. Results of F u e l Corrosion S t a t i c Tests on Newly Developed Brazing Alloys

Test Conditions: Time, 100 h r
Temperature, 1300°F (704,"C)

Alloy Type of Test F u e l Used

(Test Container) Spec imen as Bath Weight
(mgChange
) Metallographic Results

60Au-30Ta-lONi Alloy b u t t o n 130 - 3 S l i g h t , s c a t t e r e d , sub-

(nickel capsule) surface voids t o 1
m i l i n depth
I
62Au-26Ta-12Ni Graphite -Mo 130 +36 S l i g h t , s c a t t e r e d , sub-
( n i c k e l capsule) T- j o i n t s u r f a c e voids t o 2
m i l s i n depth
5 EQu-27Ni-ma-3Mo- Alloy b u t t on 30 - 0.9 No a t t a c k observed
, 2 ~ r 2 ~ (Inconel
e
capsule )
I
63Au-29Ni-3.5Mo- Alloy b u t t o n 30 N.A.* No a t t a c k observed
2 . 5 ~ r - 2 ~ e (Inconel
capsule )

*Not a v a i l a b l e .
 UNCLASSIFIED
ORNL-LR-DWG 5 0 3 9 0

BERYLLIUM COUPONS WIRED

TO TOP FOR PRE-TEST GETTERIN
OF OXYGEN FROM THE NaK BATH

MOLYBDENUM WIRE SPACER

HOLLOW BERYLLIUM CYLINDER

MACHINED TO PROVIDE 2, 5,
40,45,25,AND 5 0 - m l l NaK ANNULI

TYPE 304 STAINLE

STEEL CAPSULE

NOT DRAWN TO SCALE

BERYLLIUM-TYPE 304 STAINLESS

STEEL COUPLE IN DIRECT CONTACT

MOLYBDENUM WIRE SPACER

F i g . 16.1. A s s e m b l y for Compatibility T e s t : Type 304

S t a i n l e s s Steel-Beryl1 i um-NaK.

magnitude. The weight gains on t h e type 304 s t a i n l e s s s t e e l coupon s p e c i -

mens approximately equaled t h e weight l o s s e s on t h e beryllium specimens
h e l d i n c o n t a c t with them.
Metallographic examination revealed a two-phase r e a c t i o n l a y e r on
t h e s t a i n l e s s s t e e l specimens which were h e l d i n c o n t a c t with t h e b e r y l -
l i u m during t h e 1000-hr t e s t s . The t h i c k n e s s of t h e r e a c t i o n l a y e r v a r i e d
markedly with t e s t temperature, being l e s s than 1 / 2 m i l i n t h e 1112'F
(500°C) t e s t s and about 10 m i l s t h i c k i n t h e 14'72°F (800°C)t e s t s . X-ray
analyses i n d i c a t e d t h a t t h i s r e a c t i o n l a y e r w a s composed of 60 t o '708
NiBe .

233
 Table 16.8. R e s u l t s of Beryllium-NaK-Type 304 S t a i n l e s s S t e e l Compatibility T e s t s

Weight Change (mg/in. )

Test
I Type 304 S t a i n l e s s
Temperature Beryllium Cylinder Beryllium Coupon
S t e e l Coupon
("c) 500 h r 1000 h r 500 h r 1000 h r
I 500 h r 1000 h r

600 -0.66 - 0.01 Nil Nil Nil Nil

700 -1.7 - 1.8 -1.1 -1.4 +1.1 +1.7
800 -6.2 -10.9 -7.9 -8.4 +7.9 +7.8

c
 The amount of b e r y l l i u m t r a n s f e r r e d t o t h e s t a i n l e s s s t e e l c o n t a i n e r
used i n t h e 500-hr, 1472°F (800°C) t e s t w a s determined by chemically ana-
l y z i n g d r i l l i n g s t a k e n t o a depth of 35 m i l s from t h e s u r f a c e of t h e con-
t a i n e r a t p o s i t i o n s corresponding t o t h e v a r i o u s a n n u l i . The r e s u l t s a r e
g i v e n i n Table 16.9 and show t h a t t h e amount of b e r y l l i u m p i c k e d up by
t h e s t a i n l e s s s t e e l i n c r e a s e d as t h e annulus became s m a l l e r .

B O I L I N G POTASSIUM COMPATIBILITY STUDIES

D . H . Jansen E . E . Hoffhan

8 Refluxing Capsule T e s t s

A r e c e n t s t u d y i n d i c a t e d t h a t potassium i s one of t h e most a t t r a c t i v e

working f l u i d s f o r r e a c t o r - t u r b i n e - g e n e r a t o r power s o u r c e s f o r space ve-
4) h i c l e s .13 I n o r d e r t o i n v e s t i g a t e t h e c o m p a t i b i l i t i e s of v a r i o u s con-
t a i n e r materials w i t h b o i l i n g potassium, a t e s t i n g program has been i n i -
tiated.

"A. P. F r a a s , P. G . I a f y a t i s , and J. R . Simmons, A ComDarative Studv

Table 16.9. Beryllium Content of S t a i n l e s s S t e e l D r i l l i n g s "

as a Function of Annular N a K Spacing i n
Beryllium-Type 304 S t a i n l e s s Steel-NaK
C ompat i b .ilit y Te st s
T e s t Conditions: Time, 500 h r
Temperature, 14'72°F (800°C)

Beryllium Content of
NaK Annulus
Stainless Steel
( m i 1s )
(mg/in. )

2 31.8
5 15 .O
10 5.1
15 2 .o
25 1.1
50 0.9

* D r i l l i n g s were approx 35 m i l s deep.

235
 Refluxing c a p s u l e systems made of t y p e s 310 and 316 s t a i n l e s s s t e e l
and I n c o n e l have been o p e r a t e d a t a b o i l e r temperature of 1600°F (871°C)
f o r 500 h r . Specimens made of t h e same material as t h e c a p s u l e s were
suspended i n t h e vapor, a t t h e l i q u i d - v a p o r i n t e r f a c e , and t h e l i q u i d
r e g i o n s of each t e s t . Weight-change d a t a and m e t a l l o g r a p h i c examination
of t h e specimens following t e s t i n d i c a t e d no s i g n i f i c a n t c o r r o s i o n . No
i n c r e a s e i n t h e potassium c o n c e n t r a t i o n of s t a i n l e s s s t e e l w a s d e t e c t e d
by chemical a n a l y s e s of t h e t e s t specimens.
Since h e a t removal i n a r e f l u x i n g c a p s u l e t e s t i s through t h e wall of
t h e capsule i n t h e vapor region, it w a s d e s i r e d t o determine c o r r o s i o n e f -
f e c t s as a f u n c t i o n of p o s i t i o n a l o n g t h e c a p s u l e w a l l . This was achieved
by l i n i n g t h e i n s i d e of a t y p e 316 s t a i n l e s s s t e e l c a p s u l e w i t h tight-
f i t t i n g , s l e e v e - t y p e i n s e r t specimens ( F i g . 1 6 . 2 ) . Weight-change d a t a
showed a d e f i n i t e g a i n f o r t h e i n s e r t specimens l o c a t e d i n t h e b o i l i n g
l i q u i d r e g i o n and a weight loss f o r t h o s e l o c a t e d i n t h e vapor r e g i o n .
These r e s u l t s a r e a t t r i b u t e d t o d i s s o l u t i o n of t h e c o n t a i n e r m a t e r i a l i n
t h e vapor r e g i o n and subsequent d e p o s i t i o n on t h e s u r f a c e s of t h e s p e c i -
mens i n t h e l i q u i d ( b o i l e r ) s e c t i o n of t h e t e s t c a p s u l e .

B o i l i n g P o t a s s i W y p e 316 S t a i n l e s s S t e e l Loop Tests

A t y p e 316 s t a i n l e s s s t e e l - b o i l i n g potassium loop, i l l u s t r a t e d i n

F i g . 16.3, w a s o p e r a t e d f o r 200 h r . The 2 - f t b o i l e r s e c t i o n and t h e 4 - f t
c o o l i n g s e c t i o n were o p e r a t e d a t temperatures of 1550°F (843°C) and 1430'F
(777"c ) , r e s p e c t i v e l y .
The mass flow of potassium i n t h e system, 65 g/min, w a s determined
by means of a h e a t b a l a n c e on t h e a i r c o o l e r . F o r t h i s c a l c u l a t i o n , it
w a s assumed t h a t o n l y s a t u r a t e d potassium vapor a t 1550°F (843°C) e n t e r e d
the cooler. The vapor flow r a t e f o r t h i s loop w a s c a l c u l a t e d t o b e approx
20 f t / s e c (ref 1 4 ) .
Metallographic examination of t y p e 316 s t a i n l e s s s t e e l coupon s p e c i -
mens l o c a t e d a t v a r i o u s p o i n t s around t h e loop ( b o i l e r , vapor, c o l d l e g ,

1 4 R . N . Lyon ( e d . ) , Liquid Metals Handbook ( r e v . e d . ) , O f f i c e of

Naval Research, NAVEXOS P-733, June 1952. Mass flow r a t e c a l c u l a t i o n
w a s based on thermodynamic d a t a from t h i s s o u r c e .

236

a
ei UNCLASSIFIED
O R N L - L R - D W G 50644

FLAT ECIMEN

i
TC
(1580°F)

T
r
i
I
\

TC
(16OOOF)

-2.0 -1.0 0 4 .O 2 .o 3.0

WEIGHT CHANGE ( rng/in2)

Fig. 16.2. Boiling Potassium-Type 316 Stainless Steel Capsule Test.

23 7
 n
UNCLASSIFlED
ORNL-LR-DWG 44927R2

bZ-in-SCHED 40 PIPE

12-in HEATERS

12-in HEATERS

COOLING FINS

1 I S TYPE316 STAINLESS
STEELTABS 1
Fig. 16.3. Boiling Potassium-Type 316 Stain-
less Steel Loop T e s t No. 1.

l i q u i d - v a p o r i n t e r f a c e s ) and specimens c u t from t h e loop w a l l r e v e a l e d no

detectable corrosion.
A similar t y p e 316 s t a i n l e s s s t e e l loop system i n which s e v e r a l de-
s i g n m o d i f i c a t i o n s were i n c o r p o r a t e d i s i n o p e r a t i o n a t t h e p r e s e n t t i m e .
The system i s o p e r a t i n g a t a b o i l e r temperature of 1600°F (8'71°C)
and a minimum c o o l e r w a l l temperature of 1355°F (735°C). These c o n d i t i o n s
y i e l d a c a l c u l a t e d mass flow of 145 g/min and a vapor v e l o c i t y of 54 f t / s e c .
The loop had o p e r a t e d 1800 h r under t h e s e c o n d i t i o n s as of J u l y 1, 1960,
and w i l l b e t e r m i n a t e d a f t e r 3000 h r of o p e r a t i o n .
Q

MASS TRANSFER I N L I Q U I D METAL SYSTEMS

G, J. R . DiStefano E . E . Hoffman

I n a s t a t i c i s o t h e r m a l system, where t h e r e i s a s o l i d i n c o n t a c t w i t h
a l i q u i d metal, t h e l i q u i d becomes p r a c t i c a l l y s a t u r a t e d w i t h s o l u t e a f t e r
a c e r t a i n p e r i o d of time and no f u r t h e r r e a c t i o n o c c u r s . I n t h i s case
c o r r o s i o n can b e i n h i b i t e d i f t h e l i q u i d metal i s p r e s a t u r a t e d a t t h e tem-
p e r a t u r e of o p e r a t i o n w i t h t h e c o n t a i n e r m e t a l . However, i n dynamic s y s -
tems where t h e r e are r e l a t i v e l y h o t and c o l d s e c t i o n s , t h e phenomenon of
temperature g r a d i e n t mass t r a n s f e r becomes important. I n t h e hot region
t h e l i q u i d metal can become s a t u r a t e d w i t h t h e s o l u t e ( c o n t a i n e r m e t a l ) ;
when i t reaches t h e c o l d zone, t h e e q u i l i b r i u m s o l u b i l i t y i s l e s s and p r e -
c i p i t a t i o n of t h e s o l u t e t e n d s t o o c c u r . A s t h e l i q u i d p a s s e s through t h e
h o t zone, it a g a i n d i s s o l v e s t h e c o n t a i n e r w a l l and it i s c l e a r t h a t p r e -
s a t u r a t i o n of t h e l i q u i d m e t a l w i t h t h e s o l u t e m e t a l w i l l b e i n e f f e c t i v e
f o r more t h a n s e v e r a l c y c l e s .
I n o r d e r t o s t u d y t h i s phenomenon, a t e s t program has been i n i t i a t e d
t o determine (1)t h e s o l u b i l i t y of a pure c o n t a i n e r m e t a l i n an a l k a l i me-
t a l , ( 2 ) t h e r a t e s of s o l u t i o n , and (3) temperature g r a d i e n t mass t r a n s f e r
i n a thermal-convection-loop system. The g e n e r a l o b j e c t i v e of t h e program
i s t o i n c r e a s e e x i s t i n g knowledge on t h e b e h a v i o r of s o l i d m e t a l s i n l i q u i d -
m e t a l environments. Immediate o b j e c t i v e s of t h e program a r e t o (1)d e s i g n
and develop e x p e r i m e n t a l equipment i n which q u a n t i t a t i v e m a s s t r a n s p o r t
d a t a can b e determined and ( 2 ) analyze t h e r e s u l t s i n terms of c u r r e n t m a s s
t r a n s f e r t h e o r i e s o r new t h e o r i e s which might b e developed t o p r e d i c t c o r -
r o s i o n r a t e s under s e r v i c e c o n d i t i o n s .
A r e c e n t thermal-convection-loop t e s t conducted i n c o n j u n c t i o n w i t h
a n o t h e r program y i e l d e d i n f o r m a t i o n which w i l l be of c o n s i d e r a b l e u s e f u l -
ness i n t h e fundamental m a s s t r a n s f e r s t u d y o u t l i n e d above. I n t h e loop
t e s t t o be described, s l e e v e - t y p e i n s e r t specimens (1.5 i n . l o n g ) l i n e d
t h e e n t i r e h o t and c o l d l e g s of t h e system. Specimens of t h i s t y p e were
used i n o r d e r t o determine q u a n t i t a t i v e l y t h e s o l u t i o n and d e p o s i t i o n r a t e s
i n t h e two zones of t h e system. The e n t i r e loop and t h e i n s e r t specimens
were c o n s t r u c t e d of t y p e 430 s t a i n l e s s s t e e l and t h e c i r c u l a t i n g f l u i d was
lithium. The loop w a s o p e r a t e d f o r 5000 h r w i t h h o t - and cold-zone t e m -
p e r a t u r e s of 1100 and 900°F, r e s p e c t i v e l y .

239
 Each s l e e v e specimen w a s weighed b e f o r e and a f t e r t e s t , and t h e r e - Q
s u l t s shown i n F i g . 16.4 i n d i c a t e t h a t maximum d i s s o l u t i o n of t h e s t a i n -
l e s s s t e e l occurred i n a s e c t i o n halfway up t h e h o t l e g . A temperature
p r o f i l e of t h e h o t - l e g s e c t i o n i n d i c a t e d t h e r a t e of i n c r e a s e i n tempera-
t u r e as a f u n c t i o n of d i s t a n c e a l o n g t h e h o t l e g i n t h e d i r e c t i o n of flow,
dT/dx, w a s decreasing. Since t h e t o t a l temperature i n c r e a s e i n t h e h o t
l e g w a s s m a l l , t h e r a t e of d i s s o l u t i o n appeared t o b e s t r o n g l y i n f l u e n c e d
by t h e degree of s a t u r a t i o n E which i s d e f i n e d as

E = C
e
-cx ,
50392
UNCLASSIFIED
ORNL-LR-DWG

-4600

- (400

-1200

I I 20
- I I
m
0
X
-1000 I c
N I I
E
Y I I
m
E -800 A
I

W
0
I I
z
a
I
0 -600
+
I
'3
W
3
e
- 400

- 20c a
0

20(
3
) 4 8 12 1 44

SPECIMEN NUMBER

Fig. 16.4. Weight Change as a Function of Specimen Location i n a Type 430 Stainless Steel-Lithium
Therm a I-Convection Loop.
where

C = equilibrium or saturation concentration at a particular tempera-

e
ture,
C = actual concentration at that temperature in the loop.
X

The section where maximum dissolution occurred indicates that in this

region dC /dx began to increase rapidly and E was a maximum.
X
The weight increases exhibited by the cold-leg specimens were very
small compared to the weight losses shown by the hot-leg specimens; how-
ever, some crystals were observed in the cold trap at the bottom of the
cold leg. This is an indication that the precipitation phenomenon in the
cold-leg section occurred either by nucleation in the liquid or by crystal
growth on the cold-leg wall in such a way that the crystals were subse-
quently sheared away from the wall by the force of their weight and the
flowing lithium. It is significant, however, that under the conditions
of the test there appeared to be no tendency for plugging to occur in the
5000-hr interval.
Metallographic examination of hot- and cold-leg specimens indicated
that no intergranular or pitting type of attack occurred. There appeared
to be a small amount of uniform attack extending to a maximum depth of
2 mils in the hot leg and 1 mil in the cold leg.
From the results of this loop test it can be concluded that tempera-
ture gradient mass transfer is not a serious problem in type 430 stainless
steel systems circulating lithium at low velocity (< 3 ft/min) for tem-
peratures up to 1100'F. It can also be concluded that the use of an in-
sert specimen is a satisfactory method of evaluating mass transfer quan-
titatively in a thermal-convection-loop system.

CORROSION OF PROCESS CONTAINER MATERIALS USED

IN REPROCESSING SPENT REACTOR FUELS
A. P. Litman

Assistance was given to the Chemical Technology Division in connec-

tion with corrosion, selections of materials of construction, fabrication,
welding, brazing, and failure analysis. The majority of this support was
for the Pilot Plant Section and the Volatility Studies Groups in the Unit

24 1
Operations and Chemical Development Sections concerning their work on the
ORNL Fluoride Volatility Process for recovering uranium from spent reactor
fuels.
Installation of head-end cycle equipment (Hydrofluorination Addition)
plus revision of some fluorination stage units in the Volatility Pilot
Plant (VPP) has essentially been completed. The former will enable the
plant to handle zirconium-uranium heterogeneous fuels. A number of ex-
perimental nickel-rich alloys containing individual additions of Mg, Al,
Co, Mn, and Fe have been produced and fabricated into rods to be used
during screening corrosion tests in the Mk-I11 VPP L-nickel fluorinator.
Previous studies have indicated that the addition to nickel of elements
which form fluorides having low vapor pressures in their highest valence
state at the fluorination temperature improves the corrosion resistance
of nickel to the fluorination environments. 1 5
The Mk-I1 VPP fluorinator, fabricated from L nickel in a like manner
as the Mk-I vessel,16 sustained similar interior bulk-metal loss rates,
interior intergranular modifications, and exterior oxidation attack. Maxi-
mum total attack found was 1.1 mil/hr, based on fluorine sparge time, and
was concentrated in the salt-bath region of the vessel.
Miniature fluorinators fabricated from A nickel, INOR-8, and Hy Mu
80 (80 Ni--16 Fe-4 Mo) have been fabricated and subjected to simulated
fluorination cycling to determine the comparative corrosion resistance
of these materials. Maximum resistance to wall thinning by the fluorina-
tion environment was generally shown by the nickel vessels, although, under
certain conditions, Hy Mu 80 demonstrated equal or better resistance than
nickel. INOR-8 selectively lost Cry Mo, and Fe from the interior exposed
surfaces of the reactors tested and was less corrosion resistant than
nickel or Hy Mu 80 (ref 15).

15A. P. Litman and A. E. Goldman, Corrosion Affiliated with Fluori-

nation of Fused Salt Fuels and Associated Operations in the ORNL Fluoride
Volatility Process, ORNL-2832 (in press).
16A. P. Litman and A. E. Goldman, Met. Ann. Prog. Rep. Sept. 1, 1959,
ORNL-2839, p 234.

242

.. -. ~ . . -- __ .. . . - I ... . _ _. . .. ..~.
.. __
 A copper-lined type 347 stainless steel dissolver that had been fab-
ricated at ORNL and used during Unit Operations HF dissolution studies on
Zircaloy-2 dummy fuel elements demonstrated exceptional resistance to the
salt phase of the hydrofluorination environment. However, in the vapor
phase, extensive wall thinning was noted.17

243
 17. MECHANICAL PROPERTIES

D. A. Douglas, Jr.
4
DIMENSIONAL BEHAVIOR OF ENCAPSULATED UO2

W . R . Martin

One of t h e problems a s s o c i a t e d with t h e Experimental Gas-Cooled Re-

a c t o r (EGCR) i s t h e dimensional behavior of t h e f u e l capsule during op-
e r a t i o n of t h e r e a c t o r . The thermal conditions t o which t h e f u e l cap-
s u l e i s subjected vary s u b s t a n t i a l l y with t h e p o s i t i o n of t h e capsule
within t h e r e a c t o r . Hence, one cannot p r e d i c t t h e behavior of a l l f u e l
capsules i n t h e r e a c t o r from one set of thermal and pressure conditions.
To evaluate t h e s e f a c t o r s , an apparatus w a s designed and b u i l t i n which
a simulated f u e l capsule could be subjected t o t h e various thermal and e
pressure conditions predicted f o r t h e EGCR. A schematic of t h i s device
i s shown i n Fig. 17.1. Axial expansion measurements of t h e simulated
EGCR f u e l capsule a r e being made a t e l e v a t e d temperatures through t h e use
of low-voltage radiography. Typical radiographs have been shown i n ear-
l i e r reports. l

Expansion data2 i n d i c a t e t h a t t h e a x i a l expansion of uranium dioxide

p e l l e t s subjected t o radial thermal gradients i s a function of t h e cen-
t r a l uranium dioxide temperature. These data were obtained i n t h e tem-
perature range from room temperature t o 2750'F.
The a x i a l expansion behavior of t h e f u e l capsule i s dependent upon
t h e s i z e of t h e diametral gap, c e n t r a l U02, and cladding temperature. If
t h e r e i s no i n t e r f e r e n c e between t h e uranium dioxide p e l l e t and cladding,
t h e expansion of t h e p e l l e t i s a function of i t s c e n t r a l temperature. 0
However, if t h e r e i s i n t e r f e r e n c e between t h e f u e l p e l l e t and capsule
w a l l , t h e expansion behavior of t h e capsule i s dependent upon both t h e
cladding and c e n t r a l uranium dioxide temperatures.
Fuel capsules have been thermally cycled between t h e temperature
limits of 500 and 2500'F. A thermal-cycle t e s t , stopped a f t e r 100 cycles,
showed no change i n t h e dimensional behavior of t h e f u e l capsule as a

'GCR -- --31, 1960, ORNL-2929, p 89.

Quar. Prog. Rep. March
2GCR Quar. Prog. Rep. March 31, 1960, ORNL-2929, p 90.

244

0
 U N C L A S S IF l E D
ORNL-LR-DWG43707

WEIGHT

OUTLET ELECTRODE COOLING - I N L E T ELECTRODE COOLING

ELECTRODE SEAL
Cu BELLOWS

He GAS I N L E T
WATER OUTLET

COOLING WATER

TYPE 3 0 4 STAINLESS STE' E L

UO, PELLETS

ALUMINUM S H E L L

To HEATING ELEMENT

He ATMOSPHERE

Pt -Pt-Rh THERMOCOUPLE
W-Re

CHROMEL-ALUME
THERMOCOUPLE CHROMEL - A L U M E L
THERMOCOUPLE

4) WATER I N L E T

Fig. 17.1. Apparatus for Radiography o f Heated Fuel Capsule.

245
 n
f u n c t i o n of c y c l i n g t i m e . I n t h i s t e s t t h e r e w a s a diametral clearance
between U02 and cladding. The dimensional behavior of a f u e l capsule
without a diametral gap between t h e p e l l e t and cladding does change dur-
i n g thermal cycling.
The accumulation of U 0 2 powder f i n e s w i t h i n t h e f u e l capsule could
r e s u l t i n l o c a l i z e d overheating. However, t h e thermal cycling of f u e l
elements as described previously does not produce a s i g n i f i c a n t amount
of U02 powder f i n e s although t h e p e l l e t s a r e prone t o crack.3

IN-PILJ3 EXTENSOMETER

J. T . Venard

A major problem i n conducting i n - p i l e c r e e p experiments i s t h e meas-

urement of s t r a i n . E l e c t r i c a l sensing devices i n general a r e unable t o
withstand high temperatures and f r e q u e n t l y undergo c a l i b r a t i o n shifts due
t o r a d i a t i o n damage. A new system, using a i r gage techniques, provides
an answer t o t h e problem of an a c c u r a t e and dependable i n - p i l e extensom-
e t e r by use of a device whereby t h e previously l i m i t e d range of t h e a i r
gage may be extended i n d e f i n i t e l y without l o s s of i t s i n h e r e n t s e n s i t i v -
i t y and accuracy. Preliminary work done w i t h t h i s device i n d i c a t e s a
s e n s i t i v i t y of 1 X i n . i n displacement and good r e p r o d u c i b i l i t y .
It i s a n t i c i p a t e d t h a t t h e r e w i l l be no radiation-induced c a l i b r a t i o n
changes. A method has a l s o been conceived which w i l l allow automatic
recording and readout from t h e extensometer. Figure 17.2 shows a sche-
matic sketch of t h e system and Fig. 17.3 i s a p l o t from t h e c a l i b r a t i o n
curve. A t p r e s e n t , a mockup i s being s t u d i e d t o determine t h e e f f e c t s
of temperature, supply pressure, o r i f i c e s i z e , and rate of flow on t h e
accuracy and r e p r o d u c i b i l i t y of t h e system.

'------ --- 1960, ORNL-2964 ( i n p r e s s ) .

GCR Quar. Prog. Rep. June 30,

246
 UNCLASSIFIED
ORNL-LR-DWG 48006

SUPPLY
PRESSURE - I 4 1

COUNTER
AIR MOTOR

SOLENOID VALVE

Fig. 17.2. S c h e m a t i c Drawing of I n - P i l e E x t e n s o m e t e r .

AN EVALUATION OF INCO 713C AND HAYNES 8294 AT 1500 TO 1700°F

J. T. Venard
Advances in many areas of power production and conversion, particu-
larly with regard to better turbine performance, depend upon the devel-
opment of high-strength alloys capable of high-temperature application.
For this reason INCO 713C, developed by the International Nickel Company,
and Haynes 8294, developed by the Haynes Stellite Company, have been eval-
uated and compared at 1500 and 1700°F by creep testing and tensile testing.
Creep tests were run in air and argon to determine possible environmental
effects on the strength of these alloys.
Table 17.1 summarizes alloy composition and specimen history before
testing and Tables 17.2 and 17.3 give results of the tensile and creep
tests run on these materials.
Figure 17.4 is a plot of t h e predicted stress-rupture curves of I N C O
713C and Haynes 8294 as well as those of other high-temperature alloys.

247
 UNCLASSIFIED
ORNL-LR-DWG 48007
100

90

80

70

60

50
LINEAR RANGE
7
40

30

20

40

0
0 44 46
CLEARANCE ( i n . x 403)

Fig. 17.3. Operating Characteristics of an Air Gage.

Figures 17.5 and 17.6 a r e photomicrographs of I N C O 713C and Haynes

8294, t e s t e d under similar conditions, showing t h e v a s t l y d i f f e r i n g m i -
c r o s t r u c t u r e s of t h e m a t e r i a l s .
I n comparing and e v a l u a t i n g t h e s e two a l l o y s it can be seen t h a t nei-
t h e r i s very d u c t i l e and, although INCO 713C has b e t t e r d u c t i l i t y than
Haynes 8294, it i s f e l t t h a t b o t h would e x h i b i t appreciable notch s e n s i -
t i v i t y and low r e s i s t a n c e t o thermal f a t i g u e . The g r e a t e r d u c t i l i t y of n

248
€ 9 6
e 8

Table 17.1. Composition of Cast Alloys

Element
Alloy
Ni C Mn Si Cr Mo Al Ti cb Fe B P + S zr

INCO 713C Bal 0.12 0.06 0.38 12.5 5.11 5.9 0.58 2.16 0.90
Haynes 8294 Bal 0.02 0.20 0.30 15.0 5.0 6.7 1.0 0.07 0.015 0.10

Metallurgical History Before Testing

INCO 713C Vacuum melted and investment cast into test bars. Material tested in as-cast
condition.
Haynes 8294 Vacuum melted and investment cast with a (3.1%Zr addition immediately prior
to casting. Annealed at 2100°F f o r 1/2 hr and air cooled before testing.

Table 17.2. Hot Tensile Test Data on Cast Alloys

Original Maximum Rupture Original Tensile Yield Strength

Material Temperature Strain
Diameter Load Load Area Strength (2$ Offset)
(OF)
(in.) 1 1 ($1 (in.*) (Psi) (Psi1

INCO 713C 1500 0.252 5950 5700 7.5 0.04981 119,310 97,755
Haynes 8294 1500 0.247 5770 5770 2 .o 0.04790 120,460 113,150
 Table 17.3. Summary of Cast Alloy Creep Data
B
Stress Temperature Test Time t o Strain
Environment
(psi) (OF) NO Rupture
(hr I (%I
I N C O 713C

,
30 000 1500 206 Air 2645 2 .o
35,000 1500 80 Air 2625 3.7
35 ,000 1500 127 Argon 2300 4.8
40,000 1500 164 Argon 840 6 .O
40,000 1500 61 Air 803 4.0
30 ,000 1600 174 Argon 335 6.3
30,000 1600 279 Air 283 1.0
35,000 1600 186 Argon 161 6.3
30,000 1700 168 Argon 52 6- 3

Haynes 8294

30 ,000 1500 100 Air 4764 3.1

30 ,000 1500 11 Argon 2163 3.2
35 ,000 1500 78 Air 1542 4.8
35,000 1500 110 Argon 1046 2.7
40,000 1500 59 Air 744 2 .o
40,000 1500 104 Argon 741 1.9
8
30,000 1600 294 Air 227 4.8
30,000 1700 278 Air 23 9.4

I
0

INCO 713C may be a t t r i b u t e d t o i t s more homogeneous s t r u c t u r e as compared

w i t h t h e f a i r l y gross and apparently b r i t t l e g r a i n envelopes of Haynes
8294.
No e f f e c t of environment w a s observed i n t h e case of INCO 713C, b u t
Haynes 8294 e x h i b i t s d e f i n i t e a i r strengthening. However, INCO 713C i s
t h e b e t t e r a l l o y so far as s t r e s s - r u p t u r e behavior i s concerned.

250
 UNCLASSIFIED
ORNL-LR-DWG 48910

-
.- 4
-a
v)

v)
v)
W
[r
I-
v)

4
10
i 10 t 00 roo0 i0,ooo
TIME TO RUPTURE ( h r )

Fig. 17.4. Predicted Stress-Rupture Curves of INCO 713 and Haynes 8294, with Predicted Curves
o f Other High-Temperature Materials; 1500OF.

Both alloys are seen to be superior in stress-rupture behavior to

Haynes 21, Hastelloy B, and Rene 41, and are outperformed by Nicrotung
and Unimet 600 or 700.

GRAPHITE TESTING

J. T. Venard
An examination of the mechanical properties of AGOT graphite has
been made in order to predict its performance in the EGCR. The graphite
columns in the reactor w i l l initially be under a compressive loading, but
after the reactor g3es critical these columns will be subject to radia-
tion-induced shrink'zge. Because of the variation of the neutron flux f r o m
point to point in the reactor, tensile stresses will be produced in the
columns. It was therefore desired that the fracture stress and strain,

251
* * t 0 ' UNCLASSIFIED
a
Y-28409

X
- 0.
0

Fig.17.5. INCO 713C Tested at 1500°F. Ruptured in 803 hr with 4.0%strain. ( u ) Unstressed area,
200X; ( b ) ruptured end, 1OOX.

252

a
 Fig. 17.6. Haynes 8294 Tested at 1500OF. Ruptured in 744 hr with 2.0% strain. ( u ) Unstressed
area, 200X; ( b ) ruptured end, 1OOX.

253
t i m e and temperature dependence of t h e s e values, and t h e creep behavior
of AGOT graphite be investigated, i n order t o p r e d i c t how much t e n s i l e
loading would result i n f a i l u r e of t h e m a t e r i a l .
Specimens of AGOT graphite taken from two blocks have been examined
using incrementally loaded, long-time t e n s i l e t e s t s , and short-time ten-
sile tests. Table 17.4 summarizes a l l t e n s i l e t e s t r e s u l t s t o date.
Normally t h e s t r e n g t h of graphite i s g r e a t e r i n t h e d i r e c t i o n p a r a l -
l e l t o t h e extrusion a x i s than i n t h e normal d i r e c t i o n , b u t , as can be
seen from t h e table, t h e converse w a s found t o be t r u e i n t h e second block
of g r a p h i t e t e s t e d . It w a s f e l t t h a t t h i s second block must contain some
rather gross d e f e c t s which were a l i g n e d normal t o t h e extrusion a x i s and
radiography of specimens from t h i s block showed t h a t such defects, appar-
e n t l y low density areas, d i d e x i s t .
Results of creep t e s t s a t room temperature, 750 and llOO°F, i n d i c a t e
t h a t t h e r e may be an i n i t i a l s t a g e of creep r e s u l t i n g i n perhaps 0.005s
E i n t h e f i r s t 1 5 h r and t h a t no creep occurs a f t e r t h a t . Total s t r a i n s
C
of approx 0.16% a t a s t r e s s of 1800 p s i have remained constant f o r w e l l
over 1000 h r .
It can be concluded from t h e s e r e s u l t s t h a t t h e f r a c t u r e s t r e s s e s
and s t r a i n s of AGOT graphite a r e on t h e order of 2300 p s i and 0.200%, re-
s p e c t i v e l y , t h a t within t h e operating conditions of t h e r e a c t o r t h e s e
values are n e i t h e r time nor temperature dependent, and t h a t t h e r e i s es-
s e n t i a l l y no creep of t h e graphite between room temperature and 1100'F.
I f , t h e r e f o r e , t h e v a r i a b l e r a d i a t i o n dose r e c e i v e d ' i n t h e EGCR i s suf-
f i c i e n t t o produce s t r e s s e s or s t r a i n s i n excess of t h e above values, then
f a i l u r e of t h e g r a p h i t e w i l l r e s u l t . The p o s s i b i l i t y of radiation-induced
creep would present a p o s s i b l e escape from a graphite f a i l u r e i n t h e reac-
tor.

MECHANICAL TESTING OF TYPE 304 STAINLESS STEEL

J. W. Woods

I n order t o u t i l i z e t h e advantages of U02 as f u e l i n t h e EGCR, i t i s

necessary t o provide a m e t a l l i c capsule t o contain t h e U02 and t h e gaseous

254

0
“E
Test Specimen Modulus of Fracture Fracture
Block Type Temperature
NO
No. and a No. Testb Elasticity Stress Strain
Orientation (Psi) (psi1 ($)
~ ~~ ~~ ~~~

x 106
288 8 1 Inc. Load 78 1.75 2050 0.174
231 1 1 Inc. Load 750 1.90 1900 0-165
303 12 1 Inc. Load 1100 1.50 1920 0.220
314 14 1 Tensile 78 1.70 2635 0.205
315 18 1 Tensile 78 1.81 2310 0.175
316 26 1 Tensile 78 1.88 2270 0.178
317 23 1 Tensile 78 1.67 2370 0.205
339 24 1 Tensile 78 1.56 2290 0.206
343 19 1 Tensile 78 1.60 2300 0.200
344 17 1 Tensile 78 1.73 2315 0.206
283 10 1 Tensile 750 1.88 2270 0.178
381 8N 2 Tensile 78 0.63 1865 0.406
382 1N 2 Tensile 78 0.78 1645 0.299
383 23 N 2 Tensile 78 0.53 1770 0.357
384 24 N 2 Tensile 78 0.62 1895 0.342
385 26 P 2 Tensile 78 1.14 1170 0.119
386 25 P 2 Tensile 78 1.07 965 a .OB
405 27 P 2 Tensile 78 0.94 1335 0.146
a
A l l specimens for Block No. 1 oriented parallel to extrusion axis of blcck. N indicates speci-
h)
cn men oriented normal to extrusion axis and P indicates a parallel orientation.
cn
bIncremental load tests loaded at approx 2 psi/hr and tensile tests at approx 161 psi/sec.
C
Tests at 750 and 1100’F run in argon.
f i s s i o n products r e l e a s e d during operation of t h e r e a c t o r . With t h e se-
l e c t i o n of type 304 s t a i n l e s s s t e e l as t h e capsule m a t e r i a l , an investiga-
t i o n w a s i n i t i a t e d t o study t h e mechanical p r o p e r t i e s of t h i s m a t e r i a l .
The experimental program has included tube-burst t e s t i n g , s t u d i e s of t h e
e f f e c t of midplane spacers, thermal cycles, and creep-buckling t e s t s .

Tube-Bur st Tests

F a i l u r e of an EGCR f u e l capsule can r e s u l t i f t h e i n t e r n a l pressure

exceeds t h e e x t e r n a l pressure. The r e l e a s e of a l a r g e percentage of f i s -
s i o n gas from t h e U02 could produce pressures i n excess of t h e coolant
pressure, thus causing creep i n t h e t a n g e n t i a l d i r e c t i o n and eventual
f a i l u r e of t h e capsule w a l l . Also, an accident with a l o s s o f t h e p r i -
mary coolant pressure could l e a d t o f a i l u r e of the capsule i n a rela-
t i v e l y s h o r t time. Therefore, t h e t i m e - t o - f a i l u r e as a function of t h e
temperature, pressure d i f f e r e n t i a l , and s t r u c t u r a l changes produced by
t h e s e r v i c e environment i s being i n v e s t i g a t e d on 3/4-in.-OD type 304
s t a i n l e s s s t e e l tubes having a 0.020-in. wall. A summary of t h e r e s u l t s
obtained i n a i r has been reported.'
Since Inconel and o t h e r s t a i n l e s s s t e e l s have shown a s u s c e p t i b i l i t y
t o r a d i a t i o n damage, i n - p i l e b u r s t t e s t s on type 304 s t a i n l e s s s t e e l tubes
have been conducted i n t h e ORR poolside f a c i l i t y by t h e S o l i d S t a t e Divi-
sion. The r e s u l t s obtained from t e s t s i n a i r a t 1500°F have been re-
ported.' Out-of-pile t e s t s a l s o have been conducted using t h e same heat
of m a t e r i a l . These r e s u l t s , previously reported, 3D i n d i c a t e t h a t neu-
t r o n bombardment reduces t h e rupture l i f e by a considerable degree. Ad-
d i t i o n a l b u r s t t e s t s , both i n - p i l e and out-of-pile, are currently i n
progress a t 1300°F. a
E f f e c t of Midplane Spacers

A s a r e s u l t of t h e asymmetrical temperature d i s t r i b u t i o n inherent i n

t h e EGCR f u e l elements, bowing of t h e capsules presents a serious problem.
Midplane spacers, a t t a c h e d t o t h e capsules by brazing, have been designed

-Quar. Prog.
'GCR Rep. Dec . 31, 1959, ORNL-2888, p 77-78.
'GCR Quar. B o g . Rep. March 31, 1960, ORNL-2329, p 115-117.
I

256
Q

t o r e s t r a i n t h i s movement. The b r a z i n g operation, e i t h e r by furnace o r

c) induction brazing, r e q u i r e s t h e capsule t o be heated t o 2150"F. Because
of t h e m e t a l l u r g i c a l changes induced by t h i s h e a t treatment, a d d i t i o n a l
b u r s t and buckling t e s t s were necessary t o o b t a i n r e a l i s t i c design data.
D e t a i l s of t h e s e t e s t s have been r e p o r t e d . 6 The furnace b r a z i n g c y c l e
w a s found t o produce a tube c o n t a i n i n g a r e a s of abnormal g r a i n growth.
Subsequent b u r s t t e s t s r e v e a l e d t h e s e capsules t o have a much s h o r t e r t i m e -
t o - f a i l u r e than m a t e r i a l t e s t e d i n t h e as-received condition, and cracking
w a s found t o have occurred only i n t h e a r e a s c o n t a i n i n g t h e extremely l a r g e
grains. Induction b r a z i n g a l s o induced g r a i n growth; however, it w a s l o -
c a l i z e d t o a s m a l l a r e a on each s i d e of t h e spacer. I n b u r s t t e s t s it i s
i n d i c a t e d t h a t t h e spacer strength.ens t h e tube w a l l s u f f i c i e n t l y s o t h a t
t h e r u p t u r e l i f e i s not a f f e c t e d by t h e presence of t h e l a r g e g r a i n s .
Q Collapsing t e s t s conducted at 1800°F on capsules having midplane
spacers have shown t h a t t h e spacer w i l l c o l l a p s e along with t h e tube w a l l .
Additional c o l l a p s i n g t e s t s a r e i n progress a t 1300 and 1500°F.

Thermal-Cycling Tests

The temperature t r a n s i e n t of t h e cladding m a t e r i a l , f o r a t y p i c a l

scram of t h e EGCR, has been e s t i m a t e d t o be i n t h e order of 600 t o 800°F
a t t h e r a t e of 100°F/min. A maximum of 100 c y c l e s of t h i s type can be
p r e d i c t e d during t h e l i f e of a f u e l element. I n order t o determine t h e
behavior of a capsule o p e r a t i n g under t h e s e conditions, thermal c y c l i n g
t e s t s w e r e conducted using 6-in.-long t u b u l a r specimens of type 304 s t a i n -
less steel. Capsules, previously c o l l a p s e d around U 0 2 p e l l e t s and t h e n
c y c l e d between 1000 and 1600°F a t t h e r a t e of lOO"F/min, were found t o
have i n c r e a s e d i n l e n g t h by approx 0.1% a f t e r LOO such c y c l e s . Empty cap-
s u l e s s u b j e c t e d t o t h e same t e s t c o n d i t i o n i n a d d i t i o n t o a 2-hr hold
time a t t h e higher temperature i n c r e a s e d i n l e n g t h by 0.8%.
Additional t r a n s i e n t s of 600 to 800°F a t a r a t e of 250"F/min may b e
expected i n t h e event of an accident such as t h e l o s s of a blower. Speci-
mens s u b j e c t e d t o t e n c y c l e s of t h i s n a t u r e between 1000 and 16OOOC i n -
c r e a s e d i n l e n g t h by only 0.05%.

-
6GCR Quar. Prog. Rep. March 31, 1960, ORNL-2929, p 115-116.
----

257
Creep Buckling of Loop Material

It i s a n t i c i p a t e d t h a t t h e experimental loops i n t h e EGCR w i l l be

exposed p e r i o d i c a l l y t o an e x t e r n a l pressure of 300 p s i a t e l e v a t e d tem-
peratures. Such a condition can l e a d t o c o l l a p s e of t h e w a l l due t o creep
buckling. Since few d a t a a r e a v a i l a b l e on creep buckling, a program has
been i n i t i a t e d t o e s t a b l i s h f a i l u r e c r i t e r i a . Tests a t 1200°F on s m a l l
s i z e tubes, type 304 s t a i n l e s s s t e e l , with equivalent r a t i o s of w a l l thick-
ness t o diameter a r e being p e r f o r m e d t o produce a more complete set of data.
The program includes : (1)obtaining curves of pressure vs time-to-col-
l a p s e a t t h r e e d i f f e r e n t r/t r a t i o s - 15, 18.5, and 24.33; ( 2 ) determining
t h e e f f e c t of o v a l i t y on t h e buckling behavior; and ( 3 ) determining t h e
e f f e c t of v a r i a b l e w a l l thickness on t h e buckling behavior. The t e s t s are
being i n t e r r u p t e d p e r i o d i c a l l y - approximately every 500 h r - i n order t o
t a k e measurements of t h e specimens.

FRACTURE OF METALS UNDER DYNAMIC LOADS

R . W. Swindeman

The Mechanical P r o p e r t i e s Group has been attempting t o e s t a b l i s h a

f a i l u r e c r i t e r i o n f o r high-temperature low-cycle f a t i g u e . Two equations
which have been used t o c o r r e l a t e low-temperature f a t i g u e data have been
studied. These equations make use of e i t h e r s t r e s s o r p l a s t i c s t r a i n as
a design parameter and may be w r i t t e n i n t h e form:
a
N E = C 1
P
and

NB u = C ~ ,
where N i s t h e number of cycles t o f a i l u r e , i s t h e p l a s t i c s t r a i n ab-
E
P
sorbed per s t r e s s cycle, rn i s t h e s t r e s s amplitude, and a, B, C1, and C 2
are m a t e r i a l c o n s t a n t s .
Several techniques have been used t o introduce t h e s t r e s s e s and
t h e most promising of which i s t h e c y c l i c creep t e s t . The

7C. R . Kennedy and D. A. Douglas, P l a s t i c S t r a i n Absorption as a

-- ORNL-2360 (April 17, 1958).
C r i t e r i o n for High-Temperature Design,
8J. F. Gorree, Jr., "Thermal Fatigue Tests -
111," Memorandum Report
No. 9, Bur. Engr. Res., University of Alabama (Aug., 1957).
---
'R. G. Carlson, Fatigue Studies of Inconel, BMI-1355 (June 26, 1959)

258

a
 advantage of t h i s t e s t from an a n a l y t i c a l viewpoint i s t h a t t h e a b s o l u t e
value of t h e s t r e s s and t h e e l a s t i c and p l a s t i c s t r a i n amplitudes a r e
constant throughout t h e t e s t .
The v a l i d i t y of E q . ( 2 ) a t high temperatures f o r s e v e r a l m a t e r i a l s
has already been established'' and a t y p i c a l set of s t r a i n - f a t i g u e d a t a
f o r Inconel a t 1500°F i s shown i n Fig. 17.7. For t h e c y c l i c c r e e p t e s t s ,
however, Eq. ( 2 ) has been found t o be a p p l i c a b l e f o r Inconel as i s i n d i -
c a t e d by t h e curve drawn i n Fig. 17.% through s t r e s s - f a t i g u e d a t a . Since
s t r e s s and s t r a i n a r e i n t e r r e l a t e d , f o r a set of given c o n d i t i o n s one
should expect t h a t t h e c o n s t a n t s of E q s . (1)and ( 2 ) could be i n t e r r e l a t e d
by an expression f o r t h e s t r e s s - p l a s t i c s t r a i n r e l a t i o n s h i p . Data f o r
Inconel suggest an expression such as:

my
P = c3 , (31

where y and C3 are m a t e r i a l c o n s t a n t s . A p l o t of such a r e l a t i o n s h i p i s

shown f o r Inconel i n F i g . 17.9. From E q s . ( 2 ) and (3) one can derive:

The complexities introduced i n t o th.ese expressions by t h e tempera-

t u r e v a r i a t i o n of t h e m a t e r i a l c o n s t a n t s and t h e e f f e c t of c y c l e time a r e

'OR. W. Swindeman and D. A. Ikuglas, "The F a i l u r e of S t r u c t u r a l Ma-

t e r i a l s Subjected t o S t r a i n Cycling Conditions," Trans. Am. SOC. Mech. --
Engrs.
- -
- 81(2), S e r i e s E, 203 (1959).
UNCLASSIFIED
ORNL-LR-DWG 36841
1oc
I UNCLASSIFIED
6 ORNL-LR-DWG 36839
I

W
40,000
u
* IC -
.-
"7
w
a
;
I

z 20,000
n n
111 Li
F t
Ln
a
w
W
4, 6 t0,ooo
b-
wk

0.1 6000
1 10 100 1000 10,000 100,000 10 400 4000 10,000 100,000
N(CYCLES TO FAILURE) N (CYCLES TO FAILURE)

Fig. 17.7. Plastic Strain per Cycle v s Number Fig. 17.8. Cyclic Creep Stress v s Number of
of Cycles to Failure for Fine-Grained Inconel Cycles to Failure for Fine-Grained Inconel Tubes
Tubes Tested at 1500°F. at 1500°F.

259
 UNCLASSIFIED

.-
I
40,000 1
ORNL-LR-DWG 36840

Q
a

3 20,000
(L
Li
a
w
W

8 10,000

6000
0.04 0.4 4 10 400
ep, PLASTIC STRAIN P E R CYCLE (70)

Fig. 17.9. Cyclic Creep Stress vs Plastic Strain

per Cycle for Fine-Grained lnconel Tubes Tested
at 1500OF.

important factors in establishing the usefulness of Eqs. (1)and (2).

Since the strength properties are temperature sensitive and the strain is
a function of time under the stress at elevated temperatures, one should
expect the constants of E q s . (2) and ( 3 ) to be sensitive to these factors.
Indeed, most metals exhibit variations in the stress-fatigue properties
with temperature and cycle time above the equicohesive temperature. Un-
fortunately, no general expression has been formulated for high-tempera-
ture fatigue which includes temperature and cycle time.
Much interest has risen in the last few years concerning the varia-
tion of the constants of Eq. (1)with cycle time and temperature. This
interest has been stimulated by attempts to apply Eq. (1) to thermal
stress cycling problems. At the present time the creep cycle data for
Inconelareinsufficient to establish the temperature or cycle time de-
pendence of the constants in Eqs. (l), (2), and (3). Data so far ob-
tained for Inconel at 1300 and 1600°F scatter about the strain fatigue
curve shown in Fig. 17.9. This is also true for cycle times which range
from 0.5 to 0.05 hr. Such data are in contrast to thoseobtained from the
"relaxation cycle" where a definite cycle time effect has been observed."
It is interesting to compare the cyclic creep life with that pre-
dicted by monotonic creep. If one substitutes the equation:

N = v t , (5)

where v is the frequency and t is the rupture life, into Eq. (2) and re-
arranges the terms, m equation similar to the stress-rupture function

260
 may be obtained. That i s :
1 n

where A i s (v/C;) and n i s (l/B). A s shown f o r Inconel i n F i g . 17.10, a

curve may be drawn through t h e fa-tigue d a t a which has approximately t h e
same slope as t h e monotonic creep data. The c y c l i c c r e e p t e s t s , however,
l a s t approximately 6 times l o n g e r .
Several t e s t s have been performed -to e s t a b l i s h t h e e f f e c t of mono-
t o n i c c r e e p on t h e c y c l i c c r e e p l i f e . Creep t e s t s were performed on
Inconel rod specimens a t 7000 p s i and 1500'F. These t e s t s were discon-
t i n u e d a t various s t r a i n l e v e l s and t h e specimens c r e e p cycled st 1%
s t r a i n per c y c l e . The r e s u l t s of t h e s e t e s t s a r e shown i n Fig. 17.11. Up
t o 5% p r i o r c r e e p s t r a i n , no s i g n i f i c a n t l o s s i n t h e f a t i g u e l i f e i s evi-
dent and s t r a i n s as g r e a t as 26% decrease t h e l i f e by o n l y about 25%.
T e s t s of t h i s t y p e a r e being continued. A program i s now i n progress i n
which a mean c r e e p s t r e s s i s being imposed on a c y c l i c creep s t r e s s . The
i n t e r r e l a t i o n of t h e t i m e under t h e m a x i m u m s t r e s s , t h e c y c l i c s t r e s s ,
t h e mean s t r a i n , and t h e c y c l i c s t r a i n i s being s t u d i e d .

UNCL ASS1 F I ED
ORNL-LR-DWG 49576

UNCLASSIFIED
ORNL-LR-DWG 49575
40,000
I I I I I
-
3 20,ooc
v) 0" 2.8
LT
t

:60,000 t MONOTON'IC CREEP

SPECIMENS WERE CREPT AT 7000 psi TO
5 8000 2.4 ~

INDICATED STRAINS AND CREEP CYCLED

6
6000 ~ AT 4 % STRAIN PER CYCLE
m CYCLIC CREEP 0.5 TO 001 hrlcycle
, I I I
4000 I I I I d
0.6 6 10 100 1000 10,000
I, TIME TO FAILURE (hri

Fig. 17.10. Cyclic and Monotonic Creep Stress Fig. 17.11. T h e Effect of Small Creep Strains
v s T i m e to Failure for Fine-Grained Inconel Tubes on the Strain Fatigue Properties of Inconel Rods
a t 1500OF. a t 15OOOF.

26 1
 ZIRCALOY-2

C. R. Kennedy
Zircaloy-2 is a very attractive reactor structural material because
of its low cross section and high resistance to aqueous and liquid-metal
corrosion. Zirconium-base alloys at low temperatures have hexagonal.
structures and are very prone to exhibit preferred orientations which af-
fect the deformation characteristics. The mechanical anisotropy of
Zircaloy-2 has been demonstrated by impact energy testing and tensile
testing;” however, a previous investigation12 of the elevated-temperature
behavior of this alloy demonstrated no effect of orientation on the me-
chanical properties. This apparent anomaly is probably a result of the
rotational symmetry sometimes found in Zircaloy-2 sheet and tubing. A
common orientation for sheet material. is with the poles of the basal planes
normal to the surface. With this particular orientation, the principal
shear stresses producedby uniaxial stress states in the plane of the sheet
act on the same slip systems with the same resolved shear stresses. The
only way to demonstrate the effect of this type of mechanical anisotropy
is to test the material under stress states which are not symmetric to the
basal poles. The simplest manner in which this may be accomplished is to
uniaxially test sheet material having a different preferred orientation.
Although this type of testing does not yield sufficient data to completely
describe the behavior of the material, it does demonstrate the magnitude
of the anisotropy effect on the elevated-temperature mechanical properties.
A test series to accomplish the above consisted of performing tensile and
creep-rupture tests at temperatures of 75 to 900’F in air and argon on
sheet specimens having transverse and longitudinal orientations with re-
spect to the rolling direction.
The tensile test results, giving the 0.2% offset yield strength and
ultimate tensile strength, are shown in Fig. 17.12. It is immediately ob-
vious that the longitudinal and transverse specimens exhibit wide differ-
ences in the yield strengths but have, however, almost identical ultimate

llM. L. Picklesimer --
et -- --
al., Met. Ann. Frog. Rep. Sept. 1, 1959,
ORNL- 2839, p 11Sl-27.
l*F. ---
R. Shober et al., The Mechanical Froperties of Zirconium and
-----,
Zircaloy-2 BMI-11687Fz. 18, 1957).

262

0
 UNCLASSI FlED
ORNL-LR-DWG 50393

TEMPERATURE (OF)
70 200 300 400 600 900
m-

Fig. 17.12. Tensile Test Data v s l/T(’R) for

Zircaloy-2 0.060-in.-thick Sheet Tested in Direc-
tions Longitudinal and Transverse to Rolling
Direction.

tensile strengths. This behavior is not uncommon and has been noted pre-
viously.
The tendency of the short-time tensile properties of zirconium and
its alloys to be sensitive to impurity content, particularly oxygen, in-
dicates that Zircaloy-2 is strengthened by solute-atom interaction appar-
ently of the Cottrell type. This is further indicated by the linear re-
lationship of yield strength with the reciprocal of absolute temperature
as shown in Fig. 17.12. Thus, as would be expected, the mechanical prop-
erties of this alloy are very temperature sensitive and fall off rapidly
with increasing temperature. Since the yield strengths in both direc-
tions decrease at approximately the same rate with temperature, the rel-
ative importance of the mechanical anisotropy is demonstrated to be
greater as the temperature increases.
All of the creep-rupture tests performed on longitudinal and trans-
verse specimens had fairly high stress levels and in many cases, the

263
 s t r e s s w a s g r e a t e r than t h e y i e l d s t r e n g t h f o r t h a t temperature. The
creep r a t e values, shown i n Fig. 17.13, demonstrate t h a t unlike t h e short-
time t e n s i l e r e s u l t s , t h e creep r a t e s may b e i d e n t i c a l f o r l o n g i t u d i n a l B
and t r a n s v e r s e specimens. However, t h e creep r a t e s a r e only i d e n t i c a l
when t h e s t r e s s l e v e l i s g r e a t e r than t h e y i e l d s t r e s s i n t h e l o n g i t u d i n a l
direction. Below t h i s s t r e s s l e v e l a d e f i n i t e d i f f e r e n c e i n creep r a t e s
i s obtained. This may be a r e s u l t of t h e l o n g i t u d i n a l specimen y i e l d i n g
on loading and e i t h e r work hardening o r r o t a t i n g i t s s t r u c t u r e through
twinning. Although t h e r e i s a s i m i l a r i t y i n creep r a t e s a t high s t r e s s
l e v e l s , t h e l o n g i t u d i n a l specimen e x h i b i t s a l a r g e i n i t i a l deformation on
loading. Thus t h e t o t a l s t r a i n at any given s t r e s s l e v e l f o r a given time
w i l l vary considerably, as demonstrated i n F i g . 17.14 by t h e isochronous
10,000-hr s t r e s s - s t r a i n curves for 600°F.
UNCLASSIFIED
ORNL-LR-DWG 49346
I 1 I I I I
I a
I

--
-0
.--
___
/-

- C~

a
e
7OO0F
7 - A
I
400°F
600°F
__ I

I
- 0

0 LONGllUDlNAL IW KWLLINC, U I K t L I I U I \ l
A TRANSVERSE TO ROLLING DIRECTION
900°F

(o-~ (o-~ 10-2 IO-’ 100 10’

102
CREEP RATE (%/hr)

Fig. 17.13. Stress v s Strain Rate for Zircaloy-2 Tested in A i r .

UNCLASSIFIED
ORNL-LR-DWG 50395
28 I I I I

T
0
YI
2 20
m
,
’ _ _ ~
I
m
W
LONGITUDINAL TO ROLLING DIRECTION
rr
16 _ _ _ ~

12
0 0.4 0.8 1.2 1.6 2.0 2.4 2.8
TOTAL STRAIN (S.)

Fig. 17.14. 10,000-hr Isochronous Stress-Strain

Curves for Zircaloy-2 Tested i n Air a t 600°F.

264
 As s t a t e d previously, although u n i a x i a l t e s t i n g of t h e s e a l l o y s w i l l
demonstrate t h e degree of mechanical anisotropy, t h e t e s t r e s u l t s do not
y i e l d s u f f i c i e n t information t o completely describe t h e behavior of t h e
material. I n f a c t , t h e t e s t r e s u l t s may be very misleading, i n p a r t i c u -
l a r , as t o t h e e f f e c t of anisotropy on t h e d u c t i l i t y under complex s t r e s s
s t a t e s which a r e normally found i n s e r v i c e . A simple r e l a t i o n s h i p w a s
shown13 t o describe t h e f r a c t u r e s t r a i n s and thus t h e d u c t i l i t y of i s o -
t r o p i c m a t e r i a l under complex s t r e s s s t a t e s . This r e l a t i o n s h i p can be
made more g e n e r a l t o include a l l m a t e r i a l s :

where
f f f
€1, € 2 , €3 = principal s t r a i n s at fracture,

ul, u2, 0-3 = p r i n c i p a l s t r e s s e s ,

A, B, C, A = m a t e r i a l c o n s t a n t s .

For i s o t r o p i c m a t e r i a l s A = B = C and t h e r e l a t i o n s h i p given13 f o r i s o -

t r o p i c m a t e r i a l s i s i d e n t i c a l t o Eq. ( 7 ) . For t h e case of Zircaloy-2,
which most u s u a l l y demonstrates r o t a t i o n a l symmetry, two of t h e c o n s t a n t s
a r e equal. To demonstrate t h e v a l i d i t y of t h e expression, combined stress
d a t a , I 4 obtained by loading tubes under t e n s i o n and i n t e r n a l p r e s s u r e a t
room temperature, a r e shown i n F i g . 17.15 where r u p t u r e - s t r a i n r a t i o s are
p l o t t e d vs s t r e s s r a t i o s . The data show a very good f i t c o n s i d e r i n g t h e
u s u a l s c a t t e r i n t h e s e types of r e s u l t s . As noted, t h e maximum l o s s of
d u c t i l i t y , as c a l c u l a t e d by t h e shear s t r a i n , r e s u l t s under balanced b i -
axial tensile stresses. The most common s t r e s s r a t i o i s t h a t of 1 / 2 f o r

13C. R. Kennedy e t a l . , M u l t i a x i a l Creep Studies on Inconel a t

1500"F, ORflL-2622 (Jan, 19,1-99).
I4R. L. Mehan, E f f e c t of Combined S t r e s s on Y i e l d and F r a c-
t u-
r e-Be-
-
havior of Zircaloy-2TKAPL-2060 (Sept . 1.5, 1959) .

265
 UNCLASSIFIED

0
0
A
SHEAR S T R A I N RATIO
A X I A L RUPTURE-STRAIN RATIO
ORNL - LR- DWG 50396

T A N G E N T I A L RUPTURE-STRAIN RATIO
8
A R A D I A L RUPTURE-STRAIN RATIO

CURVES ACCORDING TO EO. ( 7 )

---J
za LO
n
S T
n
a
,\"" 0.8
y&
n
2a 0.6
3 L L
a
i-
0.4
2
Y

4 .O

0.8

-
L-2"
0.6

0.4
.
!
L ,
c 0.2
ii
n
5 0
a
n
cI - 0 . 2
rn

w
LL
3
k -0.4
3
LL

-0.6

-0.8

- 1 .O
0 0.5 0.5 0

STRESS RATIO
e
F i g . 17.15. P l o t of Rupture Strain Ratio v s
Stress R a t i o for Z i r c a l o y - 2 T e n s i l e T e s t s .

an internally pressurized tube. For this case, the ductility is reduced

to 43$ less than that obtained by uniaxial testing.
These test results demonstrate that mechanical anisotropy can, and
most generally will, reduce the ductility under realistic complex stress
states. As was shown previously, the relative mechanical anisotropy in-
creases with temperature; thus the loss of ductility under complex stresses
will become greater than that shown at room temperature. A test series to
evaluate the seriousness of this loss of ductility under complex stress is
proposed for the coming year.

266

49
 PREDICTION OF CREEP RATES FROM RELAXATION TESTS

C. R. Kennedy

The use of stress-relaxation test results to obtain reliable creep

rate values by direct computation has been demonstrated previously15 for
Inconel. In this report the analysis of the relaxation data relied upon
the fact that the creep rate of Inconel had the following function:

iC =(!I n
,
where

iC = creep rate,

cr = stress,
A and n = material constants.

For inaterials obeying this relationship, the relaxation test results are
very easily converted to creep rate values. However, it is not necessary
for Eq. (8)to be valid to convert the relaxation data to creep rate data.
A second, more direct, method may be utilized, realizing that for the
stress-relaxation test:

E
t = E
C
+Ee = constant ,
where

E = total strain,
@ t
E = creep strain,
C

E
e
= elastic strain porportional to the stress by the modulus of
e elasticity.

Differentiating Eq. (9)with respect to t:

dEC dEe 1 do
-=--=---
dt dt E dt

A graphic solution of the relaxation data can readily be accomplished to

obtain creep rate values.

I5C. R. Kennedy and D. A. Douglas, Relaxation Characteristics of

-
- ORNL-2407 (Jan. 29, 1960).
Inconel at Elevated Temperatures,

267
 The graphic method w a s u t i l i z e d i n obtaining creep r a t e values from
s t r e s s - r e l a x a t i o n r e s u l t s f o r two d i f f e r e n t a l l o y s . The f i r s t a l l o y w a s B
type 304 stainless s t e e l f o r which t h e creep r a t e values from 1200 t o
1600°F were needed i n t h e s t r e s s a n a l y s i s of t h e Gas-Cooled Reactor de-
sign. The s t r e s s - r e l a x a t i o n test r e s u l t s a r e shown i n Fig. 17.16 and
t h e r e s u l t i n g creep r a t e values a r e shown i n Fig. 17.1'7. Creep r a t e val-
ues obtained from t h e l i t e r a t u r e L 6 and constant l o a d creep t e s t s performed
a t ORNL a r e a l s o shown i n Fig. 17.17 f o r comparison. The agreement i s
very good considering t h a t t h e creep s t r e n g t h of type 304 s t a i n l e s s s t e e l
v a r i e s considerably with p r i o r thermal h i s t o r y . Thus, it i s demonstrated
t h a t u s e f u l and needed creep s t r e n g t h data can be generated rapidly and
e a s i l y by t h e use of t h e r e l a x a t i o n t e s t .
The second a l l o y , Zircaloy-2, w a s t e s t e d i n r e l a x a t i o n t o determine
t h e e f f e c t of o r i e n t a t i o n on t h e creep s t r e n g t h of t h e a l l o y . The relax-
a t i o n r e s u l t s of t e s t i n g specimens o r i e n t e d l o n g i t u d i n a l and transverse
t o t h e r o l l i n g d i r e c t i o n at 900°F a r e shown i n Fig. 1'7.18. The r e s u l t i n g
creep r a t e values a r e shown i n Fig. 17.19 i n comparison with constant-load
creep rate values obtained from t h e l i t e r a t u r e 1 2 and t e s t s performed a t

-
16Digest of S t e e l s f o r High Temperature Service, The Timkin Roller
Bearing Company, Canton, Ohio, 6 t h ed., 1957.
UNCLASSIFIED
ORNL-LR-OWG 4 8 8 0 8

UNCLASSIFIED
ORNL-LR-DWG 48807
zX1o4

{o4

-
a
0
'

5
I

ffl
W
ffl

k
2

to3
10-3 2 5 10-2 2 5 10-1 2 5 io0 2 5 io1 2 5 1 0 ~
TIME (hr) STRAIN RATE (%/hr)

Fig. 17.16. Relaxation Characteristics o f Type Fig. 17.17. Strain Rate v s Stress for Type
304 Stainless Steel. 304 Stainless Steel.

268
 UNCL ASS I F1ED
ORNL - L R - D W G 49522
20,000

10,000

-
-m 5000
a

m
W
r TRANSVERSE TO ROLLING DIRECTION
m
c

2000

IO00
10-3 10-2 10-1 100 I 0' IO2 10-5 IO-^ IO-^ 10-2 lo-' IO0
TIME (hr) STRAIN RATE (%/hr)

Fig. 17.18. Stress Relaxation Properties of Fig. 17.19. Stress v s Strain Rate for Zircaloy-2
Zircaloy-2 a t 900'F. at 9OOOF.

ORNL on a different heat. of material. The values obtained from the liter-
ature are for both longitudinal and.transverse specimens which did not
show the strong influence of orientation.
As discussed in the section describing the elevated-temperature me-
chanical properties of Zircaloy-2, the effect of preferred orientation
may or may n o t be demonstrated by longitudinal and transverse testing.
The effect of preferred orientation, however, is relatively greater as
the temperature is increased. Thus, small effects at room temperature
will result in a large mechanical anisotropy at elevated temperatures.

COM€'UX STRESS STUDIES

C. R. Kennedy
A previous study13 of the effect of complex stresses on the creep
rate and rupture life left no doubt that the shear stresses control the
creep rates. The rupture life results, though not definitive, tended to
indicate a principal stress criterion for fracture. The explanations
given in this study were not of the magnitude to explain the wide discrep-
ancy in results and failure criterion. A suggestion was made by A . E.
Carden17 that the pressure used to produce the tangential stress was the
factor which reduced the rupture life. The actions of the pressure in a
crack region would be to produce a stress concentration at the root of

17Private communication from A. E. Carden, University of Alabama.

269
the crack. In general, rupture under creep conditions is a two-stage
process, crack initiation which occurs early in the life and crack propa-
gation to complete failure. The stress concentration at the root of the
crack caused by the pressure will assist in the propagation of the crack
and thus shorten the life of the specimen. A test series to demonstrate
the effect of pressure was accomplished by axially stressing Inconel tubes
and applying equal increments of internal and external pressure. The re-
sults of the test series are shown in Fig. 1’7.20 and are compared with
previous results of tubes where the stresses were produced by axial loads
only and internal pressures only. The results demonstrate that the effect
of pressure is to reduce the rupture life.
A second type of test, designed to demonstrate that pressure was the
factor reducing the rupture life, is creep testing under torsion. The
stress state under torsion is that of pure shear having biaxial-princi-
pal stresses equal and opposite. One such creep test was performed and
the result is also shown in Fig. 17.20. This test result also demon-
strates that the maximum principal stress is the criterion for fracture
and supports the contention that the action of pressure reduces the creep-
rupture life.

UNCLASSIFIED

20,000

-
la 10,000
In
8
rr
8000

6000
a
J
-
Q

p- 4000
a
K
a

e
3

$
-!A
0 , 6000 855 855
2000 ~ Op 4000 570 570 ~

a S 4000 1000 1000

4000 1285 715
0 TORSION CREEP TEST WITH U , = - u 2 = T = 5 0 0 0 P S ~
1000 I I 1

Fig. 17.20. Results o f Complex Strain T e s t s

on Inconel a t 1500OF.

270

QD
 BERYLLIUM IRRADIATION EFFECTS

J. R. Weir
Beryllium has for many years been attractive to reactor designers as
a moderator for low-temperature reactors. Recent interest in gas-cooled
reactors at ORNL has resulted in investigation of beryllium as a possible
canning material for fuel elements. This interest is warranted because
of the potential economic advantages of using low-enrichment fuel clad
with beryllium which has a very low thermal neutron cross section.
The Mechanical Properties Group is studying the effects of the (n,2n)
a and (n,CX) reactions in beryllium on its mechanical and physical proper-
ties. This program is being conducted in conjunction with the Solid State
Division.
0 According to Ells and Perryman18 the nuclear reactions and related
physical data pertinent to this investigation are as shown in Table 17.5.

l 8 C . E. Ells and E. C. W. Ferryman, "Effects of Neutron-Induced

- - -l(1) (1959).
Gas Formation on Beryllium," J. Nuclear Materials
-
Table 17.5. Data on the (n,2n) and (n,CX) Reactions in Beryllium

Threshold Cross
Gas Produced at lo2' nvt
Reaction Energy Section
(> 1 Mev)
(Mev) (mb1

(n,2n) 2.71 600 0.2 cc He4/cc Be

a Be9 + n Be8 + 2n

Be8 +2 He4
8 (n,4 0.71 80 0.03 cc He4/cc Be
0.036 cc H2 + H1H3/ce Be
Be9 + n __j He4 + He6
He 8- -pi6

Li6 + n- He4 + H3
H3 '- > He3

He3 + n H1 + H3

27 1
E a r l i e r i n v e s t i g a t o r s reported somewhat d i f f e r e n t t h r e s h o l d energies and
cross s e c t i o n s f o r t h e s e r e a c t i o n s . Calculations by Redding and Barneslg Q
i n d i c a t e d t h a t t h e compositions of t h e gases formed a t lo2' nvt would be
s i m i l a r t o those predicted by Ells and Perryman, b u t t h a t t h e t o t a l gas
produced per cubic centimeter of beryllium would be 0.146 cc i n s t e a d of
approx 0.23 cc. The e f f e c t s of t h e gases may be t o cause swelling by t h e
p r e c i p i t a t i o n and growth of bubbles containing t h e helium generated. In
addition, t h e mechanical p r o p e r t i e s may be d e l e t e r i o u s l y a f f e c t e d .
I n order t o i n v e s t i g a t e t h e e f f e c t s t h e gas generation would have on
beryllium i r r a d i a t e d while a t an elevated temperature, an experiment w a s
prepared and i n s e r t e d i n t h e ORR core, p o s i t i o n B-8. The constructional
d e t a i l s of t h e experiment have been described previously.20 Briefly, the
experiment consisted of an aluminum can s i z e d t o f i t an ORR f u e l element
p o s i t i o n with an access tube t o t h e pool surface t o accommodate furnace
l e a d s , thermocouples, e t c . The aluminum can contained twenty-one beryl-
l i u m sheet specimens c l a d i n s t a i n l e s s s t e e l j a c k e t s . Each specimen w a s
contained i n a s m a l l r e s i s t a n c e furnace and w a s themocoupled t o allow
temperature c o n t r o l .
Experimental d i f f i c u l t y w i t h t h e furnace leads caused removal of t h e
experiment before t h e d e s i r e d exposure w a s reached; however, t h e specimens
received s u f f i c i e n t neutron exposure t o warrant d e t a i l e d examination.
P o s t i r r a d i a t i o n density and dimensional measurements of t h e beryl-
lium specimens have been completed and t h e r e s u l t s i n d i c a t e t h a t from 1.5
t o 5% swelling (density decrease) had occurred during t h e exposure t o lo2'
nvt (> 0.6 MeV). The temperature of t h e specimens w a s 500 t o 600°C as
measured by Chromel-Alumel thermocouples l o c a t e d on t h e outside of t h e
s t a i n l e s s s t e e l j a c k e t s approximately 0.015 i n . from t h e beryllium speci-
mens.
The data of Ells and Perryman obtained by p o s t i r r a d i a t i o n annealing
of beryllium specimens i r r a d i a t e d a t - 50°C i n d i c a t e a density decrease
of 1.5% on annealing a t 595°C f o r a t i m e period equivalent t o t h e ORNL
high-temperature experiment. T h i s beryllium had received a neutron dose

19G. B. Redding and R . S. Barnes, Neutron Induced Nuclear Reactions

- mE-M/R-1750 (1955).
i n Solids Resulting i n Gas Formation,
20GCR Quar. B o g . Rep. Dec. 31, 1959, ORNL-2888, p 133.

272
 of nvt (> 1 MeV) in the MTR which is roughly a factor of 100 greater
exposure than in the ORNL experiment. The lack of correlation between the
two types of experiments is surprising. Speculation on the reasons for
the apparently anomalous results is not warranted until metallographic ex-
amination of the specimens is completed and an out-of-pile mockup of the
experiment is operated to reproduce the environmental history of the speci-
mens so that any systematic inherent error may be detected.

AXALYTICAL WORK ON THE FAILURE OF UO2-STAINLESS STEEL

DISPERSION FUELS
8 J. R. Weir
Enriched uranium oxidestainless steel dispersion fuel elements, a
cross section of which is shown in Fig. 17.21, have been developed for the
B,
UNCLASSIFIED
Y-13t 66

Fig. 17.21. Cross Section o f a Fuel P l a t e of UO, Dispersed i n Stainless Steel.

273
U. S. Army Pressurized Water Reactors, the Vallecitos Boiling Water Re-
actor, and the Organic Moderated Reactor Experiment. These fuels are re-
quired to operate to high burnup at temperatures between 500 and 1000'F.
In the past, irradiation experiments on U02 dispersion-type fuel elements
have not yielded sufficient quantitative information on the performance
of these fuels to determine the relative influence of important fabrica-
tion variables and fuel design parameters such as the U02 particle size,
shape, and density, the fuel loading, and the properties of the matrix
material. It has therefore been impossible to fabricate fuels capable of
known performance and, further, it has been difficult to optimize fuel
element parameters for the maximum performance in terms of allowable burnup
before failure .
It was the purpose of this work to propose an analytical model which
would permit quantitative predictions of the achievable burnup for these
fuels and compare the effect of the following parameters on the burnup
lifetime: U02 density, U02 particle size, volume fraction of U02 in the
stainless steel matrix, temperature of the matrix, and strength of the
matrix.
The analysis was developed by assuming the matrix of the fuel element
to be made up of a uniform, close-packed array of spherical U02 particles,
each surrounded by and associated with a hollow stainless steel sphere.
Equations were then written for the amount of fission gas released into
the stainless steel cavity in terms of the U02 particle size and density
and the burnup. Release of the gases formed on fission is by recoil only,
since diffusion is unimportant for the particle sizes and temperatures
(< 1000°F) of interest. The gas atoms recoiled from the U 0 2 particle were
assumed to diffuse from the stainless steel shell into the cavity, that is,
the space between the U02 and the surrounding stainless steel shell. The
pressure thus exerted inside the stainless steel sphere was then computed
by application of a suitable P-V-T relationship for the gases. The failure
criterion for an internally pressurized, heavy-walled metal sphere was as-
sumed to be when the sphere becomes entirely plastic. Thus, equations were
obtained for the pressure at failure and the displacements (radial strains)
of the spheres in terms of the U 0 2 loading and the strength properties of
the steel. By suitable combination of the equations resulting from the

274
 . . ... . - .. . . ...

above, the burnup of uranium (by fission) required to cause failure was
calculated. The effects of U02 density and particle size, temperature,
strength of the matrix material, and LJO, loading on the burnup at failure
were predicted. 21
Representative results showing these effects are shown in Figs. 17.22
to 17.25. In these figures the values for a0 indicate the U02 particle
radius in microns, d the U02 density as the fraction of theoretical den-
sity, and F the volume fraction of U02 in the matrix. The theory predicts
a decrease in the burnup lifetime of the fuel with increasing volume frac-
tion of U02, decreasing U02 particle size, and increasing temperature. De-
creasing the U02 particle density is predicted to be the strongest param-
eter in increasing the performance of these fuels because of the "built
in" void space provided for the fission gases by the lower density U 0 2
particles.

J. R. Weir, A Failure Analysis for the Low-Temperature Perform-

- ORNL-2902 (May 1960).
ance of Dispersion Fuel Elements,

UNCLASSIFIED
ORNL-LR-DWG 45535
W 500
(r
3 b
1
I? 400
G oo= 30
cn F = 0.20
E
0
2 300 d = 0.95

5z
a
E
. = I

% 200
a
3
z
K
3 3 47
m 430
I- 316
z
W
0
LT 304 SS
W
a
100
300 400 500 600 700 800 900 1000
TEMPERATURE (OF)

Fig. 17.22. Comparison of S t a i n l e s s S t e e l s .

275
 e

500
UNCLASSIFIED
ORNL-LR-DWG 45543
Q
304 SS
400

2 300
0
k
z
2
z
2 200
3
LL
0
a
3
z
K
3
m
k-
z
W
100
LT
90

80
70

60

50

Fig. 17.23. Effect of UO, Loading.

A comparison of t h e p r e d i c t e d b u r n u p required t o cause f a i l u r e w i t h

experimental r e s u l t s w a s made and t h e c o r r e l a t i o n w a s found t o be reason-
The reason for t h e discrepancy between t h e ex-
a b l e although not exact.
perimental r e s u l t s and t h e theory i s probably due t o t h e i n a b i l i t y t o ac-
a
count for t h e experimentally observed "swelling" of t h e UOz p a r t i c l e s i n
t h e theory. Attempts t o c o r r e c t t h e a n a l y s i s for t h e swelling a r e being
made.

276

0
 600

5 00

4 00

cn
300

I
3

LL
0

c
z
w
0
g 100
a
90
80
70

60

50
0 20 40 60 80 100 12 0 140
RADIUS OF UO, PARTICLE (microns)

Fig. 17.24. Effect of UO, P a r t i c l e Size.

277
 700
4
600

500

4 00

In
5 300
k
a
E
2
z
23 200
LL
0
a
3
z
U
3
m
+
z
W
0
(L
I00
W
a 90
80

70

60

50

40
65 70 75 80 85 90 95 100

DENSITY OF UO2 (O/o O F THEORETICAL]

Fig. 17.25. Effect o f UO, Density a n d UO, Loading.

278
c)

cs EFFECT OF OXYGEN, NITFLOGEN, AND HYDROGEN ON TKE

M?XHANICAL PROPERTIES OF NIOBIUM

H. E . McCoy, Jr.

I n r e c e n t y e a r s , t h e r e has been i n c r e a s i n g i n t e r e s t i n r e f r a c t o r y
metals and a l l o y s as design needs have imposed higher temperatures and
s t r e s s e s t h a n t h e c u r r e n t l y a v a i l a b l e n i c k e l - and cobalt-base a l l o y s a r e
a b l e t o withstand. O f t h e s e v e r a l p o s s i b l e metals i n t h e r e f r a c t o r y c l a s s ,
niobium possesses p r o p e r t i e s which make it e x c e p t i o n a l l y a t t r a c t i v e f o r
s t r u c t u r a l a p p l i c a t i o n s i n t h e temperature range of 1000-1400°C. I n ad-
d i t i o n t o i t s r e f r a c t o r y n a t u r e , ni3bium i s of p a r t i c u l a r i n t e r e s t t o nu-
c l e a r technology because of i t s low capture c r o s s s e c t i o n f o r neutrons.
Among i t s o t h e r f a v o r a b l e q u a l i t i e s a r e i t s d u c t i l i t y , w e l d a b i l i t y , ease
of f a b r i c a t i o n , and t h e low melting p o i n t of i t s major oxide, N b 2 O 5 .
Niobium has t h e d i s t i n c t disadvantsge of b e i n g highly r e a c t i v e w i t h
contaminants, such as oxygen, water vapor, and hydrogen, at temperatures
of only a f e w hundred degrees c e n t i g r a d e . Above 1000°C t h e r e a c t i o n r a t e
w i t h n i t r o g e n becomes appreciable. These r e a c t i o n s produce compounds such
as n i t r i d e s , oxides, and hydrides, which may be p a r t i a l l y s o l u b l e i n t h e
metal, depending on t h e temperature. The presence of t h e s e i m p u r i t i e s ,
e i t h e r as a second phase p r e c i p i t a t e o r as a s o l u b l e i n t e r s t i t i a l impu-
r i t y , g r e a t l y a l t e r s t h e p h y s i c a l and mechanical p r o p e r t i e s of pure n i -
obium. For many a p p l i c a t i o n s t h e s e i m p u r i t i e s d e l e t e r i o u s l y a f f e c t t h e
e p r o p e r t i e s of t h e m a t e r i a l , b u t i n o t h e r c a s e s t h e c o n t r o l l e d contamina-
t i o n of p a r t s already f a b r i c a t e d may be used t o an advantage much as n i -
t r i d i n g and c a r b u r i z i n g a r e used. i n f e r r o u s m a t e r i a l s .

e The p r e s e n t s t u d i e s a r e d i r e c t e d toward determining t h e s p e c i f i c e f -

f e c t s of oxygen, nitrogen, and hydrogen on t h e mechanical p r o p e r t i e s of
niobium a t roon and e l e v a t e d tem.peratures. The d e t a i l s of t h i s work have
been p r e s e n t e d i n and w i l l be summarized only h e r e .
Moderate a d d i t i o n s of oxygen, n i t r o g e n , and hydrogen s t r e n g t h e n n i -
obium a t room temperature. Oxygen p r e s e n t i n s o l u t i o n i n concentrations

22H. E. McCoy and D. A. Dmglas, "Effect of Various Gaseous Con-

taminants on t h e S t r e n g t h and F o r n a b i l i t y of Columbium, " presented a t
Columbian Metallurgy Symposium, :Lake George, New York, June 9-10, 1960
( t o be p u b l i s h e d ) .

279
 n
in excess of 3000 ppm causes serious embrittlement. Surface oxides formed
by annealing in oxygen at 400°C cause cracking when the material is tested
in bending. Oxygen concentrations of the order of 2000 ppm increase the
mechanical strength of niobium at elevated temperatures, but do not appear
to reduce its ductility seriously.
Nitrogen present in excess of 1000 ppm reduces the room-temperature
bend and tensile ductilities of niobium to essentially zero. The tensile
and creep strength of this material at 1000°C is increased by nitrogen and
the observed reductions in ductility are not as serious as at room temper-
ature. However, heavy surface cracking can be noted which may cause prob-
lems in fabrication.
Eydrogen concentrations in excess of 500 ppr! seriously embrittled ni-
obium at room temperature. The absorption rate of hydrogen in niobium
seems to be greatest in the temperature range of 500 to 600°C where a sta-
ble hydride, NbH0.89, is formed. The kinetics of formation of this hy-
dride were observed to be quite rapid and the hydride is formed in all
specimens cooled through the above temperature range in the presence of
hydrogen or water vapor. Hydrogen and water vapor increase the creep rate
of niobium at 982OC although no reduction in ductility is observed.

EFFECT OF EJKIRONMENT ON THE CREEP PROPERTIES OF TYPE 304

STAINLESS STEEL AT ELEVATED TEMPERATURES

H. E. McCoy, Jr.
The creep behavior of materials has been studied by metallurgists
from both the theoretical and applied viewpoints for many years. In gen-
eral, these studies have been directed towards understanding the effects
of service variables such as stress and temperature. In recent years it
has become apparent that in certain cases one must be concerned with an-
other variable; namely, the environment which surrounds the material in
service. The problem is more widespread than is commonly recognized and
a number of examples have been documented in the literature.2 3
In considering the problem o f predicting the mechanical behavior of
the type 304 stainless steel fuel element capsules in the Experimental

23R. F. Hehemann and G. Marvin (eds.), High-Temperature Materials,

p 429-497, John Wiley and Sons, New York, 1959.

280
QB

cd Gas-Cooled Reactor, it was appreciated that the service environment was

an important variable pertaining to the creep and rupture of the struc-
tural metal. Although the EGCR will be cooled by helium, significant
quantities of other gases will result from the outgassing of the graphite
moderator and the reaction between the graphite and inleaking air and
steam. Thus, it is expected that COY C02, CH4, H2, N2, and H20 will be
present in the coolant stream in small quantities which will vary through-
out the operating life of the I-eactor. Because of the uncertainty of the
composition of the gas in contact with the fuel element capsule, the ap-
proach taken to this problem has been to study the behavior of type 304
stainless steel in each of the gases cited above in its pure form. It is
believed that data from these tests represent the maximum effects which
would be produced. Tests were carried out over the temperature range of
1300 to 1700°F.
The details of this investmigationhave been presented24 and only the
conclusions reached as a result of this work will be enumerated.
1. Equivalent creep behavior is obtained in argon and in helium en-
vironments when other testing variables are the same.
2. Creep properties determined in pure argon are conservative val-
ues for design purposes as compared with all environments except pure ox-
ygen and possibly hydrogen.
3. Air and nitrogen increase the creep resistance of this material
at 1500 and 1700°F over that observed in argon. No strengthening was
noted in an environment of pure oxygen, hence suggesting that nitrogen is
responsible for the strengthening observed in air.
4. Carburization occurs in an environment of pure carbon monoxide
at 1300 through 1700°F. Carburization occurs in carbon dioxide in the
same temperature range even if the carbon monoxide level in the gas is
less than 500 ppm. As a result,,both environments increase the creep
resistance.

24H. E. McCoy, Jr. and D. .A. Douglas, Jr., Effect of

--Environment
-_
on the Creep Properties of Type 304 Stainless Steel at Elevated Temper-
ORNL-2972 (to be published).
-atures,
-

28 1
 5. n
Loss of ductility due to gross carburization and oxidation is
believed to be the only problem in using type 304 stainless steel at
1300-1'700°F in environments composed of helium and small amounts of im-
purities. Tensile tests conducted at room temperature have not as yet
shown this to be a serious problem.
6. Copper plating is effective at 1300°F in decreasing the car-
burization rate of this material under stress in a carbon monoxide en-
vironment .

i'

28 2
 18 L
-
N T A L-
FORMING AND CASTING

R.. J . Beaver

DEVELOPMENT OF A.LUMINUM-BASE FUEL ELEMENTS

Development of Research Reac-tor Aluminum-Base F u e l

Elements Containing 20% Enriched Uranium

W. J. Kucera C . F. k i t t e n , Jr. R . J. Beaver

The o b j e c t i v e of t h i s program i s t o develop an optimum f u e l m a t e r i a l

f o r t h i n - p l a t e aluminum-base r e s e a r c h r e a c t o r f u e l elements which are l i m -
i t e d t o uranium Niith a m a x i m u m enrichment o f 20$ i n t h e U235 i s o t o p e . The
e f f e c t of t h i s l i m i t a t i o n i n enrichment r e s u l t s i n t h e n e c e s s i t y f o r i n -
c o r p o r a t i n g approximately 1000 g of uranium p e r f u e l element compared w i t h
200 g i n a f u e l element u t i l i z i i i g h i g h l y e n r i c h e d uranium. An important
4p segment i s t o c o n c l u s i v e l y demonstrate t h a t such f u e l elements can b e p r o -
duced r e l a t i v e l y economically and w i l l p e r f o m r e l i a b l y i n r e s e a r c h r e a c -
t o r s cooled and moderated w i t h -30 t o 90°C w a t e r . Previous r e s u l t s have
shown t h a t f o r t h i s a p p l i c a t i o n , , U-A1 a l l o y s i n t h e range of 40 t o 50 w t
$ U a r e i n h e r e n t l y expensive and d i f f i c u l t t o f a b r i c a t e . ' D i s p e r s i o n s of
UC2 i n aluminum show good f a b r i c a t i o n p o t e n t i a l , b u t i n t h e event of a n
i n a d v e r t e n t c l a d d i n g d e f e c t t h e m a t e r i a l will corrode c a t a s t r o p h i c a l l y when
exposed t o w a t e r . 2 Dispersions of t h e oxides, U02 and U308, o f f e r e d t h e
most promising s o l u t i o n . Uraniun d i o x i d e w a s r e j e c t e d as t h e f i s s i l e phase
because of i t s r e a c t i o n w i t h alGminum during f a b r i c a t i o n , and p o s s i b l y dur-
i n g r e a c t o r operation, and t h e requirement f o r a high-grade and conse-
q u e n t l y expensive UO;?. D i s p e r s i o n s of U3O8 i n aluminum were developed f o r
t h i s a p p l i c a t i o n and s u c c e s s f u l l y t e s t e d i n t h e a c t i v e l a t t i c e s of b o t h t h e
MTR and OR? t o e s t i m a t e d U 2 3 5 burnups of 30 and 50$ r e s p e c t i v e l y . ' Addi-
t i o n a l i r r a d i a t i o n t e s t i n g of m i n i a t u r e composite p l a t e specimens of ma-
t e r i a l s i n v e s t i g a t e d i n t h i s program has e s s e n t i a l l y been completed, and

'W. C . Thurber and R . J. Beaver, Development o f Silicon-Modified 48$

U - A 1 Alloys f o r Aluminum Plate-Type F u e l Elements, ORNL-2602 (Mar. 9, 1959).
2W. C . Thurber and R . J. Beaver, D i s p e r s i o n s of Uranium Carbides i n
Aluminum Plate-Type Research Reactor F u e l Elements, ORNL-2618 (Nov. 5,
1959).
3R. C . Waugh, The Reaction and Growth of Uranium Dioxide-Aluminum
F u e l Elements and Compacts, ORNL-2701 (Mar. 9, 1 9 5 9 ) .
4Met. Ann. Prog. Rep. S e p t . 1, IL959, ORNL-2839, p 270.
t h e y a w a i t p o s t i r r a d i a t i o n examination.
i s g i v e n i n Table 18.1.
The s t a t u s of t h e s e specimens
Q
The only examination made t o d a t e on t h e s e samples i s t h e v i s u a l ex-
amination; no evidence of d i s t o r t i o n o r damage w a s n o t e d . The program h a s
been climaxed w i t h f u l l - s c a l e f a b r i c a t i o n of 78 f u e l elements of t h i s t y p e
f o r t h e p o o l r e a c t o r a t t h e P u e r t o Rico Nuclear Center, and it h a s been
demonstrated t h a t t h e s e elements can b e produced r e l a t i v e l y economically.
These p l a t e - t y p e elements c o n t a i n e d 65$ U3O8 d i s p e r s e d i n aluminum. The
elements were mechanically j o i n e d by e i t h e r p i n n i n g o r r o l l b o n d i n g . By
supplementing t h e mechanical j o i n i n g w i t h improved Alodized c o a t i n g s on
t h e f u e l element, i t i s now a n t i c i p a t e d t h a t t h e l i m i t i n t h e l i f e o f t h e s e
pool-type elements w i l l n o t b e governed b y c o r r o s i o n b u t , i n s t e a d , by t h e
burnup of t h e U 2 3 5 .
The use of uranium, e n r i c h e d t o t h e 20$ l e v e l i n t h e U 2 3 5 i s o t o p e ,
i n v a r i a b l y i n c r e a s e s t h e c o s t of t h e f u e l element because of t h e fivefold
i n c r e a s e i n t h e q u a n t i t y of uranium r e q u i r e d . A s a r e s u l t of t h e develop-
ment work on t h i s program, it appears t h a t , compared w i t h an element con-
t a i n i n g h i g h l y e n r i c h e d uranium, t h e c o s t of a U3O8 element c o n t a i n i n g 2O$
e n r i c h e d uranium i s 73$ h i g h e r , whereas t h e c o s t of an a l l o y element con-
t a i n i n g a 48$ F A 1 a l l o y i s 114s h i g h e r . The p r i n c i p a l reason f o r t h e
h i g h e r c o s t s o f t h e 48$ F A 1 a l l o y element i s a consequence of t h e d i f f i -
c u l t y i n h a n d l i n g t h i s r a t h e r b r i t t l e a l l o y , r e s u l t i n g i n h i g h machining
c o s t s and r e j e c t i o n r a t e s . D i s p e r s i o n s of U308 i n aluminum, on t h e o t h e r
hand, can b e f a b r i c a t e d w i t h r e j e c t i o n r a t e s l e s s t h a n f o r similar p l a t e s
c o n t a i n i n g an 18% U-A1 alloy. Compared w i t h t h e s e low-alloy p l a t e s , how-
ever, c o s t of t h e f i s s i l e U3O8 compound and f a b r i c a t i o n c o s t s a r e h i g h and
c o n t r i b u t e t o t h e s i g n i f i c a n t l y h i g h e r c o s t f o r t h i s t y p e of f u e l element.
e
It i s concluded t h a t a d i s p e r s i o n of U3O8 i n aluminum i s a n optimum f u e l
material f o r use i n a r e s e a r c h r e a c t o r f u e l element a p p l i c a t i o n where 205
e n r i c h e d uranium i s r e q u i r e d .
" C

Table 18.1. I r r a d i a t i o n S t a t u s of M i n i a t u r e A l c l a d P l a t e s Containing High

Investments o f 20% Enriched Uranium

Core Desired Irradiation Estimated

Capsule
No. Composition Exposure Expo s u r e F u e l Burnup Comments
(wt k) (X 1021 n v t ) ( X 1021 n v t ) ($ U235 Atoms)

ORNL- 35- 1 48 U-3 Si-bal A 1 0.49 0.40 20 Sample r e t u r n e d

t o ORNL
ORNL- 35 -2 48 U-3 Si-bal A 1 0.49 0.43 20 Sample r e t u r n e d
t o ORNL
ORNL- 35- 3 48 U-3 Si-bal A 1 1.12 1.18 40 Sample r e t u r n e d
t o ORNL
ORiiL- 35 -4 48 U-3 Si-bal A 1 1.12 1.16 40 Sample r e t u r n e d
t o ORNL
ORNL- 35- 5 48 U-3 Si-bal A 1 2.01 2.02 60 Sample completed
irradiation
ORNL-35-6 48 U-3 Si-bal A 1 2.01 60 Sample r e t u r n e d
t o ORNL
ORNL-35-7 48 U-3 Si-bal A 1 3.53 2.41 80 S a p l e under
irradiation
ORNL- 35- 8 48 U-3 Si-bal A1 3.53 3.63 80 Sample completed
irradiation
ORNL-35 - 11 60 UC2-bal A1 1.12 1.22 40 Sample r e t u r n e d
t o ORNL
-
ORNL- 35 1 2 60 UCz-bal A1 1.12 1.27 40 Sample r e t u r n e d
t o ORNL
-
ORNL-35 14 60 UC2-bal A1 1.02 0.98 35 Sample r e t u r n e d
t o ORNL
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. . . .. . . . . -. . . .

Dispersions of U02, U30i3,and B4C in Type 1100 Aluminum

M. M. Martin .
C F. kitten, Jr.

The objective of this progi?am is to investigate the irradiation be-

havior of dispersions of U02 and U308 in aluminum in reactors of high spe-
cific power, operating with temperatures up to 315°C (600°F). Dispersions
both with and without burnable poisons are being studied. Preparatory to
the fabrication of the irradiation specimens, preliminary investigations
have been conducted to evaluate fabrication procedures and the homogeneity
of boron and uranium in the dispersion-type fuel plate.
Several plates containing the fuel oxide and B4C dispersed in aluminum
have been roll clad with type 1100 aluminum. The concentrations investi-
gated were : 24 wt $ U02-0.3 wt $I B4C-bal Al, 29 wt $I U308-c .3 wt % B4C-bal
Al, and 18 wt $ U3O8-0.2 wt $ B4C-balAl. In all but one experiment the
hot reduction was limited to 91$ reduction in thickness. In the exception,
the reduction was increased to 95$. Rolling temperatures were varied from
400 to 600°C. Two sizes of fissile compounds were examined, namely, -140
+200 mesh and -200 +325 mesh. A l l fuel compacts were prepared by conven-
tional dry blending and pressing techniques. Chemical analyses were per-
formed to determine the boron and uraniuni content of six 3/4-in.-dia samples
sectioned along the fuel core of each rol-led plate. Table 18.2 lists the
test conditions and results.
Homogeneity of uranium generally is superior to boron and, in most
cases, w a s w i t h i n k2$ of nominal. Boron homogeneity is satisfactory and
considerably better than that obt,ained in A1-U-B alloys. Dispersions con-
taining U3O8 with a mesh size in the -140 +200 range shoved variations as
high as ?4$ of nominal. This difference may be due to the Larger mesh
size of U3O8 in relationship to the selected blending procedure. No cor-
relation appears to exist between segregation and hot-working temperatures.

5W. C. Thurber, J. A. Milko, and R. J. Beaver, Boron-Aluminum and

Boron-Uranium-AluminumAlloys for Reactor Application, ORNL-2149 (Sept.
26, 1957).

287
f I

Table 18.2. Homogeneity of Boron and Uranium in Dispersions of

B ~ and BhC in Aluminum
U ~ O U02,

Boron Uranium
Total Fissile
Reduction Fissile Particle Temperature Average Inhomogeneity Average Inhomogeneity
in Thickness Compound Size Boron (Standard Uranium (Standard
(Ratio ) (Mesh) ("c 1 Content*- Deviation) Content* Deviation )
(wt $1 (5) (wt 5 ) (%)
!

11 to 1 uo2 -200 +325 400 0.101 k2 10.38 +1

11 to 1 uo2 -200 +325 45 0 0.105 +3 10.34 +1
11 to 1 u308 -140 1200 400 0.103 +7 11.63 +3

11 to 1 u308 -140 +20O 450 0.103 t4 11.56 t3

11 to 1 u308 -140 +2OO 500 0.099 +3 11.58 +4
11 to 1 u308 -200 +325 400 0.093 +3 11.48 +2
11 to 1 u308 -200 +325 450 0 .loo +3 11.64 +1
11 to 1 u308 -200 +325 500 0.095 k5 11.58 +1
18 to 1 u308 -200 1-325 600 0.066 +5 7.09 +1

*Precision of chemical analyses : boron +5$ uranium *O. 5%.

i: 0 0
 Roll Cladding of X8001-Type Aluminum

M. M. Martin

The o b j e c t i v e of t h i s s t u d y i s t o develop methods f o r c l a d d i n g X8001-

t y p e aluminum a l l o y t o d i s p e r s i o n s of U308 and U 0 2 i n X 8 0 0 l b y r o l l b o n d -
ing. ITse o f such a n a l l o y i s a t t r a c t i v e because of i t s s u p e r i o r mechanical
properties. The c r i t e r i o n f o r bond e v a l u a t i o n i s t e n s i l e t e s t i n g o f bonded
i n t e r f a c e s , s u p p o r t e d by m e t a l l o g r a p h y . Since t h e environment under which
t h e f u e l composites a r e t o be t e s t e d i s i n b o i l i n g v a t e r i n t h e 260 t o
310°C range, it w a s a l s o deemed a d v i s a b l e t o observe t h e c o n d i t i o n of X8001
bonded i n t e r f a c e s a f t e r exposure t o s t a t i c p r e s s u r i z e d w a t e r a t 290°C
a (550'F). P l a t e s of X8001 were r o l l bonded a t 550°C w i t h a t o t a l r e d u c t i o n
i n t h i c k n e s s o f 91$.
Specimens s e c t i o n e d from t h e p r o d u c t were b r a z e d t o aluminum r o d s
4D w i t h an 11.$ Si-A1 a l l o y , and t h e u l t i m a t e s t r e n g t h of t h e r o l l - b o n d e d
i n t e r f a c e e v a l u a t e d by t e n s i l e t e s t i n g . The r e s u l t s of t h r e e t e s t s i n d i -
c a t e t h a t t h e bonded i n t e r f a c e h a s a n u l t i m a t e s t r e n g t h g r e a t e r t h a n 9800
p s i , s i n c e a l l t e n s i l e b a r s f a i l e d a t t h e b r a z e d j o i n t and n o t t h e bonded
interface.
Autoclave t e s t i n g of specimens from t h i s r o l l - c l a d p r o d u c t f o r seven
days a t 290°C r e v e a l e d t h e p r e s e n c e o f numerous s m a l l b l i s t e r s , a p p a r e n t l y
a s s o c i a t e d w i t h b o n d - l i n e a t t a c k , around t h e periphery of t h e specimen.
M e t a l l o g r a p h i c examination of t h e a f f e c t e d zone r e v e a l e d v o i d s a t t h e b l i s -
tered sites. Measurements of t h e s i z e of t h e s e c a v i t i e s i n d i c a t e t h a t t h e y
0 v a r y from 0.033 t o 0.010 i n . i n d i a m e t e r and a p p e a r t o be as much as 0.015
i n . deep. A s i l l u s t r a t e d i n F i g . 18.1, m e t a l l o g r a p h y shows t h e p r e s e n c e
of i n t e r m i t t e n t oxide i n c l u s i o n s , s u s p e c t e d as b e i n g t h e s o u r c e of b l i s t e r
e formation.

Development o f an Aluminum-Base F u e l Element

f o r t h e High-Flux I s o t o p e R e a c t o r

J. H . ErVyTin W. J. Kucera D. T . B o u r g e t t e R . J . Beaver

The o b j e c t i v e o f t h i s program i s t o develop a high-performance a l u -

minum f u e l element f o r t h e High-Flux I s o t o p e R e a c t o r ( H F I R ) , c u r r e n t l y
i l a n n e d f o r producing r e s e a r c h q u a n t i t i e s of t h e heavy t r a n s p l u t o n i c e l e -
ments. The r e q u i r e m e n t s f o r h i g h performance stem from t h e f a c t t h a t t h e

289
 -
02

-
O!

F i g . 18.1. Longitudinal Cross Section of X8001 Bonded to X8001 by Rolling at 45OOC with a Re-
duction i n Thickness o f 91%, Showing Appearance of Oxide Inclusions at the Bonded Interfaces. Etchant:
0.5% HF.

h e a t f l u x i n t h e system i s 1 . 5 X lo6 Btu*hr-1.ft-2. Heat removal i s ac-

complished by flowing w a t e r w i t h an i n l e t temperature of 50°C (120°F) a t
a p r e s s u r e of 600 t o 900 p s i g through 0.05-in. f u e l element c o o l a n t chan-
n e l s a t a v e l o c i t y of 40 f p s . The r e a c t o r i s designed t o produce 100 Mw
( t h e r m a l ) and achieve a n unperturbed n e u t r o n f l u x of 5 X 1015 n e u t r o n s .
cm-2*sec -1
i n the c e n t r a l flux-trap region. e
The f u e l element designed t o meet t h e r e a c t o r requirements c o n s i s t s
of t h i n A l c l a d composite p l a t e s c o n t a i n i n g h i g h l y e n r i c h e d uranium d i s -
p e r s e d i n aluminum. The p l a t e s a r e formed i n t o an i n v o l u t e shape and
spaced 0.050 i n . a p a r t between two c o n c e n t r i c t u b e s . The f u e l element
c o r e c o n s i s t s of two c o n c e n t r i c f u e l u n i t s : an i n n e r annulus c o n t a i n i n g
190 p l a t e s and a n o u t e r annulus c o n t a i n i n g 380 p l a t e s . A t y p i c a l example
of t h e i n n e r annulus f u e l element i s i l l u s t r a t e d i n F i g . 1 8 . 2 . Pertinent
design data a r e l i s t e d i n Table 18.3. Boron i s a l s o added t o t h e f u e l

290

a
e)

Fig. 18.2. HFlR Inner Annulus Fuel Element Containing Plates

Joined to Inner Tube by Mechanical Peening and Fastened at Periphery
with Welded Bands.

p l a t e s of t h e i n n e r annulus, b u t n o t t o t h e f u e l - b e a r i n g s e c t i o n o f t h e
o u t e r annulus.
To accomplish t h e p r e s e n t o b j e c t i v e s , i n v e s t i g a t i o n s have been i n i -
t i a t e d t o (1)determine homogeneity and t o develop f a b r i c a t i o n procedures
. f o r uranium and boron i n aluminum-base a l l o y s and i n d i s p e r s i o n s , ( 2 ) de-
v e l o p t e c h n i q u e s f o r r o l l c l a d d i n g b o t h t y p e s of composite f u e l c o r e s ,

29 1
 Table 18.3. P e r t i n e n t Design Data of HFIR F u e l P l a t e s "

Cladding and s t r u c t u r a l m a t e r i a l 6061-grade aluminum a l l o y

Core m a t e r i a l 93% e n r i c h e d U-A1 a l l o y o r
u308 + A 1 powder d i s p e r s i o n
Maximum f u e l concentration 30 w t $ U-A1 a l l o y o r equiva-
lent
M a x i m u m b u r n a b l e p o i s o n concen- 0.05 w t $ BN o r 0.01 w t '$ BIO
tration i n t h e core
Nominal composite p l a t e dimen-
sions
Inner r i n g 22 i n . long X 3.5 i n . wide X

Outer r i n g
0.040 i n . t h i c k e,
22 i n . long X 3.5 i n . wide X
0.040 i n . t h i c k
Nominal " m e a t 'I dimensions
Inner ring 18 i n . long X 3.295 i n . wide
0.005-0.020 i n . t h i c k
X cp
Outer r i n g 18 i n . l o n g X 3.044 i n . wide X
O.Olo-O.020 i n . t h i c k
Cladding t h i c k n e s s 0.010 i n .
Number of f u e l p l a t e s p e r as- 590
s emb l y
Dimensions of f u e l annulus 5.5 i n . I D X 14.9 i n . OD X
24.0 i n . long
Water c o o l a n t s p a c i n g 0.050 i n .
Fuel content per core loading approx 6 kg U235
Expected c o r e l i f e t i m e a t 100 Mw 10 days
power l e v e l

*T. E . Cole, High Flux I s o t o p e Reactor -A General D e s c r i p t i o n ,

ORNL CF-60-3-33 (March 1 9 6 0 ) .
Q
(3) i n v e s t i g a t e methods f o r forming f u e l p l a t e s i n t o t h e i n v o l u t e shape,
and ( 4 ) develop procedures f o r j o i n i n g t h e p l a t e s i n t o a c o n c e n t r i c f u e l
array.
F u e l Core F a b r i c a t i o n . - The r e f e r e n c e method s e l e c t e d by t h e F a b r i -
c a t i o n Group f o r i n c o r p o r a t i n g t h e h i g h l y e n r i c h e d uranium i n t h e f u e l e l e -
ment u t i l i z e s an aluminum-base a l l o y c o n t a i n i n g 30 w t $ U. The a l l o y f o r
t h e i n n e r annulus f u e l element a l s o c o n t a i n s 0.05 w t $ E. No data ar?
a v a i l a b l e on t h e s e g r e g a t i o n of uranium i n 30 -dt 5 U-A1 alloys. Previous

292
experience with the U-A1 alloys indicates that this can be a problem.6 It
has also been shown that it is difficult to distribute boron homogeneously
in U-A1 alloys .7 Extrapolatine, data on A1-B alloys indicates, however, that
solubility of boron at 600°C may be approximately 0.05$1and it is antici-
pated that satisfactory homogeneity inay result if the concentration of
boron is restricted to a maximum of 0.05 wt $.8

Alloys containing 30 wt $ U-2 wt $ Si4.05 wt 5 B-bal A1 were vacuum

induction melted at 1050°C in a stabilizedZrO2crucible and cast into a
water-cooled copper mold, 3 in. in diameter X 12 in. long. One of the
castings was sectioned transversely at the midplane and two billets sub-
sequently successfully extruded at 510°C to 3/4-in.-dia rod. Results of
chemical analyses of uranium and boron along the length of the rod are
shown in Fig. 18.3. Although the deviations in uranium concentration are
greater than those found in alloys with less uranium concentration, the
results are encouraging and in the main are satisfactory for the HF'IR ap-
plication. Boron results showed good homogeneity but indicated a 5 0 s loss
in boron. The cause for such a loss at present has not been r?solved. Me-
tallographic examination of the microstructure of the extruded rod, as il-
lustrated in Fig. 18.4 reveals a significant difference in the size of the
UAl3 internetallic compound in the radial direction. The cause of this
effect has not yet been resolved.

-
Plate Forming. - One of the most critical problems in the development
of the € F I R fuel element is the selection and development of a method for
forming the involute curvature to the stringent tolerances required to
maintain the close tolerances on the spacing between fuel plates. This
spacing must be 0.050 k 0.003 in. average, with a maximum variation of
kO.010 in. After examining the merits of marforming, stretch forming,
compressive forming, explosive forming, and hot forming, marforming at

6W. C. Thurber and R. J. Beaver, Segregation in U-A1 A l l o y and Its

Effect on the Fuel Loading of Aluminum-Base Fuel Elements, ORNL-2476
(Sept. 5, 1958).
7W. C. Thurber, J. A. Milko, and R . J. Beaver, Boron-Aluminum and
Boron-Uranium-AluminumA l l o y s for Reactor Application, ORNL-2149 (Sept.
26, 1957).
8W. L. Fink and L. A. Willey, Metals Handbook, 1948 ed., p 1155, The
American Society for Metals, Cleveland, Ohio.

29 3
 0.04

EXTRUSION B I L L E T FROM EXTRUSION B I L L E T

UNCLASSI F l ED
ORNL-LR-DWG 50399

FROM
33 B
-TOP OF INGOT BOTTOM OF INGOT - -
- 32 '
t
-
3
0.03
BORON
, -
t
3

t-
F z
z W
W
+ - 0 - 31 5
0
z 0
8 0.02 H
z 3
0
[L
0
m
- 30 5
3
n n
W W
N 0.04 N
1;
a
Z
- INTENDED PERCENTAGES - 29 2z
a B
U
0.05 w t Yo
30 wtYo
II a c,
, I
0
4 6 8 10 12 14
1
16
28
0 2
DISTANCE FROM HOTTOP END OF T H E ROD ( f t )

Fig. 18.3. Boron and Uranium Distribution of an AI-30 U-2 Si-0.05 B (wt %) Composition Obtained
from Extruded Rods.

room tempe.rature w a s s e l e c t e d as t h e reference method. More t h a n 500 f u l l y

annealed, s o l i d , type 6061 aluminum p l a t e s , 0.040 i n . t h i c k , have now been
formed by t h i s method. Experimental d a t a obtained from measurements of
spacings between assembled p l a t e s have s t r o n g l y i n d i c a t e d t h a t s u f f i c i e n t
c o n t r o l of t h e i n v o l u t e curvature can be maintained. The following con-
d i t i o n s have been e s t a b l i s h e d f o r forming p l a t e s t o be used i n t h e i n n e r
annulus f u e l element: p r e s s i n g speed - 30 in./min, punch curvature - 3.875
i n . i n v o l u t e , rubber hardness - 70 durometer, and p r e s s u r e - 1.0 tsi. It
i s t o be recognized t h a t t h e s e conditions may change s l i g h t l y as a r e s u l t
of experiments w i t h composite f u e l p l a t e s .
F u e l Element Assembly. - The concept of j o i n i n g t h e f u e l p l a t e s i n t o
t h e concentric a r r a y i l l u s t r a t e d i n F i g . 18.2 (which i s t y p i c a l of both
i n n e r and o u t e r annulus f u e l elements) i s based on p r e c i s e machining of
grooves i n t h e o u t s i d e diameter of t h e tube, c a r e f u l placement of t h e p l a t e
i n t h e groove, and mechanically j o i n i n g i n t o p o s i t i o n . Two methods of a t -
tachment of t h e o u t e r p l a t e edges a r e contemplated. I n one, spacers a r e

294

a
Q

MICROSTRUCTURE AT EDGES OF ROD

Fig. 18.4. Size and Distribution o f UAI, Intermetallic Compound i n 30 wt % U-2 wt % Si-0.05 wt 76
B-bal AI Alloy at Center and Edge of t - i n . - d i o Rod Extruded from 3-in.-dia Casting at 51OOC. Etchant:
1 perchloric-15 H,O.

295
used t o space t h e p l a t e s properly, followed by pinning t h e p l a t e s and spa-
cers together. I n t h e o t h e r , a similar procedure i s u t i l i z e d except t h e 4
p l a t e s and spacers a r e welded a t p e r i o d i c i n t e r v a l s . The element i l l u s -
t r a t e d i n F i g . 18.2 r e p r e s e n t s one of t h e e a r l i e r welded concepts.
R e s u l t s obtained i n making 2900 measurements of t h e spacings between
t h e 190 p l a t e s of t h e i n n e r annulus f u e l element a r e g r a p h i c a l l y i l l u s -
t r a t e d i n F i g . 18.5. The d a t a a r e . n o t only a r e f l e c t i o n of t h e p r e c i s e
method of j o i n i n g t h e p l a t e s b u t a l s o , as mentioned previously, d i r e c t l y
r e l a t e d t o uniformity i n curving p l a t e s i n t o i n v o l u t e s . The average p l a t e
spacing based on a l l measurements w a s 0.052 i n . , which i s w e l l w i t h i n t h e
s p e c i f i c a t i o n f o r average p l a t e spacing v a l u e . It i s a l s o encouraging t h a t
98.6s of t h e measurements were w i t h i n t h e kO.010-in. m a x i m u m v a r i a t i o n of
t h e 0.050-in. nominal dimensions. Considering t h e s t r i n g e n t requirements

UNCLASSIFIED
ORNL-LR-DWG 50400
350 7
I I I I

300

250
1
c
200

I
LL
0

':E
150
W
m
I
3
z

0
0.035 0.040 0.045 0.050 0.055 0.060 0.065 0.07C
PLATE-SPACING MEASUREMENTS (in.)

Fig. 18.5. Plate-Spacing Measurements o f HFlR Mark IIA-1 Inner

Annulus Fuel Element.
 f o r t h i s f u e l element, t h e r e s u l t s obtained on t h e f i r s t assembled e l e -
ment a r e considered outstanding. There i s l i t t l e doubt t h a t with addi-
t i o n a l assembling experience, t:hose few measurements which were beyond L e
p e r m i s s i b l e m a x i m u m can be e l i m i n a t e d .

DEVEMPMENT OF STAINIJCSS-STEEL-BASE FUEL ELEMENTS

Dispersions of U02 i n Type 430 S t a i n l e s s S t e e l

J. H. Cherubini C . I?. k i t t e n , Jr. R . J. Beaver

The o b j e c t i v e of t h i s program i s t o o b t a i n i n one a l l - i n c l u s i v e ex-

periment t h e i r r a d i a t i o n behavior a t 260°C of d i s p e r s i o n s of U02 i n type
430 s t a i n l e s s s t e e l by i r r a d i a t i n g a f u l l - s i z e f u e l element c o n t a i n i n g
composite f u e l p l a t e specimens j-n t h e a c t i v e l a t t i c e of t h e V a l l e c i t o s
Boiling Water Reactor. I n t h i s manner, it i s p o s s i b l e t o accumulate more
t h a n 35 r e l a t i v e l y l a r g e samples, thereby p e r m i t t i n g a more complete evalu-
a t i o n t h a n i s p o s s i b l e i n small capsule t e s t s . The i r r a d i a t i o n program
i n c l u d e s examination of damage t o t h e m a t e r i a l s as a f u n c t i o n of U02 s i z e
(44 t o 88 p ) and concentration (25 t o 35 w t $ U02) a t U235 burnups varying
from 5 t o 50s. The f u e l p l a t e specimens w i l l be assembled i n t o a mechani-
c a l l y j o i n e d f u e l element, depicted i n F i g . 18.6. The f a b r i c a t i o n sequence
f o r such p l a t e s has been develorled and discussed.

'J. H. Cherubini, Met. Ann. Prog. Rep. Sept. 1, 1959, ORNL-2839,

p 264-66.
UNCLASSIFIED
Y-32407

Fig. 18.6. Over-All View of Plate-Type Fuel Element Containing Dispersions of UO, i n Type 430
IGu3 Stainless Steel for Irradiation Testing in A c t i v e L a t t i c e o f VBWR.

297

@
 Compared w i t h a u s t e n i t i c s t a i n l e s s s t e e l , type 430 s t a i n l e s s s t e e l
not only o f f e r s t h e advantages of higher thermal conductivity, lower coef-
f i c i e n t of thermal expansion, and lower neutron-absorption c r o s s s e c t i o n ,
b u t a l s o markedly reduces t h e p o t e n t i a l of ~ $ because
0 ~ t~h e m a t e r i a l '

contains almost no n i c k e l .

U02 Swage-Clad w i t h S t a i n l e s s S t e e l

J. T . Lamartine

Primary e f f o r t s i n t h i s program have been t h e development of tech-

niques f o r h o t and c o l d swaging of U02 c l a d w i t h a u s t e n i t i c s t a i n l e s s s t e e l
and t h e i n i t i a t i o n of an i r r a d i a t i o n program of t h e m a t e r i a l i n t h e Mari-
time Loop i n t h e ORR. Developments of s i g n i f i c a n c e i n c l u d e : (1)determi-
n a t i o n of t h e e f f e c t of temperature on cracking i n t h e s t a i n l e s s s t e e l w a l l
of swaged rods, ( 2 ) t h e determination of t h e e f f e c t of h e a t treatment a t
900°C on t h e s i n t e r a b i l i t y o f cold-swaged U02 c l a d w i t h s t a i n l e s s s t e e l ,
and ( 3 ) t h e p r e p a r a t i o n o f bundles of UO2 swage-clad s t a i n l e s s s t e e l rods
for t h e i r r a d i a t i o n program. R e s u l t s on swaging U02 t o d e n s i t i e s g r e a t e r
t h a n 90$ of t h e o r e t i c a l have p r e v i o u s l y been r e p o r t e d . l o
One of t h e problems encountered i n c o l d swaging of U02 with type 304
s t a i n l e s s s t e e l w a s t h e appearance of cracks on t h e i n s i d e of t h e s t a i n l e s s
s t e e l cladding. A t y p i c a l crack i s i l l u s t r a t e d i n F i g . 18.7. An i n v e s t i -
g a t i o n w a s t h e r e f o r e i n i t i a t e d t o determine t h e i n t e r r e l a t i o n s h i p between
swaging temperature and t o t a l reduction i n a r e a on t h e tendency of t h e
s t a i n l e s s s t e e l towards cracking. The r e s u l t s of t h i s study a r e p r e s e n t e d
i n F i g . 18.8. It i s apparent t h a t w i t h c o l d reductions i n a r e a l e s s t h a n
65% and swaging temperatures l e s s t h a n 6OO0C, c r a c k - f r e e cladding i s ob-
tained. Outside of t h e s e boundary conditions, cracks of various magnitude
a r e l i k e l y t o occur. To determine whether t h e U02 i n cold-swaged rods can
be h e a t t r e a t e d t o o b t a i n lower s u r f a c e a r e a s , experiments were conducted
a t 900°C i n a hydrogen atmosphere f o r various p e r i o d s of time. The d a t a
l i s t e d i n Table 18.4 show t h a t a f t e r 8 h r a t t h i s temperature a s i g n i f i c a n t
decrease o f 33$ i s obtained i n s u r f a c e a r e a . This appears t o be t h e m a x i -
mum decrease p o s s i b l e a t t h i s temperature. Compared w i t h t h e value of 0.09

"Maritime Reactor P r o j e c t Ann. Prog. Rep. Nov. 30, 1959, ORNL-2865,

p 41-42.

298
3 UNCL A S S I Fl ED

Fig. 18.7. Photomicrograph of Transverse Section of Room-Temperature Swaged UO, Fuel Rod,
Clad with Type 304 Stainless Steel, Illustrating a Typical Wall Crack. Rod was swaged at room tem-
perature to a total reduction in area of 67.5%. Depth o f crack i s approximately 0.004 in. As polished.
1oox.
UNCLASSIFIED
ORNL-LR-DWG 45455

45 50 55 60 65 70 75 80 85 90
REDUCTION IN A R E A (7')

Fig. 18.8. Effect of Swaging Temperature and

Reduction on Wall Cracking of Type 304 Stainless
Steel Tubing Containing UO,.

299
 Table 18.4. E f f e c t of Postswaging Heat Treatment on
Surface Area of Fused and Ground U02 Cold Swaged
t o Approximately 90% of T h e o r e t i c a l Density

Surface Area
Sample Time a t 900°C i n H2
(m2/g 1

1 Cold swaged a t room temperature 0.37

2 4 hr 0.34
3 8 hr 0.25
4 24 h r 0.25

(D
m2/g f o r U02 rods h o t swaged a t 800°C, t h e h e a t - t r e a t e d value o f 0.25 i s
s t i l l high.
Both h o t - and cold-swaged rods containing U02 w i t h s e v e r a l d i f f e r e n t Q
p a r t i c l e s i z e combinations and two U235 enrichments have been prepared f o r
t h e Maritime Loop I r r a d i a t i o n Program. P e r t i n e n t data a r e l i s t e d i n Table
18.5, and t h e f u e l element bundle design i l l u s t r a t e d i n F i g . 18.9. At
p r e s e n t , s e v e r a l of t h e s e bundles have been exposed without i n c i d e n t i n
two cycles i n t h e OF3 a t 20-Mw r e a c t o r power.

F a b r i c a t i o n of Plate-Type S t a i n l e s s S t e e l F u e l Element
Containing Dispersions of UOz i n S t a i n l e s s S t e e l

C . F . k i t t e n , Jr. J. H. Cherubini R. c . williams''

The f u e l element proposed f o r Core I11 of t h e sodium-cooled Enrico
Fermi F a s t Breeder Reactor c o n s i s t s o f 14 f l a t p l a t e s containing a dis-
p e r s i o n of UOz i n a u s t e n i t i c s t a i n l e s s s t e e l c l a d with a u s t e n i t i c s t a i n -
less steel. The o r i g i n a l l y designed element i s i l l u s t r a t e d i n F i g . 18.10
Q
with p e r t i n e n t design d a t a l i s t e d i n Table 18.6. The o b j e c t i v e s of t h i s
program have been t o (1)s e l e c t a s t a i n l e s s s t e e l cladding b e s t s u i t e d f o r
u t i l i t y i n t h e temperature range 800 t o 1200°F, ( 2 ) develop powder metal-
l u r g y p r a c t i c e s f o r i n c o r p o r a t i n g s p h e r i c a l U02 i n s t a i n l e s s s t e e l , ( 3 )
demonstrate t h a t r o l l - c l a d d i n g methods can be u t i l i z e d f o r t h e f a b r i c a t i o n
of t h i c k p l a t e s containing t h i s type of f u e l d i s p e r s i o n , and ( 4 ) e s t a b l i s h
methods f o r j o i n i n g t h e f l a t p l a t e s i n t o a f u e l a r r a y .

"Atomic Power Development A s s o c i a t e s .

300
 Table 18.5. F u e l Loading and Operating Parameters
f o r Swaged Rods i n I r r a d i a t i o n Test

Anticipated No, of
Rod
uo2
Particle
Swaging
UOz Center Cycles Enrichment
Experiment LOOP
Leg No. Size Temperature Tempe rat u r e ( w t $I $ 3 5 )
("C) i n ORR
(Mesh) ("C)

1 A-l 1 -20 +35 RT 2200 4 2.05

2 -20 +35 RT 2'775 4 2.05
3 -170 +325 RT 2775 4 2.05
A-2 4 -170 +325 RT 2200 4 0.81 .
5 -20 800 2200 4 0.81
6 -20 800 2775 4 0.81
2 A-l 1 -20 +35 RT 2200 8 2.05
2 -20 +35 RT 2775 8 2.05
3 -170 +325 RT 2775 8 2.05
A-2 4 -170 +325 RT 2200 8 0.81
5 -20 800 2200 8 0.81
6 -20 800 2775 8 0.81
 UNCLASSIFIED
Y-34004

Fig. 18.9. Swaged-Rod Irradiation Test Bundle.

UNCLASSIFIED
ORNL-LR-DWG 43099

FUEL
PLATE -

FUEL CORE-

SIDE
RETAINER
BAR 1

Fig. 18.10. Flat-Plate Core Bundle.

Austenitic stainless steel was selected as the cladding and matrix

material for the U02 primarily because of its corrosion resistance in sodium
a
at 800°F.12 Three austenitic types, 347, 310, and 316, were chosen for ex-
amination to determine which should be the reference structural material.
Selection was to be based on the U potential and yield strength at the
l l O O ° F fuel center line operating temperature. Sheet specimens of the
three types of stainless steel were cold reduced 25$ in thickness to ac-
celerate transformation to U and heat treated for 1000 hr at 1200°F. As
illustrated in Fig. 18.11, all the steels examined showed the presence of
CJ with type 310 forming the most. Criteria for selection were therefore

302

a
 Table 18.6. P e r t i n e n t Design Data f o r t h e Proposed U02-Stainless S t e e l
Gs F u e l Element f o r Core 111 of t h e Enrico Fermi F a s t Breeder Reactor

Reactor power, Mw 300

Core power, Mw 250
AT, "F
Sodium c o o l a n t 550-800
Uranium enrichment, $ u~~~ 93
F u e l p l a t e s p e r f u e l element 14
Nominal p l a t e dimensions, i n . 37.5 X 2.40 X 0.116
Nominal c o r e dimensions, i n . 36 X 2.15 X 0.102
Clad t h i c k n e s s , i n . 0 .OO7
Q
U02 l o a d i n g , w t $ 33.6
Maximum f u e l temperature, "F 1100

Q Average U235 burnup, a t . $ 25

Average h e a t flux, Btu-hr-".ft-2 405,000

based p r i n c i p a l l y on t h e t h e o r y t h a t y i e l d s t r e n g t h of t h e s t a i n l e s s s t e e l
m a t r i x m a t e r i a l i s probably one o f t h e more important f a c t o r s i n irradia-
t i o n b e h a v i o r of UO2-stainless s t e e l d i s p e r s i o n s a t t e m p e r a t u r e s up t o ap-
proximately l100"F.13 A s l i s t e d i n Table 18.7, a t 1100°F t y p e 347 h a s a
y i e l d s t r e n g t h 16% h i g h e r t h a n t,ype 310 and 28$ h i g h e r t h a n t y p e 316.14
Type 347 was t h e r e f o r e s e l e c t e d as t h e m a t r i x and c l a d d i n g m a t e r i a l .
The l a c k of i r r a d i a t i o n t e s t d a t a a t 1100°F coupled w i t h t h e d e s i r e
to o b t a i n 25% burnup of t h e U235 atoms i n a d i s p e r s i o n of 33 w t $ U02 i n
s t a i n l e s s s t e e l s t i m u l a t e d t h e s e l e c t i o n o f s p h e r i c a l U02 which, f o r a spe-
c i f i c volume of f i s s i l e material, minimizes t h e volume of s t a i n l e s s s t e e l
between f u e l p a r t i c l e s which i s damaged b y f i s s i o n fragments. l 5 The s i z e
of U02 deemed most compatible w i t h p l a t e design, f a b r i c a t i o n parameters,
and irradiation-damage t h e o r y i s i n t h e range 105 t o 149 p (-100 +140
mesh).

13J. R . Weir, A F a i l u r e A n a l y s i s f o r t h e Low-Temperature Performance

of D i s p e r s i o n F u e l Elements, 0RN.L-2902 (May 27, 1960).
''*Steels f o r E l e v a t e d Temperature S e r v i c e , U . S . S t e e l Corp., 1953.
~-
"H. M. F i n n i s t o n and J. P. Howe, Metallurgy and F u e l s , s e r . V,
p 301-26, Pergamon P r e s s , 1959.

303
 4

F i g . 18.11. Sigma Formation in Types 347, 316, and 310 Stainless Steels During Simulated Reactor
Operation Conditions. All specimens c o l d reduced 25% and heat treated 1000 hr at 65OOC. Etchant:
g l y c e r i a regia. (a) Sigma i n type 347 stainless steel sheet; dark precipitate i s sigma. ( b ) Sigma i n
type 316 stainless steel sheet; delineated grain boundary phase i s sigma. Carbides are precipitated
throughout the grains. (c) Sigma in t y p e 310 stainless steel sheet; delineated phase i s sigma.

304

0
 Table 18.7. P e r t i n e n t P r o p e r t i e s of S t a i n l e s s S t e e l s
Considered f o r Fermi Reactor S t a i n l e s s
S t e e l F u e l Element*
~

S t a i n l e s s S t e e l Type
~~

347 316 310

Yield s t r e n g t h : ~O'F, p s i x 39.5 38.5 40.0

1100"~~psi x 3 '
0
1 28.5 20.5 24.0
Ultimate s t r e n g t h , 70"F, p s i X 91.0 851.5 92 .O
1$ Elongation i n 10,000 h r , 1100"F,
psi x 13.5 18.2 13.0
Grain size,** ASTM 4-5 1
F a b r i c a b i li.t y Excellent Good Good

" S t e e l s f o r E l e v a t e d Temj?erature S e r v i c e , U.S. S t e e l Corporation,

1953.
**Full a n n e a l a t 1200°C.

P l a t e F a b r i c a t i o n . - Considerable s e g r e g a t i o n w a s encountered i n
b l e n d i n g a 33 w t $ d i s p e r s i o n i n t y p e 347 s t a i n l e s s s t e e l under r e l a t i v e l y
dry conditions. A t y p i c a l example of a s e g r e g a t e d f u e l p l a t e i s i l l u s -
t r a t e d i n F i g . 18.12a. A "wet" b l e n d i n g method, u s i n g 2 t o 3 w t 5 of 5%
p a r a f f i n i n CCl4, was developed. and r e s u l t e d i n homogeneity as i l l u s t r a t e d
i n F i g . 18.12b.
T o minimize fragmentation and s t r i n g e r i n g o f t h e s p h e r i c a l U02, pre-
v i o u s i n v e s t i g a t i o n s recommended temperatures of 1200°C o r h i g h e r and mini-
mum r e d u c t i o n s i n t h i c k n e s s . 1 6 It w a s t h e r e f o r e e s t a b l i s h e d t h a t t h e h o t -
r o l l i n g temperature b e 1200°C; and by u s i n g evacuated p i c t u r e - f r a m e t e c h -
niques i n t h e p r e p a r a t i o n of b i l l e t s , it w a s f e l t t h a t p l a t e s could be
r o l l bonded w i t h a h o t r e d u c t i o n i n t h i c k n e s s of 87$. No c o l d r o l l i n g w a s
permitted. F u l l - s i z e p l a t e s were r e a d i l y f a b r i c a t e d u s i n g t h e s e param-
e t e r s and, as shown i n F i g . 18.:13a, r e s u l t e d i n a n i c e l y d i s t r i b u t e d d i s -
p e r s i o n of o v a t e f i s s i l e partic1Les. Under i d e n t i c a l c o n d i t i o n s , however,
a d i f f e r e n t l o t of UO;! showed f r a c t u r i n g and s t r i n g e r i n g . The e f f e c t i s

16J. E . Cunningham -
et -
a l . , p 2 4 3 6 8 , i n F u e l Elements Conference,
P a r i s , November 1&23, 1957, TID-75146, Book 1 (March 1958).

305
 I

w
0
o*

Fig. 18.12. Prints of Radiographs Illustrating Macroscopic Uranium Distribution as Effected by the Powder Metallurgy Compact Prep-
aration Practice. Dark areas indicate fields of high uranium concentration. ( a ) Segregation due to dry blending; ( b ) homogeneity due to
"wet" blending.

a
LOC
i l l u s t r a t e d i n F i g . 18.13b. The d i f f i c u l t y i s a s s o c i a t e d w i t h t h e UO;! par-
t i c l e , b u t t h e f a c t o r s a f f e c t i n g t h e s e d i f f e r e n c e s a r e as y e t unresolved.
Twelve miniature composite p l a t e s were prepared f o r i r r a d i a t i o n t e s t -
i n g i n t h e MTR.17 These specimens contained 33.6 w t $ s p h e r i c a l UOz i n
s t a i n l e s s s t e e l and were f a b r i c a t e d by using procedures described above.
Radiographs of t h e U02 d i s t r i b u t i o n revealed good homogeneity of t h e f i s -
s i l e compound.
F u e l Element Assembly. - The proposed Fermi f u e l element assembly de-
s i g n i s i l l u s t r a t e d i n F i g . 18.10. The 0.116-in.-thick p l a t e s a r e spaced
0.058 i n . a p a r t by bushings, which a r e i n s e r t e d through t h e c e n t e r of t h e
f u e l p l a t e a t 2-in. i n t e r v a l s along t h e l e n g t h of t h e p l a t e . Alignment
p i n s , 1/8 i n . i n diameter, a r e i n s e r t e d through t h e s e bushings. The bush-
ings a r e f i x e d i n t o p o s i t i o n and t h e exposed f u e l i n t e r f a c e s s e a l e d by
brazing. A d d i t i o n a l support i s gained by t h e attachment of combs a t 2 - i n .
i n t e r v a l s along t h e s i d e s of the f u e l element. T h e combs a r e f i x e d i n t o
p o s i t i o n by welding. P r i o r t o i n s e r t i o n i n t o t h e reactor grid, t h e f u e l
element i s housed i n a s t a i n l e s s s t e e l wrapper can.
The following b r a z i n g a l l o y s were examined during t h i s i n v e s t i g a t i o n :
Coast Metals No. 52 (89 Ni-5 Si-4 €32
- Fe, w t $), E l e c t r o l e s s n i c k e l (90
Ni-10 P, w t $), and General E l e c t r i c No. 81 (66 Ni-19 Cr-10 Si-4 Fe-1 Mn,
w t $). Coast Metals No. 52 formed e x c e l l e n t s e a l s and j o i n t s w i t h t h e
s t a i n l e s s s t e e l b u t w a s eliminated because of i t s boron content, which i n -
creased t h e p o t e n t i a l embrittlement of t h i s a l l o y under i r r a d i a t i o n , Elec-
t r o l e s s n i c k e l w a s r e j e c t e d because of d i f f i c u l t y i n p r e p l a c i n g a s u f f i -
c i e n t q u a n t i t y t o guarantee a high percentage of s e a l s . General E l e c t r i c
No. 81 w a s u l t i m a t e l y s e l e c t e d because it has none of t h e disadvantages
c i t e d f o r Coast Metals No. 52 and E l e c t r o l e s s n i c k e l , and metallographic
e
examination revealed it t o be very e f f e c t i v e i n s e a l i n g t h e j o i n t s between
t h e f u e l p l a t e s and t h e bushings. Typical j o i n t s brazed with General Elec-
t r i c No. 81 a r e i l l u s t r a t e d i n F i g s . 18.14 and 18.15. Using General Elec-
t r i c No. 81 as t h e b r a z i n g metal, an a l l - s t a i n l e s - s t e e l subassembly w a s
j o i n e d i n t o t h e proposed f u e l p l a t e a r r a y with no apparent d i f f i c u l t y .

--
17J. I . Federer e t a l . , F a s t Breeder Assistance Program, Phase I :
I r r a d i a t i o n of UO2-Stainless S t e e l F u e l Specimens, ORNL CF-60-1-14 (Jan.
7, 1 9 6 0 ) .

308

a
 =IED
c) 7

Fig. 18.14. Fillet Showing Joint Between Bushing and Fuel-Plate Cladding Brazed with General
Electric No. 81 Alloy. Etchant: glyceria regia,

P o s t i r r a d i a t i o n Examination of D i s p e r s i o n s of
U02 i n S t a i n l e s s S t e e l
e C . F . k i t t e n , Jr. A. E. R i c h t 1 8 R . J. Beaver

The f i r s t p l a t e - t y p e U02 s t a . i n l e s s s t e e l f u e l elements which have op-

e r a t e d s u c c e s s f u l l y i n t h e a c t i v e l a t t i c e of a power r e a c t o r a r e n e a r i n g
8 t h e completion of t h e i r p o s t i r r a d - i a t i o n examination. The elements were
developed and f a b r i c a t e d a t ORNL as p a r t o f t h e f i r s t c o r e l o a d i n g of t h e
SM-1 R e a c t o r a t F o r t B e l v o i r , V i r g i n i a . l g Two elements which c o n t a i n 26
w t $ U02 d i s p e r s e d i n s t a i n l e s s s t e e l were removed from t h e r e a c t o r a f t e r
10 Mwyr and, a l t h o u g h t h e y had o p e r a t e d w i t h o u t i n c i d e n t , it w a s f e l t ad-
v i s a b l e t o examine them i n d e t a i l as a guide f o r c o n t i n u i n g o p e r a t i o n w i t h

1- 8- S o l i d S t a t e D i v i s i o n .
"J. E . Cunningham - et - a l . , S p e c i f i c a t i o n s and F a b r i c a t i o n Procedures
f o r APPR-1 Core I1 S t a t i o n a r y F u e l Elements, ORNL-2649 ( J a n . 29, 1 9 5 9 ) .

309
 I
S3H3NI
N
9
n
0
0
I
XOOl
1
4

Fig. 18.15. Interface Between Bushing and Exposed Fuel Section

of Composite P l a t e Showing Effective Sealing by Brazing with General
Electric No. 81 Alloy. Etchant: glyceria regia.

t h e b a l a n c e of t h e f i r s t c o r e l o a d i n g . A s l i s t e d i n Table 18.8, t h e average

burnup of U235 due t o f i s s i o n w a s 13 and 18$, r e s p e c t i v e l y , f o r t h e sta-
t i o n a r y and c o n t r o l r o d f u e l elements, w i t h a maximum of 31 and 32$, r e -
spectively. Q u a l i t a t i v e examination r e v e a l e d no g r o s s damage. Detailed
e v a l u a t i o n of a l i m i t e d number of specimens s e c t i o n e d from t h e f u e l e l e -
ments showed no evidence of s t r u c t u r a l f a i l c r e s i n t h e f u e l d i s p e r s i o n

310
 Table 18.8. Burnup Data on SM-1 F u e l Elements
A f t e r 10 Mwyr Exposure

U235 F i s s i o n U235 Depletion

(k ) ($)

S t a t i o n a r y Element (OWL S-75)

Average burnup c a l c u l a t e d 15.45 19.00

Average burnup observed 13.00 16.00
M a x i m u m burnup c a l c u l a t e d 51.22 63.00
M a x i m u m burnup observed 31.00 38.13
a
C o n t r o l Rod Fuel Element (ORNL-CR-13)

Average burnup c a l c u l a t e d 17.07 21.00

(io Average burnup observed 17.89 22 .oo
M a x i m u m burnup c a l c u l a t e d 43.90 54.00
M a x i m u m burnup observed 32.00 39.36

o r clad-core separations. The m.icrostructure of t h e m a t e r i a l a f t e r 30%

burniip of t h e U235 a l o n e i s i l l u s t r a t e d i n F i g . 18.16. The i n t e g r i t y o f
t h e s t a i n l e s s s t e e l m a t r i x appears good and t h e o n l y evidence of t h e r e l a -
t i v e l y h i g h burnup of t h e U235 i s t h e appearance of v o i d s i n t h e U02. This
e f f e c t w a s observed p r e v i o u s l y i n m i n i a t u r e specimens o f s i m i l s r composi-
tion irradiated in the M!TR, after approximately 30% burnup of the U235
atoms.20 The b a l a n c e of t h e f u e l elements making up t h e f i r s t c o r e l o a d -
i n g o f SM-lhave r e c e i v e d 3376 a d d i t i o n a l burnup i n t h e a c t i v e l a t t i c e w i t h
a p p a r e n t l y no d i f f i c u l t y . P r e s e n t p l a n s i n c l u d e i r r a d i a t i n g t h e s e elements
t o s t i l l h i g h e r burnup.

20A. L. Boch, Army Package Power Reactor P r o j e c t P r o g r e s s Report,

ORNL-2703 (Mar. 24, 1959), p 25-32.

31 1
 Q

Fig. 18.16. Microstructure of P l a t e No. 3 of SM-1 Stationary Fuel Element (ORNL-S-72) After Esti-,
mated Burnup of 30% o f U235Atoms. A s polished. 500X.

BURNABLE POISONS A.ND CONTROL-ROD MATERIAL DEVEMPMENT

Boron Losses i n 0.05 t o 0.25 w t $ Boron-Stainless S t e e l

J. H. Cherubini

A s i g n i f i c a n t problem i n t h e powder m e t a l l u r g i c a l p r e p a r a t i o n of aus-

t e n i t i c s t a i n l e s s - s t e e l - b a s e f u e l compacts containing t h e burnable poison,
boron, e i t h e r i n elemental o r compound form, i s t h e e r r a t i c l o s s of boron
which occurs while s i n t e r i n g i n hydrogen a t e l e v a t e d temperatures .21 Re-
s u l t s of s t u d i e s of s t a i n l e s s - s t e e l - b a s e compacts containing 0.05 w t $ B
incorporated by a d d i t i o n s of a 0.25 w t $ €3-stainless s t e e l master a l l o y ,
s i n t e r e d a t 1175OC revealed t h a t l o s s e s could be reduced from as much as
75% when s i n t e r e d i n hydrogen t o l e s s t h a n 10% when s i n t e r e d i n vacuum o r

21Met. Ann. Prog. Rep. Sept. 1, 1959, ORNE2839, p 2 4 G 4 2 .

I

312
 dry helium.22 A d d i t i o n a l s t u d i e s w i t h t h e p r i n c i p a l elements of a u s t e n i t i c
s t a i n l e s s s t e e l indicated t h a t the loss i s associated with the i n t e r r e l a t e d
e f f e c t s of (1)f o r m a t i o n of B2O3 b y r e a c t i o n w i t h t h e H20 o r m e t a l oxide i n
e i t h e r hydrogen o r i n e r t g a s e s , ( 2 ) v o l a t i l i t y of t h e B2O3, and (3) r e a c -
t i o n of B2O3 w i t h R e a c t i o n of boron t o form v o l a t i l e boron-hydrogen
compounds i s a l s o p o s s i b l e . 2 3 Recent s t u d i e s have shown t h a t boron l o s s e s
i n 0.25 w t $ s t a i n l e s s s t e e l compacts s i n t e r e d i n hydrogen a t 1135°C a r e
independent o f t h e 220 c o n t e n t and t h e :Flow r a t e of t h e g a s w i t h i n dew
p o i n t s r a n g i n g from -100 t o +70°F and f:Low r a t e s from 20 t o 40 f t 3 / h r (STP).
The l o s s i n c r e a s e d w i t h s i n t e r i n g time i n t h e manner i l l u s t r a t e d i n F i g .
18.17. It i s p o s t u l a t e d t h a t t h e r a t e - c o n t r o l l i n g f a c t o r i n boron-stain-
l e s s s t e e l m a t e r i a l i s p r i m a r i l y a r e s u l t of d i f f u s i o n of boron t o t h e
metal. S i m i l a r h e a t - t r e a t m e n t s t u d i e s were made on 0.14 B - s t a i n l e s s steel
wrought s h e e t and t h e r e s u l t s compared w i t h t h e s i n t e r e d compact d a t a . As
i l l u s t r a t e d i n F i g . 18.18, w i t h i n t h e l i m i t of e x p e r i m e n t a l accuracy, t h e
f r a c t i o n of boron l o s t i s p r o p o r t i o n a l t o t h e s q u a r e r o o t of t i m e as a n t i c i -
p a t e d from t h e t h e o r y t h a t d i f f u s i o n of a n element such as boron from t h e

22APPR Ann. Prog. Rep. J a n . 31, 1960, ORNL-2907, p 1 3 1 4 .

.~

"W. J o s t , D i f f u s i o n i n S o l i d Liquid and Gases, p 72-73, Academic

P r e s s , New York, 1952.

Fig. 18.17. Relationship Between Boron L o s s and Time for 5-g Compacts of 0.25 wt % B-Type
304 Stainless Steel A l l o y Powder Sintered i n Hydrogen a t 1135OC.

313
 UNCLASSIFIED
ORNL-LR-DWG 50404
i.0
1
- -
0.8
sz 0.25 w t %E-TYPE 304
STAINLESS STEEL COMPACTS
,,/ -
g0.6 /
m
8
5 0.4
+
u
a
E
< 0.2

0
0 I 2 3 4
fl(
hr''z)

Fig. 18.18. Relationship Between Fraction of

Boron Lost and Square Root of Heat-Treatment
Time for Compacts of 0.25 wt % 6-Type 304 Stain-
less Steel Alloy Powder and Wrought 0.14 wt %
6-Type 304 Stainless Steel Alloy Heat Treated
at 1135% in Hydrogen.

i n t e r i o r of metal p l a t e specimens t o t h e surface i s t h e r a t e - c o n t r o l l i n g

f a c t o r . 2 4 The i n c r e a s e i n t h e loss r a t e i n t h e powder m e t a l l u r g i c a l l y pre-
pared specimens would be expected, p r i m a r i l y because t h e surface a r e a i s
higher.

Reaction of Boron and Metal Borides i n A u s t e n i t i c S t a i n l e s s S t e e l

J. H. Cherubini T . D . Watts
C . F. k i t t e n , Jr. R . J. Beaver

Previous s t u d i e s have shown t h a t a t elevated temperature processing

required i n t h e f a b r i c a t i o n of t h e UO2-stainless s t e e l plate-type f u e l e l e -
ment which u t i l i z e s burnable poison, B, B4C, ZrB2, and BN, w i l l r e a c t with
t h e type 304B s t a i n l e s s s t e e l and d i f f u s e t o s i g n i f i c a n t depths i n t o t h e
type 304L s t a i n l e s s s t e e l cladding.25 Recent s t u d i e s of couples of SrB6
and YB6 r e v e a l t h a t a similar e f f e c t w i l l occur with t h e s e compounds a l s o .
Figures 18.19 and 18.20 i l l u s t r a t e t h e r e a c t i o n and d i f f u s i o n of t h e boron
i n t o t h e s t a i n l e s s s t e e l a f t e r a 20-hr vacuum heat treatment a t 115OOC.

2 4 C . A. Brown and J. S . Hashman, MCC-1023-TR-54 (June 1954) ( c l a s -

sified).
25Army Package Power Reactor P r o j e c t Progress 'Report, ORNL-2703,
p 18-25 (Apr. 6, 1959).

314
 , UNCLASSIFIED
Y - 351 22

./
1
'
8

f
0

BD

(9

INTERFACE

Fig. 18.19. Diffusion of Boron into Type 304 Stainless Steel After Vacuum Heat Treatment
of YB6-Stainless Steel Couples for 20 hr at 115OOC. A s polished.

It i s e v i d e n t t h a t i n e i t h e r c a s e , t h e d e p t h of d i f f u s i o n i s a t l e a s t 0.030
in., and it c a n b e concluded t h a t from a s t a n d p o i n t of r e a c t i o n and d i f -
f u s i o n t h e s e compounds a r e s i m i l a r t o t h o s e p r e v i o u s l y s t u d i e d .
I n a d d i t i o n t o u t i l i z i n g boron as a b u r n a b l e p o i s o n i n f u e l elements,
e f f o r t s have a l s o been d i r e c t e d t o i n c o r p o r a t i n g as much as 4 w t $ of e l e -
m e n t a l boron ( h i g h l y e n r i c h e d i n BIO) i n a u s t e n i t i c s t a i n l e s s s t e e l b y
powder m e t a l l u r g i c a l t e c h n i q u e s . Experiments showed t h a t when i n c o r p o r a t -
i n g t h e boron i n t y p e 347 s t a i n l e s s s t e e l powder a u s t e n i t i z e d w i t h n i c k e l ,

315
 UNCLASSIFIED
Y - 31607

INTERFACE

Fig. 18.20. Diffusion of Boron into Type 304 Stainless Steel After Vacuum Heat Treatment
o f SrB6-Stainless Steel Couples for 20 hr at 1150OC. A S polished.

melting occurs at the normal sintering temperature of llOO°C, resulting in

a poorly made product. This is attributed to the 990°C eutectic tempera-
ture in the Ni-B systems.26 Investigations to sinter boron with a type 200
series stainless steel austenitized with manganese (0.03 C-20.7 Mn-16.4

26M. Hansen, Constitution of Binary A l l o y s , p 256, McGraw-Hill, New

York, 1958.

316
 C 4 . 5 Ni-0.06 Si-bal F e ) have been e n t i r e l y s u c c e s s f u l . The powder metal-
l u r g i c a l l y p r e p a r e d compacts c o n t a i n i n g 1.00, 2.5, and 4.0 w t $ B i n s t a i n -
l e s s s t e e l were c l a d w i t h t y p e 347 s t a i n l e s s s t e e l by r o l l bonding a t llOO°C
w i t h a 90% r e d u c t i o n i n a r e a . The roli-bonded i n t e r f a c e s a r e i l l u s t r a t e d
i n F i g . 18.21 and c l e a r l y show t h e d i f f u s i o n o f boron from t h e c o r e i n t o
t h e s t a i n l e s s s t e e l cladding. From a m i c r o s t r u c t u r a l s t a n d p o i n t t h e d i f -
f u s i o n l e n g t h appears t o be approximately 0.001 i n . from t h e bonded i n t e r -
f a c e i n t o t h e c l a d d i n g w i t h t h e c o n c e n t r a t i o n i n t h e zone i n c r e a s i n g with
i n c r e a s e d weight p e r c e n t . This low l e v e l of d i f f u s i o n i s n o t c o n s i d e r e d

a s e r i o u s i n i t s e f f e c t on t h e d e s i g n of such a c o m p n e n t .

I r r a d i a t i o n Damage tcl Dispersions of

Elemental Boron i n I r o n

0 C . F . L e i t t e n , Jr. R . J. Beaver

The r e f e r e n c e p l a t e - t y p e n e u t r o n a b s o r b e r s e l e c t e d f o r Core I of t h e
SM-1 Reactor, F o r t B e l v o i r , V i r g i n i a , was a d i s p e r s i o n o f 3 w t $ B ( h i g h l y
e n r i c h e d i n BIO) i n i r o n , c l a d w i t h t y p e 304 s t a i n l e s s s t e e l . Fabrication

UN CLASS1 F I ED
PHOTO-50791

CORE

BONDED
INTERFACE

CLAD - ,

. ‘
e”
\
0 , -

I-

(0)

F i g . 18.21. Longitudinal Cross Sections o f Stainless-Steel-Clad Plates Containing Boron.

Type 200 stainless steel r o l l bonded at llO&C with 90% reduction i n thickness. ( a ) 1.0 wt %
boron; ( b ) 2.5 wt % boron; (c) 4.0 wt % boron. 5% Cr0,-95% H,O, electrolytic. 500X.

317
procedures were developed, s p e c i f i c a t i o n s w r i t t e n , and seven neutron ab-
sorber s e c t i o n s f a b r i c a t e d f o r t h e f i r s t core l o a d i n g . 2 7 A t t h e same time,
miniature i r r a d i a t i o n t e s t s were conducted i n t h e NTR. The e v a l u a t i o n of
s e v e r a l of t h e s e specimens i r r a d i a t e d t o average BIO burnups ranging from
4 t o 30% revealed that, s i g n i f i c a n t damage occurred a t an average burnup o f
A f t e r 10 Mwyr o p e r a t i o n i n t h e SM-1 Reactor, t h e B-Fe absorber sec-
t i o n s were removed and replaced with s e c t i o n s containing a d i s p e r s i o n of
38 w t $ Eu2Og i n s t a i n l e s s s t e e l . Two were s u b j e c t e d t o an i n t e n s i v e post-
i r r a d i a t i o n examination.
Since t h e exposure of t h e absorber s e c t i o n t o neutrons v a r i e s from a
m a x i m u m near t h e end of t h e s e c t i o n adjacent t o t h e f u e l element t o a mini-
mum along t h e length of t h e s e c t i o n , BIO burnup measurements were made a t
i n t e r v a l s along t h e s e c t i o n from t h e high burnup end t o 20-1/2 i n . from
t h i s region. The r e s u l t s a r e l i s t e d i n Table 18.9. The average peak burnup
o f t h e BIO ranged between 18.0 and 22.0$, and decreased t o between 0.03 and
0.06% a t t h e 20-1/2-in. location. O f t h e e i g h t p l a t e s examined i n t h e two
absorber s e c t i o n s , a l l b u t one e x h i b i t e d clad-frame and clad-core separa-
t i o n s a t t h e high-burnup t i p end. This t y p i c a l f a i l u r e i s i l l u s t r a t e d i n
F i g . 18.22. The average BIO burnup a t t h e t i p end of a p l a t e which d i d
not f a i l i n t h i s manner w a s measured t o be 14.5 a t . 5. However, t h e p l a t e
t h i c k n e s s i n c r e a s e d 10s. A s p r e v i o u s l y reported, swelling and f a i l u r e of
cladding-frame and cladding-core i n t e r f a c e s i s a r e s u l t of t h e helium gen-
e r a t e d from t h e extremely high burnup of BIO atoms a t t h e bonded i n t e r -
face.28 I n t h e p l a t e s examined, t h e bonded i n t e r f a c e s destroyed by t h e
i r r a d i a t i o n v a r i e d from 1 t o 7 i n . from t h e t i p end of t h e p l a t e .

Boron Gradient f o r Control Rod Applications a

T . D . Watts C . F . k i t t e n , Jr. R . J . Beaver

Previous i n v e s t i g a t i o n s have shown t h a t i n s t a i n l e s s - s t e e l - c l a d p l a t e s

containing 3 w t '$ BIO i n i r o n , because of s e l f - s h i e l d i n g of t h e boron, t h e
s u r f a c e l a y e r s o f t h e boron-bearing material a r e burned up t o appreciably
~~

27R. J. Beaver, R . C . Waugh, and C . F. k i t t e n , Jr., S p e c i f i c a t i o n s

f o r Amy Package Power Reactor (APPR-1) F u e l and Control Rod Components,
ORNL-2225 ( J u l y 24, 1957)
28C. F . k i t t e n , Jr., R . J. Beaver, and A. E. Richt, J. Nuclear
Materials 2, p 1 3 6 4 4 (1959).
-
318
B)

Table 18.9. Burnup P r o f i l e s f o r l h o I r r a d i a t e d SM-1 Reactor

dv) Core I Absorber S e c t i o n s

Distance from Lithiurn Average BIO

C r i t i c a l End Content Burnup
(in. ) ( w t $1 (at. $ )

C e n t r a l Absorber (ORNL-5)

0.75 0.44 22.O"

3.5 0.19 9.5
6.5 0.14 7.0
12.5 0.026 1.3
20.5 0.0006 0.03

Shim Absorber No. 3 (ORNL-2)

0 .?5 0.36 18.0**

3.5 0.19 9.5
6.5 0.12 6.0
12.5 0.03 1.5
20.5 0.0012 0.06

"Average of only t h r e e p l a t e s ; p l a t e 18 had t i p burnup o f 14.5%

BIO.
**Average of a l l f o u r p l a t e s .

h i g h e r l e v e l s t h a n t h e underlying F o r example, t h i s s p e c i f i c
m a t e r i a l w i l l n o t s u f f e r s i g n i f i c a n t i r r a d i a t i o n damage when t h e average
burnup of B l 0 atoms i n t h e specimens i s l i m i t e d t o 4%. The BIO burnup i n
t h e s u r f a c e l a y e r s , however, i s as h i g h as 30$. If t h e average burnup i n -
c r e a s e s t o 9$, t h e burnup a t t h e o u t e r s u r f a c e s i n c r e a s e s t o 65% and r e -
s u l t s i n s e v e r e damage i n t h i s a r e a . It i s obvious t h a t t h e i r r a d i a t i o n
performance of materials i n which t h e boron i s homogeneously d i s t r i b u t e d
i s l i m i t e d by t h e h i g h burnup of t h e BIO atoms i n t h e s u r f a c e l a y e r s of
the material.
C a l c u l a t i o n s show t h a t by c o n s i d e r i n g t h e s e l f - s h i e l d i n g f a c t o r s of
BIO and based on t h e p o s t i r r a d i a t i o n d a t a of 3 w t $ B-Fe specimens t h a t
a boron c o n c e n t r a t i o n g r a d i e n t , which i s l i m i t e d t o burning out 4.7 X 1021

319

9
 4

Fig. 18.22. Magnified View of High Burnup End o f Central Control

Rod Absorber Section. 3X.

atoms of B l 0 p e r cm3, can be designed through t h e t h i c k n e s s of t h e p l a t e . 2 9

The c a l c u l a t e d curve shows t h e minimum concentration a t t h e s u r f a c e w i t h e
an experimental i n c r e a s e as t h e c o n c e n t r a t i o n curve approaches t h e mid-
plane of t h e t h i c k n e s s dimension. However, because of t h e i m p r a c t i c a l i t y
of f a b r i c a t i n g numerous t h i n l a y e r s of m a t e r i a l containing various boron e
concentrations, it i s d e s i r a b l e from an economic standpoint t o minimize
t h e number of compacts which need t o be prepared f o r i n c o r p o r a t i o n i n t o
a g r a d i e n t absorber p l a t e . The boron g r a d i e n t designed t o o b t a i n an aver-
age burnup o f 25$ of B l 0 atoms i n an S M - 1 control-rod p l a t e i s i l l u s t r a t e d
i n F i g . 18.23. The number of boron concentrations i s l i m i t e d t o four; thus,
seven compacts a r e considered a minimum f o r t h i s g r a d i e n t . The shaded a r e a
I

2 9 C . F. k i t t e n , Jr., R . J. Beaver, and A. E . Richt, J. Nuclear

Materials 2,
- p 136-44 (1959).

320
Q)

cs UNCLASSIFIED
ORNL-LR-DWG 50405

30 I

6'' CONCENTRATION IN
STAINLESS STEEL COMPACTS -

25

- 2 0

-
B
I
CENTER LINE I
THROUGH PLATE I
0 THICKNESS\
m
1.5 I

1.0

05

I I I I I
0 005 0 010 0 015 0020 0025 0030 0035 0040 00
PLATE THICKNESS ( i n )

F i g . 18.23. P r o f i l e o f Boron Concentration Gradient and B'O Burnup L i m i t s i n the H a l f Thickness

4) of a Neutron Absorber P l a t e Designed to Obtain an Average Burnup of 25% o f B'O Atoms with No Signif-
icant Damage. Other h a l f thickness i s symmetrical with the section illustrated.

r e p r e s e n t s t h e amount of BIO burned o u t .

The e f f e c t of s i g n i f i c a n t l y ex-
ceeding t h e 25% burnup value would, i n t h e main, r e s u l t i n a p p r e c i a b l y
higher burnups approximately 0.030 t o 0.040 i n . i n from t h e s u r f a c e . This
c o n d i t i o n would cause d e l e t e r i o u s e f f e c t s i n t h i s region.
A t p r e s e n t no
g r a d i e n t f u e l p l a t e has been f a b r i c a t e d ; however, compacts containing 1.0
t o 4.0 w t $I B i n type 200 s t a i n l e s s s t e e l have been r o l l bonded w i t h no
difficulty .

32 1
1

Dispersions of Eu2O3 i n A u s t e n i t i c S t a i n l e s s S t e e l

C . F. k i t t e n , Jr. R . J. Beaver

Previous i n v e s t i g a t i o n s have demonstrated t h e f e a s i b i l i t y of incorpo-

r a t i n g 38 w t $ d i s p e r s i o n s of Eu7-03 i n s t a i n l e s s s t e e l and r o l l cladding
i n t o composite p l a t e s f o r t h e neutron absorber s e c t i o n i n t h e c o n t r o l rod
of t h e SM-1 Reactor a t F o r t Belvoir, Virginia.30 It had been shown during
t h e development o f t h i s p o t e n t i a l l y e x c e l l e n t neutron-absorbing m a t e r i a l
t h a t it w a s not compatible with s i l i c o n even when s i l i c o n w a s p r e s e n t as
a n impurity i n excess of 0.03 w t $ S i i n Fe, Ni, o r C r . 3 1 This incompati-
b i l i t y i s g e n e r a l l y evidenced by volume i n c r e a s e s i n powder m e t a l l u r g i c a l l y
prepared compacts s i n t e r e d i n hydrogen a t 1200°C and t h e d e p o s i t i o n of a
europium-bearing yellow-green f i l m on t h e s u r f a c e s o f t h e compacts . 3 2 The
r e a c t i o n i n a d i s p e r s i o n of 30 w t $ Eu2O3 i n type 347B (2.0 w t $J S i ) stain-
l e s s s t e e l a f t e r s i n t e r i n g 1-1/2 hr a t 1230°C i s i l l u s t r a t e d i n Fig. 18.24.
A d d i t i o n a l evidence t h a t s i l i c o n i s t h e b a s i c cause f o r i n c o m p a t i b i l i t y
w i t h s t a i n l e s s s t e e l i s shown i n F i g . 18.25, which i l l u s t r a t e s t h e reac-
t i o n of 30 v o l $I EuzO3 i n s i l i c o n . E x t r a c t i o n of t h e white phase i n t h i s
m i c r o s t r u c t u r e l e d t o t h e i d e n t i f i c a t i o n of E S i 2 as one of t h e r e a c t i o n
32
products.
Although f o u r a d d i t i o n a l europium oxide-stainless s t e e l absorber sec-
t i o n s were made a t ORNL f o r t h e SM-lA Reactor, using t h e procedures recom-
mended as a r e s u l t of previous d e ~ e l o p m e n t ,t ~
h e~r e has been r e c e n t e v i -
dence t h a t c e r t a i n p h y s i c a l p r o p e r t i e s of Eu2O3 i t s e l f may be important t o
c o n t r o l swelling i n s i n t e r e d compacts. This swelling had been demonstrated
t o be independent of t h e s t a i n l e s s s t e e l and s t r i c t l y a s s o c i a t e d w i t h t h e
Eu203 .33 These observations have been based on preliminary i n v e s t i g a t i o n s
of s e v e r a l batches of Eu2O3 which have e x h i b i t e d i n c o n s i s t e n t behavior

3 0 C . F. k i t t e n , Jr., R . J . Beaver, and J . E. Cunningham, S p e c i f i -

c a t i o n s and F a b r i c a t i o n Procedures on Europium-Bearing Absorber Sections
for R e a c t i v i t y Control i n Core I1 of SM-1, ORNL-2733 ( J u l y 29, 1959).
31A. L. Boch, Army Package Power Reactor P r o j e c t Progress Report,
ORNL-2703, p 44-47 (Apr. 6, 1959).
3 2 C . F. k i t t e n , Jr., The S t a b i l i t y of Europium Oxide i n S i l i c o n -
Bearing S t a i n l e s s S t e e l , ORNL-2946 ( i n p r e s s ) .
33Unpublished ORNL work.

322
0
B)
:IED

cs 0

-
-
f.
,002

-
,001

-
004

005

a 306

X
0
0-
In

Fig. 18.24. Dispersion o f Eu,O, (30% by Weight) i n Type 3478 Stainless Steel Sintered at 1230T
for 1'/2hr Under Hydrogen. Light-gray phase, unreacted Eu203; dark-gray phase, reaction product; white
phase, stainless steel; black phase, void. A s polished.

IFlED
77
w
-I
0
z
-
c02

-
003

-
004

-
00 5

306

X
0
0-
In

Fig. 18.25. Dispersion o f Eu,O, (30% by Volume) i n Silicon Heat Treated at 120OOC for 1 \ hr
Under Hydrogen. White phase identified as EuSi,. A s polished. 500X.

323
 Table 18.10. S t a t u s of I r r a d i a t i o n Tests of Eu2O3
Dispersions i n S t a i n l e s s S t e e l Q
Unperturbed Exposure
Composition (Neutrons see-’)
Sample S t a t u s
(wt $ Eu203 )
Desired Present

x 1020 x 1020

20 7.2 7.0 I r r a d i a t i o n completed;

awaits r e t u r n
20 14.4 8.8 P r e s e n t l y under irra-
d i a tion
20 28.8 7.0 P r e s e n t l y under irra-
diation
20 43.2 9.6 P r e s e n t l y under i r r a -
diation
30 7.2 7.1 P r e s e n t l y being s t o r e d
i n p i l e canal
30 14.4 9.8 P r e s e n t l y under irra-
diation
30 28.8 7.2 P r e s e n t l y under i r r a -
d i a t i on

30 43.2 10.0 P r e s e n t l y under irra-

diation
40 7.2 7.2 I r r a d i a t i o n completed;
awaits r e t u r n
40 14.4 7.0 P r e s e n t l y under irra-
diation
e
40 28.8 10.4 P r e s e n t l y under irra-
diation
40 43.2 9.6 P r e s e n t l y under irra- 9
diation
a f t e r t h e s p e c i f i e d conditioning treatment and subsequent s i n t e r i n g as a
d i s p e r s i o n i n t h e low-silicon s t a i n l e s s s t e e l . Studies t o resolve the
e f f e c t of crystallography, p a r t i c l e s i z e , i m p u r i t i e s , e t c . , a r e i n prog-
ress.
Supporting i r r a d i a t i o n t e s t s of specimens c o n t a i n i n g 20, 30, and 40
w t $ Eu2O3 i n s t a i n l e s s s t e e l have been conducted i n t h e Engineering Test
Reactor.34 These miniature p l a t e specimens were f a b r i c a t e d i n t h e same
manner as t h e f u l l - s i z e absorber p l a t e s now o p e r a t i n g i n t h e c o n t r o l rod
of t h e SM-1 Reactor. Although none of t h e specimens have been examined
extensively, t h e r e has been no evidence of f a i l u r e under i r r a d i a t i o n , The
s t a t u s o f t h e specimens i s l i s t e d i n Table 18.10.

ADVANCED FUEL ELEMENT MATERIALS DEVELaPMENT

Fabric a t i o n and Cladding o f Uranium-Molybdenum

Alloys Containing 10 t o 17 w t $ Mo

T . K . Roche M. M. Martin
D . T . Bourgette R . J. Beaver

One of t h e promising f u e l systems f o r an advanced f u e l element f o r

Core I V of t h e Enrico Fermi F a s t Breeder Reactor i s a d i s p e r s i o n of a f i s -
s i l e compound, h i g h l y enriched i n U235, i n a f e r t i l e uranium matrix de-
p l e t e d i n U235. I n v e s t i g a t i o n s have t h e r e f o r e been i n i t i a t e d f o r studying
uranium a l l o y s containing 10 t o 17 w t $ Mo and f o r d i s p e r s i n g UC i n t h e
G 1 5 Mo powder, followed by cladding i n t o composite p l a t e s by r o l l bond-
ing. The Metal Forming and Casting S e c t i o n has confined i t s work t o t e c h -
niques f o r melting, c a s t i n g , and extruding t h e s e U-Mo a l l o y s and s e l e c t i o n
of a cladding m a t e r i a l p r e p a r a t o r y t o roll-bonding s t u d i e s .
Uranium-molybdenum a l l o y s were i n d u c t i o n melted under a vacuum o f
approximately 10 p i n a s t a b i l i z e d Z r O 2 c r u c i b l e and c a s t i n t o a water-
cooled copper mold. The r e s u l t a n t c a s t i n g s were 3 i n . i n diameter and
8-3/4 i n . long. No d i f f i c u l t y w a s experienced w i t h t h i s r a t h e r conven-
t i o n a l induction-melting technique. Melting and pouring temperatures a r e
l i s t e d i n Table 18.11.

‘C . .
F k i t t e n , Jr ., The I r r a d i a t i o n of Miniature Eu203 -Bearing
Absorber P l a t e s . I r r a d i a t i o n Request ORNL-MTR-39, ORNL CF-59-9-25 (Sept .
14, 1959).

325
 Table 18.11. Melting and Pouring Temperatures and Vacuum
Utilized in Casting U-Mo Alloys
~

Equilibr i m
Pouring Pouring
Me Iting Temperature Vacuum
Composition
Temperature
( O C )** (P)
("C)*

U-10 wt $ MO 1250 1400 %

-13 wt $ Mo 1410 1570 10
U-13.5 wt $ MO 1480 1660 10
U-15 wt $ MO 1520 1700 11
U-16.75 wt $ Mo 1600 1790 10
u-10 wt $ N-b 1510 1660 5%
U-UI wt $ ~ b ,4 wt 5 Zr N 1500 1625 10
-

*H. A. Saller and F. A. Rough, Compilation of U.S. and U.K. Uranium

and Thorium Constitutional Diagrams, BMI-1000 (June 1, 1955).
**Pyrometer corrections were made assuming h = 0.065 p and emissivity
of 0.34.

Molybdenum analysis of the casting was established by chemical analy-

ses of three diametric samples sectioned from the bottom and top of the
extrudable portion of each casting as well as the hot top. The micro-
structure adjacent to these samples was also examined metallographically
and the hardness measured. Prior to sampling these castings, small inert-
atmosphere arc melts of U-Mo alloys were prepared to determine the accu-
racy of analytical chemistry in analyzing the molybdenum content. The re-
sults are listed in Table 18.12. The weights of material charged and the
arc-melted alloy were essentially the same; therefore, the differences
in the analytically reported values and charged weights of molybdenum are
attributed to the variances in analytical chemistry techniques. It is
apparent that the Analytical Chemistry Division is able to analyze for
molybdenum within l$ of the actual molybdenum concentration. Table 18.13
shows the results of analysis of the vacuum-cast alloys. In general, the
majority of alloys exhibited molybdenum loss, which may be attributed to
melting in vacuum. Although the body of the castings was not sampled ex-
tensively, it may be inferred from the average deviation of analyses, from

326
0
 .

Table 18.12. R e s u l t s of Analyses of 10-g U-Mo Alloys Arc Melted

i n an I n e r t Atmosphere f o r A n a l y t i c a l Chemistry
C o n t r o l Samples

Molybdenum Molybdenum
Difference
Charged Analyzed
(wt Z) (wt $>
(5)

9.28 9.25 4.312

11.50 11.47 4.260
12.95 13.06 +0.85
15.50 15.50 0.0000
16.81 16.65 +O. 958
~ ~~

Table 18.13. R e s u l t s of A n a l y t i c a l Chemical Analyses of U-Mo Alloys

Intended Analyzed Mo l y b de nun, Maximum D e v i a t i o n

Molybdenum Arithmetic Mean from Arithmetic Mean
( w t $1 (wt P) (wt P)

10.00 9.75 0.55

10.00 9.79 0.67
13.00 13.05 0.73
13.50 13.48 0.73
13.50 13.81 0.86
15.00 14.17 0.68
16.75 16.58 1.10

t h e t o p and bottom of t h e c a s t i n g s , t h a t s e g r e g a t i o n i n a l l b u t t h e 16.75

w t $ Mo a l l o y i s low. Hardness measurements l i s t e d i n Table 18.14 r e v e a l
t h a t , i n g e n e r a l , t h e h i g h e r t h e molybdenum c o n t e n t , t h e h i g h e r t h e hard-
ness value. An unexplained anomaly e x i s t s , however, i n t h e c a s e of t h e
13 and 13.5 w t $ Mo a l l o y s i n t h e i r , r e p o r t e d h i g h e r hardness v a l u e s com-
p a r e d w i t h t h e 15 w t $I Mo a l l o y . The r e a s o n f o r t h i s i s unresolved.
Metallographic examination of c o r i n g as a f u n c t i o n of molybdenm con-
c e n t r a t i o n i s i l l u s t r a t e d i n F i g . 18.26. Magnitude of c o r i n g i n c r e a s e s
from bottom t o t o p f o r any s p e c i f i c c o n c e n t r a t i o n . It a l s o becomes more
p e r c e p t i b l e as t h e molybdenum c o n c e n t r a t i o n i n c r e a s e s . A s p r e d i c t e d by

327
 Table 18.14. Room-Temperature Hardness Values
of U-Mo Castings Q
Compo
(wt I " /

A-10 MO 28.83 29.66 29.25

B-10 MO 30.30 28.40 29.30
A-13 MO 34.00 35.60 34.80
A-13.5 MO 35.74 36.86 36.30
A-15 MO 31.16 32.66 31.91
B-15 MO 36.23 34.33 35.28
A-16.75 MO 37.43 38.40 37.91

UNCLASSIFIED
PHOTO 50792

e
BOTTOM OF TOP OF BOTTOM OF TOPOF BOTTOM OF TOP OF
CASTl NG CASTl NG CASTl NG CASTING CASTl NG CASTING
U-43.5 w t Yo MO U-46.75 w t Yo M O

Fig. 18.26. Coring i n U-Mo Castings as a Function o f Molybdenum Concentration. Etchant: elec-
trolytic, 10% H,O-40% lactic acid-50% acetic acid. 250X.

328

a
 the equilibrium diagram, the terminal solid solution phase, highly con-
centrated in molybdenum, precipitated in the 16.75 wt $ Mo alloy.35 The
size and distribution of this phase is illustrated in Fig. 18.27 as a
function of location along the length of the casting.
Extrusions of the 2-3/4-in.-dia X 6-in.-long U-Mo, U-Tsb, and U-Nb-Zr
alloys were readily accomplished in a 700-ton horizontal extrusion press.
Billet design consisted of encasing the uranium-base alloys in a 0.083-
in.-thick Inconel can, with molybdenum foil between these two materials
as a barrier against eutectic formation. A mild-steel nose cone was at-
tached to the leading end of the billet. (Previous experience with In-
@ conel nose cones was unsuccessful.) Pertinent data in the extrusion of
six of these uranium-base billets are listed in Table 18.15. As expected,

e the pressure required to extrude the U-Mo alloys increased with increased
molybdenum concentration.

35H. A. Saller and F. A. Rough, Compilation of U . S . and U.K. Uranium

-
and Thorium Constitutional Diagrams,
U NCLASS I FIED
PHOTO 50793

BOTTOM MIDDLE TOP

Fig. 18.27. Size and Distribution o f Precipitated Molybdenum i n

U-16.75 w t 5% Molybdenum Castings. A s polished. 250X.

329
 Table 18.15. Average Running Pressure Required f o r Extruding
U-Mo, U-Nb, and U-Nb-Zr Alloys
\
B i l l e t s i z e , 3-in. d i a ( a l l o y plus can)
Die design, 3/4-in. dia, 45' c o n i c a l
Extrusion r a t i o , 10.5:l
Preheat temperature, 950°C
Soaking time a t temperature, -19 h r
Extrusion r a t e , 1/2-1 i n . o f b i l l e t length per see

Average Running
Composition Extrusion Pressure
( w t $1 (tsi)

U-10 Mo* 59
U-13 MO 65
U-13.5 MO 65
-15 Mo 78
-10 Nb 47
-10 Nb-4 Z r 58
-

*Preheated a t lO0O'C f o r 24 h r and extruded.

A review of t h e l i t e r a t u r e t o s e l e c t a cladding m a t e r i a l f o r UC d i s -
persed i n U-Mo a l l o y r e s u l t e d i n t h e s e l e c t i o n of t h e following a l l o y s
f o r a d d i t i o n a l study:36 (1)n i c k e l w i t h a molybdenum b a r r i e r between t h e
f u e l dispersions and t h e n i c k e l cladding, ( 2 ) z1-3 w t $ A l , Nb-1.8 wt $
C r , and (3) F a n s t e e l 82 (Nb-33 w t '$ Ta-0.7 w t '$ Z r ) .

BERYLLIUM FABRICATION

T . K. Roche

To assess t h e p o t e n t i a l of beryllium tubing as a container m a t e r i a l

f o r UO2 and/or UC f u e l s f o r advanced gas-cooled r e a c t o r s , purchase orders
were placed with experienced beryllium f a b r i c a t o r s , f o r e i g n and domestic,
f o r t h e procurement of beryllium tubing.37'38 P a r t i a l shipment on 500 f t
of seamless tubing, 0.300- X 0.040-in. w a l l , from each of t h e following
36M. M. Martin and R. J. Beaver, Cladding Survey f o r Enrico Fermi
Reactor:
-~ U-15 w t $ Mo-Base Dispersion-Type
- - Fuel Element, ORNL CF-60-4-118
(Apr. 29, 1960).
37GCR Quar. Prog. Rep. Mar. 31, 1960, ORNL-2929, p 138.
38GCR Quar. Prog. Rep. June 30, 1960, ORNL-2964 ( i n press ) .
330
or
 .... .. -.- - -.

t h r e e vendors has been r e c e i v e d : C h e s t e r f i e l d Tube Company, Limited of

England; Pechiney of France; and Brush B e r y l l i u m Company of t h e United
States. An a d d i t i o n a l 140 f t of 0.520-in.-ID, 0.040-in.-wall seamless
t u b i n g h a s been o b t a i n e d from Pechiney. The t u b i n g i s undergoing exten-
s i v e e v a l u a t i o n f o r q u a l i t y and mechanical p r o p e r t i e s .
To f u r t h e r e v a l u a t e and determine t h e p o t e n t i a l of b e r y l l i u m t u b i n g ,
s u b c o n t r a c t s and purchase o r d e r s were i s s u e d t o Nuclear Metals, Incorpo-
r a t e d , Cambridge, Massachusetts, and t o Superi,or Tube Company as United
S t a t e s a g e n t s f o r C h e s t e r f i e l d Tube Company, Limited of England. The ob-
j e c t i v e of t h e s u b c o n t r a c t w i t h Nuclear Metals, I n c o r p o r a t e d i s t o i n v e s -
t i g a t e t h e e f f e c t s of p e r t i n e n t e x t r u s i o n parameters, t h a t i s , speed, tem-
p e r a t u r e , r e d u c t i o n r a t i o , and b i l l e t design on t h e q u a l i t y and p r o p e r t i e s
o f b e r y l l i u m t u b i n g w i t h s i z e s ranging from 0.300 t o 0.750 i n . diameter
and w a l l t h i c k n e s s e s ranging from 0.030 t o 0.100 i n . The purchase o r d e r
w i t h t h e C h e s t e r f i e l d Tube Company w a s d e v i s e d t o o b t a i n p e r t i n e n t B r i t i s h
experience i n p r o c e s s i n g a s - e x t r u d e d t u b i n g t o c l o s e f i n i s h i n g t o l e r a n c e s .
It i s a n t i c i p a t e d t h a t t h e d a t a w i l l b e used i n t h e n e a r f u t u r e t o f a b r i -
c a t e a d d i t i o n a l t u b i n g f o r t h e Gas-Cooled Reactor Program.

Arc-Melted Uranium Monocarbide

D. T . Bourgette

Because of t h e h i g h thermal c o n d u c t i v i t y of uranium monocarbide r e l a -

t i v e t o uranium dioxide, a program h a s been d e v i s e d t o e v a l u a t e t h e poten-
t i a l of t h i s material f o r r e a c t o r s . P r e p a r a t i o n s f o r a r c - m e l t i n g uranium
c a r b i d e were i n i t i a t e d t o shape cast t h e f i s s i l e material i n t o two s i z e s :
(1)0.315 i n . i n diameter and 0.7'50 i n . long, and ( 2 ) 0.400 i n . i n diameter
and 3.25 i n . l o n g . Considerable d i f f i c u l t y w a s encountered i n c a s t i n g t h e
uranium c a r b i d e t o shape because o f i t s h i g h m e l t i n g p o i n t and t h e r m a l
conductivity. By d e s i g n i n g a copper mold i n s u l a t e d w i t h alumina, flame
sprayed on t h e copper, and combining p r e h e a t i n g of t h e molds w i t h p r o p e r
power d e n s i t y , time and mechanical movement of t h e a r c , it w a s p o s s i b l e
t o c a s t i n t o t h e d e s c r i b e d shapes w i t h r e l a t i v e l y good s u r f a c e q u a l i t y , 3 8
E f f o r t s a r e p r e s e n t l y d i r e c t e d t o t h e p r e p a r a t i o n of 15- and 125-g c y l i n -
d e r s , 10% e n r i c h e d i n U235 f o r i r r a d i a t i o n specimens.

33 1
 Elec tron-Beam Melting

T . Hikido

The electron-bombardment furnace p r e v i o u s l y described3 i s being used

t o prepare h i g h - p u r i t y metals and a l l o y s , p r i m a r i l y r e f r a c t o r y metals.
Figure 18.28 i s a cutaway drawing of t h e furnace, i l l u s t r a t i n g some of i t s
s a l i e n t components. The furnace c o n s i s t s e s s e n t i a l l y of an e l e c t r o n gun,
a vacuum pumping system, a melting chamber, a water-cooled copper mold,
and a melt-stock charging device. Separate c a b i n e t s house t h e power supply
and c o n t r o l s .
I n t h e main power supply, a c o n t r o l l a b l e v a r i a b l e transformer (0- t o 0
480-v o u t p u t ) feeds a high-voltage transformer (maximum output, 20,000 v )
whose output i s r e c t i f i e d t o d i r e c t c u r r e n t v o l t a g e by s i x vacuum diode
tubes. A secondary power supply with 3000-v, 0.5-amp c a p a c i t y i s used t o h
heat the electron-gun cathode to thermionic-emission temperatures. The
m a x i m u m r a t e d electron-beam power i s 60 kw (20,000 v, 3 amp).
The e l e c t r o n beam, a c c e l e r a t e d from t h e gun, i s focused by an e l e c -
tromagnetic c o i l through an a p e r t u r e and onto t h e m a t e r i a l t o be melted.
The h e a t i n g c a p a c i t y of an e l e c t r o n beam can be c a l c u l a t e d t o be 1 . 4 X

V I cal/min, where V i s t h e a c c e l e r a t i n g p o t e n t i a l i n v o l t s and I i s

t h e beam c u r r e n t i n amperes. This r e p r e s e n t s t h e conversion of approxi-
mately 98% of t h e k i n e t i c energy of t h e e l e c t r o n s t o h e a t ; t h e o t h e r 276
produces x r a y s .
The furnace i s evacuate4 t o 5 X mm Hg o r lower b e f o r e t h e melt-
ing operation i s s t a r t e d . I n some m e l t s , gas b u r s t s cause an i n i t i a l p r e s -
s u r e i n c r e a s e , b u t t h e f i n i s h i n g p r e s s u r e i s almost always below 1 X
mm Hg. The combination of high vacuum and noncontaminating water-cooled
copper molds permits p u r i f i c a t i o n of many metals.
The e f f e c t of electron-beam melting on t h e chemical a n a l y s i s and m i -
c r o s t r u c t u r e of V, Nb, Mo, Ta, and W i s presented i n Table 18.16 and F i g s .
18.29-18.33. The melts weighed between 50 and 75 g each.
-~

39ANP Semiann. Prog. Rep. Apr. 30, 1960, ORNL-2942 ( i n p r e s s ) ( c l a s -

sified).
 UNCLASSIFIED
ORNL-LA-DWG 45791
COOLING AIR

FEEDER

.MELTING CHAMBER

ASIGHT
PORTS

- WATES-COOLED MOLD

-MOLD CUP ASSEMBLY

Fig. 18.28. Electron-Bombardment Furnace.

333
 Table 18.16. Vacuum-Fusion Analysis of Electron-Beam-Melted
R e f r a c t o r y I.letals

Analysis (ppm )
Metal
Oxygen Nitrogen

Vanadium
Before+ 700 130
After 47 12
Niobium
Before* 1730 520
After 23 18
Molybdenum
Before 29 10
After 10 < 5
Tantalum
Before 24 16
After 12 5
Tungsten
Before 130 <5
After 50 < 5

"Vendor's a n a l y s i s .

The p u r i f i c a t i o n due t o t h e electron-beam p r o c e s s i s i l l u s t r a t e d i n

t h e t a b l e and t h e photomicrographs, although n o t w i t h o u t anomalies. For
example, t h e vanadium a n a l y s i s i n d i c a t e s a much h i g h e r degree of p u r i f i -
c a t i o n t h a n i s e v i d e n t i n t h e photomicrographs of F i g , 18.29, although
t h e g r a i n boundaries and m a t r i x of t h e melted vanadium do appear somewhat
cleaner. The i n c l u s i o n s remaining i n t h e electron-beam-melted vanadium
could, of course, b e due t o compounds o t h e r t h a n t h e oxide o r n i t r i d e .
The niobium m e l t i n g s t o c k c o n s i s t e d of s i n t e r e d p e l l e t s produced b y r e -
a
ducing Nb205 w i t h NbC i n a vacuum f u r n a c e . The l a r g e r b l a c k a r e a s appear-
i n g i n t h e premelt m i c r o s t r u c t u r e a r e v o i d s , which would a l s o l a r g e l y be
removed by i n e r t - g a s o r vacuum-arc m e l t i n g . The degree of p u r i f i c a t i o n
achieved w i t h r e s p e c t t o oxygen and n i t r o g e n could not be d u p l i c a t e d b y
t h e s e p r o c e s s e s , however. Although a p p a r e n t l y p u r i f i e d considerably, t h e
molybdenum and t u n g s t e n specimens f r a c t u r e d i n t e r g r a n u l a r l y i n a b r i t t l e
manner under impact l o a d s . Under h i g h e r m a g n i f i c a t i o n (approximately
750X), a p r e c i p i t a t e could b e s e e n i n t h e t u n g s t e n g r a i n boundaries b u t

334
 Fig. 18.29. Vanadium (a) Before and (6) After Electron-Beam Melting. Etchont: 50 H20-25HN0,-10
H2S04-10 HF.

335
 Fig. 18.30. Niobium ( a ) Before and ( b ) After Electron-Beam Melting. Etchant: 50 H,O-25 HNO,-lO
H,SO,-lO HF.

336
 Fig. 18.31. Molydbenum ( a ) Before and ( b ) After Electron-Beam Melting. Etchant: 50 H,O,-50
NH,OH.

337
 ED I Q

UNCLASSIFIED
Y- 33700

--.- _/--

Fig. 18.32. Tantalum ( a ) Before and ( b ) After Electron-Beam Melting. Etchant: 50 HN03-20
H,S04-20 HF.

338
 ., c .
I

UNCLASSIFIED

.I.
0
E
-
002

* .
-
003

0
* *
i w -
004

. *
? r.
a . o e
Do5
' e clr'

)08

x
0
0-
v)

Fig. 18.33. Tungsten ( a ) Before and ( b ) After Electron-Beam Melting. Etchant: 50 H,O,-50
NH,OH.

339
w a s not as c l e a r l y evident i n t h e molybdenum. The appearance of t h e molyb-
denum g r a i n boundaries i n F i g . 18.31 i s due p r i m a r i l y t o r e l i e f polishing,
whereby a d j a c e n t g r a i n s u r f a c e s were removed a t d i f f e r e n t r a t e s . The p r e -
melt a n a l y s i s of t h e tantalum seems t o be low considering t h e gas evolu-
t i o n t h a t occurred during t h e i n i t i a l melting of t h i s m a t e r i a l .
The i n c r e a s e i n g r a i n s i z e evident i n t h e photomicrographs i s a func-
t i o n of t h e time t h e m e t a l i s h e l d i n t h e molten s t a t e and i s probably due
both t o i n c r e a s i n g p u r i t y of t h e metal and growth of t h e nucleating s i t e s
f o r c r y s t a l formation. The water-cooled copper h e a r t h keeps t h e bottom
s u r f a c e of t h e b u t t o n frozen b u t not c o o l enough t o prevent g r a i n growth
i n t h i s layer. When t h e beam power i s t u r n e d o f f , c r y s t a l s nucleate on
t h e enlarged g r a i n s and grow toward t h e upper s u r f a c e . With most metals,
t h e g r a i n s can be grown l a r g e enough t o permit c u t t i n g out u s e f u l s i n g l e
crystals. Vanadium s i n g l e c r y s t a l s f o r deformation s t u d i e s were made i n
t h i s way.
The m a j o r i t y of t h e work on electron-beam melting has been on niobium
and s e l e c t e d a l l o y s of niobium and has been r e p ~ r t e d . ~ ’
I n a d d i t i o n t o t h e r e f r a c t o r y metals, uranium, y t t r i u m , i r o n , n i c k e l ,
t i t a n i u m , zirconium, copper, aluminum, s i l i c o n , uranium carbide, niobium
carbide, zirconium carbide, and aluminum oxide have been melted. The
uranium carbide l o s t uranium p r e f e r e n t i a l l y and a t moderately high r a t e s
t o change composition from s t o i c h i o m e t r i c UC t o UC p l u s UC2. A s expected,
high v a p o r i z a t i o n r a t e s precluded s u c c e s s f u l melting of U02, Zr02, and
chromium. No systematic e v a l u a t i o n has y e t been made of t h e s e e l e c t r o n -
beam-melted m a t e r i a l s .

340
 19. METALLOGRAPHY

R. J. Gray

DEVELOPMENT OF NEW EQUIPMENT IN METALLOGRAPHY

Ultrasonic Microchisel

G. Hallerman
Improvements on the performance of the ultrasonic microchisel (jack
hammer) have continued.' The transducer-horn assembly, the most critical
component of the apparatus, was redesigned to obtain consistent dependa-
bility and accuracy in removal of inclusions. The technique for pointing
wires electrolytically during preparation of styli was standardized.
Various methods of analysis of the extracted particles were investi-
gated. Examination of the results of spectrographic and activation analy-
ses revealed that the amount of the material from an average extraction
is insufficient for identification.
X-ray diffraction, employing a Debye-Scherrer camera and copper tar-
get, was found suitable for most of the specimens examined. This method
requires the use of a flame-polished quartz fiber coated with adhesive as
means of collecting the extracted debris. The x-ray method works well
when the phases or inclusions of interest are hard and brittle and thereby
less susceptible to cold-working and excessive deformation. The exposure
time is 40 to 48 hr.
Electron diffraction techniques are also being investigated. This
method of analysis shows promise, since the amount of material required
for identification is less than with the other methods and the time of
Y)
processing should be considerably shorter.
The following examples serve to illustrate the capabilities of the
microchisel. The phase of interest in a specimen of sintered europium
oxide (Eu203)and silicon powders was extracted and then identified by
x-ray diffraction techniques as europium disilici.de (EuSi2).
A sample of vacuum-induction-melteduraniml6.75% Mo was submitted
for extraction. Figure 19.1 shows the scattered debris, following partial

'G. Hallerman, Met. Ann. Prog. Rep. Sept. 1, 1959, ORNL-2839, p 327.

34 1
 Fig. 19.1. P a r t i a l l y Extracted Molybdenum Segregate in y-Uranium. Unetched.

removal of the inclusions which were believed to be U2Mo. X-ray analysis,

however, showed the phase of interest to be molybdenum. Other diffraction
lines were identified as y-uranium and U02. The presence of y-uranium is
believed to be due to partial removal of the matrix of the specimen and
the UO2 due to oxidation as a result of the frictional heat of the vibrat-
ing stylus.

Elevated-Temperature Hardness Testing

G. Hallerman
The need for hot-hardness testing has been increasing with the prob-
lems imposed on the Metallurgy Division to develop alloys with desirable
high-temperature properties. Correlation of hot-hardness data with those
obtained from conventional tests, such as from high-temperature-tensile
measurements, has been reported as far back as 1947 (ref 2). Hot-hardness
testing is also the quickest method to obtain some ideas of the high-tem-
perature deformation characteristics of metals and alloys, such as those

2G. P. Bens, Trans. Am. SOC. Metals -

85, 505 (1947).

342
encountered in extrusions of duplex materials or the use of brazing alloys
for high-temperature applications. ,-

Two high-texperature hardness testers, designed and constructed in

this laboratory, are shown in Fig. 19.2. The standard-load hot-hardness
tester, shown on the left, is capable of processing the bulk of routine
work. The high-temperature microhardness tester, shown on the right in
the figure, is designed to handle hard, brittle materials, specimens in
which hardness of individual phases is to be determined, reactive samples,
and specimens in which the depth of indentation is critical.
The standard-load tester consists of a specially designed furnace
which is incorporated into a large-vertical-capacityRockwell tester. The
indentor is free to move vertically through water-cooled O-rings on the
top of the furnace. The furnace proper can be moved horizontally on the
machine table by means of two cross-feed screws. Thus, numerous hardness
readings can be made by moving the entire furnace assembly. The tester
operates in an inert atmosphere. The testing temperature range is from
room temperature to 890°C. A Brale indentor, specially adopted for ele-
vated-temperature service, is made of synthetic sapphire mounted in In-
conel. The load range is 15 to 150 kg.
Progress on establishment of design criteria of the high-temperature
microhardness tester was reported previously. The construction of the
instrument is now completed and the unit is being calibrated.
The testing chamber of the microhardness tester operates in an inert
atmosphere or in a vacuum produced by pumps located behind the control
panels shown in Fig. 19.2. In operation, the sample, which rests on the
pedestal, is raised by means of a micropositioner attached to the pedestal
control (Fig. 19.3). The raising specimen lifts the indentor rod which
in turn opens an electrical circuit of the electronic relay. The relay
is so designed that only a few microamperes pass through the contact points
of the indentor assembly. With this arrangement the operator of the micro-
hardness tester is aware of the position of the specimen relative to the
indentor. It a l s o permits the operator to control the time of applica-
tion of theload,which is especially critical in hot-hardness testing. The

3G. Hallerman, Met. Ann. Prog. Rep. Sept. 1, 1959, ORNL-2839, p 326-7.

343
 Fig. 19.2. High-Temperature Standard-Load Tester and Microhardness Tester.

344
 Fig. 19.3. T e s t i n g Chamber of the Elevated-Temperature Microhardness Instrument with B e l l Jar
i n Raised Position.

345
 rotation of the indexing disk allows up to one hundred indentations on a
single specimen without the need for breaking the vacuum or turning off
the heating elements. The applied load on the indentor may be varied from
180 to 1000 g. Indentations are made at the desired temperature but the
resulting impressions are measured at room temperature. The correction
for thermal contraction is insignificant and may be neglected. The inden-
tor itself is a 136-deg square-based pyramid synthetic sapphire set in
Inconel.
To test the capability of the standard-load tester, a series of ma-
terials were investigated. Average values of two to five hardness meas-
urements at various temperature levels are shown in Table 19.1. In Figs.
19.4 and 19.5 these results are plotted as hardness vs temperature with
constant time of application of load (15 sec). The hardness values of
metals and alloys shown on Fig. 19.4 were obtained from specimens in the
as-received condition. The effect of secondary hardening is clearly dem-
onstrated on the type 347 stainless steel at approximately 5OOOC. Inconel-
X is softer than INOR-8 in the temperature range from 25'C to approximately
700'C; at higher temperatures Inconel-X is slightly harder.
The effect of age-hardening of Inconel-X is shown on Fig. 19.5. The
I
"as-received" curve is reproduced from Fig. 19.4. The "aged" curve was
obtained from a second run of the same specimen. The "aging treatment"
consisted of heating the Inconel-X specimen to about 900°C (while hardness
measurements of the first run were made) and slow cooling (12 hr) to room
temperature. It can be seen on Fig. 19.5 that the hardness of the treated
specimen is considerably greater than the as-received specimen up to about
750°C. A second run was performed also on the INOR-8 specimen. No aging
effects were observed and the hardness values were much the same as for
the as-received specimen.
Further work will involve the application of hot-hardness testing to
studies of creep behavior of metals. It has been observed that at ele-
vated temperatures the hardness of metals decreases with the time of ap-
plication of the load at constant temperature. If this decrease in hard-
ness and, consequently, the rate of penetration of the indentor can be
correlated with creep, then hot-hardness testing may be used as a quick

346
"c

Table 1 9 . 1 . Hardness of Some Metals and Alloys

Hardness (Rockwell 1 5 N )
Temperature
("c) Copper
Carbon Type 347
Stainless Inconel INOR-8
Inconel-X~ Inconel-X,
As -
Steel Aged
Steel Received

25 22.5 51 56.5 63 73 68 78.5

50 21 54 58.5 65 73.5 69 81
100 19.5 55 56.5 63.5 74.5 69 80
150 17.5 56 54.5 60.5 73.5 68.5 80
200 12.5 57 55 62.5 73 66.5 79.5
250 10 57 54 62.5 73 66.5 79.5
300 5 56 52.5 62.5 73 66.5 80.5
350 56 50 62.5 72.5 66 80.5
400 53 47 62 73 65.5 82.5
45 0 48 46.5 62 73 67.5 82
500 43 53 64 73.5 68.5 82
550 29 52 63.5 74 68.5 82.5
600 19 50.5 63.5 74 68.5 81
650 11 47.5 62 73.5 69 81
700 46 60 72 70 77
750 41 51.5 70 72 74.5
800 30 35 66.5 71.5 70.5
825 26 31.5 59 68 69
85 0 15 26.5 57.5 67 65.5
875 6.5 14 49.5 59 56
890 53 49
 UNCLASSIFIED

Q
UNCLASSIFIED
ORNL-LR-DWG 50465 ORNL-LR-DWG50466
75
90

65 z
80
Y
z
'D 55
J
W
3 45
Y
0
V
CARBON STEEL
m- 35
m
z
0
25
I 40
0 (00 200 300 400 500 600 700 800 900
45 TEMPERATURE [OCl

5 0 Fig. 19.5. Hardness as a Function o f Temper-

TEMPERATURE ( " C ) ature o f Inconel-X.

F i g . 19.4. Hardness as a Function of Temper-

ature of Some Metals and Alloys.

method of s t u d y i n g c r e e p p r o p e r t i e s . Encouraging r e s u l t s were r e p o r t e d 4

on a s e r i e s of zirconium alloys i n which t h e data of hot-hardness t e s t i n g
were s i m i l a r t o t h o s e o b t a i n e d by s t a n d a r d c r e e p t e s t s .

METALLOGRAPHY FOR THE HIGH FXDIATION

LEVEL EXAMINATION W O R A T O R Y
Design and S t a t u s of Metallographic Equipment

E . L. Long, Jr. J. E . VanCleve, Jr. R. J. Gray

The Metallography Group i s r e s p o n s i b l e f o r equipping and o p e r a t i n g

f o u r of t h e c e l l s i n t h e High R a d i a t i o n Level Examination Laboratory(HRI;EL). 0
The f u n c t i o n s of t h e f o u r c e l l s are: c e l l 4, cutting, nickel plating,
mounting, and g r i n d i n g o p e r a t i o n s ; c e l l 5, m e t a l l o g r a p h i c p o l i s h i n g only;
c e l l 6, chemical, e l e c t r o l y t i c , and vacuum c a t h o d i c e t c h i n g and p r e l i m i n a r y
(D
examinations; c e l l 7, m e t a l l o g r a p h i c examination, s u p e r f i c i a l , regular,
and microhardness t e s t i n g , r e p l i c a t i o n f o r o p t i c a l and e l e c t r o n micros-
copy, and s p e c i a l t e c h n i q u e s .
The f i r s t c e l l i n t h e i n - l i n e o p e r a t i o n w i l l be No. 4,where t h e samples
w i l l be s e l e c t e d and s e c t i o n e d . A c u t o f f machine has been designed and i s
i n the f i n a l stages of fabrication. The machine w i l l a c c e p t a work p i e c e

'G. A. Geach, Associated E l e c t r i c a l I n d u s t r i e s , England, P r i v a t e

communication, Apr. 29, 1960.

348

a
f o r sampling of a maximum s i z e of 2 i n . i n d i a m e t e r by 1 2 i n . l o n g . All
f u n c t i o n s are e i t h e r e l e c t r i c a l l y o r h y d r a u l i c a l l y o p e r a t e d .
A f t e r s e c t i o n i n g , t h e samples w i l l be n i c k e l - p l a t e d , i f so warranted.
A n i c k e l - p l a t i n g b a t h h a s been designed and i s i n t h e f i n a l s t a g e s of fab-
rication.
The t h i r d o p e r a t i o n w i l l be t o mount t h e samples i n a p l a s t i c . A
commercial mounting p r e s s i s b e i n g modified f o r remote o p e r a t i o n . To de-
termine t h e m a t e r i a l o r m a t e r i a l s s u i t e d f o r h o t - c e l l a p p l i c a t i o n f o r both
x - r a y and m e t a l l o g r a p h i c r e q u i r e m e n t s , a s t u d y w a s made on t e n mounting
materials. O f t h e t e n o r i g i n a l m a t e r i a l s , only f o u r were s u i t e d f o r x
r a y from t h e x-ray background i n t e r f e r e n c e s t a n d p o i n t . A radiation t e s t
w a s conducted on t h e s e f o u r m a t e r i a l s by s u b j e c t i n g them t o a t o t a l a c -
cumulated dosage of approximately 5 X lo8 1". Only two m a t e r i a l s , r e d
B a k e l i t e and a n epoxy r e s i n , 5 w i t h s t o o d t h e r a d i a t i o n t e s t .
A f t e r mounting, t h e samples w i l l be ground t o a f i n i s h s u i t a b l e for
subsequent p o l i s h i n g o p e r a t i o n s . S e v e r a l g r i n d i n g methods a r e b e i n g con-
sidered.
The second i n - l i n e c e l l , No. 5, w i l l be equipped f o r m e t a l l o g r a p h i c
polishing. The d e s i g n , f a b r i c a t i o n , and r e m o t i z i n g of equipment f o r t h i s
c e l l i s p r a c t i c a l l y complete.
C e l l 6 w i l l be e s s e n t i a l l y an e t c h i n g c e l l . Design and f a b r i c a t i o n
o f a vacuum c a t h o d i c e t c h e r and r e m o t i z i n g of a commercial e l e c t r o l y t i c
p o l i s h e r a r e complete e x c e p t f o r t h e e l e c t r i c a l c o n t r o l s . A means of
c h e m i c a l l y e t c h i n g m e t a l l o g r a p h i c samples i n - c e l l remains t o be d e v i s e d .
The f i n a l f u n c t i o n i n t h i s c e l l w i l l be t o make p r e l i m i n a r y examinations
of t h e e t c h e d samples w i t h an i n - c e l l microscope b e f o r e s e n d i n g them t o
t h e next c e l l i n l i n e . The microscope w i l l p r o j e c t an image of t h e s u r -
f a c e of a sample on a s c r e e n and w i l l be viewed t h r o u g h t h e c e l l window.
The end c e l l , No. 7, w i l l be t h e o p t i c a l , h a r d n e s s t e s t i n g , and r e p -
lication cell. Located w i t h i n t h e c e l l w i l l be a Rockwell h a r d n e s s t e s t e r
d e s i g n e d f o r regular and s u p e r f i c i a l h a r d n e s s t e s t i n g . The h a r d n e s s t e s t e r
h a s been purchased b u t minor m o d i f i c a t i o n s f o r remote o p e r a t i o n remain t o
b e made. Also l o c a t e d w i t h i n t h i s c e l l w i l l be f a c i l i t i e s f o r r e p l i c a t i o n

5Hys01, Em-2774, Manufactured by t h e Houghton L a b o r a t o r i e s , I n c . ,

Olean, New York.

349
of s u r f a c e s f o r e v e n t u a l examination by e l e c t r o n microscopy. Only p r e -
l i m i n a r y work h a s been done i n developing r e p l i c a t i o n techniques, b u t it
i s planned t o employ b o t h p l a s t i c and vacuum-deposited f i l m s .
O p t i c a l examination and microhardness t e s t i n g w i l l be made o u t s i d e
of t h e c e l l s . To m a i n t a i n containment and s h i e l d i n g requirements, t h e
metallographs and microhardness t e s t e r s w i l l be p l a c e d w i t h i n s h i e l d e d
b l i s t e r s a t t a c h e d t o t h e o u t s i d e w a l l of t h e end c e l l . The samples w i l l
be c a r r i e d through t h e c e l l w a l l and p l a c e d on t h e s t a g e of t h e m e t a l l o -
graph o r hardness t e s t e r by means of a t r a n s f e r mechanism. The t r a n s f e r
mechanism has been designed and a working model has been c o n s t r u c t e d .
A schematic drawing o f one of t h e two s h i e l d e d and s e a l e d remote-
c o n t r o l metallographs planned i s shown i n F i g . 19.6. The l i g h t source
and camera bellows a r e o u t s i d e t h e b l i s t e r w i t h remote c o n t r o l s through
t h e f r o n t of t h e b l i s t e r s .
Two views of the remotized microhardness tester in a mock blister
a r e shown i n F i g s . 1 9 . 7 and 19.8.

T e s t i n g Program

A t e s t i n g program h a s been i n i t i a t e d t o ensure t h a t t h e planned op-

e r a t i n g p h i l o s o p h i e s of t h e HRLEL w i l l be p o s s i b l e insomuch as t h e i n - c e l l
o p e r a t i o n s are concerned. A mockup c e l l ( F i g . 1 9 . 9 ) , which s i m u l a t e s t h e
c o n f i n e s of one c e l l , h a s been c o n s t r u c t e d and equipped w i t h a p a i r of
m a s t e r - s l a v e m a n i p u l a t o r s , a power manipulator, a p e r i s c o p e , a n d a t h r e e -
t o n h o i s t , as planned i n t h e HRLEL. I n t h i s c e l l , o p e r a t i o n a l procedures
can be t r i e d and c o r r e c t e d and equipment design and f u n c t i o n checked b e f o r e
c o n s t r u c t i o n o f t h e HRLEL has been completed.
A s an example, t h e purpose of t h e f i r s t mockup o p e r a t i o n , now i n prog-
r e s s , i s t o e s t a b l i s h p o l i s h i n g procedures f o r m e t a l l o g r a p h i c samples. In
a c t u a l p r a c t i c e t h e p o l i s h i n g c e l l w i l l be t h e second i n - l i n e o p e r a t i o n .
A f t e r assurance t h a t i n s t a l l a t i o n , removal, and i n - c e l l maintenance of t h e
p o l i s h i n g equipment can be done remotely t h e p o l i s h i n g procedures w i l l be
established.
S e v e r a l i n - c e l l maintenance procedures t h a t w i l l be encountered rou-
t i n e l y i n t h e HRUL have been e s t a b l i s h e d i n t h e mockup. F i g u r e 19.10 re-
v e a l s what t h e o p e r a t o r s e e s a s he l o o k s i n t o t h e p o l i s h i n g c e l l through
c"
350
a
e
351
 Fig. 19.7. Remote Microhardness Tester i n Mock Blister. Hardness tester will be located
within blister attached to outside wall o f end cell.

352
6

Fig. 19.8. Same Remote Microhardness Tester as Shown in Fig. 19.7 but Showing Controls
and Viewing Ports.

353
 4

Fig. 19.9. Mockup Cell Designed to Simulate Operating Conditions Expected in High Radiation
Level Examination Laboratory.

t h e window. One of t h e v i b r a t o r y p o l i s h e r s i s being removed from t h e c e l l

as would be necessary i f a major breakdown occurred. The sequence of F i g s .
19.11, 19.12, and 19.13 shows how a new p o l i s h i n g c l o t h would be placed i n
a polisher. A new c l o t h , which had been placed on t h e s t e e l hoop o u t s i d e
t h e c e l l , i s being removed from a p l a s t i c bag with master-slave manipula-
t o r s as shown i n F i g . 19.11. The new c l o t h and hoop i s t h e n placed i n
t h e p o l i s h i n g bowl, as shown i n Fig. 19.12, and t h e whole assembly i s
secured by clamps, as shown i n Fig. 19.13. The bowl would t h e n be charged
with a new a b r a s i v e s l u r r y before p l a c i n g t h e samples i n t h e bowl f o r
polishing. Figure 19.14 shows t h e abrasive s l u r r y being added by pouring
from a polyethylene b o t t l e which had been f i l l e d o u t s i d e t h e c e l l .
Present plans a r e t o t e s t each piece of equipment i n t h e mockup t h a t
i s t o be i n s t a l l e d i n t h e HRLF,L. The next simulated c e l l o p e r a t i o n planned

354
9
Q
G3
355
 9SE

0
e 3
T
0
0
U
0
5 d
!?. d
Q
(D

%
n
s
-

a
3

6)
m
a
(P

W
Y

?L
0
n
(D
Q

b
Q)
 357
e,
I

have been established to ensure

Fig. 19.13. Entire Assembly Shown Being Secured b y Closing Three Clamps. Dimensional tolerances
- -.
that t h i s operation can be performed w i t h master-slave type of manipulator.

c d Q
359
t o follow t h e p o l i s h i n g c e l l mockup i s t h a t of t h e c u t t i n g , mounting, and
grinding c e l l - c e l l 4.

Training Program

I n order t o have a nucleus of personnel t r a i n e d i n a c t u a l h o t - c e l l

operation, a metallographer has been assigned t o work with t h e Solid S t a t e
Division i n t h e i r h o t - c e l l f a c i l i t y . Technicians a r e assigned i n p a i r s
t o work with him f o r about t h r e e months.
The work i n t h e S o l i d S t a t e Division hot c e l l s may be divided i n t o
two very broad areas: t h e a c t u a l manipulation of a c t i v e m a t e r i a l s within
t h e h o t c e l l and t h e maintenance of t h e equipment and surrounding a r e a s .
@
It was f e l t t h a t each man should spend more time with i n - c e l l manipula-
t i o n t h a n with decontamination work. I n some cases t h i s was not p o s s i b l e
during t h e three-month assignment, and i n t h e s e cases an extension of
e
t i m e w a s requested and granted.
The manipulation o f i n - c e l l samples i s by f a r t h e simplest and most
d i r e c t p a r t of t h e operation. This c o n s i s t s p r i m a r i l y i n l e a r n i n g which
b u t t o n t o push a t t h e proper time and must be l e a r n e d by r e p e t i t i o n u n t i l
it becomes second n a t u r e . The t e c h n i c i a n s gained some p r o f i c i e n c y b u t
d i d not have t h e time t o become accomplished c e l l operators.
The equipment maintenance and cleanup i s a much more complex p a r t
o f t h e operation. This involves very c l o s e cooperation with t h e Health
Physics personnel and a thorough understanding of t h e r e g u l a t i o n s cover-
ing the different-type areas. The t e c h n i c i a n s r e q u i r e d very c l o s e super-
v i s i o n by t h e S o l i d S t a t e personnel during such operations. The most
valuable experience gained i n t h i s work w a s f a m i l i a r i z a t i o n with tech-
niques of decontamination and of t h e various means of contamination de-
tection.

The t r a i n i n g program has i n a l l cases s o f a r achieved t h e o b j e c t i v e s

as o r i g i n a l l y planned and t h e personnel involved have expressed a d e s i r e
t o continue t h i s type of work.

360
 METALLOGRAPKY OF CERAMIC MATERIALS

R. J . Gray C . K. H. DuBose

The metallography of ceramic m a t e r i a l s has expanded i n t h e l a s t y e a r

t o i n c l u d e t h e p r e p a r a t i o n of samples f o r p e t r o g r a p h i c e x a m i n a t i o n s . In
a d d i t i o n t o r o u t i n e examinations, t h e r e has been c o n s i d e r a b l e work on t h e
development of new t e c h n i q u e s .

Thorium Oxide

Due t o t h e i n c r e a s i n g i n t e r e s t i n thorium oxide, new t e c h n i q u e s were

developed f o r t h e m e t a l l o g r a p h i c examination o f t h e m a t e r i a l . The p o l i s h -
i n g procedure w a s found t o be s i m i l a r t o t h a t f o r o t h e r ceramic materials6
i n t h a t a long-time v i b r a t o r y p o l i s h i n g 7 o p e r a t i o n w a s n e c e s s a r y . As
g r a i n s i z e and g e n e r a l m i c r o s t r u c t u r e were of primary i n t e r e s t , a s u c c e s s -
f u l chemical e t c h a n t h a s been developed, c o n s i s t i n g of 100 m l of b o i l i n g
M HF.
c o n c e n t r a t e d HNO3 w i t h one drop of 20 - U n f o r t u n a t e l y , s t a n d a r d metal-
l o g r a p h i c mounting m a t e r i a l s would n o t w i t h s t a n d t h e b o i l i n g HN03, n e c e s -
s i t a t i n g t h e removal of t h e specimen from t h e mount b e f o r e e t c h i n g . Fig-
u r e 19.15 i s r e p r e s e n t a t i v e of t h e m i c r o s t r u c t u r e i n an e t c h e d , h i g h - f i r e d ,
Tho2 p e l l e t .

UO;!-Bearing M a t e r i a l s

Samples of commercially a v a i l a b l e f u s e d U02 were examined m e t a l l o -

g r a p h i c a l l y and were found t o c o n t a i n a Widmanstgtten s t r u c t u r e i n t h e
UOz m a t r i x . X-ray a n a l y s i s of t h e samples r e v e a l e d t h e p r e s e n c e of U409
(ref 8). A s e r i e s of f o u r samples were h e a t - t r e a t e d a t l00OoC and each
sample w a s cooled a t v a r i o u s r a t e s t o e s t a b l i s h t h e d i s s o l u t i o n of t h e
Widmanstgtten s t r u c t u r e . A s shown i n F i g . 19.16, t h e Widmanstgtten p r e -
c i p i t a t e w a s p r o g r e s s i v e l y s u p p r e s s e d by t h e more r a p i d c o o l i n g r a t e s .

6 R . J . Gray and C . K. H. DuBose, Metallography of Ceramic F u e l Ma-

t e r i a l s ORNL-2827 ( t o be p u b l i s h e d ) .
--J

7E. L. Long, Jr., and R . J. Gray, P r e p a r a t i o n of M e t a l l o g r a p h i c

Specimens Through V i b r a t o r y P o l i s h i n g , ORNL-2494 ( S e p t . 1 0 , 1958).
'Met. Ann. Prog. Rep. S e p t . 1, 1959, ORNL-2839, p 313.
'D. L . McElroy and T. G. K o l l i e , " P h y s i c a l P r o p e r t i e s , " P a r t I1 of
t h i s report.

36 1
 Fig. 19.15. Metallographically Polished and Etched Cross Section of Tho, Pellet Fired a t 180OaC.
Etchant: HNO,, HF. 200X.

The water-quenched and oil-quenched samples contained thermal cracks from

.
t h e r a p i d quench.
Q
The etchant normally used f o r U 0 2 , 70 p a r t s H20-10 p a r t s H2S04-20
parts H202(30’$), was u n s a t i s f a c t o r y f o r t h e h e a t - t r e a t e d samples, b u t by
r e p l a c i n g t h e H2S04 with HNO3, t h e etchant produced highly s a t i s f a c t o r y
results. The procedure normally used f o r p o l i s h i n g fused U02 was a l s o
u n s a t i s f a c t o r y f o r t h e h e a t - t r e a t e d samples. A much longer time, up t o
36 h r , w a s required on t h e v i b r a t o r y p o l i s h e r .
The technique of e t c h - p i t t i n g U02 has been improved considerably by
varying t h e temperature of t h e e t c h a n t . Larger p i t s and well-defined p i t
edges a r e obtained by using t h e e t c h a n t , 70 p a r t s H20-10 p a r t s H2S04-20
parts H202(30$), a t 8OOC.

I 362
 Fig. 19.16. Metallographically Polished, Fused, and Heat-Treated UO,. ( a ) As-received material
showing U,O, Widmanstatten structure in UO, matrix. Heat treated at lOOOOC for 88 hr then ( b ) furnace
cooled, (c) air cooled, (d) water quenched, and (e) oil quenched. Note suppression of U,O, phase.
Etchant: H,O-HNO, -H,O,. 1OOOX.

363
 Petrographic Thin Sections

The p r e p a r a t i o n of t h i n s e c t i o n s of ceramics o f f e r s problems not en-

4
countered i n t h e p r e p a r a t i o n of standard t h i n s e c t i o n s of minerals. The
f i r s t s t e p i n making a t h i n s e c t i o n i s t o break o r s l i c e a t h i n fragment
from t h e specimen. I n t h e case of porous o r b r i t t l e m a t e r i a l , it i s some-
times necessary t o impregnate t h e specimen with a r e s i n before sawing t o
prevent dust o r f o r e i g n m a t e r i a l from remaining i n t h e pores of t h e sec-
t i o n o r t o prevent f r a c t u r i n g . One s u r f a c e of t h e s l i c e i s prepared f o r
mounting on a g l a s s o b j e c t s l i d e . A f t e r mounting, t h e exposed face of
t h e specimen i s polished t o t h e required thickness f o r viewing through a
microscope with t r a n s m i t t e d l i g h t . A sample thickness of approx 30 IJ. i s
u s u a l l y s a t i s f a c t o r y f o r t h e petrographic examination of minerals; how-
ever, ceramic m a t e r i a l s generally have a much f i n e r g r a i n s i z e ; t h e r e f o r e ,
much t h i n n e r s e c t i o n s , i n t h e order of 10 t o 15 p, a r e required.
The s e r v i c e of preparing p e t r o g r a p h i c t h i n sections i s n o w m a d e a v a i l -
able by t h e Metallography Section.

Europium S i l i c i d e s

A s e r i e s of vacuum-arc-melted europium s i l i c i d e samples, ranging from

9.35 w t % E P S i t o 91 w t % E w S i , w a s received f o r metallographic examina-
t i o n . l o Europium being highly pyrophoric n e c e s s i t a t e d t h e p o l i s h i n g of
t h e s e samples i n a water-free o i l . A s i l i c o n e o i l , Dow-Corning 702 d i f -
f u s i o n pump o i l , was found q u i t e s a t i s f a c t o r y . The p o l i s h i n g operation
w a s c a r r i e d out by hand, using diamond p a s t e and t h e s i l i c o n e o i l on a
canvas c l o t h . I n a sample of 27.5 wt % Eu-Si t h e s i l i c o n , being i s o t r o p i c ,
appears a s a dark-gray phase i n t h e b r i g h t - f i e l d photomicrograph of Fig.
19.17a and a black phase i n t h e corresponding p o l a r i z e d - l i g h t photomicro-
graph of Fig. 19.17b. The a n i s o t r o p i c phase has been i d e n t i f i e d a s EuSiz .
Figures 1 9 . 1 7 ~and 19.17d, b r i g h t - f i e l d and p o l a r i z e d - l i g h t , respectively,
show mainly t h e a n i s o t r o p i c phase E S i 2 i n a sample of 63.4 w t EwSi.
Figure 19.18 i s a r a r e photomicrograph of f r e e europium. The sample d i d
not l a s t more than t h r e e minutes a f t e r t h e p o l i s h i n g operation because of
t h e pickup of moisture from t h e a i r . The sample was 91 w t % EwSi.

loC. F. L e i t t e n , J r . , The S t a b i l i t y of Europium Oxide i n S i l i c o n -

Bearing S t a i n l e s s S t e e l , O m - 2 9 4 6 ( i n p r e s s ) .
a
364

e
 UNCLASSIFIED
'
1
J * * Y-33254
1 1 1

*-
i s . "
I

Fig. 19.17. Metallographically Polished Cross Sections of Arc-Cast Eu-Si Buttons. As-polished.
(u) 27.5 wt % Eu-Si, arc-melted in vacuum, bright field; ( b ) same, polarized light; (c) 63.4 wt % Eu-Si,
arc-melted in vacuum, bright field; (d) same, polarized light. 500X.

365
 -
u)
w
S-
o
f
902

003

,004

005

X
0
0-
v)

008

Fig. 19.18. Metallographically Polished Cross Section of 91 wt % Eu-Si Pellet. Sintered 1.5 hr at
2200°F i n hydrogen. White precipitate i s an unknown Eu-Si compound; massive gray area i s free euro-
pi um. As-pol i shed.

*
Another series of Eu203 powder and metal compacts was examined metal-
lographically to determine the reaction products.l o These combinations
were Eu20, powder plus nickel powder, Eu203 powder plus iron powder, and
Eu2O3 powder plus various stainless steel powders. The Eu203 p l u s type
304B stainless steel showed considerable amounts of reaction products,
some of which were found to be soluble in the diamond-oil thinner, as well
as water. Therefore, the silicone oil was again employed. For these
samples it was necessary to use the vibratory-polishing method to best
preserve the reaction-stainless steel interface. A Linde "A"-silicone
oil slurry on a silk cloth was used f o r approx 16 hr. Figure 19.19a is
a metallographically polished cross section of a 30 w t % Eu203-type 304B
stainless steel compact, cold pressed at 4000 psi, and sintered at 2200°F
in hydrogen for 1-1/2hr. Figure 19.19b shows the same area after one

366
d) UNCL4SSlFlED

3048 S.S. E'203 WATER- SOLUBLE PHASE

Fig. 19.19. P e l l e t o f 30 vol 72 Eu,O,-Type 304B Stainless Steel Metallographically P o l i s h e d i n

Silicone Oil. Sintered a t 2200°F i n hydrogen for 1.5 hr. As-polished. ( u ) Before water was put on
specimen; ( b ) after water had been on specimen 15 rnin.

367
 drop of water had been on the specimen for 15 min and dissolved the water-
soluble reaction products. Q
Photomicrography of Ceramic Fuel Powders

Considerable information can be gained from a morphological study of

ceramic fuel powders. In addition to the size of the powder, the shape
can foretell its working characteristics if it is to be rolled in a fuel
element. Other points of information include surface porosity and color.
A technique has been developed to utilize a research metallograph
with dark-field illumination to examine and photograph opaque and trans-
lucent powders up to 500 diameters. Dark-field illumination is essenti-
ally a 360" oblique illumination. By dispersing the powder over a stand-
ard cover glass and covering the powder with a thin white paper and a
mirror, as shown in Fig. 19.20, a diffused back lighting effect is produced
in addition to the oblique lighting.
~
F o r translucent powders, the thin
white paper and the mirror are eliminated to produce a black background.
Examples of this technique are shown in Figs. 19.21, 19.22, 19.23, and
19.24.

UNCLASSIFIED
ORNL-LR-DWG 48830
Y-35351

HIN WHITE PAPER

SUPPO
GLASS

METALLOGRAPH
STAGE

PLANE GLASS

TO EYEPIECE 9
-
Fig. 19.20. Method for Photographing Powders by Dark-Field
I I I urni n at ion.
 001

003
ul
w
-I-
o
f-
006

00 7

008

5!Q%

910

01,

012

013

-
014

015

X
0
0-
N

-
Fig. 19.21. Uranium N i t r i d e (UN) Powder. Produced by passing nitrogen over uranium chips at
850°C, forming U2N3; the U2N3 was converted to UN by passing helium over the U2N, at 1800°C; -60
+lo0 mesh. Photographed according to method shown i n Fig. 19.20. Reduced 12%.

F i g . 19.22. Uranium O x i d e (U30,) Powder. Prepared from U03.H20 by c a l c i n i n g at 1000°C i n a i r

and cooling in air; -100 +325 mesh. Photographed according to method shown i n F i g . 19.20. Reduced
12%.

369
 - a 19.23.
-Fia. Uranium Oxide (UO,) Powder. Spherical commercial uranium dioxide; -100 +200 mesh.
L

Photographed according to method shown i n Fig. 19.20. Reduced 12%.

Fig. 19.24. Uranium Oxide (UO,.H,O) Powder. Translucent yellow crystals; -100 +325 mesh.
h
Photographed according to method shown in Fig. 19.20, but without thin white paper and mirror. Re-
duced 12%.

370

~ ..._.._.I._.__...._._.._______._..___ ~ ~ ~

.
 EIECTRON MICROSCOPY AND OTHER ELECTRON EQUIPMENT

W . H. Bridges

The E l e c t r o n Metallography of Tungsten Compacts

A s e r i e s of s i n t e r e d t u n g s t e n powder compacts w a s s t u d i e d t o d e t e r -
mine whether o r n o t t h e r e were obvious d i f f e r e n c e s i n t h e v a r i o u s s t r u c -
t u r e s which c o u l d b e c o r r e l a t e d w i t h d i f f e r e n c e s i n t h e s t a r t i n g m a t e r i a l s .
The compacts were p r e p a r e d from hydrogen-reduced t u n g s t e n powders, com-
p a c t e d a t 30,000 p s i , and s i n t e r e d i n a hydrogen atmosphere. The d i f f e r -
e n c e s were t h e oxygen c o n t e n t , c r y s t a l l i t e s i z e and s u r f a c e a r e a of t h e

e t u n g s t e n powders, and t h e d e n s i t y of t h e f i n a l s i n t e r e d compact.

Two t<ypes of specimens were p r e p a r e d from each compact sample: a
f r a c t u r e s u r f a c e and a p o l i s h e d - a n d - e t c h e d m i c r o s e c t i o n . These were r e p l i -
c a t e d and (examined i n t h e e l e c t r o n microscope. F i g u r e 19.25 shows t h e p r e -
4)
l i m i n a r y r e s u l t s of i n v e s t i g a t i o n . A s can b e s e e n from t h e p a n e l , the
g r e a t e r d e n s i t y m a t e r i a l i s t h e l e s s porous. The f i r s t compacts which
s i n t e r e d t o only 77% t h e o r e t i c a l d e n s i t y w e r e almost spongy. It i s d i f -
f i c u l t t o t e l l from t h e f r a c t o g r a p h s of t h e l o w - d e n s i t y m a t e r i a l whether
t h e compact f r a c t u r e d t r a n s - o r i n t e r g r a n u l a r l y . It would seem t h a t t h e
h i g h e s t oxygen c o n t e n t r e s u l t e d i n i s l a n d s o f l a r g e r g r a i n e d material i n
a matrix of s m a l l e r g r a i n s . T h i s i s a tenuous c o n c l u s i o n and more samples
would have t o b e examined t o j u s t i f y i t . About a l l t h a t can be concluded
i s t h a t t h e m a t e r i a l of f i n a l l a r g e r g r a i n s i z e f r a c t u r e d i n t e r g r a n u l a r l y .

S e l e c t i o n of E l e c t r o n Microprobe Equipment

During, t h e y e a r , i n f o r m a t i o n w a s c o l l e c t e d on t h e e l e c t r o n microprobes
b e i n g developed on a commercial b a s i s by v a r i o u s i n s t r u m e n t m a n u f a c t u r e r s .
S i n c e a t l e a s t one v e r y u s e f u l and v e r s a t i l e microprobe w a s t o be manu-
f a c t u r e d an o r d e r w a s p l a c e d f o r t h e d e l i v e r y of a u n i t by June 30, 1961.

E l e c t r o n D i f f r a c t ion

The a c q u i s i t i o n of an e l e c t r o n - d i f f r a c t i o n a d a p t e r f o r t h e RCA EMlJ-3B

e l e c t r o n microscope e x t e n d s t h e use of t h e microscope t o a p r e c i s i o n d i f -
f r a c t i o n camera. I n t h e few months s i n c e i t s r e c e i p t , s t u d i e s have been
made of t h e growth o f Be0 on b e r y l l i u m and NbO on niobium, e x t r a c t i o n s
from t h e m i c r o c h i s e l , and o f p r e c i p i t a t e s i n s t a i n l e s s s t e e l .

37 1
 UNCLASSIFIED
PHOTO 508090

FRACTURE SURFACE POLISHED AND ETCHED

Fig. 19.25. Comparative Electron Micrographs of Sintered Tungsten Powder Compacts.

372
G) UNCLASSIFIED
PHOTO 50809 b

e FRACTURE SURFACE
MAGN I F IC AT I ON : 3 6 00 X
POLISHED AND ETCHED
E T C H A N T : N a O H - K3Fe(CNIG

POWDER CHARACTERISTICS A I3 C D E
OXYGEN,?'-- 0.3 0.64 4.52 1.70 0.70
CRYSTALITE SIZE, A 1018 903 292 226 142
SURFACE AREA, rn2/grn 0.7 3.81 6.99 10.12

THEORETICAL DENSITY OF
COMPACT, 7'0 77 94 92 95 88

Fig. 19.25 (continued).

373
 THE METALLOGWHY OF NIOBIUM-ZIRCONIUM ALLOYS

R. S. Crouse
Q
Niobium containing 1-276 Z r i s being considered as a p o s s i b l e construc-
t i o n a l m a t e r i a l f o r high-temperature a p p l i c a t i o n . The metallography of
such a l l o y s i s d i f f i c u l t due t o t h e l a c k of r e p r o d u c i b i l i t y of etching.
To i l l u s t r a t e t h e s o r t of problems encountered, two specimens of t h e same
batch of m a t e r i a l were heat t r e a t e d t o g e t h e r (500 h r a t 1700'F) and were
etched f o r 24 see i n 25 p a r t s HNO3, 10 p a r t s HF, and 50 p a r t s H20. Com-
p a r i n g Figs. 19.26 and 19.27, it would seem t h a t major d i f f e r e n c e s i n t h e
alloy existed. Apparently t h e r e i s s u f f i c i e n t microheterogeneity t o make
t h e a l l o y highly e t c h s e n s i t i v e . It has been determined t h a t , i n general,
acceptable microstructures can be obtained by e t c h i n g i n 3 t o 4 increments
of 6 to 8 see each f o r a t o t a l of about 24 s e e . If glycerine were used
i n s t e a d of water t h e t i m e of e t c h i n g could be increased.
Since carbon, n i t r o g e n , and oxygen a r e known t o a f f e c t t h e proper-
t i e s of niobium and niobium-zirconium a l l o y s , i d e n t i f i c a t i o n of microcon-
s t i t u e n t s containing t h e s e elements by metallographic techniques i s de-
sirable. Many times microconstituents may be i d e n t i f i e d by s i z e , shape,

Fig. 19.26. Nb-1% Zr Alloy Aged 500 hr a t 1700OF. 200X.

 Fig. 19.27. Nb-1% Zr Alloy Aged 500 hr at 1700OF. Compare with Fig. 19.26. 200X.

o r co.lor. U n f o r t u n a t e l y , t h e compounds of carbon, n i t r o g e n , and oxygen

i n niobium and niobium-zirconium a l l o y s are e i t h e r i n v i s i b l e as p o l i s h e d
o r s o completely removed by e t c h i n g as t o b e u n i d e n t i f i a b l e . This i s es-
p e c i a : l l y t r u e of carbon and n i t r o g e n . The anodic s t a i n technique’’ was
t e s t e d t o determine i t s a p p l i c a b i l i t y .
I n anodic s t a i n i n g , t h e p o l i s h e d m e t a l l o g r a p h i c specimen i s made t h e
anode i n an e l e c t r o l y t i c c e l l w i t h a s u i t a b l e e l e c t r o l y t e and d i r e c t c u r -
ren5 applied. When t h e c o r r e c t c o n d i t i o n s o f t i m e and p o t e n t i a l a r e se-
l e c t e d , a f i l m i s produced on t h e p o l i s h e d s u r f a c e t h a t v a r i e s i n t h i c k -
n e s s depending upon t h e m a t e r i a l b e n e a t h i t . T h i s can g i v e r i s e t o v a r i o u s
colors.

I n t h e c a s e of niobium and niobium-zirconium a l l o y s t h e matrix i s

c o l o r e d b l u e t o p u r p l e , c a r b i d e s and n i t r i d e s are r o s e p i n k t o yellow,
and t h e oxides a r e b l u e . The u t i l i t y of t h i s t e c h n i q u e i s somewhat l i m i t e d
by t h e s i m i l a r i t y of t h e c a r b i d e s and n i t r i d e s and t h e f a c t t h a t carbon
and niitrogen may occur as c a r b o - n i t r i d e s . Consequently, it i s i m p o s s i b l e
t o d e f i n i t e l y d i f f e r e n t i a t e between t h e two elements, a l t h o u g h N b 2 N seems

ILIPrivate c o n v e r s a t i o n w i t h F. J. Huegel, CANEL, Middleton, Conn.,

March 1960.

375
 t o s t a i n r o s e p i n k i n c o n t r a s t t o yellow f o r NbN, Nb2C, and NbC. This
technique i s a u s e f u l t o o l , s i n c e it d e f i n i t e l y d e l i n e a t e s t h e s e phases
Q
without e x a g g e r a t i n g t h e i r s i z e and l o c a t i o n and i n t r o d u c i n g a r t i f a c t s as
chemical e t c h i n g seems t o .
F i g u r e 19.28 i s a photomicrograph of a Nbl% Z r c a s t i n g c o n t a i n i n g
500 ppm carbon t h a t has been a n o d i c a l l y s t a i n e d from t h e a s - p o l i s h e d con-
dition. The c a r b i d e n e e d l e s and t h e grain-boundary m a t e r i a l s a r e a b r i l -
l i a n t yellow.

Fig. 19.28. Anodically Stained Nb-1% Z r Cast Alloy with 500 pprn C. Phase i s bright yellow.
 METALLOGRAPHIC SUPPORT FOR THE EXPERIMENTAL
GAS-COOLED REACTOR PROGRAM

R . S. Crouse

F a i l u r e i n Type 304 S t a i n l e s s S t e e l Tubing

I n a d d i t i o n t o t h e r o u t i n e c o r r o s i o n examinations f o r t h e Experimental
Gas-Cooled R e a c t o r (EGCR) Program, some f a i l u r e a n a l y s e s were performed.
One of t h e more i n t e r e s t i n g problems w a s t h e f a i l u r e of some l / g - i n . type
304 s t a i n l e s s s t e e l t u b i n g f o r one of t h e t e s t l o o p s . The t u b i n g f a i l e d
i n a b r i t t l e manner w h i l e b e i n g b r a z e d i n t o a bulkhead b e f o r e t e s t . The
b r e a k o c c u r r e d some d i s t a n c e o u t s i d e t h e b r a z i n g f u r n a c e , a p p a r e n t l y from
t h e s t r a i n of t h e t u b i n g weight a l o n e .
The t u b i n g w a s s e c t i o n e d l o n g i t u d i n a l l y i n t h e area of t h e b r e a k and
a l s o approx 3 i n . away from t h e f a i l u r e . An u n u s u a l phase o c c u r r e d a t t h e
b r e a k a l o n g w i t h numerous i n t e r g r a n u l a r c r a c k s , as s e e n i n F i g . 19.29.
T h i s phase was o b v i o u s l y q u i t e b r i t t l e as evidenced by t h e many c r a c k s .
None of t h e phase w a s found away from t h e f r a c t u r e , s o it must have been
localized .

-
00

-
00

X
0
0
0
10’

Fig. 19.29. Zirconium-Rich Phase in Interior of Type 304 Stainless Steel Tubing. Note
cracks i n phose.

377
 The area of failure was chemically analyzed and found to have an un-
usual amount of zirconium present. Although one can only speculate as to
'
why the zirconium was present, its presence could account for the brittle-
ness since a eutectic is formed in both the Ni-Zr and Fe-Zr alloy systems
at 930 to 960°C (ref 12). In all probability the tubing was at one time
subjected to such a temperature during fabrication, which formed such a eu-
tectic. It is speculated that a zirconium chip from a forming die used
previously on zirconium may have been pressed into the stainless steel
tubing surface during its fabrication,

Examination of Reaction Products in U02-Graphite

Sintered Compacts

When U02 is heated to a sufficiently high temperature in contact with

graphite, a reaction resulting in conversion of the oxide to carbide takes
place. A convenient way to study this conversion is in the form of pressed
and sintered compacts of U02-graphite mixtures. X-ray diffraction can es-
tablish that conversion occurs and identify the carbide formed, but it is
unable to confirm complete conversion or detect the very small amount of
carbide sometimes formed at low temperatures. Metallographic techniques
were used to study the occurrence of UC in U02-graphite compacts which
X
had been sintered in hydrogen at temperatures ranging from 100 to 2200°C
and times of 24 to 72 hr. It was seen that complete conversion takes place
at temperatures above approx 1600°C and that only partial conversion occurs
at temperatures around 1300°C in the times explored. Figure 19.30 is a
photomicrograph of a UO2-graphite compact sintered at 1300°C in which x-
ray diffraction detected no carbide. Note the partial conversion of one
small U02 particle to carbide. It is recognized, of course, that this
reaction is time dependent and given sufficient time at 1300°C would prob-
ably go to completion. Establishing the complete time dependency was not

All of the UO2 -

the purpose of this investigation.
UC
X
conversion samples were polished by conventional
vibratory methods using water polishing slurries. Some question was raised
as to whether all carbide reaction products were being retained by this

l2M. Hansen, Constitution of Binary Alloys, 2nd ed., pp 742, 1062,

McGraw-Hill, New York, 1958.

378
 Fig. 19.30. U0,-Graphite Compact Showing Minor Conversion of UO, to UC,.

method s i n c e uranium c a r b i d e s t e n d t o hydrolyze i n c o n t a c t w i t h water.13

To check t h i s some o f t h e samples were r e p o l i s h e d u s i n g diamond-polishing
t e c h n i q u e s i n v o l v i n g no water. The r e s u l t i n g m i c r o s t r u c t u r e s were t h e
same as t h o s e produced i n w a t e r p o l i s h i n g e x c e p t n o t as s c r a t c h f r e e . It
w a s t h e r e f o r e concluded t h a t t h i s U02-UC - g r a p h i t e system can be s u c c e s s -
X
f u l l y p o l i s h e d u s i n g c o n v e n t i o n a l methods s i n c e t h e c a r b i d e formed i s prob-
a b l y i n e x c e s s o f 85% UC2 which i s ~ t a b 1 e . l ~
With carbon i n e x c e s s of
s t o i c h i o m e t r i c amounts, as i n t h i s system, UC2 f o r m a t i o n should r e s u l t .

M e t a l l o g r a p h i c P r e p a r a t i o n of B e r y l l i u m

D . M. Hewett I1

Two t e c h n i q u e s a r e c u r r e n t l y i n use for t h e m e t a l l o g r a p h i c p r e p a r a -

t i o n o f be:ryllium: p o l i s h i n g on t h e S y n t r o n v i b r a t o r y p o l i s h e r and p o l i s h -
i n g by hand u s i n g an a t t a c k - p o l i s h t e c h n i q u e .
BerylILium and i t s compounds are of a h i g h l y t o x i c n a t u r e . The g r e a t e s t
danger e x i s t s i n i n h a l i n g t h e a i r b o r n e d u s t of b e r y l l i u m and i t s compounds.
T h e r e f o r e , a l l c u t t i n g and g r i n d i n g o p e r a t i o n s s h o u l d be performed under
-___
,J. Gray, W . C . Thurber, and C . K. H. DuBose, " P r e p a r a t i o n o f
l3R.
74(1)p 6 5 6 7 ( 1 9 5 8 ) .
Arc-Melted Uranium C a r b i d e s , " Metal P r o g r . -

379
water, and it is advisable to hood all equipment used in handling beryl-
lium.

Sectioning, Mounting, and Grinding

A hooded metallurgical cutoff machine is used to section beryllium.

To avoid the possibility of cold-working, samples are mounted in a room-
temperature-setting epoxy resin.14 Grinding is carried out by using a
hooded belt grinder with a 240-grit silicon carbide belt, followed by hand
grinding in a hood on 320-, 400-, and 600-grit silicon carbide papers under
flowing water.

Vibratory Polishing

Beryllium samples are polished on the Syntron vibratory polisher15 in

two steps. A silk cloth and a polishing slurry of ethylene glycol and 0.3 p
alumina are used in the first polishing stage. The polishing time varies
from 4 to 16 hr, depending on the cross-sectional area of the sample and
the magnification to be used in the examination. By using ethylene glycol
rather than water as a carrier for the abrasive, hygroscopic inclusions
such as beryllium carbide are retained; also, if there is any spillage of
the abrasive slurry, there is no danger of evaporation of the carrier with
the subsequent danger of airborne dust. In the second step a deep-nap cloth
is used with a polishing slurry of ethylene glycol, alcohol, and 0.1 p
alumina. Polishing time for this operation should not exceed 1 hr to
avoid excessive relief and rounding over of the edges.
Good results have been obtained by polishing beryllium with the vi-
bratory polisher; examples of resulting microstructures are shown in Fig.
19.31. However, some difficulties have been encountered in polishing
multimetallic beryllium samples such as beryllium brazed to stainless
steel, nickel-clad beryllium, or nickel-plated beryllium.l 6 The beryl-
lium adjacent to the dissimilar metal undergoes galvanic corrosion. The

l4Hysol, ERL-2774, manufactured by Houghton Laboratories, Incorpo-

rated, Olean, New York.
I 5 R . J. Gray and E. L. Long, Jr., "Polishing by Vibration," Metal
- --
Progr. 74(4) p 145-148 (1958).
1 6 D . M. Hewett 11, A Galvanic Corrosion Problem Associated with the
.
,. .
Preparation of Multimetallic Beryllium Samples, ORNL CF-60-4-111 (Apr.
20, 1960).

380
18E
attack of beryllium at the interface of a beryllium-type 430 stainless
steel braze is shown in Fig. 19.32a and 19.3213. The addition of a cor-
rosion inhibitor (3.33 gjliter N a N O s ) to the last polishing slurry elimi-
nated this corrosion, Fig. 19.32b.

Attack-Polish on High-speed Hand Wheel

An attack-polish technique17 in combination with conventional me-

chanical polishing has been adopted for use in the metallographic prepa-
ration of beryllium. A hooded high-speed wheel rotating at approx 1200
rpm and covered with a nylon cloth is used with an abrasive slurry of 10%
aqueous oxalic acid solution and 0.3 p alumina. Time required for this
polishing is from 5 to 10 rnin. Final polishing is accomplished on a wheel
covered with a deep-nap cloth rotating at 600 rpm using a polishing slurry
of magnesium oxide and water, in a polishing time of 5 to 10 min.
For grain-size studies under polarized light, the attack-polish tech-
nique gives the best results. Examples of the microstructures obtained
using this method are shown in Fig. 19.33a and 19.33b. In polishing multi-
metallic samples by the attack-polish technique, interactions between
beryllium and the other metals have never been observed as was noted with
vibratory polishing. Unfortunately, inclusions such as beryllium carbide
are not retained, since an aqueous solution of oxalic acid is used.

I 7 D . B. Metz and H. W. Woods, Attack-Polish Method of Metallographic

Preparation, USAEC, SEP-42, Sylvania Electric Products, Incorporated (Oct.
30, 1950).
C 8C
6
Q
t
b
d
 Fig. 19.33. Beryllium Microstructures Produced by Attack-Poli sh Technique. ( a ) Diffusion
bond; as polished; polarized light; 250X; ( b ) beryllium-braze metal interface; as polished; polar-
ized light; 1OOX.

384

Q
e

3 IvETALLOGRAPHIC SUPPORT FOR THE HOMOGENEOUS REACTOR PROJECT (HRP)

Hydrided Z i r c a l o y - 2 Toroid P i n s

T. M. Kegley, J r .

Over 100 p i n s which had been exposed t o t h o r i a s l u r r i e s i n t o r o i d s

w i t h deuterium, oxygen, o r argon o v e r p r e s s u r e s were examined f o r evidence
of h y d r i d i n g . F i g u r e 19.34a and 19.34b shows one of t h e h y d r i d e d p i n s
and a c r o s s s e c t i o n of t h e p i n which i s t y p i c a l o f t h e c o r r o s i o n o c c u r r i n g
i n t h e system w i t h a deuterium o v e r p r e s s u r e . The h y d r i d i n g r e s u l t s have
43 been r e p o r t e d p r e v i o u s l y by t h e S l u r r y Corrosion Group. l8

Z i r c a l o y - 2 Autoclave Corrosion P i n s

Q T . M. Kegley, Jr.

Z i r c a l o y p i n s e x h i b i t e d s e v e r e a t t a c k d u r i n g exposure t o t h o r i a -
u r a n i a s l u r r y a t 280°C.19 F i g u r e 1 9 . 3 5 shows t h e corroded p o r t i o n of a
p i n which had broken i n t o two p i e c e s . A s e c t i o n t a k e n through t h i s por-
t i o n r e v e a l e d t h a t t h e s e c t i o n w a s almost completely consumed by c o r r o -
sion. F i g u r e 19.36 shows a s e c t i o n t a k e n t h r o u g h a b l i s t e r e d a r e a of one
of t h e p i n s i n which an i n t e r g r a n u l a r t y p e of o x i d a t i o n has o c c u r r e d . The
i n t e r g r a n u l a r a t t a c k o c c u r r e d i n s p i t e of t h e f a c t t h a t no chemical d i f -
f e r e n c e s c o u l d be found between t h e material i n t h e g r a i n s and m a t e r i a l
i n t h e g r a i n b o u n d a r i e s by u s i n g microspark s p e c t r a l a n a l y s i s and an e l e c -
tron microprobe. Metallographic etching techniques, including cathodic
etching, f a i l e d to show any d i f f e r e n c e s t o account f o r t h e i n t e r g r a n u l a r
nature.
8
Transformations i n Z i r c a l o y - 2

J. R . R i d d l e

The l i n e a r t h e r m a l expansion of a - Z i r c a l o y - 2 h a s been determined i n

d i r e c t i o n s p a r a l l e l and t r a n s v e r s e t o t h e r o l l i n g d i r e c t i o n f o r t h r e e

et -
1 8 E . :L. Compere - a l . , HRP Q u a r . Prog. Rep. Oct. 31, 1959, ORNL-2879,
p 191-95.
"E. L . Compere - a l . , HRP Q u a r . Prog. Rep. J a n . 31, 1960, ORNL-2920,
et -
p 108.

385
 UNCLASSIFIED
T- 17440

Fig. 19.34. Z i r c a l o y - 2 Toroid P i n Exposed 762 hr to Thoria Slurry a t 28OoC, D, Overpressure

of 25 psi, and Flow R a t e of 26 fps. (a) Pin after test, 8X; ( b ) cross section of pin, 26X.

386
 UNCLASSIFIED
T- I 7 7 I Q

Fig. 19.35. Zircaloy-2 Pin Exposed 602 hr to Oxygenated Thoria-Uronia Slurry at 280°C.
20x.

Fig. 19.36. ljection Through Blistered Area of Zircaloy P i n Which Was Exposed 260 hr to
Oxygenated Thorilz-Urania Slurry a t 280OC.

387
 f a b r i c a t i o n schedules. The program w a s i n i t i a t e d t o v e r i f y t h e anomalous
behavior of r e s i s t i v i t y curves between 200 and 250°C. Slight inflections
were observed repeatedly over t h i s temperature range i n t h e l i n e a r t h e r -
m a l expansion o f t h e s e m a t e r i a l s as shown i n Fig. 19.37. A hydride reac-
t i o n due t o t h e presence of 40 ppm H2 w a s suggested as a p o s s i b l e cause
of t h e i n f l e c t i o n s . To t e s t t h i s p o s s i b i l i t y , t h e sample shown i n F i g .
19.37 w a s annealed i n a hydrogen atmosphere u n t i l t h e hydrogen content w a s
140 ppm. The thermal expansion behavior of t h i s m a t e r i a l , determined by
s e v e r a l c y c l e s and p l o t t e d i n Fig. 19.38 suggests t h a t a hydride r e a c t i o n
i s occurring. To support t h e s e observations, a d d i t i o n a l samples a r e being
prepared f o r f u r t h e r study.
Q
E l e c t r o p o l i s h i n g of Zircaloy-2

D . M. Hewett I1
Q
Microstructures of Zircaloy-2 have been obtained using a commercial
e l e c t r o p o l i s h i n g apparatus t h a t u t i l i z e s a flowing e l e c t r o l y t e . 2 o A study

20Disa-Electropol, Model 53B, manufactured by H. S t r u e r ' s Chemiske

Laboratorie, Copenhagen, Denmark. S t r u e r ' s A-3 e l e c t r o l y t e w a s used; t h e
formula i s c o n f i d e n t i a l and i s r e l e a s e d only by t h e manufacturer.

UNCLASSIFIED UNCLASSIFIED
ORNL-LR-DWG 50467 ORNL-LR-DWG 50468

4 4

3 3

- I

._c
E ,
m-
-
\
YJ
- E
E
I

2 2 2 2
2 0
m
z z
In
a
4
2 X
w
X W

0 0
0 100 200 300 400 500 600 700 800 0 100 200 300 400 500 600 700 800
TEMPERATURE ("C) TEMPERATURE ("C)

Fig. 19.37. Linear Thermal Expansion of Fig. 19.38. Linear Thermal Expansion of
a-Zircaloy-2 Containing 40 ppm Hydrogen. a-Zircaloy-2 Containing 140 ppm Hydrogen.

388
 w a s made cf t h e c u r r e n t d e n s i t y - c e l l v o l t a g e r e l a t i o n s h i p and t h e r e s u l t -
i n g m i c r o s t r u c t u r e s t o determine t h e optimum c o n d i t i o n s f o r e l e c t r o p o l i s h -
ing. The samples were mounted i n B a k e l i t e and ground t h r o u g h 4/0 s i l i c o n
carbide papers. E l e c t r o p o l i s h i n g w a s done a t 30 v and a c u r r e n t d e n s i t y
of 0.6 amp/cm2. Z i r c a l o y - 2 i s s i m u l t a n e o u s l y p o l i s h e d and e t c h e d by t h i s
technique.
M i c r o s t r u c t u r e s t y p i c a l of t h o s e produced by t h i s t e c h n i q u e a r e shown
i n F i g s . 1'3.39, 19.40, and 19.41. Areas between t h e p l a t e l e t s of a con-
s i s t of a m i x t u r e of i n t e r m e t a l l i c s of Fe, N i , and C r and a. The develop-
ment of t h e s t r u c t u r e i n t h i s a r e a i s shown i n t h e e l e c t r o n micrograph,
F i g . 19.40.

Fig. 19.39. Zircaloy-2 Annealed at 1059°C for 30 min, Furnace Cooled to 550"C, Held at 850°C, and
A i r Cooled. Note areas between grains of a . Electropolished on the Disa-Electropol; A - 3 Electrolyte.
5oox.

389
 Fig. 19.40. Z i r c a l o y - 2 Annealed a t 1050°C for 30 min, Furnace Cooled to 550°C, H e l d at 85OoC, and
Air Cooled. T h i s electron micrograph s h o w s an area between p l a t e l e t s of pure a that c o n s i s t s of a p l u s
p r e c i p i t a t e d i n t e r m e t a l l i c s of iron, nickel, and chromium. Electropoli shed surface. Faxfilm, palladium-
shadowed carbon replica. 10,OOOX.

390
e
...
3

Fig. 19.41. Zircaloy-2 Annealed a t 1000°C for 30 min and Water Quenched. T h i s microstructure
shows acicular, martensitic a formed on quenching from the /3 field. Electropolished on the Disa-
Electropol, A - 3 Electrolyte. 500X.

M E T A L L O G M H I C SUPPORT FOR THE HIGH FLUX I S O T O P E REACTOR (HFIR)

T. M. Kegley, Jr.
8 As aluminum and aluminum alloys are being considered for fabrication
of the HFIR fuel elements, the Corrosion Group of the Reactor Experimental
Engineering Division has been evaluating aluminum and its alloys with ap-
propriate corrosion tests. In support of this evaluation the following
metallographic services were performed.

Metallographic Polishing of Aluminum

Electrolytic polishing is usually the most satisfactory procedure for

polishing unalloyed aluminum. However, as the edges of the corrosion

39 1

,
specimen had t o be preserved, e l e c t r o l y t i c p o l i s h i n g w a s n o t u s e a b l e and
t h e specimens were mechanically p o l i s h e d . I n mechanical p o l i s h i n g , t h e
Q
f i n a l magnesium oxide p o l i s h i n g s t a g e i s t h e most d i f f i c u l t , as s c r a t c h e s
o f t e n r e s u l t from l a r g e p a r t i c l e s i n t h e MgO a b r a s i v e . S i f t i n g and c a l c i n -
i n g of t h e MgO were t r i e d i n an e f f o r t t o a l l e v i a t e t h i s problem, u s u a l l y
with rather indifferent r e s u l t s . F o r t u n a t e l y , a noncarbonating-type MgO
abrasive2’ w a s found which e l i m i n a t e d t h e s c r a t c h i n g problem. Interest-
i n g l y , t h e MgO a b r a s i v e p a r t i c l e s t e n d t o agglomerate i n water i n r a t h e r
s p e c i f i c forms as i l l u s t r a t e d i n F i g s . 19.42, 19.43, and 19.44 and can be
i d e n t i f i e d as t o t y p e from t h e i r appearance.

I s o t h e r m a l Dynamic Corrosion T e s t s

A s e r i e s of i s o t h e r m a l c o r r o s i o n t e s t s w a s run by t h e Corrosion Group

t o determine t h e e f f e c t of v e l o c i t y on t h e c o r r o s i o n o f aluminum i n w a t e r .
I n t h e s e t e s t s t h e temperature ranged from 200 t o 290°C and t h e f l o w r a t e
from 20 t o 126 f p s . The d u r a t i o n of each t e s t was about 1 0 days. Speci-
mens from each t e s t were examined t o determine t h e e x t e n t of l o c a l i z e d

21Magomet, produced by Buehler, L t d . , Evanston, I l l .

X
0
0
v)

Fig. 19.42. Magomet Magnesium Oxide P o l i s h i n g Compound as Agglomerated i n Water.

c;?
392
Fig. 19.43. Shamva Magnesium Oxide Polishing Compound as Agglomerated i n Water.

Fig. 19.44. J. T. Baker Magnesium Oxide as Agglomerated in Water.

393
attack. The l o c a l i z e d a t t a c k w a s t h e n added t o t h e g e n e r a l a t t a c k as de-
termined from w e i g h t - l o s s d a t a t o o b t a i n t h e t o t a l p e n e t r a t i o n . It w a s
p o s s i b l e a l s o t o measure t h e t o t a l p e n e t r a t i o n m e t a l l o g r a p h i c a l l y u s i n g
t h e p r o t e c t e d a r e a of t h e c o r r o s i o n specimen as a b a s e l i n e . Table 19.2
compares, f o r one s e r i e s of specimens, t h e t o t a l p e n e t r a t i o n determined
m e t a l l o g r a p h i c a l l y w i t h t h a t determined by a d d i t i o n of t h e l o c a l i z e d a t -
tack t o the general attack.

Heat-Flux Corrosion T e s t

To b e t t e r s i m u l a t e c o r r o s i o n which might t a k e p l a c e i n H F I R f u e l e l e -
ments t h e Reactor Experimental Engineering D i v i s i o n developed a h e a t - f l u x
corrosion t e s t . 2 2 High-purity water i s c i r c u l a t e d f o r 10 days a t 33 f p s
through an aluminum flow channel, r e s i s t a n c e h e a t e d by a c u r r e n t of 10,000
amp. During t h e t e s t an oxide l a y e r i s formed a t t h e i n n e r s u r f a c e of t h e
flow channel and a t y p i c a l s e c t i o n i s shown i n F i g . 19.45. The formation
of a t h i c k oxide l a y e r i s undesirable s i n c e it i n t e r f e r e s w i t h h e a t t r a n s f e r .

22J. C . G r i e s s -
et -
a l . , E f f e c t of Heat F l u x on t h e Corrosion of Alu-
minum by Water, P a r t I , Experimental Equipment and P r e l i m i n a r y T e s t Re-
s u l t s . ORNL-2939 ( A p r . 29, 1960).

m-
W
I
0
f

-
002

-
,003

-
004

X
.4
In
r-

Fig. 19.45. Inner Surface of Aluminum F l o w Channel from Heat

F l u x Corrosion Test. There appear to be two o x i d e layers, an inner
opaque layer and an outer transparent layer. M e t a l l i c p a r t i c l e s v i s i b l e
i n inner layer may b e intermetallic compounds.

394
 6

Table 19.2. T o t a l P e n e t r a t i o n Observed i n Aluminum Specimens Exposed 244 h r

a t 260°C i n Flowing D i s t i l l e d Water

Attack Total Penetration

Flow Rate General , by L o c a l i z e d , by BY BY

Specimen Alloy Weight-Los s Met a l l o graphy Addi t i on Metallography
( fPS) Data (mils) (mils) (mils) (mils)

AJ86- 1 1100 22-32 5.0 5.0

AJ86-5 1100 10C-113 8.5 2.0 10.5 15.5

AJ87-5 X8001 22-32 0.2 2.0 2.2 1.0

A J 8 7 -1 X800l 10@-113 10.8 0.6 11.4 12.2

AJ88-1 X2219 22-32 1.3 0.6 1.9 1.8
~38%-5 X2219 lo&-113 8.8 0.6 9.4 10.3

AJ89-5 6061 22-32 0.7 0.6 1.3 0.7

AJ89-1 6061 lo&-113 7.3 0.6 7.9 11.2
 METALLOGRAPHIC SUPPORT FOR THE ENRICO FERMI REACTOR (FERMI)
AND MOLTEN SALT F3ACTOR (MSR) PROGRAMS
Transformations in the Nickel-Molybdenum Systems

J. R. Riddle

A dilatometric study of the a l p transformation in the nickel-molyb-

denum system has revealed that a volume difference of 0.8% is associated
with the formation of the p phase.23 This dilation data initiated a di-
latometric and metallographic study of twelve other nickel-molybdenum
alloys. The alp transformation was observed not only at the ideal f3 Tom-
position ( 2 9 w t % Mo), but also in alloys containing 25, 27, 32, 35, and 6B
40 w t % Mo. These results were surprising in view of the narrow composi-
tion limits implied by H a n ~ e n . The
~ ~ observation of this transformation
in the alloys containing between 32 and 40 w t '$ Mo is undoubtedly a result
of the comparable molybdenum content between the solid-solution a phase
at elevated temperature and the f3 phase. With increasing nickel content
above that of the ideal p composition, the following trends were observed:
the volume difference between the a and p phases was decreasing; the tem-
perature of the transformation was lowered; and the temperature range of
the transformation was increasing. As in the case of the ideal p phase,
the transformation occurs at heating and cooling rates of 1-2"C/min, and
there is no evidence of a second phase in the microstructure. The tern-
perature range of the transformation (830-860°C for 27 w t '$ Mo and 760-
840°C for the 25 wt % Mo) is believed to be an indication of a two-phase 9
field in the nickel-molybdenum equilibrium diagram. The trend with these
increasing nickel contents was toward an inflection in the thermal expan-
sion curve. An inflection was observed in an 18 w t % Mo alloy and it is e
postulated that this may also be an indication of the alp transformation.
The y phase (Ni3Mo) was found to form by a sluggish precipitation
and growth process. The reaction is observed by a gradual contraction of
either the a or the p phases. The formation of the y phase can be con-
firmed by the absence of the a / @transformation on dilating the material

23Met. Ann. Prog. Rep. Sept. 1, 1959, ORNL-2839, p 295-332.

24M. Hansen, Constitution of Binary Alloys, 2nd ed., p 968, McGraw-
Hill, New York, 1958.
between room t e m p e r a t u r e and 900°C. The mode of f o r m a t i o n of t h e y phase
h a s n o t been completely determined, b u t t h e r e i s c o n s i d e r a b l e e v i d e n c e t o
i n d i c a t e t h a t it forms as Widmanstatten p l a t e l e t s i n an a matrix and as a
grain-boundary p r e c i p i t a t e from t h e @ p h a s e .

Sigma Fhase i n S t a i n l e s s S t e e l

C . K. H. DuBose

Meta:Llographic examination of a t y p e 310 s t a i n l e s s s t e e l sample which

had been cold r o l l e d t o a 25% r e d u c t i o n i n t h i c k n e s s and t h e n annealed
1000 h r a t 1200'F r e v e a l e d c o n s i d e r a b l e m phase ( s e e F i g . 1 9 . 4 6 ) .
The specimen, a f t e r p o l i s h i n g , was f i r s t e t c h e d i n V i l e l l a ' s r e a g e n t
t o r e v e a l t h e g r a i n boundaries. A s t a i n e t c h a n t of s a t u r a t e d NaOH w a s
t h e n used e l e c t r o l y t i c a l l y a t 1 . 5 v f o r 6 s e e t o s t a i n t h e LJ- phase orange
and t h e iron-chromium c a r b i d e s b l u e . When t h e same procedure was used
on a h e a t - t r e a t e d t y p e 316 s t a i n l e s s s t e e l , u s i n g a 10% KOH s o l u t i o n i n
p l a c e o f N'aOH, t h e same r e s u l t s were o b t a i n e d .

Metallography of Graphite

R . J. Gray M. D . A l l e n w. H.

P r o p o s a l s f o r t h e use of g r a p h i t e f o r t h e f a b r i c a t i o n of r e a c t o r com-
p o n e n t s have i n c r e a s e d i n r e c e n t y e a r s . Technology of manufacture and
f a b r i c a t i o n of t h e v a r i o u s grades of g r a p h i t e have improved t o p r o v i d e
very dense and impervious forms. The use of m e t a l l o g r a p h i c examination
has been developed t o t h e e x t e n t t h a t much u s e f u l i n f o r m a t i o n can b e de-
rived. To a i d i n d e v e l o p i n g i n t e r p r e t i v e m e t a l l o g r a p h i c p r o c e d u r e s , a
program w a s undertaken t o i n v e s t i g a t e t h e p o l i s h i n g and examination of
graphite.
The n a t u r e of g r a p h i t e n e c e s s i t a t e d t h e development of m o d i f i e d t e c h -
n i q u e s f o r t h e c u t t i n g , mounting, g r i n d i n g , and p o l i s h i n g of specimens.
The g r a p h i t e w a s s e c t i o n e d w i t h a high-speed s i l i c o n c a r b i d e c u t t i n g wheel
operated dry. To minimize t h e entrapment of d u s t and f o r e i g n p a r t i c l e s
i n t h e v o i d s , t h e specimens were u l t r a s o n i c a l l y c l e a n e d i n a c e t o n e and

25MateriaLs C o m p a t i b i l i t y Group.

397
b 86E
0
b
G, dried at 200°C. A room-temperature-settingepoxy resin26 was used f o r
mounting the specimens and they were hard ground through 600-grit papers
and polished for 6 to 8 hr in Syntron vibratory polishers on silk cloth
with Linde "A" slurry.
The polished specimens were examined with bright-field illumination
and photographed with a wide-latitude panchromatic film. AGOT graphite
is the old-est grade in reactor use (Fig. 19.47) and is used as a refer-
ence structure. All improved grade of graphite is illustrated by Fig. 19.48.
Cracks shown in Fig. 19.49 and other faults can be studied metallographi-
cally particularly aiding the development of nondestructive testing equip-
9
ment. Impregnation is one method to reduce the permeability of graphite.
Figure 19.50 is a graphite in which some of the voids are filled with

9 26Hysol, ERL-2774, manufactured by Houghton Laboratories, Incorpo-

rated, Olean, New York.

v)
W
I
0
5

-
.o:

-
.o

X
0
I!

Fig. 19.47. Graphite, Grade AGOT, As Received. Apparent density, 1.68 g/cc. Black areas are

LLI voids (pares); as polished.

399

Q
 -

v)
W-
I
0
E

.02
_I

Fig. 19.48. Graphite, Grade B-1, A s Received. Apparent density, 1.91 g/cc; o s polished.

Fig. 19.49. Graphite, Grade GT-123-82, As Received. Apparent density, 1.91 g/cc; as polished.

400
 cn
W-
I
0
z_

-
.02

-
.03

X
0.
0

Fig. 19.50. Graphite, Grade R-4, A s Received. Apparent density, 1.92 g/cc. Black areas are voids,
white areas are carbon, and gray material i s graphite; a s polished.

amorphous carbon which i s h a r d e r t h a n t h e s o f t g r a p h i t e m a t r i x , y e t b o t h

were r e t a i n e d . An extruded g r a p h i t e t u b e w a s t r e a t e d t o reduce i t s p e r -
m e a b i l i t y and comparison of F i g . 19.51 ( b e f o r e ) w i t h F i g . 19.52 ( a f t e r )
shows t h e e f f e c t i v e n e s s of t r e a t m e n t .
A r e p o r t i s b e i n g p r e p a r e d c o v e r i n g t h e examination of g r a p h i t e i n
e detail.

401
 Fig. 19.51. Grade CEY Base Stock Before Being Converted to a Low-Permeability Graphite. AP -
parent density, 1.79 g/cc.

Fig. 19.52. Grade CEY-82, CEY Base Stock, After Being Converted to a Low-Permeability Graphite.
Apparent density, 1.87 g/cc.

4 02
 METALLOGRAPHIC SUPPORT FOR THE AIRCRAFT
NUCLEAR PROPULSION (AJYP) PROGRAM

Chi Phase i n Type 316 S t a i n l e s s S t e e l

R. S. Crouse

During examination of a t y p e 316 s t a i n l e s s s t e e l l o o p which had op-

e r a t e d approximately 200 h r a t 1600°F w i t h b o i l i n g potassium, an unusual
phase w a s found i n t h e upper c o l d - l e g s e c t i o n . It w a s e s t i m a t e d t h a t t h i s
s e c t i o n had been a t about 1375°F. It i s f e l t t h a t occurrence of t h i s phase
w a s i n no vay connected w i t h t h e potassium environment, b e i n g dependent on
temperature and f a b r i c a t i o n h i s t o r y of t h e t y p e 316 s t a i n l e s s s t e e l . It
w a s f i r s t assumed t h a t t h e phase w a s cr and e f f o r t s t o e s t a b l i s h a d e f i n i t e
i d e n t i f i c a t i o n were made u s i n g t h e techniques of D u l i s and Smith.27
F i g u r e 19.53 i s t h e m i c r o s t r u c t u r e e t c h e d w i t h p i c r i c a c i d - a l c o h o l -
H C 1 which i?eveals u, f e r r i t e , and c a r b i d e s . F i g u r e 19.54 i s t h e micro-
s t r u c t u r e e t c h e d w i t h a l k a l i n e potassium f e r r i c y a n i d e which r e v e a l s f e r r i t e
and c a r b i d e s . The signa phase i s vaguely r e v e a l e d on l o n g exposure. Fig-
u r e 19.55 i s t h e m i c r o s t r u c t u r e as e l e c t r o l y t i c a l l y e t c h e d w i t h chromic
acid. This t r e a t m e n t removes cr phase and c a r b i d e s and o u t l i n e s f e r r i t e .
By comparing a l l t h r e e , one can t e n t a t i v e l y i d e n t i f y each of t h e phases.
Most of t h e massive grain-boundary phase appeared t o be cr and t h e g e n e r a l
p r e c i p i t a t e i n the grains was carbide. Some f e r r i t e occurred w i t h t h e
u phase.
Q
I n an attempt t o p o s i t i v e l y i d e n t i f y t h e phases, t h e m i c r o s t r u c t u r e
w a s deeply e t c h e d e l e c t r o l y t i c a l l y w i t h a s o l u t i o n of FeC13-6H20 and t h e
e x t r a c t e d r e s i d u e s u b m i t t e d f o r e l e c t r o n and x-ray d i f f r a c t i o n . Both meth-
9 ods i d e n t i f i e d t h e major phase as X, a Ni-Cr-Mo compound, t o g e t h e r w i t h
cr23c6
According t o Koh,28 the X phase i s formed i n s t e e l s and s t a i n l e s s
a l l o y s c o n t a i n i n g molybdenum h e l d a t temperatures of 1400 t o 1800°F a f t e r

27E. J. D u l i s and G. V. Smith, Tech. Pub. No. 110, Am. SOC. T e s t i n g

M a t e r i a l s ( 1 9 5 0 ) , p 3-29.
28P. EL. Koh, J. Metals -
5, 339-43 ( 1 9 5 3 ) .
-

4 03
 Fig. 19.53. Type 316 Stainless Steel Etched with Picric Acid-Alcohol-HCI in Order to Reveal (5,

Ferrite, and Carbides.

UNCLASSI FIE0
Y- 34725
f

,-

e* I

8 . v . .
)

' ( I

Fig. 19.54. Type 316 Stainless Steel Etched with Alkaline Potassium Ferricyanide i n Order to
Reveal Ferrite and Carbides.

404
Q

solution heat treatment. The X phase r e a c t s t o t h e e t c h a n t s f o r t h e cr

6) phase much as cr does and may be mistaken f o r t h e cr phase i f n o t otherwise
identified. Another t e n t a t i v e i d e n t i f i c a t i o n r e l a t e s t o t h e f a c t t h a t
t h e cr phase t e n d s t o p r e c i p i t a t e g e n e r a l l y from a cold-worked s t r u c t u r e
while X phase occurs i n t e r g r a n u l a r l y from a s o l u t i o n h e a t - t r e a t e d s t r u c -
ture.

UNCLASSIFIED
Y-34726 I
\

B)

9 Fig. 19.55. Type 316 Stainless Steel Etched with Chromic Acid Electrolytically i n Order to Reveal
Ferrite.

4 05
 20. NONDESTRUCTIVE TEST DEVELOPMENT

EDDY-CURRENT DEVELOPMENT

J. W. Allen, Jr.

Met a1 Identification Meter

R. A. Nance

A new transistorized Metal Identification Meter (see Fig. 20.1) for

the sorting of metals and alloys according to their electrical conduc-
tivity and magnetic permeability has been designed and built by the In-
strumentation and Controls Division in conjunction with the Nondestructive
Test Development Group. This instrument is smaller, lighter, and more
stable than its predecessor.lY2 It weighs 1-3/4 lb, has a battery life-
time of 400 hr, and is capable of operation at temperatures from 32 to
120°F.

Probe-Coil Instrumentation

R. A. Nance K. V. Cook
A new eddy-current instrument has been designed and built for the
measurement of cladding thickness, location of core positions in fuel
plates, and other general eddy-current probe-coil techniques. This in-
strument is relatively insensitive to variations in the spacing between
the probe coil and the inspected specimen and eliminates the difficult
problems associated with the accurate control of this spacing. A block
diagram of this instrument is shown in Fig. 20.2. An oscillator drives
a bridge which has been balanced under some initial conditions. The out-
put signal from the bridge has the same frequency as the oscillator but a
different phase, depending upon the configuration and electrical charac-
teristics of the investigated specimen. The amplitude of the bridge out-
put signal is dependent upon the spacing between the probe and the speci-
men. By measuring the phase difference between the oscillator signal and
the bridge output signal, it is possible to obtain information from the

'Met. Ann. Prog. Rep. Oct. 10, 1957, ORNL-2422, p 38 (classified).

2Met. Ann. B o g . Rep. Oct. 10, 1958, ORNL-2632, p 119 (classified).

4 06
dB
ii
t
Q,
z
e 0
.-
t

C
0
I
-0
Q
.-LN
0
+
.- v)
v)
C
E
m l-
W
r ?I
0
Z
81
0
 UNCLASSIFIED
ORNL-LR-DWG 50491

I
PROBE METERING CIRCUIT

SPECIMEN

Fig. 20.2. Block Diagram of Eddy-Current Probe-Coil Instrument.

specimen independent of t h e probe-to-specimen spacing. Measurement of

t h e phase d i f f e r e n c e i s accomplished by using t h e two s i g n a l s ( t h e os-
c i l l a t o r and b r i d g e output s i g n a l s ) t o generate p u l s e s which a c t u a t e a
flip-flop circuit. A metering c i r c u i t measures t h e average "on" time of
t h e f l i p - f l o p and can be c a l i b r a t e d i n terms of t h e specimen c h a r a c t e r -
i s t i c s producing t h e phase change. This instrument should prove very v a l -
uable i n remote-inspection problems i n which t h e p o s i t i o n i n g of probes
may be d i f f i c u l t . I n a d d i t i o n , t h e instrument i s designed t o accommodate
many d i f f e r e n t c o i l systems and w i l l g r e a t l y f a c i l i t a t e t h e design and de-
velopment of new c o i l systems f o r i n s p e c t i o n problems.

Reference Standards e
R. A. Nance
The development of r e f e r e n c e standards f o r t u b i n g i n s p e c t i o n has been
continued, with an extensive i n v e s t i g a t i o n of t h r e e types of standard de-
fects:3 (1)l o n g i t u d i n a l notches produced by a t h i n m i l l i n g c u t t e r , ( 2 )
t r a n s v e r s e notches produced by a round f i l e , and ( 3 ) l o n g i t u d i n a l notches
 produced by e l e c t r i c a l - s p a r k - d i s c h a r g e machining. Since t h e spark-dis-
charge-machined notches could be more a c c u r a t e l y reproduced t h a n t h e o t h e r
types, e f f o r t s have been concentrated on r e f i n i n g t h i s technique i n order
t o provide t h e g r e a t e s t p o s s i b l e accuracy i n t h e production of s t a n d a r d
defects. S p e c i a l t o o l holders have been designed and t h e equipment c a l i -
b r a t e d i n such a way t h a t a notch s e v e r a l thousandths of an i n c h deep can
be made with a depth accuracy of i O . 0 0 ~ 2 i n . I n a d d i t i o n , attachments
have been f a b r i c a t e d which allow t h e production of inside-diameter notches
as f a r as 12 i n . from t h e tube end i n 0.250-in.-ID tubing. However, t h e
accuracy of t h e depth for inside-diameter notches i s only about 0.0005 i n .
a
HIGH FLUX ISOTOPE REACTOR COOLANT-CHANNEL-SPACING MEASUREMElVT

R . A. Nance R. W. McClung
Q
The c r i t i c a l spacing between t h e f u e l p l a t e s i n t h e High Flux Isotope
Reactor ( I P I R ) n e c e s s i t a t e d t h e development of a method f o r measuring
coolant-channel spacing t o f a c i l i t a t e t h e development of core f a b r i c a t i o n
techniques. The following c o n s i d e r a t i o n s were of prime importance i n t h i s

development program: (1)t h e f u e l p l a t e s were contoured i n t h e form of

an i n v o l u t e ( s e e F i g . 20.3), which n e c e s s i t a t e s t h e use of a contoured
i n s p e c t i o n probe; ( 2 ) measurements must be made along t h e e n t i r e width
and l e n g t h of t h e channel; and ( 3 ) t h e range of measurements must extend
from 0.030 t o 0.070 i n . An eddy-current technique w a s chosen as t h e most
promising method of accomplishing t h i s measurement. A commercial i n s t r u -
ment, t h e Laminagage ( s e e F i g . 20.4), was adapted f o r t h i s t a s k by use of
a s p e c i a l l y designed probe i l l u s t r a t e d i n Fig. 20.5. It c o n s i s t s of a
s t r i p of f l e x i b l e - s t e e l measuring t a p e , a s m a l l f l a t c o i l , and a s t e e l
leaf spring. The measuring head i s 0.030 i n . t h i c k w i t h t h e l e a f s p r i n g
f u l l y depressed. The curvature of t h e s t e e l t a p e corresponds t o t h e
s m a l l e s t curvature on t h e i n v o l u t e p l a t e s .
The Laminagage u t i l i z e s t h e change i n t h e c o i l inductance produced
by v a r i a t i o n s i n spacing between t h e c o i l and t h e l e a f s p r i n g . Measure-
ments of t h e width of t h e coolant channel a r e being made with an accuracy
of 40.001 i n . This accuracy can b e improved i f needed.

w
409

3
 Fig. 20.3. End V i e w of HFlR F u e l Assembly.

410
0

3 UNCLASSIFIED
ORNL-LR-DWG 50492

Fig. 20.5. Schematic of HFlR Channel-Space

Measuring Probe.

Q
EXPERIMENTAL GAS-COOLED REACTOR FUEL ASSEMBLY INSPECTION
DEVELOPMENT

Q R. W. McClung R. A. Nance

A large portion of the effort during the report period has been di-
rected toward the development of nondestructive inspection techniques for
the EGCR fuel element components and assembly .4-7 Recommended techniques
for the capsule cladding (type 304 stainless steel tubing, 0.710-in. ID
and 0.020 in. wall) include the use of eddy currents and fluorescent pen-
etrants for flaw detection and resonance ultrasonics and air gaging for
dimensional integrity. Inspections for the other components included
fluorescent penetrants for the end caps and midplane spacers, radiography
and fluorescent penetrants for the spiders, and eddy currents for the
graphite sleeves. Recommendations were made for the use of radiography,
penetrants, and helium leak testing on the capsule closure welds. A top-
ical report on this development program is being prepared.

'5. W. Allen -et -al., Met. Ann. Prog. Rep. Sept. 1, 1959, ORNL-2839,
p 192-93, 213-16.
'GCR IQuar. Prog. Rep. Dee. 31, 1959, ORNL-2888, p 85-90.
6GCR (War. Prog. Rep. Mar. 31, 1960, ORNL-2929, p 4.34-4.36.
7GCR Quar. D o g . Rep. June 30, 1960, ORNL-2964 (in press).

41 1
 ULTRASONIC BEHAVIOR IN THIN METAL SECTIONS

R. W. McClung
The behavior of ultrasonic vibration in thin metal sections8' has
been further investigated. The study includes Lamb-wave propagation as
well as quantitative measurements of reflection and through transmission
of ultrasound as used on thin metal sections with varying parameters of
frequency, specimen thickness, and incident angle. A theoretical con-
sideration of reflection and through transmission assumes an optical anal-
ogy with maximum reflection and minimum transmission at perpendicular in-
cidence for specimen thicknesses equal to odd lnultiples of the quarter
wavelength. The reverse, that is, minimum reflection and maximum trans-
mission, occurs at specimen thicknesses equal to multiples of the half
wavelength. These relations are true and some experimental correlation
may be o b t a i n e d f o r t h e s i n g u l a r c a s e i n which t h e sound beam is perpen-
dicular to the specimen surface. For incident angles other than normal,
maximum reflection (by the optical analogy) may be calculated by the re-
lation

and maximum transmission may be calculated by the relation

d COS 01 = - J

where d = specimen thickness, 8 1 = refracted angle in the specimen, m =

integer, and A1 = wavelength in the specimen. This theoretical concept
fails to account for mode conversion, velocity variations, secondary vi-
bration within the specimen, and other variables. Therefore, it is nec-
essary to determine the true behavior experimentally.

.8R.W. McClung, Met. Ann. Prog. Rep. Oct. 10, 1958, ORNL-2632,
p 124-26 (classified).
'R. W. McClung, Met. Ann. Prog. Rep. Sept. 1, 1959, ORNL-2839,
p 205-207.

.. - ~ . -_ . .
 C a l i b r a t i o n i s b e i n g made on t h e p u l s i n g c i r c u i t s of t h e u l t r a s o n i c
a t t e n u a t i o n comparator t o b e u s e d as t h e u l t r a s o n i c g e n e r a t o r . The ad-
v a n t a g e of t h i s i n s t r u m e n t i s t h e completely v a r i a b l e frequency and v o l t -
age of t h e p u l s e . It h a s become e v i d e n t t h a t t h e f r e q u e n c y and v o l t a g e
may b e changed as a f u n c t i o n of any change made i n c a b l e s , t r a n s d u c e r s ,
impedance matching, e t c . For t h i s r e a s o n t h e c a l i b r a t i o n i n c l u d e s t h e s e
v a r i a b l e s , a n d i n f o r m a t i o n i s b e i n g o b t a i n e d on t h e f r e q u e n c y r e s p o n s e of
t h e t e s t system. All f r e q u e n c i e s and v o l t a g e s are b e i n g measured on an
o s c i l l o s c o p e w i t h a c a l i b r a t e d sweep d e l a y .
The mechanical equipment f o r t h i s s t u d y i s shown i n F i g . 20.6. The
equipment c o n s i s t s of two s m a l l l a t h e s and t h r e e c a r r i a g e a s s e m b l i e s . A
s e a r c h t u b e and u l t r a s o n i c t r a n s d u c e r a r e mounted t o each c a r r i a g e assembly
i n such a way as t o p r o v i d e complete freedom of movement. This w i l l allow
simultaneous measurements of r e f l e c t i o n , t r a n s m i s s i o n , and Lamb-wave prop-
a g a t i o n t h r o u g h a t h i n metal s e c t i o n . These measurements can t h e n b e made
as a f u n c t i o n of changes i n specimen t h i c k n e s s and t h e i n c i d e n t a n g l e and
f r e q u e n c y of t h e u l t r a s o n i c wave.

LOW-VOLTAGE FADIOGRAPKY

R . W. McClung

The s t u d y of low-voltage radiographic'' p a r a m e t e r s h a s been d i r e c t e d

toward t h e d e t e r m i n a t i o n of t h e r e l a t i v e advantage of a helium atmosphere
as compared t o a i r because of t h e l a r g e a b s o r p t i o n d i f f e r e n c e . T h i s has
been s t u d i e d as a f u n c t i o n of i n c r e a s i n g energy ( k i l o v o l t s ) w i t h b o t h b a r e
f i l m and i n c r e a s i n g t h i c k n e s s e s of aluminum. F i g u r e 20.7 i s a graph of
t h e r e l a t i v e r a d i o g r a p h i c exposure comparing helium and a i r atmospheres
f o r increasing kilovoltages. Data have been c o l l e c t e d t h u s f a r f o r t h i c k -
n e s s e s of aluminum up through 0.024 i n . S i m i l a r exposure d a t a w i l l b e
c o l l e c t e d for t y p e 304 s t a i n l e s s s t e e l and b e r y l l i u m , u s i n g b o t h a i r and
helium atmospheres f o r i n c r e a s i n g k i l o v o l t a g e s . It i s p l a n n e d t o f u r t h e r
e v a l u a t e t h e s e exposure d a t a t o o b t a i n i n f o r m a t i o n on a v a i l a b l e c o n t r a s t
s e n s i t i v i t - i e s and r a d i o g r a p h i c e q u i v a l e n c e f a c t o r s ( r e l a t i v e t h i c k n e s s e s

'OR. W. McClung and J. W. A l l e n , M e t . Ann. Prog. Rep. S e p t . 1, 1959,

ORNL-2839, p 212-13.

413
 A

Fig. 20.6. Mechanical Equipment for Study of Ultrasonic Behavior in Thin Sections.

414
 UNCLASSIFIED

RELATIVE EXPOSURE
( He a t m o s p h e r e )
a,mosphere

Fig. 20.7. R e l a t i v e Exposure Requirements for H e l i u m and A i r Atmospheres.

of different materials which have the sane total absorption at a given

radiation (eneralevel).
Practical applications of this equipment are made regularly for the
radiography of various items, such as beryllium tubing and closure welds,
graphite specimens, and epoxy-resin compacts.

e BERYLLIUM INSPECTION DEVELOPMENT AND TUBING EVALUATION

H. W. McClung R. A. Nance
Preliminary inspection techniques have been established for the eval-
uation of beryllium tubing by the use of low-voltage radiography, pulse-
echo and resonance ultrasonics, penetrants, and eddy currents. Among the
difficulties which must be countered are the very low radiation absorption
coefficient,, the very high ultrasonic velocity, and the presence of minute
quantities of contamination, usually iron. These techniques are being ap-
plied to 0.300-in.-IDY O.O4O-in.-wall tubing which has been received from
American, Eritish, and French sources.11' In addition, evaluation is

-GLuar. D o g . Rep. Mar.

"GCR 31, 1960, ORNL-2929, p 13Et39.

415
1

being conducted on some 0.520-in.-ID, 0.04O-in.-wall t u b i n g from t h e

French suppliel-.
The American t u b i n g which has been e v a l u a t e d contained a few shallow
pinholes and a few t i n y high-density p a r t i c l e s . The most undesirable qual-
i t y w a s t h e wall-thickness v a r i a t i o n s , which exceeded t h e 220% t o l e r a n c e
i n about a t h i r d of t h e t u b e s .
The French t u b i n g contained more pinholes, p i t s , and high-density ma-
t e r i a l than t h e American tubing. Several deep l o n g i t u d i n a l cracks and
many shallow c i r c u m f e r e n t i a l cracks have been d e t e c t e d .
The English t u b i n g has not been s u c c e s s f u l l y evaluated. The presence
of excessive high-density m a t e r i a l , s u r f a c e roughness, and outside-diameter
v a r i a t i o n s have made t h e i n s p e c t i o n s very d i f f i c u l t .

MEASUREMENT OF HOMOGENEOUS REACTOR TEST CORE

VESSEL WALL THICKNESS
R . W. McClung

Two surveys of t h e w a l l t h i c k n e s s of t h e Homogeneous Reactor Test

Zircaloy-2 core v e s s e l have been made by u s i n g u l t r a s o n i c techniques.
These measurements were made during s e p a r a t e shutdown periods between r e -
a c t o r o p e r a t i n g times. A mechanical f i x t u r e w a s used which permitted
placement of t h e t r a n s d u c e r a t any p o s i t i o n on t h e i n n e r s u r f a c e of t h e
spherical vessel. The f i r s t of t h e two examinations used a pulse-echo
r e f l e c t i o n technique, with t h e c a l i b r a t e d delay l i n e o f an o s c i l l o s c o p e
I

being used t o measure t h e time i n t e r v a l between successive back r e f l e c -

tions.'* From an average v e l o c i t y value and t h e measured time, t h e w a l l
I

t h i c k n e s s could be c a l c u l a t e d .
I n t h e second measurement s e v e r a l modifications were made. Rather
t h a n using t h e o s c i l l o s c o p e t o measure t h e time i n t e r v a l , t h e a p p r o p r i a t e
r e f l e c t i o n s i g n a l s were g a t e d t o an e l e c t r o n i c timer f o r measurement of
t h e time i n t e r v a l . To provide g r e a t e r p r e c i s i o n and t o permit a d i g i t a l
readout of t h e w a l l t h i c k n e s s , a p r e s e t counter w a s used t o allow t h e
timer t o accumulate o r i n t e g r a t e a s e r i e s of s i n g l e measurements. The
adjustment on t h e p r e s e t counter w a s a f u n c t i o n of t h e u l t r a s o n i c v e l o c i t y

'*HRP Quar. Prog. Rep. Oct. 31, 1959, ORNL-2879, p 2 3 M O .

416
 i n t h e Zircaloy-2 and t h e number of back r e f l e c t i o n s involved i n t h e meas-
u r e m e n t ~ . " ~The only modification s i n c e t h e l a s t r e p o r t has been t o pro-
vide a moire s o p h i s t i c a t e d p r e s e t counter which w i l l allow u n i t adjustment
from 1 t o lo6 counts.
The f i r s t s e r i e s of measurements were made with t h e u l t r a s o n i c trms-
ducer i n i n t i m a t e c o n t a c t with t h e v e s s e l w a l l , b u t t h i s w a s not p o s s i b l e
f o r t h e second measurement. Perhaps t h i s w a s due t o t h e unevenness of t h e
i n n e r s u r f a c e of t h e v e s s e l . It w a s necessary t o r e t r a c t t h e t r a n s d u c e r
from c o n t a c t and t o introduce t h e u l t r a s o u n d i n t o t h e w a l l through a s h o r t
column of water ( t h e immersed t e c h n i q u e ) . The second s e r i e s of measure-
e, ments i n d i c a t e d t h a t t h e w a l l w a s from 0.005 t o 0.010 i n . t h i n n e r t h a n it
w a s during t h e previous measurement.

9 PRFSSURE VESSEL WELDMEN" INSPECTION DEVELOP~NT

R . W. McClung

Several f e e t of L i n . - t h i c k weldments i n A-212B s t e e l have been eval-

u a t e d by pulse-echo u l t r a s o n i c techniques. The welds were i d e n t i f i e d ac-
cording t o t h e r e l a t i v e p o s i t i o n of t h e welds during f a b r i c a t i o n , t h a t i s ,
v e r t i c a l , h o r i z o n t a l , overhead, and downhand. These welds had been radio-
graphed i n accordance with acceptable commercial p r a c t i c e and no discon-
t i n u i t i e s vere detected. The very s e n s i t i v e u l t r a s o n i c technique d e t e c t e d
s e v e r a l d i s c o n t i n u i t i e s i n t h e welds made by each technique. However,
only t h o s e i n t h e overhead and downhand welds were considered t o be s i g -
n i f i c a n t enough f o r f u r t h e r e v a l u a t i o n . Areas which contained d i s c o n t i -
n u i t i e s were c u t i n t o 1/2-in.-thick c r o s s s e c t i o n s and radiographed through
t h e 1/2-in. thickness. Good c o r r e l a t i o n w a s .obtained between t h e s i z e
and l o c a t i o n of t h e u l t r a s o n i c i n d i c a t i o n and t h e a c t u a l d i s c o n t i n u i t i e s ,
many of wh.ich were caused by a l a c k of f u s i o n between successive weld
passes.

13J. 14. Allen and R . W. McClung, Met. Ann. Prog. Rep. Sept. 1, 1959,
ORNL-2839, p 20&11.

41 7
 GAMMA-SCINTILLATION SPECTROMETRY

B. E. Foster14

Preliminary work t o develop a s u i t a b l e technique and c a l i b r a t i o n of

gamma-spectrometry equipment f o r assaying U-A1 core blanks i s almost com-
pleted. This equipment w a s o r i g i n a l l y designed by t h e Instrumentation
and Controls Division i n 1954. Figure 20.8 i s a block diagram of t h e sys-
tem. The gamma r a d i a t i o n from t h e sample i s d e t e c t e d b y means of a NaI
(Tl) c r y s t a l , 2 i n . i n diameter and 2 i n . t h i c k . The c r y s t a l i s o p t i c a l l y
coupled t o an RCA 6655A p h o t o m u l t i p l i e r tube. The pulse from t h e photo-
tube i s f e d through a p r e a m p l i f i e r t o a l i n e a r a m p l i f i e r and pulse height Q
s e l e c t o r f o r t h e shaping and s e l e c t i o n of pulses between two d e f i n i t e
voltage l e v e l s . (The c h a r a c t e r i s t i c 184-kev gamma r a d i a t i o n a s s o c i a t e d
with t h e U235 decay i s monitored.) The output of t h i s u n i t t h e n goes t o
a timer and s c a l e r with provisions made f o r t h e d i g i t a l recording of t h e
number of p u l s e s p e r p r e s e l e c t e d time. An e l e c t r o n i c l i n e - v o l t a g e regu-
l a t o r w i t h r e g u l a t i o n of +0.1$ of l i n e voltage i s used f o r t h e e n t i r e
system.
The e a r l y s t a g e s of t h i s work c o n s i s t e d of replacement of major and
minor system components as w e l l as a d d i t i o n s t o a n d d e l e t i o n s of some p a r t s
of t h e system. This w a s necessary t o o b t a i n equipment s t a b i l i z a t i o n .

141nstrumentation and Controls Division.

UNCLASSIFIED
ORNL-LR-OWG 50495

PREAMPLIFIER
LINEAR 1 PULSE-
HE,GHT . UNIVERSAL
TIMER
DECADE
SCALER
DIGITAL
AMPLIF'ER SELECTOR RECORDER
I

REGULATED ELECTRONIC LINE-

H IGH-VOLTAGE
VOLTAGE REGULATOR
POWER SUPPLY
-

- Na r
SAMPLE

Fig. 20.8. Block Diagram of Gamma S c i n t i l l a t i o n Spectrometer.

41 8
Q

The equipment s t a b i l i t y w a s checked by counting t h e same core blank

G, a t t h e various times of t h e day f o r a p e r i o d of s e v e r a l weeks. The r e -
s u l t s showed l e s s than 0.5% d r i f t i n counting r a t e during t h i s period.
Several AI.-U core blanks c o n s i s t i n g of 7, 13, 18, 25, and 30 wt %U
were obtai-ned from t h e Metal Forming and Casting Group. The blanks of t h e
f i r s t t h r e e above percentages were counted by u s i n g t h e spectrometer. Then
two blank:; of each of t h e s e percentages were analyzed chemically. Plots
of t h e counting r a t e s of t h e s i x specimens vs mass of U 2 3 5 were made. Ad-
d i t i o n a l lcllanks were t h e n counted, and t h e s e were a l s o analyzed chemically.
The c a l i b r a t i o n curve w a s l i n e a r and i n e x c e l l e n t agreement with t h e
e d i p a n a l y s i s and t h e a n a l y t i c a l a n a l y s i s on a l l t h e 7% b l a n k s . There w a s
good agreement with t h e d i p a n a l y s i s on both t h e 13 and 18%blanks, b u t
some discrepancy e x i s t e d with t h e 13%a n a l y t i c a l d a t a . A t t h i s time t h e r e
@ i s no explanation f o r t h i s d i f f i c u l t y .
The most a c c u r a t e o p e r a t i o n of t h e equipment i s i n t h e a n a l y s i s of
the 7% U core blanks. Some n o n l i n e a r i t y of t h e c a l i b r a t i o n curve i s ex-
perienced i f a wide range of c o n c e n t r a t i o n s i s included near t h e 18% U
analysis. This i s due t o s e l f - a b s o r p t i o n , s i n c e t h e t h i c k n e s s of t h e
blanks i n t h i s region i s i n excess of 0.3 g of U 2 3 5 per em2.
Additional d a t a a r e being acquired t o determine i f t h i s n o n l i n e a r i t y
w i l l cause much d e v i a t i o n from t h e d i p a n a l y s i s . A t p r e s e n t about 140
blanks of l8% U have been counted.
Q I N S P E C T I O N PROBLEMS AND MATERIAL EVALUATION

R . W. McClung R . A. Nance

A number of s m a l l , short-term i n s p e c t i o n problems were p r e s e n t e d t o

Q
t h e Nondestructive Test Development Group during t h e p a s t year. The f o l -
lowing repi-esents a few o f t h e s e .
Several l e n g t h s of niobium t u b i n g were p r e s e n t e d f o r nondestructive
evaluation. U l t r a s o n i c examination r e v e a l e d t h e presence of inside-diam-
e t e r cracking i n most of t h e tubing, with depths varying from 0.001 t o
0.005 i n . Some of t h e cracks were more severe and approached depths of
50% of t h e w a l l t h i c k n e s s .

419
 Several f u e l rods which had been f a b r i c a t e d by swaging s t a i n l e s s
s t e e l t u b i n g onto U 0 2 powder were i n s p e c t e d by penetrant and u l t r a s o n i c
techniques. One source of concern w a s t h e p o s s i b l e presence of i n s i d e -
diameter cracking on t h e s t a i n l e s s s t e e l c l a d . However, t h e only discon-
t i n u i t i e s d e t e c t e d were outside-diameter l a p s formed during t h e swaging
process.
A few experimental f u e l rods were evaluated nondestructively. The
rods c o n s i s t e d of U 0 2 p e l l e t s c l a d i n s t a i n l e s s s t e e l tubing, with a l e a d
bonding l a y e r between t h e U 0 2 and cladding. Resonance u l t r a s o n i c tech-
niques l o c a t e d s e v e r a l a r e a s of nonbond.
S p e c i a l eddy-current techniques were used t o measure t h e l e n g t h of
s e v e r a l b o l t s which had been embedded i n concrete a t t h e ORR. The 14-in.-
long b o l t s were approx 3 i n . below and p a r a l l e l t o an a c c e s s i b l e w a l l sur-
face.

420
,' , 21. PHYSICAL METALLURGY

H. Inouye

THE REACTIONS OF TYPE 304 STAINUSS STEEL WITH CO AND C02

H. Inouye

This study i s a c o n t i n u a t i o n of an i n v e s t i g a t i o n t o determine t h e

s u i t a b i l i t y of type 304 s t a i n l e s s s t e e l f o r use i n p r e s s u r i z e d , high-
v e l o c i t y helium which c o n t a i n s CO, C02, H 2 , H 2 0 , and CH4 as t h e p r i n c i p a l
impurities. The metal temperatures contemplated w i l l range between 500
and 1800°F f o r extended p e r i o d s . The p r i n c i p a l a r e a s of study have been
concerned w i t h determining t h e v a r i a b l e s which a f f e c t o x i d a t i o n ( r e d u c t i o n )
and c a r b u r i z a t i o n ( d e c a r b u r i z a t i o n ) of t h e metal. The v a r i a b l e s which
c o n t r o l t h e above r e a c t i o n s were a l s o viewed from t h e standpoint of t h e i r
e f f e c t on t h e o p e r a t i o n of a helium-'cooled and graphite-moderated r e a c t o r .
It w a s concluded previously' t h a t a t high temperatures C02 caused ox-
i d a t i o n of type 304 s t a i n l e s s s t e e l t o form 3Cr,O3*Fe2O3 as t h e p r i n c i p a l
oxide and CO w a s t h e gaseous r e a c t i o n product. I n CO both o x i d a t i o n and
c a r b u r i z a t i o n of t h e metal occurred. The p r i n c i p a l r e a c t i o n products i n
t h i s case were Fe304, C r 4 C , and a small amount of spinel-type oxides such
as Fe0.Cr203. Subsequent s t u d i e s have been d i r e c t e d toward e s t a b l i s h i n g
experimental techniques, e s t a b l i s h i n g r e a c t i o n r a t e s , studying oxide ad-
herence, and t h e e f f e c t s of gas c o n c e n t r a t i o n and gas composition.
To d a t e , r e a c t i o n r a t e s a t 140O0F i n COz a t reduced pressures and a t
1800°F i n CO-C02 mixtures have been determined. The r a t e curves could be
f i t t e d t o equations of t h e type Aw = k t n , where Aw i s t h e weight i n c r e a s e

Q of t h e specimen i n mg/cm2, t i s t h e time i n hours, and k and n a r e con-

stants. The r e a c t i o n r a t e c o n s t a n t s ( k ) were 9.46 x mg/cm2.fi at
l 4 O O O F and 8.62 x m g / c m 2 * f i a t 1800°F. The values of n were 0.64
at 1400'F and 0.50 at 1800'F. The p a r a b o l i c r e a c t i o n r a t e s described above
i n d i c a t e t h a t t h e oxides which form on type 304 s t a i n l e s s s t e e l a r e pro-
t e c t i v e and t h a t t h e d i f f u s i o n r a t e s of t h e r e a c t a n t s through t h e oxides
determine t h e r e a c t i o n r a t e s .

'Met. Ann. Prog. Rep. Sept. 1, 1959, OWL-2839, p 17'2-17'5.

42 1
1

Inasmuch as p r o t e c t i v e oxide l a y e r s separate t h e metal from t h e gases,

it w a s expected t h a t t h e r e a c t i o n r a t e s would be independent of t h e r e -
a c t i v e gas concentration. The presence of i n e r t c a r r i e r gases such as
argon o r helium should not influence t h e r e a c t i o n r a t e s . The data i n Table
21.1 show v i r t u a l l y no pressure e f f e c t s of t h e C 0 2 or t h e c a r r i e r gas on
the reaction rates.

Table 21.1. Reaction Rates of Type 304 S t a i n l e s s S t e e l

a t Several C 0 2 Pressures and 1400°F

Weight Increase ( mg/cm2 )

Test Time
(hr) 10 CI 100 p 1000 p" 6000 p*

50 0.09 0.09
100 0.13 0.12 0.109 0.117
1 50 0.21 0.14
200 0.23 0.16
25 0 0.24 0.18

*Argon c a r r i e r gas a t atmospheric pressure.

A comparison o f t h e data reported above w i t h those of B i l l i n g t o n 2 and

Maxwell,3 who conducted t e s t s i n C02 a t pressures up t o 100 p s i , shows t h a t
t h e reported values by t h e l a t t e r authors a r e a magnitude lower than those
r e p o r t e d here. The source of t h i s discrepancy may be due t o t h e f a c t t h a t
t h e oxide s c a l e which r e s u l t e d from t h e CO2-stainless s t e e l reaction
s p a l l e d from t h e metal upon cooling. The reported values of t h e r e a c t i o n
r a t e s i n t h i s i n v e s t i g a t i o n were obtained a t t h e t e s t temperature while
t h e data t h a t t h e authors c i t e d were from weighings a t room temperature.

2 S . R . B i l l i n g t o n , C . G. Stevens, and M. W . Davis, "The Oxidation o f

Four Austenitic S t a i n l e s s S t e e l s and t h e Nickel Alloy Inconel i n Carbon
Dioxide," GCM/UK/16. Paper presented a t U.S./U.K. Gas-Coolant Compati-
b i l i t y Meeting, Oak Ridge National Laboratory, Feb. 24-26, 1960 ( t o be
published).
3W. A. Maxwell, "Studies on t h e Compatibility o f High Temperature
Carbon Dioxide with S t a i n l e s s S t e e l s and other Materials" (Preliminary
Report), GNEC-121. Paper presented a t U.S./U.K. Gas-Coolant Compati-
b i l i t y Meeting, O a k Ridge National Laboratory, Feb. 24-26, 1960 ( t o be
published).

422
! \ The :Loss of oxide from t h e metal s u r f a c e increased uniformly upon
c o o l i n g from 1800'F t o room temperature. The cause of t h e oxide s p a l l i n g
which occurred a t weight i n c r e a s e s g r e a t e r t h a n about 0 . 3 mg/cm2 i s prob-
a b l y due t o t h e s t r a i n s (caused by t h e d i f f e r e n c e s i n t h e thermal expan-
s i o n ) between t h e oxide and t h e metal. Although phase transformations i n
oxides a r e known t o cause s p a l l i n g , it i s not l i k e l y t h e cause here s i n c e
an abrupt l o s s of oxide would occur a t t h e transformation temperature.
The behavior of t h e oxide upon c o o l i n g i n d i c a t e s t h a t t h e o x i d a t i o n rate
of s t a i n l e s s s t e e l s i n CO;! might t h e r e f o r e be a f u n c t i o n of t h e thermal
cycle h i s t o r y and even s l i g h t temperature f l u c t u a t i o n s might introduce
Q p a r t i c l e s i n t o t h e h i g h - v e l o c i t y h e l i m , coolant.
From t h e foregoing remarks, it appeared t h a t type 304 s t a i n l e s s s t e e l
might not be acceptable as a c l a d m a t e r i a l f o r t h e U02 f u e l i n view of i t s
Q c a r b u r i z i n g tendencies i n CO and i t s nonadherent oxide which r e s u l t s from
exposure t o C 0 2 . The obvious s o l u t i o n would be t o remove t h e CO and CO,
by p u r i f i c a t i o n of t h e helium; however, it has been shown t h a t it might
be i m p r a c t i c a l s i n c e t h e r e a c t i o n s proceed a t impurity l e v e l s as low as
10 p (approx 13 ppm) . It w a s concluded, t h e r e f o r e , t h a t c o n t r o l of t h e
gas composition r a t h e r t h a n concentration w a s t h e s o l u t i o n t o t h e above
problems.
Experiments were conducted i n a CG-CG, atmosphere (CG + CO, approx
2% by v o l i n argon) i n which t h e CO/CO2 was 13/1. I n t h i s case it w a s
found t h a t a t 1800'F, t h e carbon content of t h e 0.002-in.-thick metal f o i l
was 0.49$ a f t e r 350 h r . B e c k e r r s 4 data on the Fe-Fe3C-CO-CO, equilibria
i n d i c a t e t h a t f o r i r o n , t h e e q u i l i b r i u m carbon content i n t h e above gas
mixture i s about 0.4%. The d a t a i n d i c a t e t h a t c a r b u r i z a t i o n of s t a i n l e s s
s t e e l s may a l s o be governed by t h e same e q u i l i b r i a and t h e r e f o r e must occur
i n two r e a c t i o n s :

3Fe + 2CO Fe3C + C02 (1)

Fe3C + 4Cr - Cr4C + 3Fe (2)

The ox.ide r e a c t i o n products which formed on type 304 s t a i n l e s s s t e e l

i n t h e above environment were p r i n c i p a l l y Fe304, Cr203, and a s m a l l amount

'M. L. Becker, "Equilibrium f o r Gas-Steel Reactions," J. I r o n S t e e l

I-
n s t .- 121, p 337-65 (1930).
-
423
of Fe0.Cr203. A record of t h e weight change during c o o l i n g showed t h a t
t h e s e oxides do not s p a l l . The formation of Fe304 as a s t a b l e r e a c t i o n
product i n a s t r o n g l y reducing atmosphere w i t h r e s p e c t t o i r o n was unex-
pected b u t v e r i f i e d by s e v e r a l experiments. Thermodynamically, i r o n oxides
of any type would be reduced t o i r o n under t h e s e c o n d i t i o n s . It i s specu-
l a t e d t h a t Fe304 i s a decomposition product of FeO-Cr,O, o r Fe(CO), which
i s a gas. +Q

BERYLLIUM OXIDATION STUDIES

W . J. Werner Q
A s e r i e s of t e s t s w a s c a r r i e d out t o study t h e c o m p a t i b i l i t y of be-
r y l l i u m w i t h carbon d i o x i d e . The t e s t s were c a r r i e d o u t i n a dynamic
I)
system i n which t h e sample w a s suspended from a c a l i b r a t e d s p r i n g and t h e
weight g a i n determined by measuring t h e d e f l e c t i o n o f t h e s p r i n g w i t h a
cathetometer. I n order t o be a b l e t o d e t e c t a weight gain by t h i s method
i n t h e Be-CO2 system where t h e r e a c t i o n r a t e i s s l i g h t , a sample w i t h a
l a r g e surface-area-to-weight r a t i o had t o be used. This w a s accomplished
by t h e use of -200 mesh powder, having an a r e a of approx 0.7 m2/g, as t h e
sample.

T e s t s were conducted i n C02 a t p r e s s u r e s of 1 x m Hg and 760

mm Hg. The C02 f o r t h e low-pressure t e s t s w a s generated by t h e decompo-
s i t i o n of CaC03; p u r i f i e d b o t t l e gas w a s used f o r t h e atmospheric p r e s s u r e
test.
I n p l o t t i n g t h e weight gain/cm2 vs time, it w a s noted t h a t t h e weight
gain f e l l o f f w i t h i n c r e a s i n g time as would be expected f o r t h e formation
of a p r o t e c t i v e oxide f i l m where t h e o x i d a t i o n r a t e i s p a r a b o l i c . The
r a t e equation f o r a p a r a b o l i c r e a c t i o n i s :

AW = k t l / n

where
AW = w t g a i n (mg/cm2) ,
t = time ( h r ) ,
k and n = c o n s t a n t s .
 When t h e n a t u r a l l o g i s taken of both s i d e s of t h i s equation, one
obtains the l i n e a r relationship

I n Aw = I n k +
1
-
n
In t . (2)

The experimental d a t a were f i t t e d t o t h i s equation by t h e method of l e a s t

squares. Table 21.2 shows t h e values of I n k and l / n t h a t were obtained
.L
i n t h i s manner.

Table 21.2. Parabolic Rate Law Constants f o r t h e Oxidation of Be i n C 0 2

Test Duration I n k a t 9% l / n a t 9%
Temp of 'Test Confidence Confidence Pressure C 0 2 Phases P r e s e n t
("C) ( :nr) Level Level ( m Hg) After Testing

850 1000 -5.869 k 0.453 0.3414 * 0.0823 1 x 10-3 Be and Be0

846 350 -5.778 ?r 0.528 0.3427 f 0.1123 1 x 10-3 Be and Be0

838 350 4.963 i 0.516 0.3838 i 0.1118 1 x 10-3 Be and Be0

720 1000 -5.461 k 0.477 0.3224 2 0.0803 1 x 10-3 Be and Be0

720 400 -5.167 f 0.667 0.4347 5 0.1331 760 Be a n d Be0

600 350 -7.354 f 0.665 0.6132 2 0.1175 1 x 10-3 Be and Be0

An important p o i n t t o be noted i s t h a t t h e r e i s only a s l i g h t d i f f e r -

ence i n th.e r a t e c o n s t a n t s obtained a t 720°C for t h e low-pressure t e s t
and t h e atmospheric p r e s s u r e t e s t . The r a t i o of p r e s s u r e s of t h e two t e s t s
was 0.76 x lo6 t o 1. This s t r o n g l y i n f e r s t h a t t h e r e a c t i o n of beryllium
with CO, i s independent of p r e s s u r e and that t h e r a t e - c o n t r o l l i n g phenom-

enon i s t h e d i f f u s i o n of t h e o x i d i z i n g s p e c i e s through t h e p r o t e c t i v e oxide

film.
Due t o t h e f a c t t h a t c e r t a i n v a r i a b l e s (such as s u r f a c e a r e a which
decreases due t o s i n t e r i n g during t h e o x i d a t i o n t e s t s , and p o s s i b l e r e a c -
t i o n of thse powders w i t h t h e platinum c o n t a i n e r which could i n c r e a s e or
decrease t:he r e a c t i v i t y of t h e powders) need t o be eliminated, a vacuum
microbalance has been s e t up f o r t h e determination of p r e c i s e r a t e curves
f o r sheet ,specimens .
Speciinens oxidized i n t h i s way w i l l be used t o study t h e e f f e c t of
time, temperature, and p r e s s u r e on t h e oxide f i l m s formed during t h e oxi-
d a t i o n process.

425
 MOLYBDENUM

W . J . Werner
Q
Since r e f r a c t o r y metals such as molybdenum a r e b e i n g considered f o r
use i n high-temperature gas-cooled-type r e a c t o r s , a l i t e r a t u r e survey has
been i n i t i a t e d t o determine t h e c o m p a t i b i l i t y of molybdenum w i t h gases
t h a t might bg p r e s e n t as i m p u r i t i e s i n t h e c o o l a n t stream of such a r e -
actcr.
Unfortunately, molybdenum c o m p a t i b i l i t y w i t h t h e v a r i o u s gases i n
q u e s t i o n h a s n o t been s t u d i e d thoroughly; t h e r e f o r e , it w a s decided t h a t
thermodynamic e q u i l i b r i a c a l c u l a t i o n s f o r t h e systems involved would be
a l o g i c a l place t o start the investigation.
Table 21.3 shows t h e r e a c t i o n s f o r which c a l c u l a t i o n s have been made,
t o g e t h e r w i t h t h e l i t e r a t u r e source f o r t h e data.

Table 21.3. E q u i l i b r i u m C a l c u l a t i o n s f o r Molybdenum Reactions

Reaction L i t e r a t u r e Reference

"K. Tonasaki, B u l l . I n s t . Phy. Chem. Res., Tokyo, -

19, 126 ( 1 9 4 0 ) .
b
M. de Kay Thompson, The T o t a l and F r e e Energy of Formation of t h e
Oxides of Thirty-Two Metals, p 21-22, Electrochem. Soc., I n c . , New York
(1942).
C
K . K . K e l l y , Bur. Mines B u l l . No. 407, ( 1 9 3 7 ) .
%. K . Kelly, Bur. Mines B u l l . No. 476, ( 1 9 4 9 ) .

F i g u r e 21.1 shows t h e r e s u l t s of t h e c a l c u l a t i o n s . The r a t i o s CO2/CO,

H20/H2, and CH4/H2 are t a b u l a t e d as a f u n c t i o n of temperature f o r t h e r e -
spective reactions. Consider t h e curve f o r t h e MoO2-Mo-CO-CO2 equilibria.
The combinations of temperature and gas r a t i o s which l i e t o t h e l e f t and

426
 UNCLASSIFIED
O R N L - L R - D W G 50496
1500

1400

1 300

1 200

4!00

1000

-
."
900

W
tc 800
3
c
a
E 700
a
H
W
c 600

0 500

400

300

200

100

0
0 1 2 3 4 5 6 7 8 9 (0
RATIOS: co,/co, C H ~ / H ~H ,* O / H ~

Fig. 21.1. Gas-Molybdenum Equilibria.

below t h e curve are r e d u c i n g t o M 0 0 2 ; t h o s e t o t h e r i g h t and above a r e

o x i d i z i n g t o molybdenum; w h i l e t h e curve i t s e l f r e p r e s e n t s t h e s p e c i f i c
t e m p e r a t u r e s and g a s p r e s s u r e s where Mo-Mo02-CO-C02 are i n e q u i l i b r i u m .
Q I n s e c t i o n A of F i g . 21.1, t h e H20/H2 r a t i o s a r e r e d u c i n g , t h e CO2/CO
ratios b o t h r e d u c i n g and c a r b u r i z i n g , and t h e CH4/H2 r a t i o s a r e de-
c a r b u r i z i n g t o molybdenum. I n s e c t i o n B, t h e H20/H2 r a t i o s a r e r e d u c i n g ,
t h e CO2/CO r a t i o s are b o t h r e d u c i n g and c a r b u r i z i n g , and t h e CH4/H2 r a t i o s
a r e c a r b u r i z i n g t o molybdenum. I n s e c t i o n C , t h e H20/H2 r a t i o s a r e r e -
ducing, t h e CO2/CO r a t i o s a r e b o t h r e d u c i n g and d e c a r b u r i z i n g , and t h e
CH4/H2 r a - t i o s are c a r b u r i z i n g t o molybdenum. I n s e c t i o n s C and A t h e r e
a r e competing r e a c t i o n s f o r c a r b u r i z a t i o n and d e c a r b u r i z a t i o n . There i s ,
r- \ of c o u r s e , some q u e s t i o n i n each c a s e as t o which r e a c t i o n i s t h e r a t e

42 7
c o n t r o l l i n g one; however, f r e e energy c a l c u l a t i o n s i n d i c a t e t h a t i n s e c t i o n
A t h e d e c a r b u r i z a t i o n r e a c t i o n should t a k e p l a c e and i n s e c t i o n C t h e c a r -
Q
b u r i z a t i o n should t a k e p l a c e .
If t h e assumption i s made t h a t t h e amounts and s p e c i e s of i m p u r i t i e s
t h a t w i l l be p r e s e n t i n t h e c o o l a n t of such a r e a c t o r w i l l be determined
by t h e o u t g a s s i n g of t h e g r a p h i t e moderator, t h e n , u s i n g t h e g r a p h i t e o u t -
g a s s i n g experiments as a g u i d e , t h e main i m p u r i t i e s i n t h e c o o l a n t w i l l
be hydrogen and carbon monoxide w i t h a moderate amount of carbon d i o x i d e
~ an atmosphere such as t h i s , t h e e q u i l i b r i u m
and v e r y l i t t l e ~ n e t h a n e . ~ ’I n
c u r v e s p r e d i c t t h a t molybdenum w i l l remain b r i g h t up t o approx 1000°C.
An i m p o r t a n t p o i n t t h a t should be n o t e d h e r e i s t h a t t h e e q u i l i b r i u m
c u r v e s show t h a t r e l a t i v e ’ l y wet hydrogen w i l l reduce MOO,, o r conversely,
molybdenum w i l l remain “ b r i g h t “ i n r e l a t i v e l y wet hydrogen. The s i g n i f i -
cance of t h i s i s t h a t i f a steam l e a k should occur i n t h e h e a t exchanger,
a large amount o f w a t e r would have t o be p r e s e n t f o r MOO, t o be formed and
s t i l l a l a r g e r amount f o r Moo3 s i n c e t h e Mo02-Mo03-H2-H20 curve w i l l l i e
below and t o t h e r i g h t of t h e Mo02-Mo-H2-H20 c u r v e .
A t t h e p r e s e n t time t h e s e c u r v e s a r e t e n t a t i v e . Further calculations,
u s i n g d i f f e r e n t r e f e r e n c e s , w i l l be made t o check t h e v a l i d i t y of t h e
curves. E q u i l i b r i u m c a l c u l a t i o n s w i l l a l s o be c a r r i e d o u t f o r t h e f o l l o w -
i n g systems: Mo-Mo03-H2-H20, Mo02-Mo03-H2-H20, Mo-Mo03-CO-C02, Moo2-Moo3-
CO-CO2, Mo-MoC-CO-COZY Mo~C-MoC-CO-(202, M o - M o C - C H ~ - H ~ , and M o ~ C - M O C - C H ~ - H ~ .

OXIDATION OF NIOBIUM AT LOW OXYGEN PRESSURES

H. Inouye

H i g h - p u r i t y electron-beam-melted niobium f o i l w a s exposed t o oxygen

a t p r e s s u r e s r a n g i n g between 3 x lom5 and 5 x lov3 mm Hg and t e m p e r a t u r e s
0
of 850, 1000, and 1200°C. The oxygen p r e s s u r e w a s r e g u l a t e d a t a c o n s t a n t
v a l u e by s e l e c t i n g t h e t e m p e r a t u r e a t which CuO was decomposed t o oxygen
and Cu20. The r e a c t i o n rates were measured by t h e e x t e n s i o n of a h e l i c a l
s t e e l s p r i n g from which p o l i s h e d m e t a l samples were suspended. The oxide

5GCR Quar. Frog. Rep. Dee. 31, 1959, 0RNL-2888, p 153-158.

6GCR Q u a r . Prog. Rep. March 31, 1960, ORNL-2929, p 196-201.

42a
Q

3 r e a c t i o n p r o d u c t s were i d e n t i f i e d by x - r a y a n a l y s i s and t h e i r c h a r a c t e r -
i s t i c s were observed m e t a l l o g r a p h i c a l l y .
C h a r a c t e r i s t i c r e a c t i o n r a t e s between niobium and oxygen were ob-
s e r v e d fo:r t h e s o l u t i o n of oxygen, i n t e r n a l o x i d a t i o n , p r o t e c t i v e oxide
l a y e r f o r m a t i o n , and n o n p r o t e c t i v e oxide l a y e r f o r m a t i o n . Under c e r t a i n
c o n d i t i o n s of oxygen p r e s s u r e , exposure t i m e , and t e m p e r a t u r e , it was
noted t h a t niobium e x h i b i t e d t h r e e r a n g e s of l i n e a r o x i d a t i o n r a t e s and
two p a r a b o l i c o x i d a t i o n r a t e s each of which w a s due t o a d i f f e r e n t o x i -
d a t i o n mechanism. I n each c a s e where a t r a n s i t i o n i n t h e r e a c t i o n r a t e
from l i n e a r t o p a r a b o l i c o r p a r a b o i i c l;o l i n e a r o c c u r r e d , it w a s p o s s i b l e
c3 t o c o r r e l a t e t h e phenomena t o oxygen s a t u r a t i o n of t h e matrix o r t o t h e
appearance of t h e t h r e e o x i d e s of niobium. A summary of t h e t e s t con-
d i t i o n s which produced t h e v a r i o u s o x i d e s and t h e i r c h a r a c t e r i s t i c r a t e
8 c u r v e s i s shown i n Table 21.4.
A t t h e l o w e s t p r e s s u r e s i n v e s t i g a t e d , l i n e a r I o x i d a t i o n r a t e s were
observed f o r t h e s o l u t i o n of oxygen, As t h e oxygen c o n c e n t r a t i o n n e a r b u t
below t h e m e t a l s u r f a c e i n c r e a s e d , p a r a b o l i c I type r a t e c u r v e s were meas-
ured. Only niobium s o l i d solution:; r e s u l t e d .
L i n e a r I1 o x i d a t i o n r a t e s were observed when t h e oxygen t a k e n i n t o
s o l u t i o n reached i t s s o l u b i l i t y l i m i t i.n niobium and p r e c i p i t a t e d a s N b O
i n t e r n a l l y and as nodules e x t e n d i n g above and below t h e m e t a l s u r f a c e .
Also observed w a s Nb02 as a n u c l e a t i n g phase on t h e crown of t h e N b O nod-
u l e s which extended above t h e s u r f a c e .
The e f f e c t of t h e oxygen p r e s s u r e on t h e l i n e a r I1 r e a c t i o n r a t e con-
s t a n t s ( i n t e r n a l o x i d a t i o n ) i n c r e a s e d i n a manner c o n s i s t e n t w i t h adsorp-
t i o n phenomena above about 1 x loy4 mm Hg. Below t h e p r e s s u r e n e g a t i v e
8 d e v i a t i o n s from t h e 0 r e l a t i o n s h i p o r Langmuir' s a d s o r p t i o n formula were
n o t e d a t a l l t e m p e r a t u r e s due t o t h e f r a c t i o n a l coverage of t h e a v a i l a b l e
adsorption s i t e s .
A s t h e growth of N b O 2 s p r e a d o v e r t h e s u r f a c e , t h e t i m e a t which it
formed a c o n t i n u o u s l a y e r over NbO w a s i n d i c a t e d by a t r a n s i t i o n i n t h e
r e a c t i o n r a t e from l i n e a r I1 t o p a r a b o l i c 11. The m i c r o s t r u c t u r e of spec-
imens e x h i b i t i n g t h e s e r e a c t i o n r a t e s w a s composed of a t h i c k l a y e r of
N b 0 2 under which w a s an i r r e g u l a r zone of N b O . The i n i t i a t i o n of p a r a b o l i c

42 9
 Table 21.4. C o r r e l a t i o n Between Reaction Rates of Niobium and I t s o x i d e s

Reaction Reaction
Test
Temp
o2 P r e s s u r e Time Rate Phases*
("C) (mm Hg) Curve

85 0 4 x 10-~ 360 P a r a b o l i c I1
2x 350 P a r a b o l i c II-
Linear I11
5 x 360 P a r a b o l i c II-
Linear I11

1000 3 x 10-5 1560 Linear I-

P a r a b o l i c I- BD
Linear I1
325 Linear I1
1770 Linear II-
P a r a b o l i c I1
1.5 x 340 Linear I1
3 x 10-4 344 Linear II-
P a r a b o l i c I1

1200 3 x 10-5 175 Linear I-

Parabolic I
5x 345 Linear I1
5 x 10-4 295 Linear II-
P a r a b o l i c I1

* I d e n t i f i e d by Debye-Scherrer d i f f r a c t i o n p a t t e r n s , C u K radiation.
a
I1 r e a c t i o n r a t e s decreased t o s h o r t e r t i m e s as t h e oxygen p r e s s u r e i n -
c r e a s e d and as t h e temperature decreased. Thus under c e r t a i n t e s t con-
d i t i o n s , r e a c t i o n r a t e s which were e n t i r e l y p a r a b o l i c were observed.
The l a s t s t a g e of o x i d a t i o n of niobium commenced upon t h e t r a n s i t i o n
from p a r a b o l i c I1 r e a c t i o n r a t e s t o l i n e a r I11 r e a c t i o n r a t e s . The ac-
c e l e r a t i o n i n t h e o x i d a t i o n r a t e c o i n c i d e d w i t h t h e appearance of Nb20,.
M i c r o s t r u c t u r a l l y a r e l a t i v e l y t h i c k l a y e r of Nb205 w a s p r e s e n t a t t h e gas
i n t e r f a c e under which w a s a t h i n n e r continuous l a y e r of Nb02 and a t t h e
metal i n t e r f a c e an irregular zone of NbO w a s found.
Inasmuch as t h e l a s t two o x i d a t i o n s t a g e s a r e c h a r a c t e r i s t i c of t h e
o x i d a t i o n of niobium a t atmospheric p r e s s u r e s , it i s suggested t h a t Nb02
@
430

e
 i s t h e oxide which, when formed, c a u s e s t h e i n i t i a l p r o t e c t i v e s t a g e of
o x i d a t i o n ,, Metallographic evidence f u r t h e r i n d i c a t e s t h a t t h e t r a n s i t i o n
t o t h e n o r i p r o t e c t i v e s t a g e i s a r e s u l t of a r e a c t i o n between Nb02 and
oxygen t o form Nb205. The f i n i t e l i n e a r r e a c t i o n r a t e s f o l l o w i n g t h e
t r a n s i t i o n have been p o s t u l a t e d by o t h e r i n v e s t i g a t o r s t o be due t o t h e
p r e s e n c e of a c o n s t a n t t h i c k n e s s suboxide o r t o a s t e a d y r a t e of b l i s t e r
formation. I n t h i s i n v e s t i g a t i o n it i s suggested t h a t t h e p r e s e n c e of an
i n t e r m e d i a t e l a y e r of NbO, i s t h e rate c o n t r o l l i n g agent.
The rate o f i n t e r n a l o x i d a t i o n and p r o b a b l y t h e s o l u t i o n of oxygen
a p p e a r s t o be an a d s o r p t i o n phenomenon. It would be expected t h a t i f t h i s
@ were t h e c a s e , exposure of niobium t o gas m i x t u r e s c o n t a i n i n g an o x i d i z i n g
gas would r e s u l t i n s i g n i f i c a n t l y d i f f e r e n t r e a c t i o n r a t e s due t o t h e com-
p e t i t i o n of t h e i n d i v i d u a l gas s p e c i e s f o r t h e a d s o r p t i o n s i t e s . There-
4 f o r e , i n z d d i t i o n t o a l l o y i n g , m a n i p u l a t i o n of t h e gaseous environment
may prove p r a c t i c a l t o minimize oxygen c o n t a m i n a t i o n a t h i g h t e m p e r a t u r e s .

NIOBIUM-ZIRCONIUM AGING STUDIES

D . 0 . Hobson

S t u d i e s have been made on t h e h i g h - t e m p e r a t u r e s t a b i l i t y of Nb-nominal

1w t $ Z r alloys. It w a s found t h a t t h e a l l o y s w i l l undergo an a g i n g r e -
a c t i o n under t h e p r o p e r c o n d i t i o n s of t h e time and t e m p e r a t u r e .
I n t h e c o u r s e of t h i s s t u d y , t h e a g i n g b e h a v i o r of n i n e a l l o y h e a t s
w a s s t u d i e d w i t h t h e zirconium c o n c e n t r a t i o n r a n g i n g from 0.6 t o 1.25 w t $.
These a l l o y s were vacuum annealed 2 h r a t t e m p e r a t u r e s from 2192°F (1200°C)
t o 2912°F (1600°C). They were t h e n aged i n evacuated q u a r t z c a p s u l e s a t

Q 1500'F (816°C) and 1700°F (927°C) f o r t i m e s from 0 t o 750 h r . After a g i n g ,

t h e a l l o y s were t e n s i l e t e s t e d a t room t e m p e r a t u r e , 1500 and 1700°F. Not
a l l a l l o y s were g i v e n t h e complete range of h e a t t r e a t m e n t s , b u t a l l were
s t u d i e d s u f f i c i e n t l y t o determine whether o r n o t a g i n g o c c u r r e d .
T y p i c a l r e s u l t s o b t a i n e d on two a l l o y s which e x h i b i t e d a g i n g a r e shown
i n F i g . 21.2. Both t h e Nb-l% Z r and Nb4.75$ Z r a l l o y were vacuum an-
n e a l e d 2 h r a t 2912°F. The Nb-l$ Z r a l l o y w a s t h e n aged and t e n s i l e t e s t e d
a t 1700°F. It can be seen t h a t t h e Nb-l% Z r a l l o y r e a c h e s an a g i n g peak
a f t e r approx 100 h r . The Nb-0.75$ Z r a l l o y w a s aged and t e s t e d a t b o t h

43
 UNCLASSIFIED
(~10~) ORNL-LR-DWG 4 1 7 2 2 R
64
NUMBERS IN PARENTHESES '
60

.j, 56

y- 40 8 H5
~m
z 2 I ~' ' " '' l ' I ' I " ' '

w
+ 44

40

36
0 20 50 100 200 500 800
AGING TIME ( h r )

Fig. 21.2. High-Temperature Tensile Test on Aged Nb-Zr Alloys.

1500 and 1700°F. A t 1500°F t h e t e n s i l e s t r e n g t h s t a r t e d t o i n c r e a s e a t

100 h r and w a s s t i l l i n c r e a s i n g a f t e r 750 h r . A t 1700°F t h e s t r e n g t h i n -
c r e a s e d a f t e r 50 h r and reached a peak a t approx 200 h r . Both a l l o y s
showed a c o n t i n u a l d e c r e a s e i n e l o n g a t i o n w i t h i n c r e a s i n g a g i n g t i m e .
The t e m p e r a t u r e a t which t h e a l l o y s were annealed w a s found t o have
a g r e a t e f f e c t on t h e a g i n g c h a r a c t e r i s t i c s . A Nb-l.l$ Z r a l l o y w a s an-
n e a l e d a t 2190, 2550, and 2910°F f o r 2 h r , and aged and t e s t e d a t 1700°F.
Specimens which were annealed a t 2910°F showed a m a x i m u m i n t h e a g i n g r e -
sponse a f t e r approx 75 h r w i t h a 6 6 i n c r e a s e i n t h e u l t i m a t e t e n s i l e
strength. Specimens annealed a t 2190 and 2550°F showed t h a t a v e r y s l i g h t
a g i n g e f f e c t might be t a k i n g p l a c e .
Q
The f o r e g o i n g r e s u l t s were t y p i c a l f o r a l l h e a t s which e x h i b i t e d
aging. O f t h e n i n e h e a t s t e s t e d , f i v e showed d e f i n i t e a g i n g and f o u r
showed no a g i n g r e s p o n s e . Table 21.5 l i s t s t h e a l l o y s which were t e s t e d
w i t h t h e i r chemical a n a l y s e s and agir:: behavior. It w i l l be n o t i c e d t h a t ,
w i t h t h e e x c e p t i o n of t h e 0 2 / C r a t i o for h e a t No. S a w , t h e 0 2 / C and 02/N2
r a t i o s show a d e f i n i t e c o r r e l a t i o n as t o whether o r not t h e a l l o y w i l l age.
I n each c a s e t h e smaller v a l u e s of t h e r a t i o s correspond t o a l l o y s which
exhibited aging. Another way of r e p r e s e n t i n g t h e same d a t a i s shown i n

432
F i g . 21.3. T h i s f i g u r e shows t h e 02/Zr r a t i o p l o t t e d a g a i n s t t h e N 2 / Z r
ratio. It can be seen t h a t for t h e p l o t of 0 2 / Z r vs N 2 / Z r , the alloys
which age can be s e p a r a t e d from t h e nonaging a l l o y s by a t r a n s i t i o n l i n e
or zone. The same i s t r u e of a p l o t of 0 2 / Z r vs C / Z r except f o r h e a t S€?Fw.

Table 21.5. Chemical Analyses of Aged Nb-Zr Alloys

Specimens annealed a t 2912°F for 1 h r and aged a t 1700°F

Remarks

PFnr 145 160 210 1.07 0.7 0.9 D e f i n i t e aging

PGVE 106 115 120 0.98 0.9 0.9 Definite aging

s4m 200 200 300 1.0 0.7 1.0 Definite aging

s23sc -1 120 85 140 1.25 0.9 1.4 Definite aging

saw 260 160 70 0.75 3.7 1.6 Definite aging

S15EC 900 140 170 0.76 5.3 6.4 No aging

PGTF 320 46 120 1.14 2.7 7.0 No aging

S16EC -1 1300 180 190 0.60 6.8 7.2 No a g i n g

S24EN 900 100 500 0.77 1.8 9.0 No aging

UNCLASSIFIED
ORNL-LR-DWG 40070

0.04

0.02
//
/_ _ _ _ _ _ _ _i S
.
P5vE
_I4KW-
PFYU
-/-
/ s23sc-I
0
0 0.01 0.02
N,
Zr

Fig. 21.3. Plot o f N,/Zr vs O,/Zr for Eight

Nb-Zr A l l o y s .
4 33
 From a s t u d y of t h e above d a t a it i s a p p a r e n t t h a t a h e a t which h a s
a h i g h oxygen c o n t e n t r e l a t i v e t o i t s carbon o r n i t r o g e n c o n t e n t w i l l n o t
e x h i b i t aging. T h e r e f o r e , it should be p o s s i b l e t o add oxygen t o a h e a t
which i s known t o age and, by t h i s a d d i t i o n , i n h i b i t t h e a g i n g r e a c t i o n .
Varying amounts of oxygen were added t o h e a t s S23SC-1 and PGVE. These
h e a t s were t h e n annealed 2 h r a t 2912"F, aged f o r 100 h r a t 1700°F, and
t e n s i l e t e s t e d a t 1700°F. The r e s u l t s are shown i n Table 21.6 and i n F i g .
21.4. If t h e " a g i n g e f f e c t " may be d e f i n e d as t h e d i f f e r e n c e between a
p r o p e r t y of t h e m a t e r i a l ( u l t i m a t e t e n s i l e s t r e n g t h , y i e l d s t r e n g t h , o r
e l o n g a t i o n ) i n t h e annealed c o n d i t i o n and t h a t p r o p e r t y i n t h e aged con-
d i t i o n , t h e n it can be s t a t e d t h a t t h e a d d i t i o n of oxygen t o t h e Nb-l$ Zr
a l l o y r e d u c e s t h e a g i n g e f f e c t i n p r o p o r t i o n t o t h e amount of oxygen added.
It i s p o s t u l a t e d t h a t n i t r o g e n and carbon r e a c t w i t h t h e zirconium i n
t h e a l l o y t o form compounds which w i l l p r e c i p i t a t e under p r o p e r c o n d i t i o n s
o f time and t e m p e r a t u r e t o c a u s e a g i n g . It i s b e l i e v e d t h a t oxygen may
p o s s i b l y have t h e e f f e c t of i n c r e a s i n g t h e s o l u b i l i t y o f t h e zirconium
n i t r i d e s and/or c a r b i d e s i n t h e a l l o y and t h u s i n h i b i t a g i n g . Another
p o s s i b i l i t y i s t h a t oxygen w i l l r e a c t p r e f e r e n t i a l l y w i t h p a r t of t h e z i r -
conium and w i l l p r e c i p i t a t e i n a form which w i l l t e n d t o n u l l i f y t h e e f -
f e c t s of t h e n i t r i d e and/or c a r b i d e p h a s e s , t h a t i s , b r e a k up c o n t i n u o u s
n i t r i d e o r c a r b i d e grain-boundary f i l m s , e t c . F u t u r e work w i l l be done on
t h e i d e n t i f i c a t i o n of t h e p r e c i p i t a t i n g p h a s e s and t h e mechanism of a g i n g .

UNCLASSIFIED
ORNL-LR-DWG 495
(x1~3)

- 36 TESTED AT 927'C
-Y)

32
v)
U.
0
LL

3 28
v0
E
W
24

n
W
20
n
W
_I

F 16 S ANNEALED

42
0 0.01 0.02 0.03 0.04 0.05 0.06 C
w t % o2
w t % Zr

Fig. 21.4. Effect of Oxygen Contamination on

Aging Behavior of an Nb-Zr Alloy.

434
 c

Table 21.6. E f f e c t of O2 Contamination on t h e Aging Reaction i n PGVE and S23SC-1

A s Annealed Aged 100 h r a t 1700°F

"Aging E f f e c t "

~~

S23SC-18 120 25,167 12,867 10.5 120 39,980 32,220 4.5 +14,823 +19,350

s23sc -la 315 23,365 12,875 8.5 34? 34,270 30,944 6.0 +10,905 +18,069
s23sc -la 329 23,055 15,230 6.0 339 32,430 27,795 5.5 +9,3'75 +12,565
s23sc -la 403 26,475 14,990 6.5 417 34,165 29,075 4.5 +7,690 +l4,085
S23SC-la 586 26,730 15,120 3.5 595 34,270 22,845 7.0 +7,540 +7,725
s23sc -la 777 27,865 14,755 8.5 800 29,690 17,695 8.5 +1,825 +2,940
PGVEb 110 24,610 10,445 8.0 110 33,920 28,440 6.0 +9,310 +17,995
PGVEb 620 32,315 15,820 12.0 650 29,846 14.5 -2,475

a
As-received chemical a n a l y s i s : 0 2 , 120 ppm; N 2 , 85 ppm; C , 140 ppm; and Z r , 1.25 w t %.
b
As-received chemical a n a l y s i s : 02, 110 ppm; N2, 115 ppm; C , 120 ppm; and Z r , 0.98 w t %.
C
L i s t e d O 2 values a r e by weight change measurements and r e p r e s e n t t h e O 2 c o n t e n t b e f o r e h e a t t r e a t m e n t s .

P
w
Ln
 22. POSTIRRADIATION EXAMINATION LABORATORY

A. R. Olsen
B
The P o s t i r r a d i a t i o n Examination (PIE) Laboratory i s a new function
i n t h e Metallurgy Division. It w a s formerly a s s o c i a t e d with t h e Reactor
Experimental Engineering Division and w a s known as t h e Remote Corrosion
Examination Laboratory p r i o r t o i t s t r a n s f e r t o t h e Metallurgy Division
i n e a r l y 1959. Since t h e scope of work performed by t h e group i s p r i -
m a r i l y s e r v i c e i n nature t o support various experimental and r e a c t o r proj-
e c t s at t h e Laboratory, t h e r e s u l t s of t h e i r e f f o r t f o r t h e most p a r t a r e
r e p o r t e d elsewhere.

HIGH RADIATION LEXEL EXAMINATION LABORATORY

A. R . Olsen R. E. McDonald
D e t a i l e d engineering design of a new h o t - c e l l f a c i l i t y w a s completed
during t h e p a s t y e a r . This new f a c i l i t y , known as t h e High Radiation Level
Examination Laboratory (HRLEL), Building 3525, i s under construction. It
w i l l be a two-story b r i c k building, 1 2 2 x 105 f t , w i t h a p a r t i a l basement.
The b u i l d i n g incorporates some o f f i c e , laboratory, and photographic dark-
room space i n a d d i t i o n t o t h e cell-bank a s s o c i a t e d operating and charging
areas. The operating c e l l bank, which i s U-shaped, i s divided i n t o t h r e e
separate s e c t i o n s f o r v e n t i l a t i o n c o n t r o l and f u r t h e r divided i n t o 1 2 op-
e r a t i o n a l areas and one charging a r e a t o provide a,n i n t e r n a l working a r e a
of 920 f t 2 . The second f l o o r above t h e c e l l bank has provisions f o r t h e
s h i e l d e d storage of contaminated equipment, remote decontamination, and
glove box maintenance. These c e l l s w i l l supplement e x i s t i n g f a c i l i t i e s
b u t a r e unique i n t h a t they a r e designed t o handle highly t o x i c alpha-
a c t i v i t y experiments as w e l l as t o provide t h e heavy s h i e l d i n g w a l l s
(high-density concrete, 3 f t t h i c k ) f o r p r o t e c t i o n a g a i n s t t h e a s s o c i a t e d
high gamma a c t i v i t y . The c e l l s w i l l be completely s e a l e d and i n general
w i l l not be re-enterable once t h e f a c i l i t y i s i n f u l l operation.
Concurrent with t h e design of t h i s f a c i l i t y t h e r e has been consider-
a b l e e f f o r t expended i n designing and developing remote experimental
equipment f o r use i n t h e s e new hot c e l l s . Since t h e equipment must be

436

0
r e m o t e l y I n s t a l l e d , maintained, and r e p l a c e d , c o n s i d e r a b l e m o a i f i c a t i o n
of standai-d u n i t s and s p e c i a l d e s i g n s were r e q u i r e d . To d a t e , approxi-
mately 8076 of t h e r e q u i r e d remote m e t a l l o g r a p h i c equipment i s b u i l t or
being b u i l t . A d d i t i o n a l m u l t i p u r p o s e equipment such as remote x-ray d i f -
f r a c t i o n equipment, a u n i v e r s a l m i l l i n g machine, s p e c i a l o p t i c a l equip-
ment f o r s u r f a c e examinations, weighing and d e n s i t y d e t e r m i n a t i o n equip-
ment, a corrosion-specimen d e f i l m i n g a p p a r a t u s , and a c o l l i m a t e d gamma
spectromet,er f o r i n d u c e d - a c t i v i t y a n a l y s e s a r e w e l l a l o n g i n d e s i g n and
construction. All t h i s equipment w i l l b e o p e r a t e d i n t h e a v a i l a b l e c e l l
mockup o r i n o t h e r l o c a t i o n s b e f o r e i n s t a l l a t i o n i n t h e new f a c i l i t y .

HOMOGENEOUS REACTOR PROGRAM SUPPORT

A major p o r t i o n of t h i s y e a r ' s e f f o r t h a s been devoted t o c o n t i n u e d

a s s i s t a n c e t o t h e Aqueous Thermal-Breeder R e a c t o r Program. S e c t i o n s and
c o r r o s i o n specimens from t h e f i r s t ORR i n - p i l e l o o p (0-1-25) (see ref 1)
have been d i s m a n t l e d and p a r t i a l l y examined. I n a d d i t i o n t o one s o l u t i o n
i n - p i l e a u t o c l a v e , L5Z-140, f o u r slurry i n - p i l e a u t o c l a v e s , L6S-l51S,
L5Z-l52S, L5Z-l53S, and C-43 (Houdry s p h e r e s ) , '' have been completely ex-
amined. During t h i s p e r i o d t h e group a l s o dismantled, examined, photo-
graphed, s e c t i o n e d and, where r e q u i r e d , weighed, defilmed, removed, and
s u b m i t t e d :scale samples f o r chemical a n a l y s e s , and p r e p a r e d and s u b m i t t e d
indue e d-ac-t i v i t y a n a l y s i s specimens from v a r i o u s components and as semblies
from t h e Homogeneous R e a c t o r Experiment No. 2. These i n c l u d e d a hydro-
c l o n e removed from t h e chemical p r o c e s s i n g p l a n t , t h e HRT c o r e sampler
probe p i p e i n s t a l l e d i n t h e r e a c t o r c o r e d u r i n g r u n 20, pump-purge t a n k s ,
and corrosion-specimen a s s e m b l i e s 1 2 5 and 225 from t h e c o r e and b l a n k e t
c i r c u l a t i n g pumps removed a f t e r r u n 20. Also i n c l u d e d were t h e f a i l e d
b l a n k e t - c i r c u l a t i n g pump i m p e l l e r removed a f t e r run 19, s e v e r a l p i e c e s of
s c r e e n and c o r r o s i o n specimens removed from t h e c o r e r e g i o n f o l l o w i n g run
20, and two c o r e a c c e s s f l a n g e s , one i n c l u d i n g a mounted s t a i n l e s s s t e e l
c o r r o s i o n specimen.

'G. H. Jenks - et -
a l . , HRP Quar. Prog. Rep. Apr. 30, 1960, ORNL-2947,
p 64-66.
2 E . L. Compere -
et - a l . , HRP Q u a r . Prog. Rep. J a n . 31, 1960, ORNL-2920,
p 102-108.

437
 OTHER SUPPORT ACTIVITIES

Other a c t i v i t i e s performed during t h e r e p o r t i n g p e r i o d a r e summa-

B
r i z e d below:
1. Complete p o s t i r r a d i a t i o n examination, weighing, and defilming
of 16 specimens from t h e ORR core-corrosion study program3 were c a r r i e d
out.
2. F a i l u r e a n a l y s i s of a gamma-heat probe f o r t h e ORR Fuel Irradia-
t i o n Program' was performed. The e x t e n t of i n s u l a t i o n d e t e r i o r a t i o n on
t h e thermocouple wires as they e n t e r e d t h e Sauereisen plug i n t h i s experi-
ment i s shown i n Fig. 22.1. This photograph w a s taken through t h e remote
stereomicroscope.

3P. D. Nemann, Corrosion i n ORR Core Cooling System, ORNL CF-60-4-97

(Apr. 25, 1960).
'T. S. Lundy, "Fuel I r r a d i a t i o n Programs," i n Chap. 11 of t h i s r e p o r t .

Fig. 22.1. External Surface of Ceramic Plug i n

Gamma-Heat Probe.
 3. Both p o s t i r r a d i a t i o n t e s t i n g and, r e c e n t l y , some p r e i r r a d i a t i o n
s t u d i e s on b e r y l l i u m specimens were conducted f o r t h e General Nuclear
Engineering Corporation. To d a t e , t h e examination of t h e i r r a d i a t e d
specimens has been r e s t r i c t e d t o dimensional a n a l y s i s , weighing, defilm-
i n g , d e n s i t y determinations, and some i n d u c e d - a c t i v i t y measurements. A
notch-benl3 a p p a r a t u s f o r use i n t h e c e l l s i s almost complete, and t h i s
group w i l l cooperate i n t h e s e t e s t s as w e l l . Some s u r f a c e r e p l i c a s on
p r e i r r a d i a t e d specimens f o r l a t e r comparison w i t h t h e same s u r f a c e s a f t e r
i r r a d i a t i o n w e r e a l s o made.

ADAPTATION OF REPLICATION TECHNIQUES TO HOT-CELL APPLICATION

The r e p l i c a t i o n of t h e s u r f a c e s of i n - p i l e c o r r o s i o n coupons would

b e a g r e a t a i d t o t h e c o r r o s i o n programs because it would a l l o w (1)un-
l i m i t e d viewing time of an almost n o n r a d i o a c t i v e s u r f a c e , ( 2 ) t h e use of
an unshiel-ded s t a n d a r d bench-type microscope, and (3) t h e release of t h e
specimens f o r f u r t h e r p r o c e s s i n g . Therefore, i f r e p l i c a t i o n c o u l d b e
adapted t o h i g h l y r a d i o a c t i v e specimens, more i n f o r m a t i o n c o u l d b e ob-
t a i n e d f a s t e r , a t l e s s c o s t , and without undue p e r s o n n e l r a d i a t i o n expo-
sure. Accordingly, c e r t a i n known t e c h n i q u e s were modified, new ones i n -
v e s t i g a t e d , and a workable p r o c e s s w a s developed.
c e l l u l o s e a c e t a t e w a s chosen as t h e r e p l i c a b a s e material. A blank
s i z e of 1 x 3 x 0.035 i n . , t h e s t a n d a r d microscope s l i d e s i z e , w a s se-
l e c t e d because it would be easy t o handle and c o u l d s t a n d rough h a n d l i n g
during decontamination.
A f t e r t r y i n g s e v e r a l s o l v e n t s and combinations of s o l v e n t s , methyl
e t h y l ketone w i t h 3 g of c e l l u l o s e a c e t a t e d i s s o l v e d i n 100 cc was se-
Q l e c t e d because it s e t slower, allowing a l o n g e r handling t i m e , and a l s o
r e s u l t e d i n l e s s gas entrapment. Contact t i m e v a r i e s roughly w i t h t h e
specimen siize. S u r f a c e s l/4 x 5 / 8 i n . r e p l i c a t e d s a t i s f a c t o r i l y , w i t h a
minimum 9cl-sec c o n t a c t t i m e . Breakaway w a s from one edge only, t h u s dis-
t u r b i n g olily a s m a l l l i n e area.
P r i o r t o r e p l i c a t i o n , a group of b l a n k s are c l e a n e d and wiped w i t h
l e n s t i s s u e t o minimize o i l and l i n t pickup during t h e o p e r a t i o n . The

5J. Fi. Weir, "Beryllium I r r a d i a t i o n E f f e c t s , " i n Chap. 1 7 of t h i s re-

port.
c;,
43 9
specimen i s h e l d i n a s m a l l v i s e w i t h s p e c i a l l y r e c e s s e d i r o n jaws which
allows t h e specimen t o s t a n d up 5 m i l s above t h e v i s e body. The surface
t o be r e p l i c a t e d i s cleaned i n p l a c e with t h e r e p l i c a t i o n solvent and
dried. Next, a measured drop of solvent i s placed on t h e c l e a n blank,
smeared evenly, and placed i n c o n t a c t with t h e s u r f a c e . A glass s l i d e i s
placed on t o p , and a 100-g Alnico horseshoe magnet a p p l i e s t h e r e q u i r e d
load. The magnet i s removed a f t e r t h e a l l o t t e d time, and t h e r e p l i c a i s
s t r i p p e d from t h e s u r f a c e .
The r e p l i c a s a r e decontaminated by u l t r a s o n i c cleaning with Electro-
sol, a nonspotting dishwashing detergent, and r i n s e d i n water. If corro-
s i o n products a r e imbedded i n t h e r e p l i c a , it may be necessary t o u l t r a - 0
s o n i c a l l y e t c h them by using 10% H"03-4'$ HF s o l u t i o n and t o follow t h a t
treatment with t h e s t a n d a r d detergent and r i n s e c y c l e . By t h i s method,
it has been p o s s i b l e t o produce smear-free r e p l i c a s having l e s s t h a n 20 e
mr/hr of r a d i o a c t i v i t y a t c o n t a c t even though prepared from specimens
t h a t had r a d i o a c t i v i t y i n excess of 10 r/hr. Figure 22.2 i s a photograph
UNCLASSIFIED
PHOTO Y-35465

Fig. 22.2. Aluminized Replica of One Entire Side of Zircaloy-2

Corrosion Specimen 2-2 from In-Pile Loop 0-1-25. 7 X .
G) of one such replica from the in-pile-loop experiment 0-1-25. The com-
plete replication coverage of the surface with such large topographical
variations has been a prime objective. Figure 22.3 is a higher-magnifi-
cation photograph of a portion of the same replica and shows how well
the fine detail is also reproduced. It should be n0te.d that the topogra-
phy and depth of field at higher magnifications prevent focusing on all
f atures simultaneously.

-
0
-0.
@ X

a -
EO'(

-
20 0

-
2
n
I
-m
v,
-

Fig. 22.3. View at Higher Magnification of Replicated Surface Showing Evidence of Stringer Cor-
rosion Attack on Zircaloy-2 Specimen 2-2 from In-Pile Loop 0-1-25.

In order to ensure 100% coverage of surfaces of this size, duplicate

replicas are made of each surface. Following the cleaning operation all
specimens are smeared, surveyed, and tagged by Health Physics personnel
for transfer to the Metallography Group for aluminizing. To date, 44
coupons have been replicated from the ORR l o o p 0-1-25.
The 4-8 coupons to be installed in the first slurry in-pile loop have
been completed and stored for comparison with the postirradiated replicas.

441
A set of 24 preirradiation-notched beryllium bend specimens have also been
completed.
Still another type of replication is being investigated by the PIE
Group. This is the replication of the internal surfaces of in-pile auto-
claves. A preliminary cold replica was made using General Electric's RTV
silicone rubber. Replication of a radioactive autoclave will be attempted
soon.
 23. POWDER METALLURGY AND FUEL CYCLE

J. P. Hammond

FUELS WITH FERTILE U-MO MATRIX CONTAINING

U02 OR UC DISPERSOID

S . A . Rabinowi-tz A. L. L o t t s J . P. Hammond

A primary e f f o r t of t h e Powder Metallurgy and F u e l Cycle Group i s

t h e development of r e a c t o r f u e l c o r e s c o n s i s t i n g of UC or U02 d i s p e r s e d
i n a d e p l e t e d U-Mo m a t r i x . A t present t h i s e f f o r t i s directed primarily
a t advanced f u e l elements f o r t h e E n r i c o Fermi F a s t Breeder Reactor. The
work has c e n t e r e d on developing procedures f o r producing s u i t a b l e U-Mo-
U02 c o r e s t o be r o l l - c l a d i n t o p l a t e - t y p e f u e l elements and i n developing
matrix materials f o r i r r a d i a t i o n testing.

Cold P r e s s i n g and S i n t e r i n g UO2-Bearing Uranium-Molybdenum Compacts

An i n v e s t i g a t i o n of t h e f a b r i c a b i l i t y of 25 v o l % U02 dispersed i n
IF-10 wt % Mo and IF-13.8 w t $ Mo (nominally E 1 5 w t % Mo) m a t r i c e s was
i n i t i a t e d d u r i n g t h e p a s t y e a r . The IF15 $ Mo a l l o y had been s e l e c t e d
as t h e r e f e r e n c e m a t e r i a l a f t e r a review of t h e technology of f e r t i l e
matrix materials Because of i t s a v a i l a b i l i t y and low c o s t , p r e a l l o y e d
U-Mo powder made by a s h o t t i n g p r o c e s s w a s s e l e c t e d f o r t h e i n i t i a l work.
F i g u r e 23.1 i s an a s - p o l i s h e d view of -100 mesh, IF-13.8 w t % Mo powder.
S e v e r a l d i f f i c u l t i e s were encountered i n f a b r i c a t i o n , some of which can
be a t t r i b u t e d t o t h e n a t u r e of t h e U-Mo powder t h a t i s b e i n g used. The
major problem appears t o be t h e presence of a f o r e i g n substance, p r e -
sumably an oxide film, on t h e s u r f a c e of t h e p a r t i c l e s .
Addition of a b i n d e r d u r i n g t h e b l e n d i n g o p e r a t i o n f a c i l i t a t e s
bonding of t h e p a r t i c l e s d u r i n g p r e s s i n g . Stearic acid dissolved i n car-
bon t e t r a c h l o r i d e and l a u r y l a l c o h o l proved t o b e t h e most s u i t a b l e b i n d -
ers. Enough b i n d e r i s added t o form a s l u r r y w i t h t h e powders. Most of
t h e carbon t e t r a c h l o r i d e i s removed by low-temperature h e a t i n g p r i o r t o

'A. L. L o t t s , Reviev o f Information on U-Mo Alloys and U-Mo-UO2 D i s -

p e r s i o n F u e l s , ORNL CF-60-6-122 ( i n p r e s s ) .

443
 1

Fig. 23.1. Prealloyed U-13.8 wt % Mo Powder, -100 Mesh. As-polished. SOOX.

I compacting. A f t e r p r e s s i n g , t h e b i n d e r i s vacuum-evaporated a t a r e l a -

t i v e l y low temperature ( a b o u t 30OOC). The compact i s t h e n vacuum-sintered

a t 1100 and 115OoC. Data f o r t h e more s a t i s f a c t o r y c o r e s developed a r e
t a b u l a t e d i n Table 23.1.
Photomicrographs r e v e a l t h a t l i t t l e o r no s i n t e r i n g h a s occurred,
even i n a compact i n which 82.3% o f t h e t h e o r e t i c a l d e n s i t y w a s a t t a i n e d
( s e e F i g . 23.2a and 23.2b). A s shown i n Table 23.1, densification did
n o t occur d u r i n g s i n t e r i n g and, i n some c a s e s , t h e d e n s i t y of t h e compacts
a c t u a l l y decreased. The r e s i s t a n c e t o s i n t e r i n g has been a s c r i b e d t o an
oxide f i l m on t h e s u r f a c e o f t h e p a r t i c l e s . Another problem i n s i n t e r i n g
i s an apparent r e a c t i o n a t t h e i n t e r f a c e s between U-Mo powder and UO2, a
phenomenon i l l u s t r a t e d i n F i g . 23.2. The n a t u r e of t h i s r e a c t i o n w i l l be
explored i n f u t u r e work.
A c u r s o r y examination i n d i c a t e d t h a t compacts can be p r e s s e d with-
out a b i n d e r i f t h e U-Mo powder i s s u r f a c e - t r e a t e d p r i o r t o compacting.
@
444
c

Table 23.1. Density of Cold-Pressed and S i n t e r e d 25 v o l % UO2-75 vol 4 (T-L13,8 wt. % Mo) Compacts

Pressed Sintered
Core Evaporation* Sinterinp
Order Binder Pressure Density Time Density
Temperature Temperature
No. (tsi) ( % of
Theoretical)
("c> ("c) (hr) (4of
The ore t i c a1)

F194 Paraffin- CC14 30 450 1100 4 73.7

F198 Paraf f in-CC14 55 450 1100 4 63.4
F201 Lauryl alcohol 35 400 1100 5 82.3
F248 S t e a r i c acid- CC14 35 1100 24 74.7
F301-B Lauryl alcohol 40 '76.5 525 1100 18 77.1
F301-D Lauryl alcohol 40 78.4 525 1150 4 73 .7
F302-C Lauryl alcohol 40 77.6 525 1100 24 77.5
F309-'1 S t e a r i c acid-CC14 45 74.5 25 0 1100 6 69.7
F309- 2 S t e a r i c acid-CC14 45 74.6 375 1150 4 68.4

"Evaporation of binder and s i n t e r i n g done i n vacuum.

 ED
-

00 3

004

00 5
a
006

X
e
0
0-
In

008

Fig. 23.2. Microstructure o f 25 vol % U0,-75 vol % (U-13.8 wt % Mo) Compact, Pressed w i t h
L a u r y l Alcohol Binder a t 35 t s i and Sintered for 5 hr at 1100OC. Uranium dioxide (dark particles)
is -80 +120 mesh; U-13.8 wt % Mo (light) i s -100 mesh. As-polished. ( u ) Observe that whereas m e
dispersoid has resisted fragmentation, very l i t t l e sintering has occurred. 1OOX. ( b ) A n enlargement of
micrograph (a), showing a reaction product dispersed largely i n t h e areas o f contact between the U-Mo
shot and the UO,. 500X.
446
 The U-Mo powder i s f i r s t , c o l d - p r e s s e d , t h e n chemically t r e a t e d i n 20%
HN03-80% H20, washed w i t h water and acetone, and f i n a l l y vacuum-dried.
The c o n d i t i o n e d powders can be c o l d - p r e s s e d without b i n d e r t o d e n s i t i e s
as h i g h a s 79% of t h e o r e t i c a l , as shown i n Table 23.2. However, t h e
c l e a n i n g procedure does n o t appear t o enhance s i n t e r a b i l i t y .
While U02 h a s been used i n t h e p r e l i m i n a r y s t u d i e s , f u t u r e work w i l l
i n c l u d e di-spersions of UC. A l s o , e l e m e n t a l uranium and molybdenum powders
as a s u b s t i t u t e f o r t h e p r e a l l o y e d s h o t w i l l be i n v e s t i g a t e d .

Table 23.2. Density of Cold-Pressed and S i n t e r e d

25 vol % UO2--75 VOl % (U-13.8 wt % Mo) Compacts*

Pre s sed Sintered

Core Sintering
Order
Pres sure Density Temperature Time Density
No. (tsi) ( % of ("c) (hr) ( % of
The o r et ic a1) Theore t i c a1 )

F319-1 50 79.0 1100 6 76.7

F319- 2 50 79.2 1100 16 76.6
F320-1 35 73.2
F320-2 35 73.2

*The U-Mo powder w a s p r e c o n d i t i o n e d by p r e s s i n g and c l e a n i n g i n d i -

l u t e n i t r i c a c i d (20% m03-80qr0 H20).

Swaging o f U-Mo Powders

To olsltain small unclad specimens of U-Mo matrix material f o r i r r a d i a -

t i o n t e s t i n g , r o t a r y swaging experiments have been performed. Prealloyed
a powders, b o t h WlO wt % and F 1 3 . 8 w t % Mo, were swaged a t room tempera-
t u r e , 650,and 1050°C t o r e d u c t i o n s i n area ranging from 40 t o 90%. Ele-
mental powders w i t h a composition of E10 w t % Mo were a l s o swaged a t
room temperature and 650°C. The powders were c o n t a i n e d i n m i l d - s t e e l
cans when swaged a t room temperature and 650°C and i n I n c o n e l w i t h a molyb-
denum b a r r i e r when swaged a t 1O5O0C. Samples of swaged U-Mo, o b t a i n e d by
s e c t i o n i n g t h e rod and removing t h e cladding, were vacuum-sintered a t e l e -
v a t e d temperatures without i n c r e a s e i n d e n s i t y o r bonding. Typical densi-
t i e s achieved i n swaging IF-10wt % Mo powders are l i s t e d i n Table 23.3.

447
 Table 23.3. E f f e c t of Temperature and Reduction of Area on Swaged
Density of V-10 w t '$ Mo Powders

Swaged
Pe r e e n t age
Specimen Type of Initial Temperature Density
D i m et e r Reduction
Number Powder
(in.) ("c> i n Area ( % of
Theoretical)

S7 Elementals 0.305 R.T. 56.1 48.2

s1 E lernent a1s 0.305 R.T. 82.7 54.2
S6 Element a l s 0.305 650 65.2 52.6
s4 Elernentals 0.305 650 74.5 51.3
s2 Element a1s 0.305 650 86.0 53.6
S23 Prealloyed 0.305 R.T. 49.9 85.9
s21 Prealloyed 0.305 R.T. 61.6 86.7
S17 Pre a l l o y e d 0.305 R.T. 79.5 89.4
s34 Pre a l l o y e d 0.305 R.T. 88.4 90.8
S36 Prealloyed 0.430 650 46.9 Powder s p a l l e d

S32 Prealloyed 0.305 650 50.3 95.4

s37 Prealloyed 0.430 650 56.0 92.4
S30 Prealloyed 0.305 650 61.6 98.3
s38 Prealloyed 0.430 650 66.7 92.5
s28 Prealloyed 0.305 650 70.0 96.0
S18 Prealloyed 0.305 650 75.9 94.2

s39 Prealloyed 0.430 650 76.3 94.5

S40 Pre a l l o y e d 0.430 650 83.2 93.2
S46 Prealloyed 0.429 1050 48.4 92.4
s47 Prealloyed 0.429 1050 54.3 96.2
s48 Prealloyed 0.429 1050 56.8 92.2
S50 Prealloyed 0.429 1050 58.3 92.8
s49 Pre a l l o y e d 0.429 1050 67.1 97.8
S51 Prealloyed 0.429 1050 78.0 91.7

44 8
G, The d e n s i - t i e s were c a l c u l a t e d by u s i n g weight and dimensional measurements
of t h e c l a d specimens. F i g u r e 23.3 i s a photomicrograph of a specimen
swaged t o 56.8% r e d u c t i o n i n a r e a a t 1050°C.
E v a l u a t i o n of t h e swaged rods i s incomplete. However, it i s a p p a r e n t
t h a t d e n s i t i e s approaching t h e o r e t i c a l might be a c h i e v e d w i t h o p t i m i z a t i o n
of t h e f a b r i c a t i o n v a r i a b l e s . It would appear t h a t p r e a l l o y e d powders are
more s w a g e a b l e t h a n f i n e l y s i z e d e l e m e n t a l powders. A s had been expected,
t h e prea1:Loyed powders a t t a i n e d h i g h e r d e n s i f i c a t i o n on swaging a t 650
and 1050°C t h a n a t room t e m p e r a t u r e . The amount of bonding between i n d i -
v i d u a l p a r t i c l e s w a s g r e a t e r i n c a p s u l e s swaged a t 1050 t h a n i n t h o s e
swaged a t 650°C.
It w a s n o t p o s s i b l e t o machine t h e c l a d d i n g from t h e c a p s u l e s swaged
a t 650°C w i t h o u t c o n s i d e r a b l e s p a l l i n g of t h e swaged powder. R e s u l t s of
machining specimens swaged a t 1050°C are n o t y e t a v a i l a b l e . However, it
- i s obvious from i n s p e c t i . o n of m e t a l l o g r a p h i c samples t h a t some p a r t i c l e s

Fig. 23.3. Transverse Section of Swaged Prealloyed U-10 wt % Mo Specimen After 56.8% Reduction

Grs in Area at 105OOC (Sample S48 of Table 23.3). As-polished.

44 9

e
 a r e removed d u r i n g c u t t i n g and p o l i s h i n g o p e r a t i o n s , i n d i c a t i n g t h a t t h e
d e g r e e of bonding between p a r t i c l e s swaged a t 1050°C a l s o may n o t be s a t i s -
factory. The p r e a l l o y e d powders used i n t h e swaging experiments were n o t
c o n d i t i o n e d by t h e c l e a n s i n g t r e a t m e n t .

DEVELOPMENT OF ALUMINUM-MATRIX FUEL CORES

T . D . Watts A. L . L o t t s J. P. Hammond

I n s u p p o r t of t h e High F l u x I s o t o p e R e a c t o r (HFIR) P r o j e c t , 2 t h e ob-

j e c t i v e i s t o d e m o n s t r a t e ' t h e f e a s i b i l i t y of producing aluminum f u e l c o r e s
c o n t a i n i n g u308 and B4C as d i s p e r s a n t s . F a b r i c a t i o n of such components
h a s been a t t e m p t e d t h r o u g h c o l d - p r e s s i n g and s l i p - c a s t i n g approaches.

Cold P r e s s i n g A l , B4C, U308 Compacts

The primary emphasis has been on c o l d p r e s s i n g and s i n t e r i n g of t h e

two d i f f e r e n t s h a p e s . The f u e l s e c t i o n of t h e c o r e s c o n t a i n s 25.7 vol $
U308 and 0.135 v o l % BQC. The f i l l e r s e c t i o n s c o n t a i n 0.135 vol $ B4C.
A 1 x 3 i n . d i e , f i t t e d w i t h a t a p e r e d p l u n g e r and punch, h a s been used
i n the pressing studies. It w a s assumed t h a t i n f o r m a t i o n o b t a i n e d by
u s i n g t h i s d i e c o u l d r e a d i l y be a p p l i e d t o f u l l - s i z e c o r e s .

S l i p C a s t i n g Aluminum, BqC, and U308

A l i m i t e d s t u d y of s l i p c a s t i n g was made as a s u p p o r t i n g method f o r

l o a d i n g of t h e d i e . S l i p - c a s t compacts would be i n s e r t e d i n t h e d i e and
p r e s s e d t o t h e r e q u i r e d s i z e and shape. The experiments showed t h a t A l -
U308-B4C compacts can b e s l i p - c a s t ; however, t h e d e n s i t y i s low ( a b o u t
50% of t h e o r e t i c a l ) . The b e s t s l i p c a s t i n g s produced were c a s t i n p l a s t e r
of P a r i s molds, w i t h soap s o l u t i o n as t h e p a r t i n g a g e n t . The s l i p con-
t a i n e d 0.4 wt '$ Marex ( a commercial ammonium a l g i n a t e ) a s a deflocculant
and had a w a t e r - t o - m e t a l r a t i o o f 0.20 and a pH of 8.0.

2J. H. Erwin - et -
a l . , "Development of Aluminum-Base F u e l Elements'' and
"Development of an Aluminum-Base F u e l Element f o r t h e High F l u x I s o t o p e
R e a c t o r , " i n Chap. 18 of t h i s r e p o r t .

I 450
 BOROIVATED GLASS PARTICLES I N STAINUSS STEEL AS BURNABLE: POISON

T . D . Watts A. L . L o t t s

The problem of r e t a i n i n g boron, e i t h e r i n e l e m e n t a l form o r as boron

compounds, d u r i n g f a b r i c a t i o n of f u e l p l a t e s h a s s t i m u l a t e d t h e i d e a of
u s i n g b o r o n a t e d g l a s s p a r t i c l e s a s b u r n a b l e p o i s o n f o r APPR f u e l p l a t e s .
The l i t e r a t u r e r e v e a l e d t h a t f u e l as w e l l as p o i s o n s can be i n c o r p o r a t e d
i n many gl-ass s t r u c t u r e s 3 and t h a t i n s t a i n l e s s s t e e l , under t h e condi-
t i o n s used t o f a b r i c a t e APPR f u e l p l a t e s , g l a s s p a r t i c l e s a r e v e r y s t a b l e .
An added advantage of g l a s s p a r t i c l e s a s used as b u r n a b l e p o i s o n i s t h e
a b i l i t y of' g l a s s t o absorb a gas, t h u s g i v i n g g r e a t e r i r r a d i a t i o n s t a b i l i t y ,
as shown by K n o l l s Atomi c Power L a b ~ r a t o r y . ~The main problem i n v o l v e d
i n t h e use o f g l a s s p a r t i c l e s f o r b u r n a b l e p o i s o n a p p e a r s t o be t h e low
s o f t e n i n g p o i n t of high-B203-content glasses. I n p r e l i m i n a r y work, t h i s
h a s r e s u l t e d i n s t r i n g e r i n g of t h e g l a s s p a r t i c l e s when r o l l e d i n s t a i n -
l e s s s t e e l s a t f a i r l y h i g h t e m p e r a t u r e (llOO°C). However, t e m p e r a t u r e -
r e s i s t a n t g l a s s e s c o n t a i n i n g s u f f i c i e n t boron t o meet t h e APPR p o i s o n r e -
quirements can be produced.
The program w i l l c o n s i s t i n (1)producing powder-metallurgy d i s p e r -
s i o n compacts of t h e v a r i o u s g l a s s e s i n t y p e 347 s t a i n l e s s s t e e l , ( 2 )
r o l l i n g t h e compacts i n t o p l a t e s , and ( 3 ) examining t h e p l a t e s m e t a l l o -
graphical1,y f o r p a r t i c l e shape and d i s t r i b u t i o n .
To d a t e only one s e t of c o r e s has been made, c o n t a i n i n g 2.6 and 5 . 2
wt % Pyrex. The g l a s s was normal Pyrex, crushed and ground to -170 +325
mesh. Two boron a n a l y s e s gave v a l u e s o f 3.54 and 3.81 w t $. No d i f f i c u l t y
w a s encountered i n t h e p r e s s i n g o r r o l l i n g of t h e compacts, b u t m e t a l l o -
g r a p h i c examination of t h e p l a t e s showed t h e s e v e r e s t r i n g e r i n g e f f e c t s .
More promising, h i g h e r s t r e n g t h g l a s s e s w i t h smaller p a r t i c l e s i z e s w i l l
be t r i e d when t h e y are r e c e i v e d from t h e m a n u f a c t u r e r s .

3 G . D . Wirkus and D. R . Wilder, Uranium Glasses No. 1, Fundamental

C o n s i d e r a t i o n s , IS-107 (Feb. 1 9 6 0 ) .
'W. K e r m i t Anderson, "Nuclear A p p l i c a t i o n s of Y t t r i u m , Scandium, and
t h e Lanthanons," Rare E a r t h s and R e l a t e d Metals, Am. SOC. Metals ( i n p r e s s ) .

451
 ADVANCED FUEL MATERIALS
Q
Liquid-Phase Sintering of Uranium Monocarbide

J. D. Sease J. P. Hammond

A program has been initiated to develop procedures for fabricating

uranium monocarbide bodies by the liquid-phase sintering approach. The
program proposes the use of metal binders as a structural component, both
to lessen sintering difficulties and to effect desired chemical and physi-
cal properties. The fuel systems to be investigated include the follow-
ing: UC-5 to 15 vol % Ni and UC-5 to 15 vol % V.
Because powder metallurgy was reinstituted as a separate laboratory
I
only in the last year, many of the programs have been delayed because of
equipment limitation. A vacuum dry box has been set up, and a vacuum fur-
nace is being acquired. No results of significant importance have been
obtained to date.

Dispersion Hardening of Thorium and y-Uranium Alloys

J. A. Burka J. P. Hammond

A program has been initiated to improve the elevated-temperature

strength of y-uranium (containing 1C-15 w t '$ Mo) and thorium alloys by the
dispersion of fine particles in the matrix phase. Complementary studies
are being made on thorium-base alloys prepared by arc-melting. Methods
that will be investigated to obtain dispersions of particles in the matrix
e
materials are as follows: (1)blending small-particle-sizemetal compounds
in amounts up to 20 vol $ in the matrix metals, (2) producing thin films
of oxide on fine powders of the matrix metals by controlled oxidation, and
(3) shotting alloys containing high-stability compounds to obtain a fine
dispersion of the compound in the matrix.
Initial studies will be performed on all alloys to determine their
recrystallization temperatures and hardnesses at elevated temperatures.
Those alloys which show a substantial increase in these properties will
be subjected to irradiation and creep-rupture tests.

I 452
 24. WELDING AND BRAZING
G. M. Slaughter

IQITERIALS- JOINING DEVELOPMENT

Beryllium

R. G. Gilliland

The use of beryllium as a cladding material for advanced gas-cooled-

reactor fuel elements depends to a large extent on the development of
suitable Joining techniques. The evaluation of various joining proce-
dures for beryllium continues, with processes including high-temperature
brazing, cliffusion bonding, and fusion welding.
The alloy development program associated with the high-temperature
beryllium brazing study has produced several potentially attractive al-
loys for high-temperature helium service, such as the 49 Ti-49 P&2 Be
(wt $) an6. the 49 Ti-49 Cu-2 Be (wt % ) materials.lJ2. Good wetting and
flow on beryllium was obtained, and joints that are leaktight to helium
have been produced on tube-to-end-cap samples. Thermal-cycling and mechan-
ical-properties tests on brazed joints are under way.
The diffusion bonding of beryllium has been successfully accomplished
by utilizing the pressures resulting from the expansion of beryllium into
a molybdenum restraining fixture. ’-‘ Joints that are leaktight to helium
are readi1,y produced, and complete grain coalescence across the interface
has been obtained after 4 hr at 1150°C in a vacuum. A photomicrograph of
such a joint is shown in Fig. 24.1.
Q Fusio.? welding appears to provide a very promising technique for seal-
ing tubes, and leaktight joints are produced by using the tungsten-arc
process. ’ Techniques have been developed for overcoming root cracks, but
slight porosity is still encountered in the weld metal. Mechanical-prop-
erties tesi;s on welded joints have been initiated.

-Quar. Prog. Rep. Mar. 31, 1960, ORNL-2929, p 14-2.

‘GCR
2GCR Quar. Prog. Rep. June 30, 1960, ORNL-2964 (in press).
3GCR Quar. Prog. Rep. Dec. 31, 1959, ORNL-2888, p 97-98.
‘GCR Quar. Prog. Rep. Mar. 31, 1959, ORNL-2929, p 142-44.

453
 ORIGINAL
BOND LINE

Fig. 24.1. Beryllium Diffusion Bond Made by Holding for 4 hr at 115OoC in Vacuum. Complete
grain coalesence across the interface i s evident. Polarized light; unetched. 250X.

Graphite

R. G. Donnelly

The utilization of graphite in high-temperature heat exchange systems

a
for advanced molten-salt reactor applications is highly dependent upon the
development of techniques for joining graphite to itself and to metals.
Studies have included the development of corrosion-resistant brazing al-
a
loys for joining graphite and the utilization of procedures for overcoming
the wide differences in thermal expansion between graphite and conventional
structural materials.
In order to demonstrate the general feasibility of fabricating compo-
nents containing graphite brazes, the assembly shown in Fig. 24.2 was con-
~tructed.~The 48 Ti-48 Zr-4 Be (Wt % ) experimental alloy,6 which readily

'MSR Quar. €Tog. Rep. Apr. 30, 1960, ORNL-2973 (in press).
6MSR Quar. Prog. Rep. Oct. 31, 1959, OWL-2890, p 4S48.
 UNCLASSIFIED
Y - 33370

GRAPHITE
TUBES .

INOR-8
PLATE - , Ti- Zr -Be
BRAZE

MOLY B DE N L Ni- S i - B
WASHER BRAZE

Fig. 24.2. Graphite Tube to INOR-8 Header P l a t e Assembly Fabricated by Brazing.

w e t s and f l o w s on g r a p h i t e , w a s u s e d t o b r a z e t h e g r a p h i t e t u b e s t o l o w -
expansion molybdenum t r a n s i t i o n washers. The molybdenum t r a n s i t i o n washers
w e r e t h e n 'brazed t o an INOR-8 header w i t h a commercial high-temperature
nickel-base a l l o y .
However, i n view of t h e poor r e s i s t a n c e of t h e Ti-Zr-Be a l l o y t o cor-
r o s i o n by t h e f u s e d s a l t s , a l l o y systems p o s s e s s i n g p o t e n t i a l l y good com-
p a t i b i l i t y have been under s t u d y . The Au-Ni system, w i t h a d d i t i o n s of such
carbide-forming elements as t a n t a l u m and/or molybdenum, has appeared es-
pecially attractive. S e v e r a l a l l o y s i n t h i s system have been developed
which r e a d i l y w e t g r a p h i t e and are s u i t a b l e f o r j o i n i n g g r a p h i t e t o i t s e l f
and t o low-expansion m e t a l s such as molybdenum. Alloys c o n t a i n i n g h i g h
p e r c e n t a g e s of c a r b i d e formers, and t h e r e b y p o s s e s s i n g t h e b e s t flow, are

455
1

somewhat b r i t t l e ; consequently, t h e s e l e c t i o n of a l l o y s i n t h e s e systems

must be based upon a balance between toughness and g e n e r a l b r a z a b i l i t y .

Refractory Metals

E . A. Franco-Ferreira

Process Evaluation

A program a s s o c i a t e d with t h e welding of r e f r a c t o r y metals i s under

way, w i t h primary emphasis placed on niobium and niobium-base a l l o y s . A
number of d i f f e r e n t welding processes have been used, including i n e r t - g a s ,
tungsten e l e c t r o d e (both i n a i r and i n a n atmosphere chamber), i n e r t - g a s
consumable e l e c t r o d e , and electron-beam welding.
It has been found t h a t with t h e use of a s u i t a b l e gas t r a i l e r s h i e l d
around t h e welding t o r c h and w i t h machine-welding p r a c t i c e s , s a t i s f a c t o r y
contamination-free welds can be r e a d i l y produced without t h e use of a con-
trolled-atmosphere chamber. Thus it appears p o s s i b l e t o f a b r i c a t e l a r g e ,
u s e f u l s t r u c t u r e s from niobium without t h e p h y s i c a l l i m i t a t i o n s which t h e
requirement of an inert-atmosphere welding chamber would impose.
The i n e r t - g a s , consumable-electrode welding experiments were con-
ducted on heavy p l a t e , 1/4 t o 1 / 2 i n . t h i c k . All welding w a s done with a
t r a i l e r s h i e l d , and s a t i s f a c t o r y welds were e a s i l y obtained. The g e n e r a l
procedure w a s t o f u s e t h e r o o t of t h e weld with a s i n g l e tungsten-elec-
t r o d e f u s i o n pass and t h e n t o f i l l t h e remainder of t h e weld groove with
a s i n g l e pass by use of t h e consumable-electrode process.
I n a d d i t i o n , a s m a l l number of contamination-free welds have been
s u c c e s s f u l l y made by using t h e electron-beam welder. A s would be expected,
t h i s new process i s uniquely a p p l i c a b l e t o t h e j o i n i n g of r e a c t i v e metals,
s i n c e t h e e n t i r e o p e r a t i o n i s conducted i n a vacuum.

Weld-Aging S t u s e s

I n t h e course of a welding study on Nb-l% Z r a l l o y s , an aging reac-

t i o n w a s observed, and an extensive program has been s e t up t o study t h i s
phenomenon. I n t h e i n t e r e s t of s e c u r i n g a b s o l u t e uniformity of t h e weld-
i n g atmosphere, a l l welds i n t h i s program have been made on sheet mate-
r i a l s i n an inert-atmosphere chamber. A f t e r welding, t h e welds a r e eval-
u a t e d by bend t e s t i n g .
 Photographic examples of t y p i c a l room-temperature-bend t e s t samples
( a f t e r aging 250 h r a t var ous temperatures) on one h e a t of m a t e r i a l a r e
shown i n Fig. 24.3. The weld shown i n F i g . 24.3a w a s aged a t 1300°F and
i s completely d u c t i l e . A weld aged a t 1500°F i s shown i n Fig. 24.3b and
i s b r i t t l e , while t h e weld shown i n F i g . 2 4 . 3 ~w a s aged a t 1600°F and ex-
h i b i t e d d u c t i l e behavior, b u t some cracking w a s e v i d e n t . Specimens aged
a t 1700 and 1800°F f o r 250 h r were completely d u c t i l e . Figure 24.4 i s a
g r a p h i c a l summary of t h e bend-test r e s u l t s . These curves show t h e time-
dependent t r e n d i n weld d u c t i l i t y when t h e welds a r e aged a t d i f f e r e n t

e temperatures. A preaging anneal of 1 hr a t 2200°F seems t o circumvent

UNCLASSIFIED UNCLASSIFIED
Y-33346

UNCLASSIFIED

Fig. 24.3. Bend Tests on Nb-1% Zr Alloy Welds. 3.5X. (a) Weld bend-test sample exhibiting
ductile behavior; aged 250 hr at 1300OF. ( b ) Weld bend-test sample exhibiting brittle behavior; aged

w 250 hr at 1500'F. (c) Weld bend-test sample exhibiting ductile behavior with cracking; aged 250 hr at
16OOOF.

457

@
 UNCLASSIFIED
ORNL-LR-DWG 48980

1600°F

DUCTILE WITH CRACKING v

I 2 5 10 25 50 100 250 500 I 2 5 10 25 50 400 250 500

TIME (hr) TIME ( h r )

Fig. 24.4. Influence o f Aging Time at Various Temperatures on the Bend-Test Behavior of Nb-1%
Zr Alloy (Heat XM-339).

aging e n t i r e l y . The a g i n g b e h a v i o r of t h i s a l l o y appears t o vary some-

what from h e a t t o h e a t , b u t t h e same g e n e r a l t r e n d s would be expected t o
occur.
The e x a c t a g i n g mechanism i s n o t y e t understood. However, a g r a i n -
boundary phase (probably a compound of zirconium w i t h oxygen, n i t r o g e n ,
o r carbon), h a s been observed i n weld specimens f o l l o w i n g aging, b u t t h e
r e l a t i o n s h i p of t h i s phase t o t h e b r i t t l e behavior of c e r t a i n aged welds
h a s n o t y e t been determined.
The u s e of all-weld-metal t e n s i l e specimens i s now under way i n an
e f f o r t t o g e n e r a t e q u a n t i t a t i v e data which w i l l h e l p t o more c l e a r l y ex-
p l a i n t h e e f f e c t s of t h e a g i n g r e a c t i o n .

D i s s i m i l a r - M e t a l Welding

G. M. S l a u g h t e r
S t u d i e s a r e under way t o determine t h e b e s t methods f o r j o i n i n g f e r -
r i t i c s t e e l s t o a u s t e n i t i c s t a i n l e s s s t e e l s f o r such a p p l i c a t i o n s as t h e
primary c o o l a n t p i p i n g f o r t h e Experimental Gas-Cooled Reactor. The f i l l e r
m e t a l used must have t h e a b i l i t y t o t o l e r a t e d i l u t i o n w i t h t h e two t y p e s
of base metals without any s e r i o u s r e d u c t i o n i n m e t a l l u r g i c a l p r o p e r t i e s ,

458

c
and t h e welded j o i n t must b e a b l e t o w i t h s t a n d t h e stresses c r e a t e d by
d i f f e r e n t i a l t h e r m a l expansion during c y c l i c temperature s e r v i c e .
A developmental n i c k e l - b a s e a l l o y e l e c t r o d e , BP-85, i s especially
promising as a f i l l e r m e t a l because i t s c o e f f i c i e n t of t h e r m a l expansion
i s i n t e r m e d i a t e between t h o s e of t h e b a s e metals b e i n g j o i n e d . 7 3 Its
d e p o s i t i o n c h a r a c t e r i s t i c s i n a l l p o s i t i o n s are e x c e l l e n t , and t h e weld
d e p o s i t s ;are f r e e from p o r o s i t y . I n o r d e r t o provide a s s u r a n c e t h a t t h i s
e l e c t r o d e i s s u i t a b l e f o r t h e f a b r i c a t i o n of l a r g e components c o n t a i n i n g
heavy s e c - t i o n s , welding procedures were developed on 1 - i n . - t h i c k p l a t e .
The procedures developed t o date i n c l u d e welding ASTM SA-212, grade B y
carbon s t e e l t o s t a i n l e s s s t e e l and welding ASTM A-387, grade D (2-1/4
Cr-1 Mo) ; s t e e l t o stain:Less s t e e l . Welds made w i t h t h e s e combinations
have s a t i s f a c t o r i l y p a s s e d t h e ASME B o i l e r and P r e s s u r e Vessel Code r e -
quirements. 9

Tubular specimens c o n t a i n i n g dissimilar m e t a l welds are b e i n g sub-

j e c t e d t o t h e r m a l c y c l i n g t e s t s by t h e Mechanical P r o p e r t i e s Group.

P r e s s u r e Vessel S t e e l s

J. J. P r i s l i n g e r

I n o r d e r t o supplement d a t a c u r r e n t l y a v a i l a b l e on t h e b e h a v i o r of
p r e s s u r e - v e s s e l s t e e l s , a program i s b e i n g c a r r i e d o u t t o e v a l u a t e t h e
pre- and p o s t i r r a d i a t i o n mechanical b e h a v i o r of ASTM A212, grade B, p a r -
e n t p l a t e and weld h e a t - a f f e c t e d zones. A 4-in.-thick plate, referred t o
i n t h e p r e v i o u s annual r e p o r t , " h a s been e v a l u a t e d e x t e n s i v e l y i n drop-
weight t e s t s , and t h e impact b e h a v i o r of s y n t h e t i c weld h e a t - a f f e c t e d
zones i s b e i n g i n v e s t i g a t e d on a s u b c o n t r a c t a t R e n s s e l a e r P o l y t e c h n i c
I n s t i t u t e (RPI) . 9 9 1 1 *l 2

- Q u a r . Prog. Rep. Dec. 31, 1959, ORNL-2888, p 91-92.

7GCR

8GCR Quar. Prog. Rep. Mar. 31, 1960, ORNL-2929, p 1 3 5 3 6 .

-
9GCR Quar. B o g . Rep. June 30, 1960, ORNL-2964 ( i n p r e s s ) .

-
"Met. Ann. Frog. Rep. S e p t . 1, 1959, ORNL-2839, p 232.
-
l1GCEI Quar. Prog. Rep. Dec. 31, 1959, ORNL-2888, p 81-84.
- Quar. Prog. Rep. Mar. 31, 1960, ORNL-2929, p 118-22.
"GCF:

459
 Information obtained from the drop-weight tests13 indicates that
the surface material has an NIYT temperature of 10°F, the one-quarter
thickness, 1B0F, and the midsection, 30°F.
The RPI impact specimens being tested are subjected to the same ther-
mal treatment as selected areas of weld heat-affected zones. Thermal cy-
cles corresponding to a weld energy input of 50,000 and 100,000 joules/in.
were studied, as were peak temperatures of 1400 and 2400°F. The conclu-
sions drawn to date from the RPI study indicate that weld thermal cycles
with peak temperatures of 2400°F raise the transition temperature markedly
if postheat is not used. An energy input of 100,000 joules/in. is less
damaging to impact strength than 50,000 joules/in. at test temperatures
above 150°F. A postheat of 115O0F for 4 hr following the 2400"F, 50,000
joule/in. synthetic thermal cycle restores the transition temperature to
a value lower than that of the as-received material. Postheating of the
2400°F, 100,000 joule/in. specimens did not significantly change the tran-
sition temperature. Also, a thermal cycle of 1400°F peak temperature at
50,000 joules/in. lowers the transition temperature about 50°F below that
of the as-received material.
In addition, 150 synthetic heat-affected-zone impact specimens have
been prepared at RPI for the first portion of an in-pile irradiation pro-
gram on ASTM A212, grade B, welded joints.' These specimens are tenta-
tively scheduled to be inserted into the ORR in September 1960.

a
GAS-COOLED REACTOR COMPONENT DEVELOPMENT

Experimental Gas-Cooled Reactor Fuel Elements e

R. L. Heestand
The Experimental Gas-Cooled Reactor (EGCR) fuel element will consist
I of a cluster of seven stainless steel fuel capsules, each containing UOz
pellets. In order to obtain information regarding the influence of manu-
facturing variables on the procedures to be employed in constructing

l3P. P. Puzak and W. S. Pellini, "Evaluation of the Significance of

Charpy Tests for Quenched and Tempered Steels," Welding J. =
35, 275-s-290-s
(1956).

46 0

e
 the first core loading of the reactor, the pilot-plant fabrication of 50
Title I fuel elements was successfully undertaken.14Jl 5 Procurement
specifications were prepared for the components of the fuel element which
were subsequently purchased on the basis of bids submitted from several
vendors. The fuel elements were successfully assembled, and it appears
that the design is such that commercial manufacture of the loading should
be possible without major difficulties. A report describing the procure-
ment of components, the fabrication, and recommendations for manufacture
of the Title I fuel element was cornpleted.16

Experimental Gas-Cooled Reactor Pressure-Vessel Penetrations

G. M. Slaughter

The design of the Experimental Gas-Cooled Reactor (EGCR) necessi-

tates the penetration of many closely spaced, thin walled, burst-slug de-
tection t-ubesand small-diameter thermocouples through thick-walled noz-
zles on t:he reactor pressure vessel. A simplified drawing illustrating
these penetrations is shown in Fig. 24.5a. Several applicable joint de-
signs for making the penetrations were investigated, and the most suitable
of these were incorporated into mockup assemblies.9 J 1 7 J
One (quadrant of a full-size EGCR burst-slug detection nozzle assembly
and one segment of a thermocouple assembly were successfully fabricated,
and these are shown in Figs. 24.5b and 2 4 . 5 ~respectively.
~ Every effort
was made to simulate conditions to be expected in the construction of the
actual coinponents. Although welder accessibility is very limited, the fab-
rication procedures appear feasible if properly trained welders are used.
Q

- Quar. Prog. Rep. Dee. 31, 1959, ORNL-2888, p 84-88.

14GCR
- Quar. Prog. Rep. Mar. 31, 1960, ORm-2929, p 123-32.
15GC:R
1 6 E . A. Wick and R. L. Heestand, Manufacture of Fifty Prototype Fuel
Elements .for the Experimental Gas-Cooled Reactor, ORNL-2936 (in press).
- Quar. Frog. Rep. Dee. 31, 1959, ORNL-2888, p 91-92.
17GCII
18GCIi
_. Quar. Prog. Rep. Mar. 31, 1960, ORNL-2929, p 132-35.

461
1

UNCLASSIFIED
BSD PENETRATIONS (1461 ...
ORNL-LR-DWG .47305
.
THERMOCOUPLE
PENETRPTIONS

(a)

EGCR BURST-SLUG DETECTION TUBE AND THERMOCOUPLE NOZZLE.

UNCLASSIFIED
Y-34510

BURST-SLUG DETECTION TUBE ASSEMBLY THERMOCOUPLE ASSEMBLY

Fig. 24.5. Burst-Slug Detection and Thermocouple-Penetration Mockup. ( a ) EGCR burst-slug-

detection tube and thermocoupl e nozzle; ( b ) burst- SI ug-detection tu be assem bl y; (c) thermocoupl e assembly.

Welding of EGCR Experimental Through Tubes

R . L. Heestand

The EGCR w i l l c o n t a i n p r o v i s i o n s f o r v e r t i c a l experimental through

l 0 0 p s . l ~ Four 5-in.-OD (nominal), t y p e 347 s t a i n l e s s s t e e l t u b e s n e a r
t h e v e r t i c a l c e n t e r l i n e of t h e c o r e and f o u r 9-1/2-in.-OD (nominal) t u b e s
a t t h e c o r e m o d e r a t o r - r e f l e c t o r i n t e r f a c e are provided f o r t h e s e experi-
mental l o o p s .
A design has been proposed f o r t h e i n s t a l l a t i o n and maintenance of
t h e s e 5 0 - f t - l o n g t u b e s which r e q u i r e s welds t o b e made remotely i n b o t h

"Experimental Gas-Cooled Reactor P r e l i m i n a r y Hazards Summary Report,

ORO-196, p 3 . 2 (May 1 9 5 9 ) .

462
 t h e overhead and downhand p o s i t i o n s . The welds must be made 6 t o 8 f t
up a c h a n n e l of approximately t h e same diameter as t h e t h r o u g h t u b e s .
Procedures are b e i n g determined f o r t h e i n e r t - g a s , consumable-electrode
d e p o s i t i o n of t h e s e remote welds, and welding a p p a r a t u s i s b e i n g m o d i f i e d
f o r t h e c o n d i t i o n of l i m i t e d a c c e ~ s i b i l i t y . ~
L i n e a r welds of e x c e l l e n t appearance have been made remotely i n t h e
overhead p o s i t i o n , and a d a p t a t i o n of t h e equipnent f o r c i r c u l a r j o i n t s i s
under way.

Uranium Dioxide F u e l I n s p e c t i o n
@ R . L. Heestand

For approximately one q u a r t e r of t h e y e a r t h e Welding and B r a z i n g

a Laboratory w a s r e s p o n s i b l e f o r t h e i n s p e c t i o n of a l l U02 f u e l r e c e i v e d
f o r u s e i n t h e Gas-Cooled R e a c t o r i r r a d i a t i o n program. An a c c o u n t a b i l i t y
s t a t i o n and an i n s p e c t i o n f a c i l i t y f o r t h e measurement of s i z e , weight,
and d e n s i t y were s e t up. Chemical a n a l y s i s and s u r f a c e a r e a measurements
were a l s o o b t a i n e d f o r each b a t c h of m a t e r i a l .

A d e t a i l e d i n s p e c t i o n procedure w a s i n i t i a t e d , and a d a t a summary

c o v e r i n g a.11 U02 f u e l u s e d i n GCR i r r a d i a t i o n experiments w a s p r e p a r e d
p r i o r t o t r a n s f e r of t h e i n s p e c t i o n f a c i l i t y t o t h e Ceramics L a b o r a t o r y .

COMPONENT FABRICATION DEVELOPMENT FOR OTHER REACTOR APPLICATIONS

@ Compartment e d F u e l E l e m e n t F a b r i c a t ion

R . G. G i l l i l a n d

a The development of s u i t a b l e p r o c e d u r e s f o r f a b r i c a t i n g compartmented

f u e l p l a t e s i s under way under s p o n s o r s h i p of t h e Merchant S h i p R e a c t o r
Program. These f u e l p l a t e s would c o n t a i n b u l k U02 f u e l b o d i e s i n a manner
similar t o t h a t i l l u s t r a t e d i n F i g . 24.6.
Two t e c h n i q u e s have been c o n s i d e r e d f o r e f f e c t i n g t h e bond between
t h e s t a i n l e s s s t e e l f r a m e - g r i d s t r u c t u r e and t h e s t a i n l e s s s t e e l cover
s h e e t s , namely, b r a z i n g and r e s i s t a n c e welding. 2 o With t h e b r a z i n g t e c h -
n i q u e , t h e cover s h e e t s and f r a m e - g r i d s t r u c t u r e are p l a t e d w i t h e l e c t r o -
l e s s nicke:L. The assembly i s t h e n clamped between p l a t e n s and b r a z e d i n

2 0--
M a r i t i m e R e a c t o r Ann. D o g . Rep. Nov. 30, 1959, ORNL-2865, p 50-54.

463
 UNCLASSIFIED
ORNL-CR-DWG 33675

CERAMIC

COVER SHEET

FUEL COMPARTMENT
FRAME
COVER SHEET

F i g . 24.6. Exploded View of Compartmented

Fuel P l a t e .

dry hydrogen. TO date, intercompartmental leakage has been a consider-

able problem, but modifications in procedure are under development in an
effort to minimize or eliminate this difficulty.
A subcontract has been in effect with Sciaky Brothers, Inc., Chicago,
Illinois, to investigate the use of resistance welding for attachment of
the cover plates to the frame-grid structure. The program has consisted
of the determination of optimum welding conditions. Sample assemblies
have been fabricated by utilizing the most promising welding conditions,
and the evaluation of the units is under way.

Solidified-Metal Seal Development

J. W. Tackett
The development of solidified-metal seal materials for high-vacuum
valves and flanges for use in experimental thermonuclear apparatus was
continued. These seals are opened and closed by melting the seal mate-
rial, and when the seal material solidifies with the valve closed, a
vacuum-tight closure is obtained.
Particular attention was given to the development of a composite
washer-type seal consisting of a porous metal compact impregnated with a
low-melting (400 to 6OO0C), low-vapor-pressure filler alloy. Numerous
l
potentially attractive filler alloys were developed, and a compatibility

464
 study, i n c l u d i n g w e t t i n g and a g i n g t e s t s on t h e more promising materials,
was condwted. The r e s u l t s of t h i s c o m p a t i b i l i t y s t u d y r e v e a l e d s e v e r a l
h i g h l y promising materials combinations, such as 6 1 Ag-24 Cu-15 I n (wt % )
w i t h molybdenum o r i r o n , 62 Au-38 I n (wt % ) w i t h molybdenum o r i r o n , and
68.5 Au-31.5 G a ( w t %) w i t h molybdenum.21
This work w a s t e r m i n a t e d i n midyear as a r e s u l t of a r e d i s t r i b u t i o n
of p r o j e c t e f f o r t .

Aluminum-Alloy F u e l Element Development

e J. W. T a c k e t t

The Mark 1 1 - A design f o r t h e aluminum-alloy H F I R f u e l element com-

p r i s e s a m u l t i t u d e of f u e l p l a t e s formed i n t o i n v o l u t e s and assembled
Q
i n t o a c y l i n d r i c a l shape w i t h extremely t i g h t t o l e r a n c e l i m i t a t i o n s , F5%
(ref 2 2 ) . A number of unique welding problems were encountered i n t h e
f a b r i c a t i o n of a mockup inner-annulus f u e l element f o r h y d r a u l i c t e s t i n g
and g e n e r s l e v a l u a t i o n of t h e Mark 1 1 - A d e s i g n .
The g e n e r a l problems i n t h e assembly of t h e t e s t element shown n e a r
completion i n F i g . 24.7 i n v o l v e d t h e attachment of each of t h e 192 t y p e
6061 aluminum-alloy f u e l p l a t e s s e c u r e l y t o t h e grooved i n n e r t u b u l a r
s i d e p l a t e of t h e element ( a l s o of t y p e 6061 aluminum), as w e l l as se-
c u r e l y anchoring t h e o u t e r t r a i l i n g edges of t h e i n v o l u t e p l a t e s .

4) With t h e e x c e p t i o n of t h e l a s t e i g h t i n v o l u t e p l a t e s i n s t a l l e d i n
the assembly, t h e attachment t o t h e inner t u b u l a r p l a t e w a s performed by
peening. However, a p l u g welding t e c h n i q u e (shown i n F i g . 24.8) w a s used
i n t h e attachment of t h e s e l a s t e i g h t p l a t e s , s i n c e space l i m i t a t i o n s d i d
Q
n o t permit peening. Each p l a t e w a s a t t a c h e d a t 5 - i n . i n t e r v a l s by t h r e e
3/4-in.-long welds. The 24 c l o s e l y spaced welds r e s u l t e d i n only minor
d i s t o r t i o n of t h e i n n e r c y l i n d e r .

21R. E. Clausing and J. W. T a c k e t t , Thermonuclear P r o j e c t Semiann.

Rep. Jan. 31, 1960, ORNL-2926, p 100-106.
2 2 J. H. Erwin e t a l . , "Development of Aluminum-Base F u e l Elements
-- -
Development of an Aluminum-Base F u e l Element f o r t h e High Flux I s o t o p e
Reactor," i n Chap. 18.

465
 Fig. 24.7. View of HFlR Full-Scale Inner Annulus T e s t Element.

Anchorage of t h e t r a i l i n g edge of t h e i n v o l u t e p l a t e s along t h e o u t e r

periphery of t h e assembly w a s accomplished by welding t o 1 9 circumferen-
t i a l b a n d s spaced a t 1 - i n . i n t e r v a l s . P r i o r t o welding, Teflon s t r i p s
were i n s e r t e d between t h e p l a t e s (shown i n F i g . 24.7) t o maintain spacing,
and grooves 3/8 i n . wide were machined on t h e o u t e r circumference where
t h e bands were t o be l o c a t e d . Each band w a s t h e n welded on one s i d e t o
t h e t r a i l i n g edge of each p l a t e , as shown i n F i g . 24.9. This method of
assembly r e s u l t e d i n t h e d i r e c t i o n of weld shrinkage being almost p a r a l -
l e l t o the plate. Thus t h e channel dimension between adjacent p l a t e s r e -
mained e s s e n t i a l l y unchanged during t h e welding o p e r a t i o n .
Comb spacers were a l s o welded t o each end of t h e t e s t element, as
shown i n Fig. 24.10. The t e e t h of t h e combs were 1/2 i n . long and were
wedged between each p l a t e t o r e i n f o r c e t h e channel spacing a t t h e water
i n l e t and e x i t .

466
Fig. 24.8. Close-up View o f P l u g Weld Attachment o f Fuel P l a t e s i n HFIR T e s t Element.

Fig. 24.9. View o f HFIR Test Element Showing Weldment of Circumferential Bands.

467
 8

Fig. 24.10. View of the H F I R Test Element Showing Weldment of End Spacer Combs.

An evaluation of 2880 measurements made on this element has been

presented. 2 2

Freparation of Aluminum-Corrosion Specimens

E. A. Franco-Ferreira

The fabrication of aluminum alloy water-corrosion-test specimens for e

the HFIR program was hindered by the excessive distortion created by con-
ventional tungsten-arc fusion welds. Electron-beam welding was suggested
as a substitute method, since the narrow weld width associated with this
process should significantly minimize distortion. Consultation services
were renderkd, and welds were made in an industrially owned machine. Ex-
cellent weld geometry and dimensional control were obtained, and a photo-
macrograph of a weld c r o s s section is shown in Fig. 24.11.
 F i g . 24.1 1. Photomacrograph of Electron-Beam Weld i n HFlR
Q Corrosion Specimen. Etchant: 10% HF. 30X.

Advanced Gas-Cooled Reactor Fuel Elements

Q R. L. Heestand
Interest has been expressed in fabricating advanced GCR-type fuel
elements containing an internal pressure of about 0.1 atm of helium in
order to extend the capsule lifetime and yet provide sufficient helium
to impart good heat-transfer characteristics. A method of fusion welding
was successfully developed at ORNL for welding in this reduced-pressure
An apparatus was con-
range and was designated as the Arvac process . 2 3
structed for investigating the welding variables as applied to sealing a
capsule.

23GCR
- Quar. Frog. Rep. June 30, 1960, ORNL-2964 (in press).
469
 PUBLICATIONS

Adams, R. E . , W. E . Berry, J . A. Milko, S. H . Paine, R . S. Peoples, and

H . A. Pray, "Thorium Alloys," Reactor Handbook ( e d . , C. R. Tipton,
J r . ) , 2nd e d . , vol I, p 227-47, Interscience, New York, 1960.
Allen, J . W . , "Eddy-Current Tube Tests," Nondestructive Testing Handbook
( e d . , R. C. McMaster), Sections 38.2338.39, The Ronald Press Company,
New York, 1959.
Borie, B., "A D i f f r a c t i o n Measurement of the S t r u c t u r e o f Cu20 Films Grown
on Copper," Acta C r y s t . - 13, 542 (1960).
Bridges, W. H . , and W. D. Manly, "Cobalt-Base Alloys," Reactor Handbook
(ed., C. R. Tipton, J r . ), 2nd ed., vol I, p 520-46, Interscience,
New York, 1960.
Carlsen, F. L., Jr., "Fueled Graphite Research a t the Oak Ridge National
e
Laboratory, I' Eighth High-Temperature Fuels Committee Meeting, December
2-3, 1959, Held a t Oak Ridge National Laboratory, Oak Ridge, Tennessee,
ORNL CF-60-2-1, p 149-52 ( c l a s s i f i e d ) .
e
-
Cathcart, J . V . , and G. P. Smith, "Oxidation Rates of K and Rb Between -79'C
and -2OoC, 'I J . Electrochem. SOC. 107(2 ) , 141-42 (1960) .
Cook, W. H . , Corrosion Resistance o f Various Ceramics and Cermets t o Liquid
Metals, ORN7L-2391 (May 31, 1960).
Cook. W. H . , "Materials f o r Valves and Bearings i n Molten Metals and Fused
il
S a l t s , Reactor Handbook (ed., C . R. Tipton, Jr. ), 2nd ed., vol I,
p 762-74, I n t e r s c i e n c e , New York, 1960.
Fulkerson, S. D . , Apparatus f o r Determining Linear Thermal Expansions of
Materials i n Vacuum o r Controlled Atmosphere, ORNL-2856 (Dee. 21, 1959).
Hamner, R . L., W. D. Manly, and W. H . Bridges, "Carbides and Cermets," Re-
a c t o r Handbook ( e d . , C . R. Tipton, Jr. ) , 2nd ed., vol I, p 502-19,In-
t e r s c i e n c e , New York, 1960.
Harris, L. A . , "The Crystal S t r u c t u r e of RbzThF6," Acta Cryst. -
1 3 ( 6 ) , 502 a
(1960) .
Harris, L. A., G. D. White, and R. E . Thoma, "X-Ray Analyses o f the S o l i d
Phases i n t h e System LiF-ThF4," J . Phys. Chem. - -
63(11), 1974 (1959).
Hoff'man, E . E . , The S o l u b i l i t y of Nitrogen and Oxygen i n Lithium and Methods
e
of Lithium P u r i f i c a t i o n , ORNL-2894 (Mar. 1, 1960).
Inouye, H . , and W. D. Manly, "Molybdenum and I t s Alloys," Reactor Handbook
(ed., C . R. Tipton, J r . ) , 2nd e d . , vol I, p 604-20, Interscience, New
York, 1960.
Jansen, D. H . , E . E . Hoff'man, and D . M. Shepherd, "Lead-Lithium Shielding
Alloy - Metallurgical Studies," J . Nuclear Materials 3, 249-58 (1959).
-
-
Kennedy, C. R . , and D . A. Douglas, Relaxation C h a r a c t e r i s t i c s of Inconel
a t Elevated Temperatures, ORNL-2407 (Jan. 29, 1960).
 L e i t t e n , C . F., J r . , "Evaluation of I r r a d i a t e d APPR Components, Eighth
High-Temperature Fuels Committee Meeting, December 2-3, 1959, Held
a t Oak Ridge National Laboratory, Oak Ridge, Tennessee, ORNL CF-60-
2-1, p 137-48 ( c l a s s i f i e d ) .
L e i t t e n , C . F., Jr., R. J . Beaver, and A. E . Richt, " S t a i n l e s s S t e e l Clad
Dispersion of Boron i n I r o n f o r P r e s s u r i z e d Water Reactors," J. Nu-
2, 13G44 (1959).
c l e a r Materials -
Lundy, T. S . , and E . E . Gross, An Evaluation of S o l i d Moderating M a t e r i a l s ,
O m - 2 8 9 1 (Apr. 11, 1960).
Manly, W. D . , and W. H . Bridges, "Nickel and I t s Alloys," Reactor Handbook
( e d . , C . R. Tipton, J r . ), 2nd ed., vol I, p 636-64, I n t e r s c i e n c e , New
York:, 1960.
Manly, W. D . , and J. H. Coobs, "Materials Development Program f o r t h e Gas-
Cooled Reactor P r o j e c t a t t h e Oak Ridge National Laboratory," G a s - -
Cooled Reactors, A Symposium Sponsored J o i n t l y by t h e Franklin I n s t i t u t e
and t h e American Nuclear Society, F r a n k l i n I n s t i t u t e Monograph No. 7,
p 15Cl-67 (May, 1 9 6 0 ) .
Manly, W. D . , J . H . Coobs, J . H. DeVan, D. A. Douglas, H . Inouye, P. P a t -
r i a r c a , T. K. Roche, and J . L . S c o t t , "Metallurgical Problems i n Molten
Fluori.de Systems, Progr. i n Nuclear Energy. Ser. I V - 2, 164-79 (1960).
McClung, E:. W., "The Immersed U l t r a s o n i c Inspection of Metal P l a t e , " J . Non-
-
d e s t r u c t i v e Testing 17(5), 27C-75 (1959) .
McClung, R . W . , "Ultrasonic Immersion Test I n d i c a t i o n s , " Nondestructive
Testing Handbook, ( e d . , R . C . McMaster), See 47.26-47.39, Ronald
P r e s s , New York, 1959.
McHargue, C . J . , L. K. J e t t e r , and J . C. Ogle, "Preferred O r i e n t a t i o n i n
Extruded Aluminum Rod," Trans. Met, SOC. AIME 215(5), 831 (1959). -
-
McHargue, C . J . , and L. K. J e t t e r , 'lUse of Axis D i s t r i b u t i o n Charts t o Rep-
r e s e n t Sheet Textures," Trans. Met. SOC. AIME a,
550 (1960).
Picklesirner, M. L., D. L. McElroy, T. M. Kegley, E . E . Stansbury, and J . H .
.,
Frye, Jr "Effect of Manganese on t h e A u s t e n i t e - P e a r l i t e Transfor-
-
-
mation, 'I Trans. Met. SOC. AIME 218, 473 (1960).
Slaughter, G. M . , W. D. Manly, W. H . Bridges, K. F. Smith, and J . R . Keeler,
"Special Purpose Alloys, I t Reactor Handbook ( e d . , C . R. Tipton, J r . ) ,
2nd ed.., vol I, p 739-61, I n t e r s c i e n c e , New York, 1960.
Slaughter, G. M., P. P a t r i a r c a , and R. E . Clausing, "Welding of Nickel-
Molybdenum Alloys, '' Welding J . 38(10),393-s-400-s (1959).
-
Smith, G. P . , and C . R. Boston, "Absorption Spectra of Fused-Salt Solu-
-
t i o n s , " Ann. N.Y. Acad. S e i . 79(11), 930-40 (1960).
,
Smith, G. ?. book review of K i n e t i c s of High-Temperature Processes ( e d . ,
W, D . ICingery), J. E l e -c t
-r o c
Swindeman, R. W . , and D . A. Douglas, t h p r o v e m e n t of t h e High-Temperature
Strength P r o p e r t i e s of Reactor M a t e r i a l s A f t e r F a b r i c a t i o n , 'I J. Nu-
c l e a r M a t e r i a l s 1,49-57 (1959).
-

471

a
1

Thurber, W. C . , and C . J . McHargue, "Deformation T e x t u r e s i n Aluminum-Ura-

-
-
nium A l l o y s , " Trans. M e t . SOC. AIME 218, 141 (1960). Q
Thurber, W. C . , and R. J . Beaver, D i s p e r s i o n s of Uranium Carbides i n A l u m i -
num Plate-Type Research Reactor F u e l Elements, ORNL-2618 (Nov. 5, 1959).
Thurber, W. C . , and R. J. Beaver, " D i s p e r s i o n s of Uranium Carbides i n Alumi-
num f o r Plate-Type Fuel Elements Requiring High-Uranium C o n c e n t r a t i o n s , "
J. Nuclear M a t e r i a l s 2, 226-32 (1959).
-
Weir, J . R., A F a i l u r e A n a l y s i s f o r t h e Low-Temperature Performance of D i s -
p e r s i o n F u e l Elements, ORNL-2902 (May 27, 1960).
W i l l i a m s , R. O . , "Aging o f Nickel Base Aluminum A l l o y s , " Trans. Met. SOC.
--
AIME 215, 102632 (1959).
-
Yakel, H . L . , J r . , D . E . LaValle, R . M. S t e e l e , and M. K. Wilkinson, "The
P r e p a r a t i o n and Crystal S t r u c t u r e o f Molybdenum( 111) F l u o r i d e , J . Am. Qy
Chem. Soc. 82, 243334 (1960).
-
e

e
PAPERS PFESEN'IXD AT SCIENTIFIC AND TECHNICAL MEETINGS

Allen, J . W., and E . Roffman, "Electromagnetic T e s t i n g Techniques," T h i r d

I n t e r n a t i o n a l Conference on N o n d e s t r u c t i v e T e s t i n g , Osaka, Japan,
March 21, 1960, and May Meeting of S o u t h e a s t e r n S e c t i o n of t h e S o c i e t y
. f o r N o n d e s t m c t i v e T e s t i n g , A t l a n t a , G a . , May 2, 1960.

Borie, B., "An X-Ray D i f f r a c t i o n Technique f o r t h e Study of Thin Oxide Films

Grown on Metals," Meeting o f American C r y s t a l l o g r a p h i c A s s o c i a t i o n ,
Washington, D . C . , J a n . 25-27, 1960.
Boston, C . R . , and G. P. Smith, " V i s i b l e Absorption S p e c t r a o f Molten B i -
B i C 1 3 S o l u t i o n , " 137th American Chemical S o c i e t y Meeting, Cleveland,
Ohio, Apr. 11-14, 1960.
C a r l s e n , F. L . , J r . , "Fueled G r a p h i t e Research a t t h e Oak Ridge N a t i o n a l Q
L a b o r a t o r y , " E i g h t h High-Temperature F u e l s Committee Meeting, Oak
Ridge N a t i o n a l Laboratory, Dee. 2-3, 1959.
C a t h c a r t , J . V., "Oxidation of M e t a l s and t h e E f f e c t of R a d i a t i o n , " U.S./U.K.
C o m p a t i b i l i t y Meeting, Oak Ridge N a t i o n a l Laboratory, Oak Ridge, Tenn.,
Feb. 24-26, 1960.
e
C a t h c a r t , J . V., "$e Formation o f Oxide Films on Niobium," Hudson-Mohawk
Chapter of AIME, Columbium Symposium, H o t e l Sagamore, Lake George, N.Y.,
June 9-10, 1960.
Coobs, J . H . , "Research on Fuel M a t e r i a l s f o r t h e GCR," Ninth High-Tempera-
t u r e F u e l s Committee Meeting, Savannah R i v e r Laboratory, Aiken, S.C.,
Apr. 19-20, 1960.
.
Cunningham, J E . , "Re sum& of Aluminum-Base Fuel Element Development Work
a t ORNL," Aluminum Task Force Meeting, Savannah River Laboratory,
Aiken, S.C., May 25, 1960.

4 72

e
 Cunningham, J . E., "Plate-Type Fuel. Element Development, Ninth High-Tem-
is p e r a t u r e F u e l s Committee Meeting, Savannah River Laboratory, Aiken,
S.C., Apr. 19-20, 1960.
DeVan, J . H . , "Reactions of Reactor Materials w i t h Contaminants Outgassed
from Graphite," U.S./U.K. C o m p a t i b i l i t y Meeting, Oak Ridge N a t i o n a l
Laboratory, Oak Ridge, Tenn., Feb. 24-26, 1960.
DeVan, J . H . , "Corrosion of Metals by High-Temperature Fused-Salt Mix-
t u r e s , " Mechanisms of Corrosion Seminar, sponsored by Chicago-Western
Chapter of American S o c i e t y f o r Metals, Apr. 14, 1960.
Douglas, D . A . , "Materials Research on Cladding f o r a Gas-Cooled Fuel Ele-
ment," Fuel Element F a b r i c a t i o n Symposium, Vienna, A u s t r i a , May 10-13,
1960.
Fulkerson, S. D . , "New Equipment f o r Thermal Conductivity S t u d i e s , South-
e a s t e r n S e c t i o n of American Ceramic S o c i e t y , Gatlinburg, Tenn., June
3&July 2, 1960.
Hamner, R . L . , and L. A. Harris, "The C a l c i n a t i o n of Beryllium Oxalate T r i -
h y d r a t e t o Beryllium Oxide," Annual Meeting of t h e American Ceramic
S o c i e t y , P h i l a d e l p h i a , P a . , Apr. 24-28, 1960.
Hikido, T . , and G. J . Nessle, 'yttrium P r e p a r a t i o n Research," N a t i o n a l
Metals Congress, Chicago, I l l . , Nov. 3, 1959.
Hoffman, E . E . , "The S o l u b i l i t y o f Nitrogen and Oxygen i n Lithium and
Methods of Lithium P u r i f i c a t i o n , I' American S o c i e t y f o r T e s t i n g Ma-
t e r i a l s , T h i r d P a c i f i c Area National Meeting, San F r a n c i s c o , C a l i f . ,
Oct. 11-16, 1959.
Inouye, H . , "The Oxidation of Niobium a t Low-Oxygen P r e s s u r e , " Hudson-
Mohawk Chapter of AIME, Columbium Symposium, Hotel Sagamore, Lake
George, N.Y., June 9-10, 1960.
Kennedy, C. R . , and D . A. Douglas, "The Relaxation T e s t : A Rapid Method
f o r Obtaining Creep-Strength Data, I' 1959 Winter Meeting, American
Nuclear S o c i e t y , Washington, D . C . , Nov. 4-6, 1959.
Kennedy, C . R . , "Complex-Stress Fatigue T e s t i n g of Inconel a t 1500°F,"
Panel Discussion on Low-Cycle F a t i g u e , ASTM Annual Meeting, A t l a n t i c
C i t y , N . J . , June 29, 1960.
K e r r , J. M., "Uranium Monocarbide Research a t t h e Oak Ridge N a t i o n a l Labo-
r a t o r y , r' Second Uranium Carbide 'Conference, sponsored by AF,C, B c t t e l l e
Memorial I n s t i t u t e , Mar. 22-23, 1960.
,
Kneip, G. D . J r . , and J. 0. B e t t e r t o n , J r . , "Low-Temperature S p e c i f i c
Heats of t h e Group IVA Metals," American P h y s i c a l S o c i e t y Meeting,
Cleveland, Ohio, Nov. 27-28, 1959.
Lamartine, J . T . , and W. C. Thurber, " F a b r i c a t i o n o f U02-Bearing S t a i n l e s s
S t e e l Fuel Rods by Rotary Swaging," 1959 Winter Meeting of American
Nuclezr S o c i e t y , Washington, D . C . , Nov. 4-6, 1959.
L e i t t e n , C . F . , J r . , "Evaluation o f I r r a d i a t e d APPR Components, I' Eighth
High-Temperature Fuels Committee Meeting, Oak Ridge N a t i o n a l Labo-
r a t o r y , Dee. 2-3, 1959.

4 73
Manly, W. D . , and J . H . Coobs, " M a t e r i a l s Development Program f o r t h e Gas-
Cooled Reactor P r o j e c t a t t h e Oak Ridge N a t i o n a l Laboratory, " Gas-
Cooled Reactor Symposium, F r a n k l i n I n s t i t u t e , P h i l a d e l p h i a , P a . , Feb.
10-11, 1960.
McClung, R . W . , "Current Trends i n U l t r a s o n i c T e s t i n g i n t h e AEC Reactor
Program," Symposium on Nondestructive T e s t i n g , sponsored b y t h e D i -
v i s i o n of Reactor Development and t h e I n d u s t r y Development Branch of
t h e AEC, Washington, D.C., May 20, 1960.
McCoy, H . E . , and D . A. Douglas, " E f f e c t of Environment on t h e Creep Prop-
e r t i e s of Type 304 S t a i n l e s s S t e e l a t E l e v a t e d Temperatures," U.S./U.K.
C o m p a t i b i l i t y Meeting, Oak Ridge N a t i o n a l Laboratory, Oak Ridge, Tenn.,
Feb. 24-26, 1960.
McCoy, H. E . , "Effect of Various Gaseous Contaminants on t h e S t r e n g t h and
F o r m a b i l i t y of Niobium," Hudson-Mohawk Chapter of AIME, Columbium @
Symposium, Hotel Sagamore, Lake George, N.Y., June 9-10, 1960.
McElroy, D. L . , and J . F. P o t t s , J r . , "Basic S t u d i e s on Base-Metal Thermo-
couples," SAE Annual Meeting, New York, A p r i l 4-7, 1960.
Nance, R. A., J. W. Allen, and F. M. Glass, "An Electromagnetic Technique
e
and I n s t r u m e n t a t i o n f o r t h e I d e n t i f i c a t i o n of Metals and Alloys,"
S i x t h Annual Meeting of t h e American Nuclear S o c i e t y , Chicago, I l l . ,
June 12-15, 1960.
Overholser, L. G., "Studies of Gas E v o l u t i o n by G r a p h i t e , " U.S./U.K. Com-
p a t i b i l i t y Meeting, Oak Ridge N a t i o n a l Laboratory, Oak Ridge, Tenn.,
Feb, 24-26, 1960.
P a t r i a r c a , P . , G. M. S l a u g h t e r , and W. D. Manly, " F a b r i c a t i o n of Liquid-
Metal and Fused-Salt Heat Exchanger Components," 1959 Winter Meeting,
American Nuclear S o c i e t y , Washington, D . C ; , Nov. 4-6, 1959.
P o t t e r , R. A . , and L. A. H a r r i s , "Preliminary I n v e s t i g a t i o n of t h e System
C a O - B O , 'I Annual Meeting of American Ceramic S o c i e t y , P h i l a d e l p h i a ,
Penn., Apr. 24-28, 1960.
Rosenberg, A. J . , " E f f e c t s o f I m p u r i t i e s Outgassed from Graphite on Reactor
I1
M a t e r i a l s , 9 t h Annual AEC Corrosion Symposium, sponsored by Nuclear
Metals, I n c . , Boston, Mass., May 1G-12, 1960.
Schulze, R. C . , "Corrosion of Nickel-Base Alloys i n Contact w i t h Molten
F l u o r i d e S a l t s , " 9 t h Annual AEC Corrosion Symposium, sponsored by
Nuclear Metals, I n c . , Boston, Mass., May 10-12, 1960.
Smith, G. P . , " E l e c t r o s t a t i c P e r t u r b a t i o n of t h e Energy o f t h e Lowest
E l e c t r o n i c T r a n s i t i o n i n NO3-" and "Absorption Spectrum o f S o l u t i o n s
of Bismuth Metal i n Molten Bismuth T r i c h l o r i d e , " Gordon Research Con-
f e r e n c e on Molten S a l t s , Meriden, New Hampshire, S e p t . 2-3, 1959.
Weir, J . R . , "A F a i l u r e A n a l y s i s f o r t h e Low-Temperature Performance of
D i s p e r s i o n Fuel Elements," S i x t h Annual Meeting of American Nuclear
S o c i e t y , Chicago, I l l . , June 12-15, 1960.

e
. ... - ..
 METALLURGY DIVISION
AT
THE OAK RIDGE NATIONAL LABORATORY
J U L Y I , 1960

DIRECTOR J H. F R I E , JR
E. F. BYRUM, SEC
ASSOCIATE DIRECTOR W. 0. MANLY
L . M ROWL, SEC.
ASSISTANT DIRECTOR J. E. CUNNINGHAM
M. 0. WHITE. SLC.

BUILDING PLANNING COORDINATION ,

M R HILL
G 8. HARRIS
w 0 MASON
L M PYATT

I 1 I

I
F U N D U I E N T A L METALLURGY

8. 5. 0ORlL' I APPLIED RESEARCH

C.1. MCHARGUL'
I 1 REACTOR PROJECTS

P. PATRIARCA I I MATERIkLS PROPERTIES

0 A. DOUGLAS, JR ' I 1 METAL ANDCERAUIC

G. M. ADAMFN, JR.
FABRICATION

I
I

I
CRYSTAL PHYSICS

G. W. CLARK
C. 8. FINCH
1.L. BOSWLLL t P w s i c * L PROPERTIES

0 L MCELROI
T. G K O L L I E
R. S. GRAVES
-
I DIVISION SERVICES

I
I MSRP - HFlR - HRP
A. T A B O A D A
F W COOKE
W J. LEONARD
C H. WODTIE
C. M. SMITH, JR.
CORROSlON ENGlNEERlNG CERAMIC< LABORATORY
1
L M. DONEI
F. L. CARLSEN. JR.
A. 1. CHAPMAN
C. E. CURTIS
METALLOGRAPHY

R. 1. GRAY
W. J. SHOCKLEY
R. 5. CROUSE
E. L . LONG, JR.

t
W. S. ERNST, JR. W. H. BRIDGES
PROCUREMENT ANDMAINTENANCE
S D FULKERSON G HALLERMAN
I OEFORMATION O F CRYSTALLINE SOLIDS 1 R J STLERE
T.G GOOFREI, JR.
R L HAMNLR
D. M. HEWLTTL II
T M. KEGLEY, JR.
R B PRATT~ M . P HAYDON J R RIDDLE

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R 0 WILLIAMS T HIKIOOf
K . P BAYNL J M. D A L L E N JR '
E. VANCLEVE,
J A WHEELER, JR FUEL EVALUATION
J. S CORUM J M.KERR
C. E DUNN R.P. Y c N E L S L. A AMBURN. JR.
J. L. SCOTT
R E. MEADOWS N M. ATCHLEY
R. E. ADAMS
R h. POTTER E R BOYD
D. F TONER
J M ROBBINS 8. F. DAY

n
HlGn.TEMPERATURE REACTIONS R A. BOWMAN
4 . W SLIFERT W E DENNY
G. P. SMITH, JR A . b TAYLOR C H. K. DUBOSE
1. I. L U N D I
C. R. BOSTON I 0. R. CHILCOAT W H. FARMER
J I. FEDERER
J. J. MCBRIDE J. F. MURDOCK
R G CARDWELL, i R b. A. GRIFFIN J C-COWER
P. A. MARTIN F P JEFFLRS E. P. GRIGGS
R. A. PAOGETT. JR. MATERIALS COMPATIBILITY
,W. M. PARKS T. J. HENSON
J. H TERRY
I I E. E. HOFFMAN W. W PROAPS J T HOUSTON
W. H. COOK D E. ROSSUN E. n. LEE

1 MICROSTRESSES I N CRYSTALS I I SECRETARIAL STAFF I R. E. CLAUSING

1. P. GORDON
1. R. DlSTEFANO
D. H. JANSEN
W H. SMITH JR. 0. C. LESLIE
R J LOCKETT
ZIRCONIUM ALLOYS A P. LITMAN 8. J. REECE
J. L. GRIFFITH L G. SHRADLR
M. L. PICKLLSIMER J W HENORICKS 5. E. SPENCER
J. C. 0ANTER R E POTTER H R. TlNCH
S PETERSON L R TROTTER H L. WHITTINGTON
P. L. RITTENHOUSE R 1. BE6VER
W A L L REACTORS C. E. ZACHARY
R . L. STEPHENSON C. F T SOUROETTL
0. LEITTEN, JR.
P. J. JONES W. C. THURBLR
I REACTIONS A T M E T A L SURFACES I I I
1. H. CHERUBlNl

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J. H. ERWIN
MECHANICAL PROPERTIES T. HIKIDO'
1. V. CATHCART POSTIRRADIATION E X M I N A T I O N
W. J. KUCERA
G. F. PETERSEN LABORATORY
R. E. PAWEL J T. LAMARTINE
J. 1. CAMPBELL M. M. MARTIN A. R OLSEN.~
J. E. EPPERSON H. 1. WALLACE R. E. MCDONALD
G E. ANGEL 0. T JONES'
G . H. CALLAWAY J E. VANCLEVE, JR:
N H FLICKINGER C M. FITZPATRICK

I
J B FLINN 0. W. MCCOLLUM
J W GEER G. A. MOORE
STRUCTUREOFMETALS
G . D. GOLDSTON J. L. WILSON
C J. MCHARGUE' J N HIX
'MULTIPLE LISTING C. W HOLLAND, JR
J. C. OGLE
'REPLACED J w ALLEN. JR wi.m H. W HOOVER
2RAOIATION CONTROL OFFICER L OUEENER
L R. TURNBILL
'L AND M PROGRAM ENGR.

I THEORY OF ALLOYING
I 'ON LOAN FROM T V A
'ON LOAN FROMACFI

I I
J. 0. 0 L T l L R T O N . JR.
G. D KNEIP. JR.
'ON LOAN FROM M O A POWDER MCTALLLIRGI AND FUEL CYCLE
'ON LOAN FROM &EPS

I
0. I. EASTON
J. P
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'ONLOAN FROMREED J 'A. 0URKA
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I X-RAY DIFFRACTION I ADVISORY COW*ITTEE R. W. MCCLUNb
I(. V. COOK T D. WATTS

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i H KOENlG 0 E. FOSTER^ F. W. COFFLY

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H. L. YAKEL. JR WITH C. HAMBY, JR
R 4.NANCE
0. 0. CAVlN
L. A. HARRIS
R. SMOLUCHOISKI 0. E CONNER w. R JOHNSON
H. A. WILHELM R A CUNNINGHAM. JR M. A. WHEELER
R M STELLL
R L FITZGERALD
W J MASON

1 PHYSICAL METALLURGY
G M SL~UGHTLR
R G. OONNELLY
H INOUYE E A. FRANCOFERREIRA
D. 0 )HOBSON R G. GILLILAND
T K ROCHE R L HLESTAND
W J WERNER J '1 PRISLINGER
J W BARNETT J. W. TACKETT
J F NLWSOME L. G. BRYSON
1. E POPE 1. D HUDSON
R G. SHWSTER
L. C. WlLLlPMS
'I 1. WOODHOUSE. JR

I
 Reports p r e v i o u s l y i s s u e d i n t h i s s e r i e s a r e as follows:

ORNL28 Period Ending March 1, 1948

ORNL- 69 Period Ending May 31, 1948
ORNL-407 Period Ending J u l y 31, 1949
O R N L 511 Period Ending October 31, 1949
ORNL- 5 83 Period Ending January 31, 1950
ORNL- 754 Period Ending A p r i l 30, 1950
ORNL- 827 Period Ending J u l y 31, 1950
ORNL- 910 Period Ending October 31, 1950
ORNL- 987 Period Ending January 31, 1951
ORN L-1033 Period Ending A p r i l 30, 1951
ORNL-1108 Period Ending J u l y 31, 1951
ORNL-1161 Period Ending October 31, 1951
ORNL- 1267 Period Ending January 31, 1952
O R N L 1302 Period Ending A p r i l 30, 1952
ORNL-1366 Period Ending J u l y 31, 1952
ORNL- 1437 Period Ending October 31, 1952
ORNL- 1503 Period Ending January 31, 1953
ORNL-1551 Period Ending A p r i l 10, 1953
ORNL- 1625 Period Ending October. 10, 1953
ORNL-1727 Period Ending A p r i l 10, 1954
ORNL- 1875 Period Ending October 10, 1954
ORNL-1911 Period Ending A p r i l 10, 1955
ORNL- 1 988 Period Ending October 10, 1955
ORNL- 2080 Period Ending A p r i l 10, 1956
ORNL-2217 Period Ending October 10, 1956
ORNL- 2422 Period Ending October 10, 1957
ORN L- 2 632 Period Ending October 10, 1958
ORNL-2839 Period Ending September 1, 1959

476