Journal of the Less-Common Metals

91
Elsevier Sequoia S.A., Lausanne - Printed in the Netherlands

THE EFFECT OF COOLING RATE ON THE ,!-a TRANSFORMATION IN

THE ZIRCONIUM/z at.:/, CHROMIUM/O.IG at.():6 IRON ALLOY

G. F. SLATTERY
U.K.A.E.A., Reactor Group, Reactor Fuel Element Laboratories, Springfields Wovks., Salwick,
Lams. (Gt. Britain)
(Received May 17th. 1968)

SUI\IMARY

The ,&a transformation in the zirconium/z at. y/bchromium/o.16 at. y(, iron alloy
shows two distinct temperature plateaux. The higher plateau at 760°C is likely to be
non-martensitic, whilst the lower plateau at 705°C is probably martensitic and repre-
sents the true MS temperature for this alloy. The separation between the two trans-
formations is in the region of 17oo”C/sec cooling rate and beyond this critical cooling
rate, the MS temperature is independent of cooling rate up to 45oo”C/sec. Quench
hardening takes place and an increase of 130 V.H. units is obtained with increase in
cooling rate.
The microstructures varied with cooling rate. At intermediate cooling rates,
the structure consisted of a coarse Widmanstatten product which changed to a fine,
acicular product with increase in cooling rate. The intermetallic phase, presumably
ZrCrz associated with a very low iron concentration, acted as a nucleus for the shear
needles of 01’. There were no surface rumpling effects due to quenching out the
martensitic structure but this may be explained by a shape change for the c.p.h.-b.c.c.
transformation which involves only small, or adjacent and opposite displacements.

INTRODUCTION

The zirconium/z at.% chromium/o.16 at. (?b iron alloy was developed at the
General Electric Company, U.S.A., by KLEPFER~ as a potential cladding alloy for
water-cooled nuclear reactors because of its good corrosion resistance, low hydrogen
absorption, and low hydrogen embrittlement in a boiling water/steam environment
between 300~ and 500°C. This alloy is intended to extend the temperature range fixed
by the wide usage of Zircaloy 2 and 4 as cladding alloys, since these are extremely
limited in their usefulness at these elevated temperatures due to excessive corrosion
and hydrogen contamination.
The ideal nuclear cladding should combine a high corrosion resistance with
good mechanical properties at these temperatures. Heat-treatment can sometimes be
used to strengthen the alloy provided its resistance to corrosion does not suffer, e.g.,

J. Less-Common Metals, 16 (1968) gI-ror

92 G. F. SLATTERY

zirconium/zi”/o niobium alloy is approximately 5094 stronger than cold-worked

Zircaloy-2 after a quenching and ageing treatmenta, although its corrosion resistance
may not be adequate at 450°C. The Zr/2 at.% Cr/o.r6 at.% Fe alloy appears to have
similar heat-treatment characteristics to the Zr/2*s& Nb alloy since quenching from
the ,!J-Zr phase produces a shear-type ,!l + 01’transformation, and it appears reasonable
to expect that this, combined with an age-hardening mechanism, should result in an
increase in strength.
The aim of this in~~estigation was to study the quenching characteristics of the
Zr/2 at.% Cr/o.xG at.% Fe alloy from the @Zr phase region using the technique of
high-speed thermal analysis by gas quenching, and in particular to study the effect of
increasing cooling rate on the MS temperature and the structure of the transformed ix
products. This study is analogous to that previously carried out on the Zrjz+c(, Nb
alloy a.

PREVIOUSWORK

STEWART, HATT ANDROBERT+ reported a lowering of the MS temperature for

the Zr/3 at. y0 Nb alloy from 750” to 695°C with increasing cooling rate from IOOO’to
3ooo”C/sec. A depression in transformation temperature from 750°C was also observed
by the present author for the Zr/2&% Nb alloy at cooling rates between 600” and 700’
C/seca. If this transformation temperature of 750°C represents the true MS for these
alloys, then these findings tend to conflict with the accepted ideas on martensitic
formation which require the MS to remain independent of cooling rate.
MCMULLENANDPARR’S results5 showed that for dilute Zr/Nb alloys containing
up to 3% Nb the transformation temperature decreased initially with increase in
cooling rate until the temperature reached a constant value at the critical coolingrate
between 60” and xoo”C/sec. Above this critical rate the transformation temperature
remained constant for cooling rates up to 5000~ C/set. HIGGINS ANDBANKS used the
KAUFMANNanalysis’ to estimate the transformation temperature at ~700’C for a
Zr/3 at. y(, Nb alloy, and they also observed an MS at 670 & IO’C for the Zr/z+% Nb alloy
containing 400 and 700 p.p.m. 02 on quenching at 700~ C/set. They suggested that the
thermal arrest observed by STEWART, HATT AND ROBERTS was associated with the
isothermal ,!l + 01+/?reaction rather than with the martensitic /3+ 0~’transformation
and that the depression in transformation temperature did not apply to the diffusion-
less MS but to the diffusion controlled /3+ oc+@ transformation. This would explain
the high transformation temperature of 75o”C, provided a lower true MS was obtained
at higher cooling rates. The present study of the Zr./2at. % Crjo.16 at.:/, Fe alloy was
intended to clarify this issue and to establish whether the transformation temperature
does approach a constant lower MS if the cooling rates are increased.

EXPERIMENTAL

Material
The nominal Zr/2 at.% Cr/o.rG at.:/, Fe alloy was produced as 0.25 in. diam.
rod from arc melted and remelted sponge ingot by hot forging at IOOO’C, followed by
hot rolling and final annealing at 725°C for 30 min. The annealed rod was cold swaged
to the final diameter. The alloy composition is given in Table I.

J. Less-Common Metals, r6 (1968) gx-xor

fi-~-cx
TRANSFORMATION IN Zr/z at.O/$ Cr/o.r6 at.% Fe ALLOY 93

TABLE I
COMPOSITION OF THE ALLOY

Ingot analysis (p.p.m. except for Cr)

___~
Element cv Fe Sn Ni Al CU TL Hf Mg MO
(wt. %i
~.___.
1.7 1035 <IO0 (50 <75 40 (50 <IO0 <IO <IO
~___~~
Elcme9zt l,V Ca C Cl Co I’b All1 si 1. H Cd

240 (30 45 <5 <IO <roe c:r5 (100 <20 <0.5 co.5

Finished Rod Analysis

Element HB NO 02
~
P.P.m. 5 35 7’75
- _.__-.

Gas-quenching apparatus
The apparatus for high speed thermal analysis has been described in a previous
papers. A thin slice of specimen was suspended by the spot-welded thermocouple wires
within the heating coil and the apparatus evacuated to z x IO-~ mm Hg. Both argon
and helium were used for quenching, the latter being used for the higher quenching
speeds. The cooling rates were also varied by using different pressures of gas between
5 and 120 lb./in.zanddifferent thicknesses of specimen down to -0.015 in. The thermal
arrests were measured by an ABEM Ultralette of the mirror galvanometer, direct
recording, oscillograph type. The start of the transformation could usually be located
easily but in difficult cases was taken as the intersection of the tangents to the cooling
curves above and below its change of curvature.
The specimens were held at the soaking temperature of 1000' C for IO min prior
to quenching. The temperature was chosen to be well inside the fl-phase region and
away from the transition zone between the /?anda phases which in this alloy extends
between 800” and gooV. Holding in the 01+@ transition region is to be avoided, since
this leads to a coarsening of the intermetallic ZrCr2 particles with a corresponding
decrease in corrosion resistancer. The time of holding at ~ooo”C was a compromise,
being maintained short to avoid undue interaction between the specimen and the
Pt/Pt-13 y/ORh thermocouple wires, yet allowing a reasonable degree of solution of the
intermetallic ZrCrg phase. The time should be sufficient to achieve the transformation
temperature characteristic of the quenching temperature.
There was no visible sign of alloying between specimen and thermocouple
although alloying has previously been found for the Zr/z$y< Nb alloys and, in general,
the cooling curve displayed only one transformation; the upper arrest at -950°C
found with Zr by MCMULLEN AND PARRY and attributed to alloying effects was not
observed in the present work. Microprobe analysis did not detect any zirconium dif-
fusion into the platinum of the weld bead but some limited diffusion of platinum into
the zirconium alloy was found. At 5 pm from the interface, approx. S wt.‘:;
platinum was detected but this dropped gradually to background level at -70 pm

J. Less-Commwz Metals, 16 (1968) gr-101

94 G. F. SLATTERY

from the interface. A tungsten thermocoupIe should be ideal for these temperatures,
but when tried, it failed each time due to extreme brittleness and had to be discarded
in favour of the more reliable Pt/Pt-Rh thermocouple. Fortunately, the lower p + 0~’
transformation does not appear to be affected by any possible alloying effects between
specimen and thermocouple5.
Tr~sformations in the cooling regions below N 4oo”C/sec were explored using
the Gleeble testing machine fitted with a vacuum container for thermal analysis. The
‘equilibrium’ values for the start and finish of transformation at very slow heating
and cooling rates (17o”C/h and go”C/h, respectively) were obtained with a Chevenard-
type dilatometera.

Metallographic preparatio%
The specimens were prepared for metallographic examination by final polishing
on Buehler cloth impregnated with high-purity chromic oxide (produced by igniting
ammonium dichromate) and a solution of 0.5% hydrofluoric acid in distilled water.
They were etched in a solution of 45 ml HNOa, 45 ml distilled Hz0 and IO ml HF for
about 30 sec.
The replicas for electron microscopy were prepared by a two-stage technique,
namely, plastic impression and carbon film with gold-palladium shadowing, the repli-
ca being supported on wax during dissolution of the bex film. For transmission,
thinning was accomplished in 10% perchloric acid in acetic acid at 12°C and 20 V
open circuit.
Prepolished specimens were examined after quenching to detect any surface
rumpling which is considered to be a criterion of the martensitic transformation.

RESULTS

The graph of transformation temperature as a function of cooling rate is

plotted in Fig. I. After the initial decrease in transformation temperature at lower
cooling rates, the graph showed two distinct plateaux. The higher plateau at 760°C
decreased slightly with increasing cooling rate until the curve dropped markedly at
N 17oo”Clsec cooling rate to the lower plateau which remained constant at 710°C for
cooling rates up to 4zoo”C/sec. At the lower cooling rates below 4oo”C/sec the trans-

it1 , , --i-~,&-Xt~g-
A x x:
qc2s..L~_,n.x -x~x-x.-x-~a’-x_

1 t
0 1000 2000 3000 4000
Cooling rate PC/see)
Fig. I. Effect of cooling rate on the transformation temperatures of the 2x/z at.% Crfo.16 at.o/b Fe
aZloy.

J. Less-Common Metals, 16 (rg68) gI-Ior

/%a TR~~SFOR~~_4TIO~IN zr./2 at.flh C-r/o.16 at.% Fe ALLOY 95

formation occurred over a relatively wide range of temperature ; the range between start
and finish of transformation is recorded as lines on the graph.
The hardness of the alloy increased with increasing cooling rate, fairly rapidly
initially, but levelled off at a V.H.N. =340 for the highest cooling rates employed,
Fig. 2, which represents an increase in hardness of -130 units due to the quenching
process.

k
i
,A 100
is
5
5 I-._.__II--LA -..d.._
0 1000 2000 3000 4000 5000 6000
Coolingrote (“C/set)
pi-7, 1, Gr:tp’1of hardness vs. cooling rate for the Zr/z at. “6 G-/o. 16 at. 46 Fe alloy.

Fig. 1. Zr/z at. O/,,Cr/o.r5 at. % Fe alloy quenched from IOOOT at rgoT/sec. Polariscd illumination
(x Go)

There was no sign of surface rumpling on quenching the prepotished specimens

at cooling rates between 450’ and 44oo”Cjsec. If rumpling existed it was so fine as to be
irresolvable on the prepolished surface. When the quenched surface was subsequently
prepared for metallographic examination a microstructure appropriate to that cooling
rate was obtained.
The grain structure as revealed by polarised light appeared to vary with
cooling rate, Figs. 3 and 4. At high rates of cooling, the structure became very indis-

J. Less-Common :%!lt?ta1s,
I6 (Iq33) qr -,OI
96 G. F. SLATTERY

tinct. A typical replica structure corresponding to a cooling rate of III oo”C/sec (on the
first plateau) consisted of coarse Widmanststten product, Fig. 5, which became
gradually finer to give a fine acicular structure, Fig. 6, at a cooling ra.te of 22c )o’C/sec
(on the second plateau). As the cooling rate was further increased, som e large il:regular

Fig. 4. Zr,k at.76 G/o.16 at.% Fe alloyquenchedfrom rooo”Cat 15oo”C/sec. Pal arised illu mination
(x 500)

Fig. 5. Zr/2 at. yO Cr/o.r6 at. yO Fe alloy quenched from IOOO’C at rrooT/sec 0x1.the higher : plateau.
Coarse Widmanstatten product. Replica ( x 3000) Reproduced ( x 4)
needles were observed within the acicular product. An early transform ation product of
x was found to separate around the original p grain boundaries during : the 4quench but
prior to the shear transformation within the /3 grains. This grain bo unda ry product
was observed at even the highest quenching rates, Fig. 7 (taken using Nomarski

*cnea 1rom IOC bo”C at 2200°C/sec on the lcriver p1atcau.

Fine acicular product. Replica reduced ( x 4)

Fig. 7, ‘h/z at.‘& ~.r,o.~o ax.~,, ~‘t: wuy quench rly gn lin boundary
transformation product. Nomarski interferenc

J. Less-Cowzwzon Metals, 16 (1968)gr-IOI

98 G. F. SLATTERY

interference-contrast to accentuate differences in height on the surfac e). The inter-

metallic phase particles, presumably ZrCr2g, appeared to act as nuclei for the shear
transformation 01’ product, Fig. 8.
Transmission electron microscopy on the faster cooled specimens , e.g., at 2850”
C/set, Fig. 9, showed a structu-e consisting of shear needles of ix’. The slower (zooled

Fig. 8. Shear a’ needles nucleated at ZrCrz particles. Nomarski interference-Contras ,t. (x zoc)O)

Fig. 9. Zrjz at.% Cr/o.xd at.% Fe afIoy quenched from IOOO’C at 285o”C/sec. Sht:ar needlqes of OL’
(x 20,000)
/%s% TRANSFORMATION IN Zr/2 at.;,: tk/O.Iii at.% Fe ALLOY 99

specimens had a very indistinct type of structure but with some evidence of faulting
within the shear needles. The product appeared to be predominantly fully transfor-
med DL’.There were no coarse particles of the intermetallic phase present, indicating
a high degree of solution during the P-phase heat treatment.
Microprobe analysis of the quenched specimens showed the intermetallic phase
to he small, chromium-rich areas randomly distributed in the alloy matrix. A very
low concentration of iron was observed in association with these areas but the iron
enrichment was extremely small and could not easily be demonstrated in full scanning
S-ray images in any of the specimens. It was only just detectable by taking line scans
across the area. X-ray diffraction traces did not reveal any signs of retained /i’-
zirconium phase.
With a few samples, an additional small arrest was obtained at 8oo”C. This was
not usual and may be related to the formation of an early transformation product at
the @ grain boundaries prior to the shear transformation, or it may also have been
connected with the possibility of a specimen-thermocouple interaction. The thermal
arrest in the higher plateau could be raised by oxygen contamination since, at one
stage, the system accidentally developed a leak with a consequent rise in pressure to
N 5 x 10-3 mm Hg for a short time. The subsequent contanlination produced a rise
of -3o*C in the equivalent transformation temperature.

The characteristics of the transformation in the Zr/z at.‘); Cr/o.rb at. O’;Fe alloy
vary according to the cooling rate from the B-phase region. This is demonstrated both
by the graph of transformation temperature ‘us. cooling rate and also by the nature
of the microstructures. At slow cooling rates near the equilibrium temperature region,
the 6 -+LXtransformation presumably involves nucleation and growth of the cy phase
by a diffusion process. At slightly higher cooling rates up to 4oo”C/sec, the grain
structure as revealed by polarised light was analogous to structures found in the
bainitic region of the dilute uranium-chromium alloys 1O~rr. This type of transfor-
mation involves a combination of shear and diffusion-controlled processes. To es-
tablish the true nature of the transformation, it will be necessary to explore the is(o-
thermal time-temperature-transformation characteristics of this alloy.
The nature of the transformation represented by the higher temperature
plateau is not clear but it is thought that the plateau is most likely to be associated
with a non-martensitic transformation. Kinetically, it appears to be intermediate
between the slower more ‘equilibriums reactions and a possible martensitic transfor-
mation represented by the lower temperature plateau. It is relevant that two ferrous
alloys, Fe-X and Fe-Co, show two temperature plateaux on the graphs of transfor-
mation temperature vs. cooling rate 12313; the higher transformation is believed to be
massive. In both the iron alloys and the Z-./z at. ‘ih Cr/o. 16 at. y(, Fe alloy, this plateau
is about 5o°C above the true Ms. Unfortunately, the microstructures of the quenched
zirconium alloy in this region are not easy to classify and hence any suggestion of a
massive transformation in this alloy must remain tentative at thisstage.
The transformation in the lower temperature plateau is probably martensitic
since the transformation temperature of 705*5’C is not depressed for cooling rates
up to 45oo”C/sec and the microstructure has a typical needle-like appearance. To
100 G. F. SLATTERY

ensure attaining the MS, it is necessary to cool at a rate faster than the critical rate of
N r7oo”C/sec and to prevent the occurrence of diffusional processes. The MS at 705°C
is now more in line with the values reported for the zirconium-niobium alloys59 6. The
previously obtained value of 750°C for the Zr-z&0/ Nb alloysis thought to be too high
since the cooling rates employed were not high enough for a true martensitic trans-
formation. Although the presence of surface rumpling on the pre-polished sample
would have provided certain evidence for a martensitic-type transformation, the
absence of surface rumpling is not indicative of the absence of a martensitic reaction.
This view is supported by PARR’S work on iron alloys where surface rumpling was
shown to be elusive and unreliable as a criterion for a martensitic transformationia+i”.
Again, pure zirconium, which is believed fairly conclusively to have a martensitic
transformation, does not show surface rumpling after rapid quenchings. Indeed, a
shear process for the c.p.h.-b.c.c. transformation has been suggested15 which would
not give any surface relief, and a shape change involving small or adjacent and opposite
displacements may thus not show as surface rumpling531*.
The zirconium alloy examined is susceptible to significant quench hardening
and the hardness obtainable increases with increase in cooling rate. Similar hardness
increases have been obtained on quenching thin-walled tubing suitable for nuclear
cladding. From a knowledge of the hardness and the cooling rate/hardness relation-
ship, it should be possible to estimate the cooling rate of quenched cladding and also
the variability in cooling rate along the length of the tube and between different
batches of tubing.

CONCLUSIONS

(I) The ,!?-a transformation in the Zr/z at.% Cr/o.rG a&($, Fe alloy displays a
separation into two modes according to cooling rate, with a distinct change in trans-
formation temperature in the region of 1700°C~sec cooling rate.
(2) The higher transformation temperature plateau occurs at a temperature
of 760°C and is likely to be non-martensitic in nature whilst the lower plateau occurs
at 705°C and is probably fully martensitic. Beyond the critical cooling rate of N 1700’
C/set, the MS temperature remains independent of cooling rate up to 45oo”C/sec.
(3) The hardness of the quenched alloy increases with increase in cooling rate
but levels off in value at the highest cooling rates employed.

ACKNOWLEDGEMENT

This paper is published by permission of the managing Director of the Reactor

Group of the United Kingdom Atomic Energy Authority.

REFERENCES

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J. Less-Common Metals. r6 (x968)gr-ror

~-LX TRANSFORMATION IN zr/z at.S/o
Cr/o.IGat.% Fe ALLOY 101

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J. Less-CommonMetals, 16 (Ig68)gI-101