i

FE-NI PHASE DIAGRAM

BY
J. 1. GOLDSTEIN
R. E. OGILVIE
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, ff 653 July 65

MARCH 1965
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Fe-Ni Phase Diagram

T
u.
-
I.
r
Guidstein

and

R. E. Ogilvie

ABSTRACT

The CY and y s o l u b i l i t y limits i n the Fe-Ni phase diagram have

been redetermined a t temperatures above 5 0 0 O C . Both a diff'usion

couple and a quench-and-annea technique were used. The s o l u b i l i t y

l i m i t s were measured with an electron probe microanalyzer.

The Ni concentration a t the y/or+y phase boundary i s increased

below 700°C and t h e 01 solid s o l u b i l i t y range is much l a r g e r than

had been previously measured. The s o l u b i l i t y l i m i t s were a l s o

extrapolated t o 30OoC. It is suggested that the boundary bends

back t o lower N i contents above 4OO0C.

J. I. Goldstein, Junior Member A m , Metallurgist, Theoretical Division,

NASA - Goddard Space F l i g h t Ceot.er.

R. E . Ogilvie, Associate PTofessor, Metallurgy Department, Massachusetts

I n s t i t u t e of Technology.
 ~ ~~~~

0
0

Tile eqQilibrium diagram has been of g r e a t use i n the f i e l d of .

meteoritics, where the Thase relatinnn hewee2 &rzcltue I-u
\ --=
. \ / auu

t a e n i t e (y) i n metallic meteorites can be described by means of the

Fe-Ni diagram. The study of metallic meteorites by electron probe

microanalysis has c a s t some doubt on the accuracy of t h e presently

a v a i l a b l e Fe-Ni dia@;ramslJ2. Recent thermodynamic s t u d i e s of the

Fe-Ni system a l s o suggest t h a t the diagram may be i n e r r o r 3 . For

these reasons the high temperature (800-500%) p a r t of the diagram

w a s redetermined.

~ODWCTION

The currently accepted Fe-Ni diagraa i s t h a t of Owen and Liu4 (Figure

1) Above 910°C, there i s a region of complete s o l i d s o l u b i l i t y , y ( f c c ) .

Below 910°C, the CY (bcc) phase i s stable i n pure Fe. The e f f e c t of

increasing amounts of N i i s t o s t a b i l i z e the y phase. The phases that

form when Fe-Ni a l l o y s a r e heated o r cooled bear l i t t l e r e l a t i o n t o the

equilibrium diagram. If an alloy i s cooled from the y s t a t e and held a t

a temperature within the Q+ f i e l d , no evidence has been found f o r the

oecurence of the ~3transf~rnation.5 If t h e a l l o y i s cooled t o low

I .
enough temperatures the y phase breaks down i n t o a supersaturated bcc

phase c a l l e d cy2. I n f a c t , i n alloys over 27$ N i the y phase i s r e t a i n e d

L. .
a t room temperature.' Tne a2 phase has the same composition as the o r i g i n a l

yo The temperature a t which a2 forms, the M, temperature, has been

determined experimentally. 7

A s t a t e of equilibrium can be approached by cooling below Ms t o

form a2 and then reheating the a l l o y i n t o t h e two phase region of the

diagram. The y phase w i l l then begin t o p r e c i p i t a t e out of the a2 phase

and grow. The growth of the phase, however, i s q u i t e slaw. Using t h e

 #

- 2 -
4

interdiffusion coefficients 8 of Goldstein, et al.8, it is estimated that

cy
it takes about 1 year to grow a 10 micron wide region of Y at 700°C in

a 5$ Ni alloy.

Owen and Liu4 used the technique just described to form the equilibrium

phases. The phases present were determined by means of X-ray analysis.

Thc a c x r a c y of? their diagram depends on the number of alloys available

near the phase boundary at a Given tenipaature.

In this study two different techniques were used to determine the

~ / o l + y and y / o j y solubility limits. The inherent accuracy of both

techniques was greatly improved over that used by previous investigators

because the phase boundary compositions were measured with an electron-

prabe microanalyzer.

PROCEDURE

The two methods used to determine the Fe-Ni diagram are the diffusion

coGple (D.2.) and the quench-and-anneal (Q. + A.) techniques. In the

firs% method, diffusion couples whose diffusion path goes through a two
phase region of the phase diagram were used. A description of the

techniqGe used for miking the diffusion couples has been described in a
previous paper o8 After the diffusion treatment a discontinuity in the
resultant concentration versus distance profile was measured. The Ni
corieentrations in the n agd y phases at the interface of the discontinuity

are the solubility limits of the CY and y phases in the phase diagram at

the diffusion temperature, If the interface compositions can be resolved

by the probe, then the phase diagram can be determined.g In the Fe-Ni

system, it is possible to determine the cy/(ysy and the y/orty s o l i d solubilities

by this method down to 500%.
. * *
- 3 -

I n the second method, a n a133y i s f i r s t cooled from the y phase

t o ro3m temperature %-herecy2 i s formed. Then the a l l o y is a,iiiiscLcZ

the two phase region of the phase diagramwhere the y phase p r e c i p i t a t e s

and grows. If the r e s u l t a n t y phase i s of s u f f i c i e n t s i z e (>5p), its

composition and the i n t e r f a c e composition of the cy phase can be measured

with the e l e c t r o n probe. These compositions a r e , therefore, the phase

boundary compositions of the equilibrium diagram. Figure 2 shows an

example of a two phase a l l o y a f t e r the annealing treatment. Nucleation

of y appears t o occur a t the grain boucdaries.

The annealing temperatures, annealing times, and the a l l o y s used

f o r lsoth techniques a r e l i s t e d i n Tables I and 11. The 8oo0c diffusion

couple was amealed i n a high temperature furnace a t a vacuum of b e t t e r

than lQ-? am Hg. The other diffusion couples a s well as the quenched

alloys were sealed i n vycor tubes under a vacuum of mm Hg and annealed

i n tube furnaces. Tke temperature control i n both types of furnaces was

b e t t e r than +- 2OC a t temperature.

Before electron-probe microanalysis, these specimens were c a r e f u l l y

polished through p diamond paste. Special care was used s o t h a t there

were no apparent height differences between the Q and y phases. Areas of

i n t e r e s t were i d e n t i f i e d with microhardness marks.

An ARL (Applied Research Laboratories) electron-beam microanalyzer

w a s used t c measure the composition gradients. A l l data were taken a t

3 0 %w
~i i i i ti spzcL-mxi e n r e n t between ,035 and .O5 microamps. Both the

NiK and the FeK r a d i a t i o n were measured. The Fe-Ni c a l i b r a t i o n curve

CY CY
was determined with 9 Fe-Ni alloys and has already been described.8 The

c a l c u l a t i o n of composition from measured X-ray data, was g r e a t l y simplified

 0

b ' e
-4-
6

by using the algebraic function Aab developed by Ziebold and OgilvielO.

This function f i t s the e n t i r e experimental c a l i b r a t i o n curve by means

of a single conversion parameter. The r e l a t i o n between t h e measured

1

i n t e n s i t y r a t i o KA and composition CA f o r a binary system i s

where KA = I/Io)Aof element A,

CA = atomic per cent of element A .

For the Fe-Ni system a t 3Okv and f o r a take-off angle, 8 = 52.5O; Aab = 1.158

for the N i and Aba = ,847 f o r the Fe i n t e n s i t y curves. The accuracy of

measurement obtained by t h i s technique was b e t t e r than 1% ( r e l . ) .

I n both the diffusion couples and the quenched and annealed a l l o y s

t h e a r e a s of i n t e r e s t were f i r s t analyzed q u a l i t a t i v e l y with the probe

using r a t e meter scans. After a t l e a s t 3 areas were selected as representative,

quantitative measurements using fixed t i m e counting were taken of these

a ,
areas. The data were compared with standards of the pure elements and

several other a l l o y s both before and ai'tcr each run. The conversion of . a

X-ray in'censity t o composition was accoinplished with the use of Equation 1.

The whole conversion process w a s programmed and run on the IBM-7094 computer.
pasuL'1's

Figure 3 shows the composition versus distance curves determined

i'rm the diffusion couple technique and t h e quench and anneal technique

a t 70OoC. The compatability 01the two methods i s shown by the excellent

 - 5 -

~ g r p e ~ nf
~ cthp
t m l . i ~ . ~nf
s CCY' /C(;Y . The data obtained from both techniques

a r e summrized i n Table I11 along with the measured values of the Fe-Ni
diagram by Owen and Liu4 .
The new phase diagram proposed from t h e r e s u l t s of t h i s work i s

shown i n Figure 4, The a s o l i d s o l u b i l i t y range i s g r e a t l y extended a t

high temperatures. The a and Y solid s o l u b i l i t y l i n e s a r e extrapolated

below 500°C and a m a x i m N i content of approximately 7 At$ N i i s

predicted i n the CY phase a t about 45OoC. The b a s i s f o r the extrapolation

w i l l be discussed l a t e r .

D ISCLTSSION

The e r r o r s inherent i n the diffusion couple technique and t h e quench

and anneal technique a r e much smaller than those of the X-ray technique

used by Owen and Liu. The measurement e r r o r s given i n Table I11 r e f l e c t

not 'ihe accuracy of probe measurement, 1% r e l . , b u t the reproducibility

of t h e measured s o l u b i l i t y l i m i t s from one area t o another i n a given

sample. Not only a r e the measurement e r r o r s s m a l l b u t the r e s u l t s of t h e

two tedmiques are compatible for the same temperature. Measurements

by Winchell'' of CCY/CCY+Cy a t 7OO0C a l s o indicate t h a t considerably more

n i c k e l i s soluble i n alpha-iron-nickel a l l o y s than indicated by the

presently accepted diagram.

The uncertainty i n the determination of the Gwen and Liu diagram

cannot be a t t r i b u t e d t o any lack of s e n s i t i v i t y i n the X-ray method used.

The uncertainty i s due t o the difference i n N i content between the two

a l l o y s which bracket t h e s o l u b i l i t y limits of the 0 or y phase. For

example, i n determining the a/* boundary, one a l l o y i s found t o be a

mixture of orb( and t h e other alloy i s a11 CY phase. The boundmy l i e s

 t
a

- 6 -

betvecn these 'cwo l i m i t s , and the uncertainty i s the composition difference

betwden the alloys. Figure 5 shows a comparison of the new diagram and

the Owen and Liu diagram. The u n c e r t a i n t i e s i n the determination of both

f

t h e phase boundaries i s a l s o shown. The r e s u l t s of t h i s study f a l l with

thz experimental l i m i t s of Oren and L i u ' s work a t a l l temperatures

except a t 700Oc.

According t o Owen and Liu's paper: I' . . . the phase boundaries

determined by t h i s method of surveying s t r u c t u r e spectra w i l l need

adjustment not exceeding 0.5 At$, the Y phase boundary having a s l i g h t l y

l a r g e r N i content, and the phase boundary having a s l i g h t l y higher

i r o n content .. This statement i s i n agreement with our findings on the

Y! phase boundary and the extrapolated CY phase boundary below 50OoC.

The diagram below 500°C was not determined i n t h i s study because the

composition gradients obtained could not be resolved by the electron

probe, even i f the a l l o y s were annealed f o r periods of more than 1 year.

Atterapts have been made by other workers t o obtain the s o l u b i l i t y l i m i t s

01P ard Y below 500°@. Theoretical calculations have been made by Jones

sild P u ~ ~ p h r eand
y ~ Kaufman and Cohen7. Jones and Pumphrey calculated the ...
.I/-* boundary by assuming [If'-y ( bhe difrerence between the heats of

soluLion of N i i n N and y iron) iiidepcndent of temperature aid composition.

"I'iicy Yound t h a t the a/c/+v boundary had a m a x i m u m N i content a t 4000C and bent

back t o s ~ ~ a l l amounts
cr or ITi coilLent a t lower temperatures. This

calculation has been c r i t i c i z e d by Kaufrflan and Cohen who s t a t e t h a t it

16 uivarrenzcd t o assume i s completely independent of temperature

arid wi.iposition. Kaufman and Cohen calculated t h a t t h e bending back of

0
thc c//c+Ir' boundary occured at, about 130 C . This c a l c u l a t i o n w a s based on
Iii? a s e u p t i o n s t h a t the y s o l i d s o l u t i o n was r e g u l a r and t k a t the Owen
and Liu diagram gave the correct solubilit,y l i m i t s above 35O0C.
7-0
I~Zulic: ~ S U I I I ~ &ai
~ <ne bcc (), solution i s i d e a l a t the high i r o n

side of the phase diagram, and that the f c c ( y ) solution i s a regular

s o l i d solution then from equation (13) of Kaufman and Cohen, 7

where: ~,FF~ = f r e e energy differences between CY and y phases

C,, C = solubility l i m i t s in CY and y

Y
E = a f'unction of the heat of mixing HM,
Using recent calculations of b,HFe- and the measured values of

C,, and C from t h i s trorlc, the above r e l a t i o n s h i p can be used t o c a l c u l a t e

Y
0
B as a function of temperature t o 500 C .

Using the values of B above 5OO0C, an extrapolation of B t o a

0
temperature a s low as 350 C can be made. Using Equation 2 and the

extrapolated values of B and C we found t h a t the m a x i m N i s o l u b i l i t y

Y'
i n a occurs a t 45O0C. The calculation of Cw i s strongly dependent on

the extrapolated value of B. Because of t h i s , the calculated values of

C below 500°C may be i n error by approximately +, 1 At$ N i . The calculated

CY

values of do however generally follow t h e extrapolated a s o l u b i l i t y

curve shown i n Figure 4.

Various attempts13,14
have been made t o produce Fe-Ni a l l o y s i n a

s t a t e of equilibrium a t low temperatures by the preparation of f i n e

p a r t i c l e s of a l l o y s from the reduction of a s a l t . I n a study of Fe-Ni

phase transformations by Kachi, e t al.,

14 f i n e p a r t i c l e s of Fe-Ni a l l o y s

were obtained by reduction of Fe-Ni oxalates i n hydrogen a t various

 - 8 -

temperatures ranging from 350 t o 6oo0c i n l e s s than 25 hours. The amounts

of the Q and y phases i n the specimens were measured by X-ray d i f f r a c t i o n .

The r e s u l t s of these studies show an increase i n the s o l u b i l i t y l i m i t

of the CL phase down t o 350°C. The speed a t which equilibrium i s said t o

occur does not allow any growth of cy o r y phase by d i f f u s i o n processes.

Because of the small p a r t i c l e s s i z e s used (411) the surface energy may

influence the f i n a l equilibrium composition of the cy and y phases.

Therefore the reported s o l u b i l i t y l i m i t s may not be representative of

equilibrium i n bulk a l l o y s .

Owen and Liu s t a t e t h a t t h e i r measurements indicate t h a t the CL/CYS~

boundary l i e s between 5.8 and 6.9 At$ N i a t 35OoC and between 4.8 and 7.5

At$ N i a t 30OoC. Therefore, since t h e o r e t i c a l calculations show t h a t the

~ / o r t y boundary w i l l bend back t o lower N i contents a t some temperature

0
below 500 C and the uncertainty of Owen and L i u ' s diagram be1.m hOO°C,

it was rcasoiiable t o suggest, as did Owen and Sully15, that the w/or+v

boundary bends back t o lower N i contents above 40OoC. The a c t u a l phase

diagram below 5OO0C, however, i s s t i l l i n doubt.

CONCLUSIONS

The CY and y s o l u b i l i t y limits i n t h e Fe-Ni phase diagram have been

redetermined a t temperatures above 50OoC. It was found t h a t with r e s p e c t

t o the Owen and Liu diagram;

(1) The N i concentration a t t h e y / ~ s yboundary below 700°C

i s increased.

( 2 ) The cy s o l i d s o l u b i l i t y range i s much l a r g e r above 50O0C.

(3) The cr/orty boundary probably bends back t o lower N i contents

above 4OO0C.
 - 9 -

Acaim-m
The authors wish to thank the Smithsonian Astrophysical Observatory

f o r their financial support and f o r the use of their facilities, and

the M.I.T. Computation Center for time 011 the I B M 7094 computer. The

authors would also like t o thank Dr. L. Kaufman f o r his comments and

suggestions,
 - 10 -

REFERENCES

'S. 0. A g r e l l , J . V . P. Long and R. E . Ogilvie: Nature, 1963,

V O ~ . 158, p . 749.
2Jj I e Goldstein: "Electron Microbeam Probe Studies of Metallic

Meteorites," 1962, M. S. Thesis, Massachusetts I n s t i t u t e of Technology.

3J. H. Smith, H. W. Paxton and C. L . McCabe: Trans. A m , 1964,

V O ~ .230, p. lb184.

h aA . Owen and Y . H. Liu: J. Iron and S t e e l I n s t . , 1949, v o l . 163,

p. 132.

'Ne P. Allen and C . C . Earley: J . Iron and S t e e l I n s t . , 1950, v o l . 166,

p a 281.
6F . W. Jones and W . I . Pumphrey: J . Iron and S t e e l I n s t . , 1949,

V O ~ 166, p. 121.
'Le Kaufman and M. Cohen, Trans. AIME: 1956, v o l . 206, p . 1393.
'J- I . Goldstein, R . E . Hanneman, and R . E . Ogilvie - t o be published

Trans AD@, vol. 233.

9R, E . Ogilvie : ScD Thesis, 1955, Massachusetts Ins-Litute of Technology.

l 0 T . 0 . Ziebold and R . E . Ogilvie: Anal. Chem., 1964, v o l . 36,

p. 322.

"PI S*Jinchell: m d u e University, Lafayet'ce, Indiana, private

c omun-i?ation.

12L Kaafrnan, E . V . Clougherty, and R . J . Weiss: Acta. Met., 1963,

v o l . 11, p. 323.

13F. Lihl : Arch. Eisenhut'i , 1954 v o l . 25, p . 475.

l L L S Kachi, Y e Bando, and Higuchi:
S. Jap. Journal of Applied

Physics, 1962, v o l . 1, p . 307.

15EaA . Owen and A . H . Sully: P h i l . Mag., 1939, vel. 27, p. 61-11.

 Alloys f o r ?hcse Boundary Determinations

Tcm?c-zture ( ) Technique Alloys Annea;;;EITime

(Composition,At$ N i )

800 D.C. 0-25.2 2. 68x106

6.05~105
720 Q+A 5.2

D.C. 0-15.2 4.85~10

6
700

5.2
4.8 5x106
700

600 0-io0 1.60~10

7

500 0-100 5.2 5x107

D.C. Diffusion Couple Technique

Q+A Guench m d Anneal Technique

TABU I1

Chemical Analysis of Fe-Ni Alloys (wt$)

* iG $2
-
N
PPm -
H
PPm
-
Fe

<o. 004 <o. 01 0.02 10 <o* 5 Remaining

5.17k. 02 <o. 01 0.02 4 0 <o. 5 I1

15.17k. 03 <o. 01 0.02 <10 <o. 5 11

I1
2 5 . 1 8 ~05 0.006 0.02 4 <LO
Remaining 0.001 .006 3 5 5PPm
 I

Conposition Limits of the a+y Phases in the Fe-Ni. System at 1 A t m .

Temp. (OC) a Solubility (At$) y S o l u b i l i t y (At$)

2,aWwe C Techriique C
Q Y
(hen + Liu) (Owen + Liu
D.C. , 1.25 D. C. 3.8
&+A 2.246 Q+A 8.2

D.C. .2*5$ 9.4

Q+A 2.58 .QtA ’ 9.4
D. C. 3.8 D. C. 07.3
D. C. 5.4 D.C. 27.5

. .

II

.,,
 Figure Captions

Figure 1 - Fe-Nf Phase D i a g r a m , Owen and Liu.

Figxxe 2 - 5.2$ N i Alloy Annealed a t 7OO0C. Two phases - cy and y.

590X, Etchant - 2$ N i t a l .

Figure 3 - Determination of the 01 and y S o l u b i l i t i e s ic t h e Fe-Ni System

a t 7OO0C (Two Methods) .

Figure 4- Fe-Ni Phase Diagram, Goldstein and Ogilvie.

Figure 5 - Comparison of Fe-Ni Phase Diagrams.

 In
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N

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0 0 0
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