132 Journal of Nuclear Materrals 105 (1982) 132-141

North-Holland Pubhshmg Company

SOLID STATE PHASE EQUILIBRIA OF ZIRCALOY-4 IN THE TEMPERATURE

RANGE 750-lO!WC

A. MIQUET, D. CHARQUET
CEZUS, Centre de Recherches d’llgme acrers, 73400 Ugme, France

and

C.H. ALLIBERT
LTPCM, B.P. 44, 38401 St. Martm d’Heres, France

Received 2 November 1981; accepted 23 December 1981

In the temperature range 750-lOSOT, the subsequent phase regtons are determined by n-ncrographrcal mvestrgatlon of
specimens heated m a temperature gradient. The phases are identified by microprobe analysis and electron dtffraction on
samples quenched after isothermal annealings. Four phase domams are found: a +Zr(Fe, Cr), up to 808”C, a + /3 +Zr(Fe, Cr),
from 808 to 845“C, a + B between 845 and 1008”C, /3 above 1008°C. From a dtlatometnc study, the utmost phase boundary
temperatures T, and Tj are found to be easily detected on samples prevtously annealed m the /3 state; T, and T, depend httle
on the heating rate. The Intermediate boundary temperature T,, as-determmed by dtlatometry, is always higher than the
equilibnum boundary. Supercooling, always present on cooling, shows some diffuston 1s involved in the transition mechamsm.
A strong texture effect, related to the initial state of the material, IS also detected by dilatometry.

1. Introduction Zircaloy-4. The results obtained by this author [2] indi-

Zircaloy4 is a Zr base alloy containmg additions of
Cr, Fe, Sn and 0. Mainly used as cladding material for
nuclear fuels, this alloy is exposed to high-temperature
water or steam corrosion. A satisfactory corrosion resis-
tance is observed [1] for alloys consistmg of a fme
dispersion of intermetallic precipitates in an hcp a:
matrix. Such a microstructure can be obtained by mech-
anical and heat treatments carried out at temperatures
corresponding to well-defined phase domains. Conse-
quently the complete processing of the material implies
an accurate knowledge of the phase boundaries as a
function of temperature.
Owing to its very high Zr content (about 98%) one
can expect this alloy to present the same crystallo-
graphic modification as pure Zr: a low temperature hcp
structure (a) and a hi temperature bee form (8).
Moreover, the large n ber of alloying elements might
induce the existence of urT everal polyphase domains be-
tween the Q and j? states. Structure evolution on heating
was previously determined by Perez [2] for Zircaloy-2,
the composition of which is very close to that of
cate a sequence of four phase domains between room
temperature and 1000°C: first a two-phase domain (hcp
(Y+ precipitates) up to 800°C; second a three-phase
domain (hcp (Y+ bee /3 + precipitates) between 800 and
86OT, then a two-phase domain (hcp a + bee /3) from
860 to 980°C; finally a single bee j3 phase above 980%
Such a sequence was confirmed by Rumnall[3] for the
Zr-rich alloys of the ternary Zr-Cr-0 system.
As for the precipitates, they were identified in
Zircaloy-4 by Vandersande [4] as a ternary Zr(Fe, Cr),
intermetallic phase of hexagonal C 14 type structure. As
shown by Rostoker [5], the binary ZrCr, Laves phase
exhibits the hexagonal C 14 type structure below 994T
and the fee C 15 type structure above this temperature.
In Zircaloy-4, this result was confirmed by Versaci [6]
who reported the Zr(Fe, Cr), precipitates to be present
as a polytype structure consisting of alternate packing
of layers of hexagonal and fee Laves phases; however
these authors [6] pointed out that the hexagonal form is
dominant in Zircaloy-4.
The study we carried out is a determination of the
solid state phase equilibria in Zircaloy-4 using several

0022-3 115/82/0000-0000/$02.75 0 1982 North-Holland

 A. Miquet et al. / Solid state phase equlhbrla of Zircaloy-4
experimental methods. According to results from the
literature, the phase transformations related to the a//3
transition of Zr occur in the temperature range 750-
1000°C. In order to determine the number of phase
domains located between the a and /3 states, annealings
are effected in the temperature gradient 750-1020°C.
The compositions of the phases present in each domain
are obtained by microanalysis of samples after isother-
mal annealings. The temperatures of the various phase
boundaries are measured by dilatometry and compared
with results deduced from isothermal annealings.
2. Experimental procedure
2.1. Startmg alloys
The initial alloy is sampled from a commercial prod-
uct prepared by vacuum arc-melting of the constituent
elements followed by several arc-remeltings. After a first
forging in the /3 phase domain, the ingot is worked m
the temperature range corresponding to (a +
precipitates) then annealed at the same temperature.
The imtial sample corresponds to an a recrystallized
structure containing an alignment of small precipitates.
The chemical composition is given in table 1; the accu-
racy of the analysis is evaluated at within 0.012% for Sn,
0.003% for Fe and Cr and 0; however, due to the low
level of the alloying elements, the relative accuracy of
this determination is rather poor.
2.2. Heating In a temperature gradient
A Zircaloy-4 bar is heated in a temperature gradient
for a time long enough to permit the phase equilibria to
be reached over the whole temperature range of the
experiment. After quenching, the subsequent domains
can be plotted from the microanalysis results of the
various phases detected along the bar.
For Zircaloy-4, its high reactivity with 0 and N,
implies a special set-up: the sample (3.5 mm in dnune-
Table I
Composition of the starting alloy (wt’k;)
Sn Fe Cr 0 C
1.41 0 250 0.126 0 1350
coo12 -co003
133
ter, 100 mm in length), wrapped in a Zr foil surrounded
by a W foil, is placed in a silica vessel sealed under
vacuum. The vessel is placed in a resistance furnace
providing a 20”/cm thermal gradient. A Pt-10 Rh/Pt
thermocouple, enclosed in a gas-tight MO sheath can
slide along the silica vessel. This equipment, maintained
in argon atmosphere is heated for 24 h in the selected
thermal gradient, then quickly cooled by water-
quenching.
The special device used for Zircaloy-4, which in-
volves silica encapsulation, prevents any contamination,
but induces a temperature discrepancy between thermo-
couple and sample. Consequently the results obtained
by this method must be completed by isothermal an-
neahngs at well-defined temperatures.
2.3. Isothermal annealrngs
Small samples wrapped in a Zr foil surrounded by a
W foil are enclosed in a silica vessel sealed under
vacuum. The vessel is placed in a large steelblock heated
in a resistance furnace. The temperature, measured by a
NiCr-NiAl thermocouple located in the steelblock, in
close contact with the vessel, is maintainted for 24 h.
The vessel is cooled by water quenching.
2.4. Characterizatton methods
On samples obtained by thermal gradient or isother-
mal treatment, the various phases are observed by opti-
cal and scanning electron microscopies. The a and B
phases are analysed with an electron microprobe. In the
case of the p phase, its transformation on quenching
produces a leather-like structure consisting of a large
number of thin precipitates at the edges of small a
needles. The high temperature composition of /3 corre-
sponds to the overall composition of the leather-like
structure observed at room temperature. This composi-
tion can be determined either by usmg an unfocussed
microprobe (3pm) or by scanning a selected area (75
pm X 75 pm) with a focus& probe. The precipitates,
N Sl Hf
0011 00035 0004 00075
134 A Mtquet et al / Soled stute phuse equrlrbno of .&w&v-4

too small for microprobe analysis, are identified by
EDAX in SEM using a 25 KV accelerating voltage.
Their crystal structure is determined by electron diffrac-
tion patterns obtained by TEM observations of thin
slices.
Samples etched by the mixture (Glycerol 16 cm3 +
HF 2 cm3 + HNO, 1 cm3) are used for optical and
scanning electron microscopy. Unetched samples are
used for microprobe analysis; Fe, Cr and Sn are mea-
sured using a 15 KV accelerating voltage; the measured
values are corrected by a computer program taking into
account the effects of atomic number (Z), absorption
(A) and fluorescence (F). For TEM, thin slices are
prepared by the electrolytic Jetting technique using a
mixture of 2-butoxyethanol 95 cm3 + methyl alcohol 10
cm3 + perchloric acid at room temperature
the expansions of the specimen and the alumma push
rod is detected by an electromagnetic sensor and re-
corded as a function of T.
Zr alloys are able to dissolve a large amount of
oxygen. As shown by the Zr-0 bmary phase diagram
[ 1I], a small increase of 0 content results in a sigmfi-
cant shift of the a + /3/p boundary temperature. In
order to check that the dilatometer atmosphere is really
inert, several runs are performed on the same sample.
For each heating rate, the sample is heated up to
105O”C, mamtained for 15 mn at this temperature then
cooled down to room temperature; the same cycle 1s
repeated four times.
3. Phase equilibria results

2.5. Ddatometry Three samples were treated for 24 h in the thermal

The a/B transition of pure Zr is associated with a
volume contraction, evaluated at 0.66% from the results
of Skinner [7]; for pure Zr, as well as Zircaloy, this
contraction can be easily detected by dilatometry [8]. As
shown by several authors [9], the pure Zr transition is a
martensitic type transformation; the transition tempera-
ture depends very little on the cooling rate. In the case
of unpure Zr, the tranntion mechanism was found by
Langeron [IO] to depend on diffusion; consequently,
heating rates can affect the transition temperatures of
the alloys. In order to measure transition points close to
the equilibrium state, the experiments are performed
using several heating rates (50,150,4OO”/h). The sam-
ple (6mm in diameter, 50 mm in length) is heated in
very pure He atmosphere; its temperature is measured
by a Pt-Rh/Pt thermocouple. The difference between
gradients 1050-900°C, 950-800°C and 850-7OO’C. The
various micrographs along the heat-treated bars reveal
four phase domains present between 750 and 1020°C.
The temperatures of the drfferent boundartes are de-
termined by comparing microstructures and phase com-
positions of samples annealed for 24h at every 10°C
interval, in the temperature range 790-102O’C. In this
way, the phase boundary temperatures are plotted with
a precision of *-cS’C.
The composition of the main phases a, p, deter-
mined by microprobe analysis of annealed samples is
given in table2. For each phase and each element
(Fe, Cr, Sn), a large number of countings effected in
several places indicate no detectable concentration
gradient; consequently a 24 h annealing time is found to
be long enough for the alloy to reach thermodynamic
equilibrium. For j3, a good agreement is observed be-

Table 2
Composltlon of (I and /3 phases as a function of T

TW) Domain a Composltlon /I Composition

(wtW) (wt%)

Sn Fe Cr Sn Fe Cr

750 a’+Zr(Fe, Cr), 1.67 0 0006 no B

810 (x + Zr(Fe, Cr), + fi 1.62 0 002 103 1.94 0 37
845 a + Zr(Fe, Cr), + /3 1.55 0 002 1 1.16 0 42
870 a+B 1.59 0.005 001 107 0 88 0.35
970 a+@ 2.04 0 0.02 144 0 26 0 15
1010 B no a 1 50 0 25 0 15
 A Msquet et al. / Sohd stute phuse equrlrbnu of Zzrculoy-4
tween the composition results determined by un-
focussed microprobe or selected area analysis; more-
over, the good consistency between the composition
results obtained by chemical analysis of the starting
mgot and microprobe analysis of the as-quenched /3
confirms the method is reliable for phase equilibria
determination.
The quantitative analysis of the precipitates by the
EDAX system m SEM detects Cr, Fe and Zr; as shown
by fig. 1, Cr and Fe seem in the same content range. The
electron diffraction patterns of these precipitates corre-
spond to the two crystal structures of ZrCr,; the hexag-
onal structure is found more often than the fee form.
The lattice parameters deduced from the electron dif-
fraction patterns are:
Q Zircaloy-4 are:
a = 7.14 A for the fee structure
0 aZr solid solution + Zr(Fe, Cr), up to 808’C.
E E 85.:: } for the hcp structure
Comparing the first value with the lattice parameters
of fee ZrCr, (a = 7.21 A [ 121) and fee ZrFe, (a = 7.07 A
[ 13]), the Fe and Cr contents in the precipitates can be
evaluated of the same order. Such a comparison is not
possible for the hexagonal form which does not exist for
ZrFe,; however, the significant decrease of the lattice
parameters of Zr(Fe, Cr), with respect to those of ZrCr,
(a = 5.08, c = 8.28 A [5]) can be attributed to an tm-
portant substitution of Cr by Fe.
From composition and structure results, the precipi-
tates are identified as Zr(Fe, Cr),, in good agreement
with results of Vandersande [4] and Versaci [6]. How-
Fig. 1. SEM analysis of precipitates.
135
ever, the present work does not give more information
either about the precise content or the crystal structure
that is stable in the temperature range investigated.
The results of microanalysis performed on thermal
gradient alloys are in good agreement with those ob-
tained on the samples annealed in the corresponding
phase domains. Moreover, a fair consistency is observed
for the phase compositions of the overlapping tempera-
ture regions of the different specimens. In all the sam-
ples, a very small amount of Zr silicide precipitates was
detected by microanalysis. Due to their very low con-
tent and their very low solubdity in Zr in the expen-
mental temperature range, their effect on the phase
equilibria of Zircaloy-4 was not taken into account.
From the previous results, the phase domains in
aZr solid solution + Zr(Fe, Cr), + j3Zr solid solution
from 808 to 845°C.
aZr solid solution + pZr solid solution
from 845 to 1008°C.
/3Zr solid solution above 1008°C.
The microstructures corresponding to the various do-
mains are presented on fig. 2. Some findings can be
deduced from a comparison of the composition results:
- In the a + Zr(Fe, Cr), region, Fe and Cr are con-
tained in the intermetalhc compound while Sn m dts-
solved in a.
- In the a + Zr(Fe, Cr), + /3 domain, Sn is present in a
as well as j3; sigmticant amounts of Fe and Cr are
detected in p
Fig. 2. Microstructures of the specimens quenched from the various phase domains. Top left: a +Zr(Cr, Fe),, up to 808°C; top right:
a +Zr(Cr, Fe), + p, 808-845’C; bottom left: a + p, 845-1008’C; bottom right: fl, above 1008°C.

- In the a + /3 region, Fe and Cr contents decrease on expect 0 to be present tn the a phase at low tempera-
heating when the Sn level increases in p ture.
- In /? as-quenched, the microprobe analysis agrees As shown by this representation (fig. 3). the p com-
quite well with the overall chemical analysis; only a position in Sn, Fe, Cr, lies between a and Zr(Fe, Cr),
slight discrepancy is observed for the Cr and Sn con- compositton: this fact indicates the p + a + Zr(Fe, Cr),
tents. reaction is eutectoid.
A sample representation of the evolutton of the phase
compositions on heating Zircaloy4 IS difficult because
of the large number of alloymg elements (Sn, Cr, Fe, 0).
Moreover, due to the low 0 content, Its analysis m each
phase 1s not possible. However, considering the sumlar The specific volume data reported in table 3 are
behavtour of Cr and Fe m Zr, we can attempt to plot deduced from the latttce parameters of pure Zr, ZrCr,
the com~sitlon changes as a f~c~on of Sn and (Cr + and ZrFe, measured by Goldak [ 141, Burgers 1151,
Fe) contents, between 790 and 1020°C. Besides the Rostoker [S], Hayes [ 121 and Rhines [13]. As already
identical behavtour of Cr and Fe, the schemattc diagram mentioned, the comparison of these data shows the a//3
plotted on fig. 3 assumes the constant compositton of transttton to occur with a volume contraction evaluated
Zr(Fe, Cr), and does not take into account the 0 effect. at 0.8%. Given the higher density of ZrCr, in the hcp as
A comparison of the Zr-0 and Zr-Sn binary phase well as in the fee structure and taking into account the p
diagrams [l l] shows the same effect of 0 and Sn, lattice parameter extrapolated at room temperature by
consequently, from a qualitative view point, one can Russell [ 161, one can evaluate the contraction related to
 A Miquet et ul. / Sohd state phase equrhhnu of Zwculoy-4 137

Cr+Fe forms can be calculated from our lattice parameter

Zr(Cr,Fe)p results, assuming the same Fe and Cr content in their
cornpositron. When the calculated densities of the vari-
ous phases are compared, the dissolution of Zr(Fe, Cr),
IS found to be related to a reduction m the rate of the
a//II contraction. In the temperature range under mves-
tigation, a posstble allotropic transformation of
Zr(Fe, Cr), could not result in a significant dilatometric
effect due to the very small difference in the specific
volumes of the hcp and fee modifications and the very
small amount of precipitates involved.
The dtlatometric curves recorded on the first and
second thermal cycles at 400°C/h are compared on figs.
4a and 4b. Three effects are detected on heating: they
are noted 1, 2, 3 on the curves. The temperatures of the
two utmost effects, T, and T,, which correspond to the
beginnmg and end of the contraction associated with
the p formation, are clearly determined; tt IS more
difficult to identify the intermediate effect temperature
T, related to the decrease in the contractton rate pro-
duced by the disappearance of Zr(Fe, Cr),. The same
remarks apply to the cooling curves for which T; IS even
Sn more difficult to detect. The dtlatometrtc effect temper-
atures are reported in table4. On comparison with
Fig. 3 Evolution of phase cornpositron on heatmg
results deduced from isothermal holdings, a good agree-
OL+ ZrCr, + j.? to be slightly lower than the o/j3 con- ment is found for T, and T3 as measured on the second
traction. heatmg curve, while T2 is slightly higher than the equi-
In Zircaloy4, the low content of alloymg elements librium result. As may be expected for solid state reac-
mtght not affect the lattice parameters of a and /3. tions, cooling results evtdence some supercoolmg and
Concerning Zr(Fe, Cr),, the densities of the two crystal are not taken mto account.

Table 3
Specific volume data of the vtious phases

Phase Crystal Number Lattrce Atonuc Calculated

structure of parameters (A) volume density
atoms/cell (A3) (S/cm3 )

aZr HcpA, 2 a=3233 23 3 6 50

c=5.149
at 25°C [ 141
a = 3.247 at 850°C 23.72 6 388
c=5.196 [14]
PZr Bee A, 2 a =3.61 23.52 6 439
at 870°C [ 151
ZrCr, HCP C 14 12 a = 5.08 1542 7.007
c=828 [5]
ZrCr, FCC C,, 24 a =7.21 [12] 15.62 6.919
ZrFe, F= C,, 24 a =7.07 [13] 14.72 7 627
Zr(Fe, Cr), HCP C 14 12 a = 5.04 I5 14 7.276
c = 8.26
Zr(Fe, Cr), FCC C,, 24 a=714 15.17 7 264
138 A Mtquer et ul / Soledstute phuse equrhhm of Z1rtulo~-4

40

700 800 900 1000 T’C

Fig 4a Ddatometnc curve on first heatmg; b Dllatometnc curve on second heatmg.

3.2. C~stallography texture effect an assumption is confirmed by comparing the curves

obtained from sample A, worked at 750°C and annealed
On first heating, amplitude and temperatures of the at the same temperature m the a + Zr(Fe, Cr), domain,
dilatometric effects are significantly different from the and sampleB, previously annealed in the j3 state (figs.
results of the other runs which are all reproducible. The 4a and b). With regard to B, A exhibits a lower coeffi-
low temperature hcp structure of aZr induces aniso- cient of thermal expansron in the a state and much
tropic properues: the different coeffrcrents of thermal smaller contraction due to the a//3 transition. Tables 5
expansion determined by Goldak [ 141 and Kearns [ 171 and 6 report the values of linear thermal expansion
on Zircaloy-4 for the c and a drrecuons suggest that the coefficients of a deduced from these curves, the corre-
first heating features are due to the preferred onenta- sponding expansions at 8lO”C, the contraction related
tion which is known to occur in wrought materials. Such to the /? formation and the overall expansion at 10IO°C.
Overall expansion is calculated taking mto account the
a and p expansion in the a + /3 region but neglecting
the small effect produced by Zr(Fe, Cr), dissolution.
Table 4 The equivalent values are estimated for pure Zr using
Temperatures of the ddatometnc effects
the thermal expansion measured by Goldak [ 141 and the
lattice parameters of a and 8.
4OO’=C/h First Second First Second
heatmg heatmg coolmg coohng
The low thermal expansion coefficient of A in the a
state 1s very close to that calculated from Kearns’ results
T, (“Cl 819 808 801 800 [ 171 for the a direction; rt indicates a strongly preferred
T, PC) 874 858 orientation corresponding to the sample axis parallel to
G PC) 983 1008 975 976 the a basal plane. For B, the thermal coefficient, which
is slightly smaller than that determined by Kearns [17]
 A Mlquet et al. / Solid state phase equdrbna of Zmaloy-4 139

Table 5
Coefftcrents of hnear thermal expanston of A and B

Lmear thermal Present work For Keams’ results [ 171

expanston
coefftctent A B II OO@l IO001 Random

4 8X lo+ 7.3x 10-6 15 78X lO-6 47x10-6 8 27X lO-6

Table 6
Lmear thermal expansrons of A, B and pure Zr

AL 810°C AL 10IO°C
- - Lsmeas ($+-), (~)~‘“”
( L I 1 ( L 1 2
talc. talc. talc.

A
Worked m a +Zr(Fe, Cr), +0.395 +o 16% -40 pm - 0.08% + 0.47%
B
Annealed m p +0.59’R, +0.16% - 130 pm -0 26% + 0.49%
Pure Zr +0 62% +o.ll% -0.28% +0.45!&
At 870°C [9]

Lmear thermal expansion of a at 810°C.

Lmear thermal expansion of (e + 8) between 810 and 1OlO’C

Measured contraction due to OL+ /3.

Overall hnear expansron at 10IO°C

Table 7
Heating rate effect on the transttton temperatures

Heating rate First heating Second heatmg

Transttron T 50°C/h 150°C/h 400°C/h 50°C/h 150”C/h 4OO”C/h

Tl 818 818 819 805 806 808

T2 867 871 874 850 851 858
? 994 986 983 1009 1007 1008
Ftrst coohng Second cooling
T; 807 805 807 805 803 800
T; 978 976 975 978 978 976
140 A Mlquet et ui / Soled stute phase equrhhnu of Zmol~v-4

for an isotropic matenal, shows the specimen gets al- intermetalhc precipitates at the edges. Nevertheless, the
most random orientation from /3 state annealmg. De- supercooling systematically evidenced by the dilatomet-
spite the large discrepancy between the A and B curves, nc cooling curves can be explained by the diffusion of
it can be noted that the overall hnear expansion at the solute elements which is reqmred for the formation
1010°C is in the same range. The values determmed on of a and Zr(Fe,Cr),, the composition of which are
Zircaloy-4 for the linear thermal coefficient of a and the different from the /? composition
a/P contraction are very close to the pure Zr values. The temperature discrepancies remarked on first
heating between the specimen quenched from the j3 and
3.3. Heatmg rate effect a + Zr(Fe, Cr), regions can also be attnbuted to a diffu-
sion phenomenon. In the as-quenched p samples, the
Experiments were performed using three different very small size of the precipitates and the large number
heatmg rates: 50, 150 and 400°C/h and two thermal of gram boundaries promote ready dissolution of the
cycles. The temperature of the various effects, measured Laves phase and rapid distribution of Fe and Cr m p by
on heating and cooling, are grouped in table 7. From gram boundary diffusion; similarly, the small size of the
these results, it 1s shown that: a platelets represents a short diffusion length: in this
- On second heating, the heating rate does not ngnifi- case, the various reactions occur on heating at tempera-
cantly affect T, and T,; a decrease m rate lowers T, and tures close to the equilibnum temperatures
brings it closer to the equilibnum results. On the contrary, the microstructure of the sample
- On first heating, a discrepancy is always observed annealed m the a + Zr(Fe. Cr), domam consists of rather
with the later heating results; however a decrease in large precipitates located inside large grains of a phase.
rate, with raises T, and lowers T, corresponds to a On heating, the dissolution of Zr(Fe, Cr), results in
change towards the equilibrium values. local supersaturation in Cr and Fe, maintained by the
- On cooling, a supercooling is always evidenced; it is lack of diffusion in a: the subsequent dissolution of the
not significantly affected by the different rates Laves phase is slowed down and (a + Zr(Fe, Cr),) state
1s maintamed at a temperature higher than the eqm-
3.4. Number of cycles effect libnum T,. Then j3, produced by the a + Zr(Fe, Cr),
reaction surrounds the a grains. The effect observed m
Four subsequent runs were performed on the same dllatometry at a temperature lower than T3 can be
sample using a 150”C/h rate: the various temperatures explained by the fast formation of a large proportion of
are measured with an accuracy of -t4”C, that is to say /3 phase; the disappearance of the small quantity of
in the same precision range as for the isothermal method. residual a, depending on the solute diffusion, occurs
The constant value of T3 illustrates the absence of 0 very slowly and cannot be easily detected.
pollution; this is confirmed by the constant 0 level
found by analysing the sample before dilatometry and
5. Conclusion
after three cycles
Concermng the sohd state phase eqmlibria of
Zlrcaloy-4 of well-defined composition, an examination
4. Discussion of the results obtamed from the different experimental
methods leads to the following conclusions:
Pure j? vrconium cannot be retained at low tempera- - The alloying elements Fe, Cr, Sn behave m Zircaloy-4
ture even by very rapid quenching; the transformation as in pure Zr.
from /3 to a generally results in the Widmannstltten Sn is present m the hcp a as well as in the bee p
structure characteristic of martensitic transformation phase.
For some Zr base alloys such as Zr-Nb or Zr-U, the . Fe and Cr, which do not dissolve in hcp a at low
large difference in composition bgtween a and /3 re- temperature, form the Zr(Fe, Cr), mtermetalhc com-
quires diffusion to be involved in the transformation pound.
mechamsm [ 16,181: in these cases, the p phase can be . All the addmon elements are m solid solution m the
totally or partially retained at room temperature. For bee B phase at high temperature.
Zircaloy-4, as shown by the foregoing results, the a + /3 - Four phase domains can be found on heating, namely:
regon is not very wide; the /? phase cannot be retamed . hcp aZr + Zr(Fe, Cr), up to T, = 808°C.
by cooling and the microstructure of the as-quenched /? hcp aZr + Zr(Fe, Cr), + bee j? Zr from T, = 808’C to
sample consists of small a platelets with some thin T2 = 845’C.
 A Mlquet et al / Sold stute phase equtlrhna of Z1reulov-4 141

. hcp aZr + bee /3Zr between T, = 845°C and T3 = [4] J B Vandersande and L Bement, J Nucl Mater 52
1008°C. (1974) 115
. bee /3Zr above T, = 1008°C. [51 W Rostoker. J Metals 5 (1953) 304
- The boundary temperatures of the domams can be [61 R A Versacl and M Ipohorskl, J Nucl Mater 80 (I 979)
180
determined by dilatometry by heating specimens previ-
[71 G B Skinner and H L Johnston, J Chem Phys 21 (I 953)
ously annealed in the bee /3 state. The accuracy of these
1383
measurements is m the range *4”C for the two extreme
PI J Intrater, Trans. AIME 221 (1961) 567
effects T, and T3. It is not so good for Tz which is
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