Discussion on the stability of the antimonyzinc binary phases

Calphad, Vol. 25, No. 4, pp. 567-581, 2001 a3 2002 Published by Elsevier Science Ltd 0364-5916/01/$ - see front matter

Pli: SO364-6916~02)00008-I

Discussion

on the Stability

of the Antimony-Zinc

Binary

Phases

VQonique Izard’ , Marie Christine Record’“, Jean Claude Tedenac’ and Suzana G. Fries2 ILPMC, UMR CNRS 5617, Universitd de Montpellier II C. C. 003, Place Eugene Bataillon F- 34095 Montpelier CEDEX 5, Ffance 2ACCESS e.V., RWH-Aachen, Intzestrasse 5, D-52072 Aschen, Germany *: Corresponding author’s e-mail: recordQlpmc.univ-montp2fr (Received October 8,200l) Abstract. Due to the interesting properties of the SbaZn, thermoelectric material, and its potential use as substitute of PbTe, a reliable preparation method of this alloy is required. As contraditions exist nat only in the experimental data reported in the literature &swell a8 in the two existent thermodynamic description for the ~uilibrium phases of the system Sb-Zn, a new inv~igation on this stem was done. As results the existence SbbZns is not confirmed, the range of homogeneity of the phase SbsZna is quantit~ively determined (56.5-57 at.%Zn), a high temperature transformation of this phase is proposed. An easy method to prepare SbaZnh from the melt is reported. Further work on characterization of the crystal structure of the high temperarum phsse &9well as a new thermodynamic reassessment is being performed. 0 2002 Published by Elsevier Science Ltd.

Introduction Sb-Zn alloys have interesting thermoelectric properties. Sb$Q is a high performance p-type thermoelectric material appearing aa a promising su~itute for PbTe due to a higher factorlof merit, ZT=1.3 at 673K (291with the advantage of being Pb free. The preparation of the SbzZnd ~rn~und is, however, not without problems. Even if some authors reported mp~urernen~ on a sin~~ph~ material or single crystals (10,291, others described it as a multi-phased alloy giving unclear explanations for the re&t baaed on the existence of metastabiliti~ due to strong interactions in the liquid phase [ll, 18, 201. Hence, the knowledge of a very trustful phase diagram of the Sb-Zn xystem is indispensable. Literature

Review

Experimental Phase Diagram The phase diagram of this sys&m is being studied since the XIX century, and the first mm&s were obtained by cooling the samples, given therefore an appr~mation for the liquids [l, 2, 3,4, 61. Curry (51was the first to obtain it on heating. It followed an e~a~tive work done by Takai (71 where the central part of the diagram was cleared up showing the high temperature tr~o~at~ns of the phasea SbaZn4 and SbZna. Tydlitat [8] accepts Talcei’s phase diagram [7] after X-ray analyses but he suggests that the phase SbzZnt does not exist at low temperature. The thermal analysis performed by Vuillard and Piton [9] leads to the proposal of a new phase: SbeZna, at high temperature, but it was not checked by X-ray analysis. Other thermal events are in

568

V. IZARD

et al.

agreement with the diagram proposed by Takei [7], but does not confirm the stability of Sb*Zns reinforcing the assumption of Tydlitat [8]. The decomposition temperature of the new phase coincides with the high temperature transformation of SbaZn4 proposed by Takei [7]. Vuillard [9] does not confirm this transformation; however he does not comment the event related to this transformation that was also reported by Tydlitat [8] in the zinc rich side of the SbsZnd phase. Mayer et al. [13] worked on the crystal structure of the phases and their range of homogeneity and stability, as Tydlitat [8] they do not confirm the stability of SbZn3 at low temperature. They do not report the existence of the SbsZns but they also do not quote Vuillard and Piton [9] who did the experiments without annealing, what was done by Mayer et al. [13]. Koneska and Mavrodiev [14] interpret their results as Vuillard and Piton did [9], and accept the existence of the SbsZns phase. In this case, at contrary of Vuillard and Piton [9], a long annealing was made. Koneska and Mavrodiev [14] report the limits of solubility of SbjZnl which does not agree with the ones reported by Vuillard and Piton [9] and Takei [7). Psarev and Dobryden [ll], Psarev et al. [16] and Dobryden [18] studied the solidification of several alloys starting for different liquid temperatures. They report several events which they interpret as possible mete&able equilibria between SbZn and SbeZns or SbaZn4. A recent doctor thesis with inedit results, done by Adjadj-Bouharkat [26], investigates the whole system. The results support Takei’s phase diagram 171. The phase SbsZns proposed by Vuillard and Piton [9], is not reported. The literature review carried out in [26] is incomplete, it seems that they have not the information about the works where this phase is proposed. When doing a thermodynamic assessment Liu et al. [33] report new measurements investigating the liquidus at the Zn rich side. Their results leads to a simpler shape of the liquidus. Table 1 sums up this literature information, Fig. 1 shows all the experimental results collected in the literature. Thermodynamic Descriptions There are two sets of parametrized Gibbs energies descriptions for the phases of this system in the literature one by Zabdyr (311 and a very recent one published by Liu et. al. [33]. These assessments take into account not only phase diagram data but thermodynamic information as well (chemical potential and mixing enthalpy for the liquid and chemical potential for solid phases). The assessments are based on distinct interpretations of the available experimental data for the phase diagram. The first thermodynamic model of this system was made by Zabdyr [25], improved by the same author [28], who tested it later on in the Cd-Zn-Sb ternary system [31]. The accepted experimental diagram was nearly the one determined by Takei [7], but without to consider the highest temperature transformation for the SbaZnl phase, neither the stability of SbeZna at low temperature. Due to the lack of quantitative experimental data all the compounds were modeled as stoichiometric ones. For the liquid phase two models were tested: a simple Redlich-Kister model and an associated one, trying to describe the complex short range order present in this phase. As many studies on thermodynamic and physical measurements in the liquid phase assumed the existence of SbsZq entity [12, 17, 22, 24, 341, its composition has been chosen to be the one of the modelled associate. Both descriptions result in a very large number of modeling coefficients, which were necessary to describe the temperature dependence as well as the liquidus shape at the Zn-rich side. The thermodynamic functions were reasonably fitted. In the test with the ternary system the Bedlich-Kister model with 11 coefficients were selected by [31]. Liu et al. [33] proposes a new modeling for the liquid phase after considering own measured data. The new model reduces to 6 the number of coefficient used, due to the simpler liquidus shape as well as considering no excess Cp for this phase. The new assessment, however, accepts, without further analysis, the existence of the phase SbsZns. Fig. 2 shows a comparison between phase diagrams calculated with [28] and with [33] descriptions. Experimental A reliable procedure for preparation

Procedure

of the compound

SbsZnd and its equilibrium

with other phases

DISCUSSION

STABILITY ‘Table 1.

Experimental Phase

Ref.

Method

PI

PI

Thermal analysis on cooling (TAc) TAc TAc TAc TAc Thermal analvsis on heatinn (TAh) TAh, electric and dilatometric measurements X-ray diffraction

PI

TAh

P31 P41

X-ray ditlktion on annealed samples dilatometric and calorimetric measurements on annealed samples

@I

TAh, X-ray diffraction

[21 131 -I;IT [61 [51

VI

Vl

OF THE ANTIMONY-ZINC Diagram,

Reported

BINARY PHASES

Literature

Data. Comments

Phases

1

)

I

1 SbZn, SbsZn3 SbZn, SbZns

I

1 1 1

SbZn, SbaZn.t, SbsZns

1

SbZn, SbsZb,

I

I

SbZns

1SbZn, SbsZw , SbsZnd, SbsZns

SbZn, SbsZm, SbZn, Sb5Zns,

SbZns

SbsZw,

SbZn, SbsZnq,

SbzZna

SbZna

1

liquidus

data

liauidus data a transformation is observed between 593 and 633 K liauidus data

-

several forms exist for I SbsZn4 and SbzZns 1 Sb2Zns exists 1 for T>678 K ) SbzZns exists for 766 K682 K SbZns exists for T>682 K Sb2Zns exists for T>682 K a shifted solubility range is reported for SbaZn, SbZn3 exists for T>680 K

569

570

V. IZARD

et al.

690

0

0.1

0.2

0.3

0.4

0.5

0.6

MOLE_FRACTION

0.7

0.8

0.9

1.0

ZN

Figure 1: Collection of all the Phase Diagram Experimental Points Reported in the Literature

930-f

’

’

’

’

’

’

’

’

’

i

0.2

0.3

0.4

0.5

0.6

I 0.7

I 0.8

I 0.9

1.0

h

900

‘.

870

‘...

0

0.1

MOLE-FRACTION

ZN

Figure 2: Previous Assessments: dotted curve-Liu et al., solid curvezabdyr

et al.

DISCUSSION

STABILITY

OF THE ANTIMONY-ZINC

BINARY PHASES

571

is aimed. As there are contradictions on the present available calculated phase diagrams, experiments are being carrying out in an attempt to clarify the conflicting experimental data. Thirty one alloys were weighed from pure antimony (Aldrich, 5N) and pure zinc (Aldrich, 4N). They were formed by melting in a silica tube (5 mm inside diameter, 6 mm outside diameter, 35 mm length) sealed under vacuum (10m3 Pa). Because of the high vapor pressure of zinc, the alloys have been kept at 773K for two days before their melting. The weight of each alloys was approximately 0.20 g. Each alloy has been annealed for 2 months at 673K. This temperature was chosen below the lowest invariant temperature of the SbZn binary phase diagram. Phase transformations were determined by differential scanning calorimetry with a heat flow apparatus calorimeter which has the following characteristics: a temperature range from 153 to 1103K, a sensitivity limit of detection from 5 to 15 mV, and a heating/cooling rate from 0.01 to 30 K/mm. The temperature of the phase transitions were taken on heating curves, in order to get a better separation between close phenomena, a low heating rate has been chosen (0.1 K/min). Silica tubes sealed under vacuum (10m3 Pa) were used as crucibles. The identification of the phases has been carried out on a 0-20 X-ray diffractometer (equipped with a monochromator) and on an electron microprobe analyzer. X-ray data acquirement has been done for 20 < 20 < 120 with a step of 0.02 and a preset time of 20 s. Results

and Discussion

The composition of alloys, temperature of both liquidus and solidus as well as the phase identification at low temperature are given in Table 2. Our experimental results are plotted in Fig. 3, together with the two available calculated phase diagrams using [28, 331 descriptions. As it can be seen our experimental data are not entirely reproduced by these assessments. Our invariant temperatures are mainly in better agreement with Liu’s assessment [33]. In the central part of the diagram, liquidus temperatures reported in this work are higher than the assessed ones. This disagreement with the calculated phase diagram also exists for the previous experimental results. Boettinger et al. have shown in a recent paper [35] that the experimental observation is an effect occuring for alloys with a small freezing range or a slow solid diffusion. Several DSC recordings had been successively performed for each alloy and no changes were observed. Annealing conditions used in this work are thus without effect on these samples. Most alloys reached the equilibrium state at once, except for three of them (with the following compositions x=2, 7, 8 at.%Zn). They consist of three phases: pure antimony, antimony with 1 at.%Zn and SbZn. Their corresponding thermal phenomenon at 758K has already been reported in older studies [3, 41 in which results were obtained from cooling curves, it was described as an unstable eutectic between antimony and SbzZn3. Our results do not agree with this description and, supported by a further thermal phenomena at 786K, seem to display a terminal solid solution based on antimony. This assumption is in accordance with the phase diagram assessed by [33], a low end solubility exists for antimony, its maximum value is 2 at.%Zn at the eutectic temperature. For the terminal solid solution based on zinc, a content lower than 1 at.%Sb can be noted from this work, this also agrees with the recent assessment of Liu et al. [33]. In the zinc rich part of this system, although the alloys consist of two phases Sb3Znl and zinc, unexpected invariants appear, one at 686K corresponding to the eutectic, for alloys between SbaZnd and SbZn3 and already reported by [14], other at 693K, which can correspond to the melting point of zinc for alloys between SbsZns and zinc. The presence of these invariants could be linked to an incomplete reaction of formation for the compound &Zn3, on heating. Low thermal phenomena observed at 677K for these samples tend to support this assumption. From DSC results and Tamman calculations, two phase transformations can be proposed for SbsZQ. The first one at 767K and the second around 800K. This phase seems to decrease its zinc content with

V. IZARD et al.

572 I

930

I

I

I

I

I

I

900~ 870 -

"".,,

>,840,

W ~ 810. W

"'.T

TT

~ 780-

"

~7S0-

ft. k.-

720690660630

0:1 0:2 0:3 0:4 0.5 0.6 0:~ 0:8 0:9 1.0 MOLE_~CTIO~ ZN

Figure 3: Comparison between our Results and the Assessed ones: dotted curve-Liu et al., solid curve-Zabdyr et al.

10. o,

805

~ -1o. ?e7 ~ -20-30. 58.3

"407§ 0

841

at.%Zn 7-=0

s~

s~

T=mpemtum

{g)

Figure 4: DSC Curve for Sbo.437Zno.563

DISCUSSION

STABILITY

OF THE ANTIMONY-ZINC

BINARY PHASES

r

Figure

5: Homogeneity

Figure

Range for SbgZn4: X-ray Diffraction Patterns

6: Homogeneity

Range for SbaZq:

Micrographs

573

574

V. IZARD et al.

i I

........... SbD.,~Znoj ~ ...... 5

"

\~

%t

Sbo~Zn0e Q '

"

e~7

"

'

"

e39

Temperature

'

'

(K)

Figure 7: DSC Curves with a Very Low Heating Rate, 0.05 K/rain

12Q • - SbZn

I

100

80

i

eo

i 40

°

.2 2O

25

e (o)

Figure 8: X-ray Diffraction Pattern for Quenched Sbo.49Zno,51

DISCUSSION

STABILITY

OF THE ANTIMONY-ZINC

BINARY PHASES

a41

850 -

600 x.

782

;. 7a7--

E 3

750-

Iv) 0% 731

iiiL

'. '\

~.,

700-

$

E &? 650 600

686

A c!

tj

. .\

7144

_-

, ‘~4

677

I;: w

II I

I

X (at.% Zn)

Figure 9: Sketch of the Phase Diagram Proposed by this Work

p

600

X (at.% Zn)

Figure 10: Enlarged Central Part of the Proposed Phase Diagram

575

576

V. IZARD et al. Table 2.

Solidus, Liquidus, Invariant Temperatures and Identification of Phases at Low Temperature (T < 673K).

DISCUSSION

STABILITY

Table 3.

Experimental

OF THE ANTIMONY-ZINC (this work) and Cahlated

BINARY PHASES

Invariant Reactions.

577

578

V. IZARD et al.

temperature and near its melting point, its composition is between 54.5 and 56 at.%Zn, very close to the SbsZns compound which was assumed by (91. For alloys with composition between 53 and 56.3 at.%Zn, a thermal phenomenon is observed at 773K. This was already reported based on dilatometric and dynamical differential calorimetry (DDC) investigations [14] but without any attempt to interpret it. The shape of this phenomenon is not so sharp as an invariant one (Fig. 4) therefore, it could be due to a crossing between a two phase field and a one phase field or to an incomplete phase transformation at 767K. Because of the presence of the same upper and lower invariants for each alloy and the absence of the opposite crossing phenomenon, the latter assumption is more probable. Any further intermediate phase appears at high temperature in this diagram. In order to check this result, a quenching has been performed on an alloy with the composition corresponding to SbsZns after annealed it for one week at 783K, this temperature lies within its assumed stability range, but without success. Only two phases BSbZn and eSbsZn4 have been evidenced, high temperature forms couldn’t be retained; the transformation kinetic might be too high. Information about the homogeneity range for the intermediate phases can also be deducted from this work; it is lower than 2 at.% for SbZn (two phases were got for Sbo.51Zno.4s and Sbe4sZno.s1), 1 at.% for SbzZna (Sbe.4rZne6e and Sbe.deZne.sa have different invariant temperatures) and 1 at.% for SbsZn4 at least for low temperatures (2’ < 673#). In this latter case, the homogeneity range has been determined with precision. SbsZnd exists for compositions from 56.5 to 57 at.%Zn. For lower zinc contents, SbZn appears as an extra phase, for upper zinc contents, zinc is in excess. X-ray diffraction patterns are presented on Fig. 5 and micrographs on Fig. 6 . For alloys with upper zinc contents, zinc is located in the vicinity of dark areas corresponding to cracks probably due to phase transformations in this compound. These results indicate a shift of the composition interval towards the lower zinc compositions in comparison with previous phase diagrams. The proposed homogeneity range agrees with that observed by [14]. This shift was also predicted by [32]: SbsZn, crystallizes in a rhomboedral lattice with 22 atoms in the unit cell distributed among three kind of sites [13]. One of them is 89% occupied by Sb and 11% by Zn atoms and each Zn atom on these sites with mixed occupation are involved in six short Zn-Zn bonds which are not energetically favorable; therefore one could expect a different stoichiometry with a lower content in zinc. Based on this assumption, our results allows us to assume that at high temperature, zinc atoms on sites with mixed occupation possess enough energy to leave their positions, then SbaZQ will decompose into Sb$nz and another phase close to SbsZns which corresponds to a total substitution of zinc on these sites by antimony. For alloys between 56 and 60 at.%Zn, temperatures for the higher phenomena are essentially the same and the heating rate 0.1 K/min does not allow us to separate the liquidus from the latter invariant and to conclude about the melting reaction type for SbsZnd and SbzZns. Therefore, DSC experiments were repeated with a lower heating rate 0.05 K/min and diierent shapes for the melting peaks were got (Fig. 7). For an alloy with the 56.6 at.%Zn composition, the invariant can be separate from the liquidus, for a lower and a higher content in zinc, 56.1 and 60 at.%Zn respectively, overlapping peaks are observed. Because of the lower melting temperature for the intermediate alloy and the higher one for SbzZns (60 at.%Zn), melting reaction for both the intermediate phases SbsZnd and SbzZns could be assumed as congruent. The leading edge of the melting peak in the case of 60 at.%Zn corresponds to a crossing of a two phase field which indicates in agreement with the proposed phase diagram that maximum of SbzZns slightly differs from this composition. A comparison between our experimental invariant reactions and the assessed ones is given in Table 3. Crystal forms for the intermediate phases are named according to [27]. The highest form till now never described for SbaZnl will be named 6’. For our work, composition of the intermediate phases involved in high temperature reactions are approximated. Table 4 presents the reported data on preparation of antimony-zinc alloys. Most of these phase compositions can be explained from our phase diagram; but presence of Zn and SbzZns in SbZn, SbZn in SbaZh, SbZn and Sb in SbeZnz can only,be due to,metastabilities in this system or eixistence of SbzZns

DISCUSSION

STABILITY

OF THE ANTIMONY-ZINC

579

BINARY PHASES

entities in the melt. Like 1111already proposed, precipitation of SbeZns for alloys near its composition could yield to an enrichment of melt in antimony and subsequently crystallization of SbZn. As no metastabilities has been evidenced in this work for this part of the system, the latter assumption might be more probable. In order to check it, an alloy with the composition of 51 at.%Zn has been quenched from the melt at 1023K. The obtained sample contains many cracks and is composed of three phases SbZn, SbzZns and SbaZnl (Fig. 8). Therefore S&Zns entity could exist in the melt. A maximum excess volume for 60 at.%Zn reported by (15) from density measurements at 923K supports this assumption. As SbeZnl entities were also evidenced in the liquid phase by previous paper [12, 17, 22, 24, 341, two kinds of associate can be proposed for this liquid: Sb3Zn4 and SbzZns. According to 1181, in SbeZne and SbsZn4, amount of SbzZns increases with the degree of superheating of the melt. At high temperature, only SbzZna entity could subsist in the liquid phase. The unusual temperature variation of sound velocity and molar volume measurements in the liquid reported by [24] support this assumption, the authors interpreted this behavior as rapid dissociation with increasing temperature of SbsZnd entity. Thii could also explain a better fitting for this temperature range with the associated model in Zabdyr’s assessment [25]. Fig. 9 and Fig. 10 show an outlined phase diagram which take into account our measurements and their interpretation. Phenomena given as non-equilibrium ones are not plotted. Summary

and Fiuther Work

Through a re-investigation of the antimony-zinc phase diagram, this work provides further information on homogeneity range of the intermediate and end phases, phase transformations, invariant temperatures and liquid constitution, which are summarised as: l

The existence of the phase Sb5Zns is not confirmed.

l

The homogeneity

l

A new high temperature on DTA measurements.

l

The congruent

l

Some thermal events obtained

l

The thermoelectric material SbsZna can easily be obtained from the melt as a single-phased compositions between 56.5 at.%Zn and 57 at.%Zn by slow cooling.

range of the compound transformation

melting temperature

SbsZnh was quantitatively of the compound

determined.

SbsZnl, 6’ SbsZnd, is proposed,

of the b’SbeZnl, compound

only based

is 841K.

in this work were not understood. for

In this system, only metastabilities near pure antimony were found. Multi-phased alloys obtained by quenching, reported in the literature, are probably caused as a consequence of two entities in the liquid phase: SbsZn4 and SbeZna. As a further experimental work a x-ray investigation at high temperature would be necessary to univocally establish the existence of the d’SbsZn4 phase. The comparision of the present experimental data and the calculated phase diagram based in two distict assessments indicates that a new thermodynamic assessment considering the non-stoichiometry of the phase SbsZnd, the non-existence of the compound SbsZns, and the evidence of two different entities in the liquid is necessary. That new modelling is ongoing work in our group.

Acknowledgements : The authors are immensely joyous for have been contagiated by the enthusiasm of Himo, who shared his understanding and discovers even during meals letting napkins decorated with Gibbs enenjes eqressions, small sketchti of phase diagmms and his prefered order-disorder modelling. The authors feel honoured for having him as teacher.

V. IZARD

et al.

References [l] R. GOSSELIN,Bull. SOC.Encounag.Ind. N&l., 5, (1896) 1301-1310. [2] C. T. HEYCOCKAND F.H. NEVILLE,J. Chem. SOL., April, (1897) 383-422. [3] K. MONKEMEYER,Z. onorg. Chem., 43, (1905) 182-196. [4] SF. ZEMCZUZNY,8. anorq. Chem., 49, (1906) 384399. [5] B.E. CURRY, J. php. [6] P.T.

them, 13, (1909) 589-597.

ARNEMANN,Z. Ges. H&t., 13, (1910) 201-211.

[fl T. TAKEI, Sci. Rep. Tohoku Univ., 16, (1927) 1031-1056. [8] T. TYDLITAT, Czech. J. Phys., 9, (1959) 638-640. [9] G. VUILLARD AND J.P. PITON, C.r. Acad. SC. Paris, 263, (1966) 1016-1021. [lo] V.I. PSAREVAND N.L. KOSTUR, I... [ll] V.I. PSAREVAND K.A.

Vyssh. Uchebn. Zaued., Fir,

10(2),

(1967) 34-38.

DOBRYDEN,Inorg. mater., e(2), (1970) 203-207.

[12] A. SINHAAND E. MILLER, Metall.

tmns., 1, (1970) 1365-1370.

[13] H. W. MAYER, I. MIKHAILAND K. SCHUBERT,J. less-commonmet., 59, (1978) 43-52. [14] S. KONESKAAND G. MAVRODIEV,Fizica, la(l),

(1980) 137-142.

[15] L. DIM, A. BATH, J.G. GASSER, J.L. BRETONNETAND R. KLEIM, Phgs. Lett., 84A7, [16] V.I. PSAREV, V.G. Km.11AND V.A.

(1981) 375-377.

ANDRONNIKOV, Znorg.mat., 17(S), (1981) 260-264.

[17] A. BATH, J.G.GASSER AND R.KLEIM, Phgs. Lett., QlA (7), (1982) 355-357. [18] K.A. DOBRYDEN,Inorg. mater.,

19(4), (1983) 494501.

[19] V.I. PSAREV, I.V. PSAREVAAND V.G. KIRII, I..

Vgssh. Uchebn. Zaued., Fiz., 9, (1984) 4550.

[20] M. TAPIERO,S. TARABICRI,J.G. GIES, C. NOGUET, J.P. ZIELINGER,M. JOUCLA,J.L. LOISONAND M. ROBINO,Sol. energy mater., 12, (1985) 257-274. [21] Bull. alloy phase diag., 7( f3), (1986) 602. [22] M.R. MIAN, A. MIKULA K.L. KOMAREKAND W. NEUMANN,2. Metallkd., [23] L.A. ZABDYR, J. Phase Equilibria,

13 (2), (1992) 130-135.

[24] Y. TSUCH~~AAND S. KANAI, J. Non-Crgst. [25] L.A. ZABDYR, Calphad, 17(S),

77 (S), (1986) 133-139.

Solids, 158158,

(1993) 434436.

(1993) 269-280.

[26] F. ADJADJ-BOUHARKAT, PHD thesis Uniuersite Phases du Systeme Tern&e Bi-Sb-Zn, (1995). (271 T.B. MASSALSKI,Binary Phase Diagmm

Claude BernanGLyon

(CD-ROM),

[26] L.A. ZABDYR, Zeszgty Naukowe Politechniki Slaskiej, w stopach trojskladnikowyehCd-SbZn, (1996).

E Le Diagramme d’Equillbre entre

ASM International,(1996). Hutnictwo,

2.50, Gliwice: Roumowagi miedzyfawwe

[29] T. CAILLATet al., J. phys. them. solids, 58, (1997) 1119-1125. [30] V.I. GORYACHEVA AND V.A. [31] L.A. ZABDYR, C&had,

GEIDEFUKH, Russ. J. Phy.

Chem., 71(4),

(1997) 526-529.

21, (1997) 349-358.

[32] S.G.

KIM, 1.1. MAZIN AND D.J. SINGH, Phgs. Rev. B, 57(11),

[33] X.J.

LIU, C.P. WANG, I. OHNUMA,R. KAINUMAAND K. ISHIDA,J. Phase Equilibria, 21, (2000) 432442.

[34] L.C. PRASADAND A. MIKUW, J. Alloys

(1998) 61946203.

Comp., 299, (2000) 175-182.

[35] W.J. BOETTMGERAND U.R. KATTNER, Acto Mater.,

to be published.

DISCUSSION

STABILITY Table 4.

Melt

temperature

OF THE ANTIMONY-ZINC

Sb-Zn alloys, Fkported Cooling treatment

Phase

BINARY PHASES

Compositions.

Phase composition

Reference