Journal of Alloys and Compounds 535 (2012) 7077

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Journal of Alloys and Compounds

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A calorimetric study of thermodynamic properties for binary CuGe alloys

W. Zhai, D.L. Geng, W.L. Wang, B. Wei
Department of Applied Physics, Northwestern Polytechnical University, Xian 710072, PR China

a r t i c l e

i n f o

a b s t r a c t
The phase transformation temperatures and enthalpy of fusion for CuGe alloys in the whole composition range are systematically measured by differential scanning calorimetry (DSC). It is found that the undercoolability of liquid CuGe alloys depends mainly on the nucleation ability of primary solid phases. Those liquid alloys solidifying with the preferential nucleation of intermetallic compounds exhibit smaller undercoolings than the others with the primary a(Cu) and (Ge) solid solution phases. Microstructural observation indicates that the n, e and e1 intermetallic compounds display non-faceted growth mode. In CuGe eutectic alloys, the n and e phases grow into lamellar structures, whereas the e2 and (Ge) phases form irregular eutectics. The peritectic reactions can rarely be completed, and the peritectic microstructures are usually composed of both the primary and peritectic phases. 2012 Elsevier B.V. All rights reserved.

Article history: Received 24 February 2012 Received in revised form 20 April 2012 Accepted 23 April 2012 Available online 1 May 2012 Keywords: CuGe Differential scanning calorimetry (DSC) Enthalpy of fusion Undercoolability Solidication

1. Introduction Binary CuGe alloys have attracted considerable research attention because of their excellent physical and chemical properties, such as low room-temperature resistance and high thermal stability, which are potentially useful in the optical and electronic devices [16]. The thermodynamic investigations of liquid Cu-based alloys and their solidication characteristics are of significance for understanding their physical and chemical properties [712]. Therefore, many efforts have been made to explore these subjects in recent years [1316]. Up to now, Castanet has determined the enthalpy of mixing of liquid CuGe alloys at different temperatures by means of hightemperature calorimeter [17]. The formation enthalpy of a(Cu) solid solution phase at 1000 K was measured by Predel and Schallner [18] using solution calorimetry. Moreover, Wallbrecht [19] determined the heat capacity of the intermetallic compound e1(Cu3Ge) in the temperature range from 230 to 1000 K by differential scanning calorimetry. The density and surface tension of liquid CuGe alloys in the temperature range between liquidus line and 1373 K were studied by Gruner et al. [14]. Recently, Wang et al. [20] have assessed the excess Gibbs energies of CuGe binary system by adopting the CALPHAD approach [21]. However, the enthalpy of fusion, which is one of the fundamental thermodynamic parameters and plays an important role in computing the

Corresponding author. Tel.: +86 29 88431666; fax: +86 29 88495926.

E-mail address: bbwei@nwpu.edu.cn (B. Wei). 0925-8388/$ - see front matter 2012 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.jallcom.2012.04.091

Gibbs free energy and determining the crystal nucleation and growth process [22], has not yet been available in the published literature. Although the enthalpy of fusion for binary alloys can be roughly estimated by NeumannKopps rule [23] from the values of the two pure components, this method usually brings in large discrepancy especially if one of the two elements is a semiconductor such as Si, Ge or Sb. This is because the enthalpy of fusion of semiconducting elements is much higher than those of metallic elements. In this point of view, the enthalpy of fusion for CuGe alloys should be measured experimentally. On the other hand, some work has been done on the directional and rapid solidication of CuGe peritectic alloys [2426]. For example, the structural morphologies of hyperperitectic CuGe alloys during unidirectional solidication were reported [24], and the microstructural evolution of peritectic CuGe alloys during rapid solidication was investigated versus undercooling [25,26]. Nevertheless, binary CuGe system is characterized by numerous types of phase transformations, such as eutectic, peritectic, eutectoid and peritectoid transitions. A comprehensive study on the solidication mechanism involved in different types of CuGe alloys under near-equilibrium conditions is still expected. The differential scanning calorimetry (DSC) is an efcient technique for quantitative thermal analysis [27,28]. Meanwhile, the DSC heatingcooling curves provide the essential information on phase transformation characteristics [3,2932]. The objective of this work is to determine the phase transformation temperatures and enthalpy of fusion for CuGe alloys by DSC method. Furthermore, the liquid undercoolability and solidication microstructures for various types of CuGe alloys are also investigated in the light of DSC calorimetric analyses.

W. Zhai et al. / Journal of Alloys and Compounds 535 (2012) 7077 2. Experimental procedures Eighteen CuGe alloys with different compositions were investigated, which are listed in Table 1 and marked in the binary CuGe phase diagram [33] shown in Fig. 1. Each sample had a mass of about 100 mg and was prepared from high purity elements of Cu (99.999%) and Ge (99.999%) by rapid laser melting under the protection of argon gas. The DSC experiments were carried out with a Netzsch DSC 404 F3 differential scanning calorimeter. The calorimeter was calibrated with the melting temperatures and the enthalpy of fusion for high purity In, Sn, Zn, Al, Ag, Au and Fe elements. The measuring accuracies of temperature and enthalpy of fusion are 1 K and 3% respectively, as veried by the measurements with pure Cu and Ge elements. Before each DSC experiment, the alloy specimen was placed in an Al2O3 crucible. The chamber was evacuated and then backlled with pure argon gas. The DSC thermal analyses were performed at a scan rate of 10 K/min, and the maximum heating temperatures were about 150 K higher than the liquidus temperatures. After the DSC experiments, the alloy specimens were polished and etched with a solution of 5 g FeCl3 + 1 mL HCl + 99 mL H2O. The solidication microstructures were analyzed with an optical microscope and an FEI Sirion scanning electron microscope.

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3. Results and discussion 3.1. Enthalpy of fusion The enthalpy of fusion for CuGe alloys, covering all the heat evolution from solidus temperature to liquidus temperature, in the whole composition range is determined by the solidliquid transformation peaks during melting process, as summarized in Table 1 and shown in Fig. 2. A polynomial relation is derived from tting the enthalpy of fusion DHf with respect to the mole fraction of Ge element C:
Fig. 1. Selection of alloy compositions and measured phase transformation temperatures illustrated in binary CuGe phase diagram.

DHf 14:44 0:96C 0:04C2 6:20 103 C3 3:14 106 C4

1
As seen from Fig. 2, the enthalpy of fusion versus Ge content rst decreases to a minimum value at 25% Ge, and then experiences a rise. By comparison, the enthalpy of fusion for CuGe alloys is lower than those of pure Cu and Ge elements in the Ge content range of 045%, and lies between them if Ge content exceeds 45%. Meanwhile, the linearly approximated values H0 estimated by NeumannKopps rule are also plotted by the dashed line in Fig. 2:
Fig. 2. Measured enthalpy of fusion of CuGe alloys versus Ge content.
2 DHo x1 DH1 f x2 DH f

2
3.2. DSC curves and microstructure characteristics In order to present a comprehensive survey on the phase transition characteristics, the DSC curves and solidied structures for different types of CuGe alloys are analyzed. 3.2.1. Single (Cu) phase alloys Fig. 3 presents the DSC melting curves of ve single a(Cu) phase alloys, in which the solidus and liquidus temperatures are marked. Clearly, the melting thermographs of these alloys are characterized by only one endothermic peak, and both the solidus and liquidus temperatures decrease with increasing Ge content. However, the shapes of melting peaks for these single-phase alloys differ from each other. When Ge content is low, for example Cu97.8Ge2.2 alloy, the endothermic peak is very sharp and smooth with a narrow solidliquid temperature interval. As Ge content rises, the inection points appear obviously in the rising stages of the melting peaks, and the peaks become broader and broader. This indicates that the solidliquid phase interval extends with the increase of Ge content in a(Cu) single-phase alloys. Fig. 4a shows a typical DSC cooling curve of these single-phase alloys. It is evident that there is only one sharp exothermic peak at 1269 K in the solidication process of Cu95.6Ge4.4 alloy, and the a(Cu) phase is found to form coarse and well-developed dendrites in the solidied specimen, as illustrated in Fig. 4b.

where xi and DHif are the molar fraction and enthalpy of fusion of the pure component i, respectively. It is apparent that all the measured data are lower than the linear tting values.

Table 1 Thermodynamic properties of CuGe alloys measured by DSC method. Alloy composition Cu97.8Ge2.2 Cu95.6Ge4.4 Cu93.4Ge6.6 Cu91.1Ge8.9 Cu89.3Ge10.7 Cu87.2Ge12.8 Cu84.8Ge15.2 Cu82.5Ge17.5 Cu78.05Ge21.95 Cu73.9Ge26.1 Cu68.0Ge32.0 Cu63.5Ge36.5 Cu53.3Ge46.7 Cu43.2Ge56.8 Cu32.9Ge67.1 Cu21.2Ge77.8 Cu11.3Ge88.7 Cu5.1Ge94.9 Liquidus temperature TL (K) 1354 1334 1312 1293 1252 1220 1172 1103 1015 1009 957 915 988 1046 1093 1134 1186 1209 Enthalpy of fusion DHf (kJ mol1) 12.729 10.774 9.890 9.735 9.418 8.074 8.068 8.062 7.156 7.050 9.175 11.022 13.282 14.347 15.698 16.833 20.691 24.761

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3.2.2. Peritectic type alloys Fig. 5a and b shows the DSC curves and solidied microstructure of peritectic Cu87.2Ge12.8 alloy. There are two endothermic events during its melting process. The rst endothermic peak corresponds to the decomposition of solid peritectic n phase into the liquid and a(Cu) phases, while the second one relates to the melting of a(Cu) phase. The solidus and liquidus temperatures of this alloy are 1096 and 1220 K, respectively. During the cooling process, the primary a(Cu) phase nucleates at 1145 K with a very sharp crystallization peak, and the following peritectic transition L + a ? n at 1091 K yields another small exothermal peak. As shown in Fig. 5b, the solidied microstructure consists of both the primary a(Cu) dendrites and the peritectic n phase. In fact, under equilibrium condition, 100% n phase is expected to be obtained at the end of solidication. However, since the peritectic transformation is mainly controlled by atomic interdiffusion and it is very slow, the peritectic reaction can rarely be completed even under slow cooling condition during the DSC experiments. Consequently, the microstructure is composed of peritectic n phase and primarily precipitated a(Cu) phase. The DSC proles of peritectic Cu73.9Ge26.1 alloy are presented in Fig. 5c. The four endothermic and four exothermic peaks are nearly

symmetrical, suggesting that the same reaction sequence takes place in reverse order during melting and solidication. In the cooling process, the rst sharp exothermal peak at 991 K relates to the phase transition L ? e, and its neighboring peak at 963 K indicates the peritectic transition L + e ? e2. Once temperature drops down to 876 K, another small exothermic peak appears, which probably corresponds to the peritectoid transition e + e2 ? e1. This is quite different from the solidication route indicated by the CuGe equilibrium phase diagram [33], in which this reaction should not take place in Cu73.9Ge26.1 alloy. In the present case, the incomplete peritectic reaction results in the coexistence of the primary and peritectic phases. This may lead to the peritectoid reaction between the primary e and peritectic e2 phases. The nal exothermal peak at 866 K coincides with the eutectoid transformation e2 ? e1 + (Ge) shown in the CuGe phase diagram [33]. As mentioned above, the solidication process of Cu73.9Ge26.1 alloy involves the nucleation and growth of e and e1 intermetallic compounds. The Jackson factor a is applied to predict the growth modes of these intermetallic compounds [34]:

a DSf =R DHf =RT L

Here, R is the gas constant. The a values deduced by the experimental enthalpy data are 0.84 and 0.85 for e and e1 phases, respectively. They are both smaller than the critical value of 2, indicating a nonfaceted growth mode. In contrast, the calculated values derived from NeumannKopps rule are found to be 2.2 and 2.1 > 2, which

Fig. 3. DSC melting curves of single-phase CuGe alloys.

Fig. 4. Typical cooling curve and structural morphology of single phase alloy: (a) cooling curve of Cu95.6Ge4.4 alloy and (b) a(Cu) phase microstructure.

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Fig. 5. Thermal and structural analyses of two peritectic CuGe alloys: (a) DSC curves of Cu87.2Ge12.8 alloy, (b) microstructure of Cu87.2Ge12.8 alloy, (c) DSC curves of Cu73.9Ge26.1 alloy and (d) microstructure of Cu73.9Ge26.1 alloy, and the inset shows enlarged eutectoid structure.

predict faceted growth. In order to conrm the crystallization behavior of these two intermetallic compounds, the structural morphology of Cu73.9Ge26.1 alloy is presented in Fig. 5d, which proves that the primary e phase grow just as normal non-faceted solution phases. The inset SEM image of Fig. 5d illustrates the eutectoid structure decomposed by peritectic e2 phase, in which the bright (Ge) phase and dark e1 phase grow as granular eutectoid structure and locate at the boundaries of e grains. Apparently, e1 phase exhibits the same growth mode as e phase. Hence, it can be concluded that the growth modes of these intermetallic compounds can be better predicted by the a values calculated from the measured values of enthalpy of fusion rather than by the values calculated from NeumannKopps rule. This further highlights the importance of experimental measurement of the enthalpy of fusion for binary alloys including Ge element. 3.2.3. Eutectic type alloys Fig. 6a depicts the DSC curves of eutectic Cu78.05Ge21.95 alloy. The rst exothermic peak at 1012 K during solidication is due to the eutectic reaction L ? n + e, during which e and n phases grow cooperatively into lamellar eutectic structure with an interlamellar spacing of 35 lm, as presented in Fig. 6b. As compared with the rst exothermic peak, the second one resulting from the eutectoid transformation e ? n + e1 at 805 K is very small, and unfortunately, the eutectoid structure cannot be distinguished in the

solidied specimen even at large magnication. The DSC curves of eutectic Cu63.5Ge36.5 alloy are shown in Fig. 6c. The two melting peaks at 885 and 915 K connect with each other, corresponding to the solid transformation e2 ? (Ge) + e1 and the melting of e2 + (Ge) eutectic structure, respectively. The relevant exothermic peaks during cooling are overlapped owing to the narrow temperature interval between these two transformations. The growth morphology of e2 + (Ge) eutectics is illustrated in Fig. 6d. Different from regular (n + e) eutectics, the (e2 + Ge) eutectics tend to grow in an irregular mode, and the microstructure is characterized by strip (Ge) phase distributing in e2 phase with an average interphase spacing of about 12 lm. In addition to eutectic Cu63.5Ge36.5 alloy, the DSC cooling curves of six different hypereutectic CuGe alloys are presented in Fig. 7a, whose common features are as follows: the (Ge) phase precipitates preferentially from the alloy melts at different temperatures. Subsequently, eutectic transition L ? e2 + (Ge) takes place at about 895 K. On further cooling, eutectoid reaction e2 ? (Ge) + e1 occurs around 870 K. Fig. 7b shows typical structural morphology of these hypereutectic CuGe alloys, in which the primary (Ge) phase grows in faceted way to form very coarse polygonal blocks, and e2 + (Ge) eutectic structure keeps almost the same morphology as that of eutectic Cu63.5Ge36.5 alloy. The measured formation enthalpy of primary (Ge) phase, e2 + (Ge) eutectic and e1 + (Ge) eutectoid structures in these hyper-

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eutectic alloys is plotted in Fig. 8 and listed in Table 2. Evidently, as Ge content rises, the formation enthalpy of primary (Ge) phase increases, whereas the formation enthalpy of eutectic and eutectoid structures decreases monotonically. The linear relationships between formation enthalpy and alloy composition are expressed as:

3.3. Undercoolability and nucleation of CuGe alloys The undercoolings (DT = TL Ts) of different liquid CuGe alloys are measured by DSC method using a scan rate of 10 K/min in the calorimeter to investigate their undercoolability versus composition. Here, TL is the measured liquidus temperature of a specic CuGe alloy during heating, and Ts is the initial solidication temperature upon cooling. As shown in Fig. 9, the undercooling DT can be divided into three regions as marked in Fig. 1, named region A (017.5 at.% Ge), B (17.536.5 at.% Ge) and C (36.5100 at.% Ge). In region A, the a(Cu) phase always solidies primarily in all the alloys, and the undercooling experiences an increase from 33 to 73 K with the rise of Ge content. Then, undercooling drops dramatically to about 20 K in the alloys of region B. As for these alloys, their solidication processes initiate with the nucleation of intermetallic compounds. By contrast, in region C, where the primary (Ge) phase nucleates preferentially from all the liquid alloys, the undercooling rises again from 46 to 73 K in the Ge content range of 36.577.8 at.%, and then falls again to a low value of 28 K in pure Ge. These results suggest that the undercoolings achieved in the DSC experiments are strongly dependent on the primarily nucleating solid phases and follow the relation:

DHsGe 0:38C 13:54 DHsGee2 15:34 0:16C DHsGee1 2:68 0:026C

4 5 6

On the basis of all the DSC melting curves, the transformation temperatures are marked by solid circles in the CuGe phase diagram [33] shown in Fig. 1, and the temperatures of typical reactions indentied by this work are also summarized in Table 3. It needs to be mentioned that the measured temperature of eutectoid reaction e ? e1 + n is 835 K, which is about 12 K higher than those values reported in Refs. [20,33]. Besides, the peritectoid transformation e2 + e ? e1in this work is determined to occur at 908 K, which is close to the value of 909 K in Ref. [33] and is about 40 K lower than that reported in Ref. [20]. Other typical reaction temperatures agree well with the published data.

DT comp < DT Ge < DT aCu

Fig. 6. DSC thermographs and microstructures of two eutectic CuGe alloys: (a) DSC curves of Cu78.95Ge21.95 alloy, (b) (n + e) eutectic structure of Cu78.95Ge21.95 alloy, (c) DSC curves of Cu63.5Ge36.5 alloy and (d) e2 + (Ge) eutectic structure of Cu63.5Ge36.5 alloy.

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Fig. 8. Formation enthalpy of different structures versus Ge content in hypereutectic CuGe alloys: (a) primary (Ge) phase, (b) (Ge) + e2 eutectic and (c) (Ge) + e1 eutectoid.

Table 2 Measured enthalpy of liquidsolid and solidsolid transformations for hypereutectic CuGe alloys. Alloy composition Enthalpy of transformation (kJ mol1) Primary (Ge) Cu63.5Ge36.5 Cu53.3Ge46.7 Cu43.2Ge56.8 Cu32.9Ge67.1 Cu21.2Ge77.8 Cu11.3Ge88.7 Cu5.1Ge94.9 0 4.337 8.221 13.808 15.337 19.897 22.901 (Ge) + e2 eutectic 11.343 6.419 5.814 4.674 3.412 1.553 0.780 (Ge) + e1 eutectoid 1.898 1.193 1.183 0.949 0.760 0.335 0.160

Fig. 7. DSC cooling curves and solidication microstructure of hypereutectic CuGe alloys: (a) cooling curves and (b) morphology of primary (Ge) phase in Cu5.1Ge94.9 alloy.

In fact, the undercoolability of liquid alloys is closely related to the nucleation processes of various solid phases within them. According to the classical nucleation theory [35], the activation energy DGc for homogeneous nucleation is given by:
2 DGc 16pr3 SL =3DGv

Table 3 Measured transformation temperatures of binary CuGe system in comparison with literature data. Reaction Type Transformation temperature (K) This work L + (Cu) ? n L?e+n L + e ? e2 L ? e2 + Ge e2 ? e1 + Ge e ? e1 + n e2 + e ? e1 Peritectic Eutectic Peritectic Eutectic Eutectoid Eutectoid Peritectoid 1096 1015 969 915 885 835 908 Ref. [33] 1097 1016.5 971 917 887 823 909 Ref. [20] 1097 1021 971 911 887 822 948

in which SL is the liquid/solid interfacial energy, and Gv is the difference of Gibbs free energies of liquid and solid phases. Gv is approximated by:

DGv Hm DT =V m T L

where Vm is the molar volume. From Eq. (10), it can be seen that the liquid/solid interfacial energy plays an important role in determining the nucleation process. In the model developed by Spaepen [36], the liquid/solid interfacial energy of a crystalline phase is expressed as:

rSL a

2 1 =3 m DSf T L =N A V m

10

where am is a structure-dependent factor and NA is the Avogadros number. According to Eq. (10), the liquid/solid interfacial energy of various phases are calculated and listed in Table 4. Due to the rather small composition differences among the three intermetallic

compounds, only e phase is considered here. Apparently, the liquid/ solid interfacial energy of e phase is signicantly lower than that of a(Cu) and (Ge) phases. On the basis of calculated liquid/solid interfacial energy, the activation energy for nucleation of the three phases versus undercooling is calculated, and the results are illustrated in Fig. 10. Clearly, if the nucleation takes place at the same undercooling,

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4. Conclusions In summary, the phase transformation temperatures and enthalpy of fusion for CuGe alloys in the whole composition range are determined by DSC method. The temperatures of eutectoid reaction e ? e1 + n and peritectoid reaction e2 + e ? e1 are determined to be 835 and 908 K, which are different from the published data. The enthalpy of fusion rst decreases in the composition range of 025%Ge, and then rises continuously with the increase of Ge content. The measured enthalpy of fusion for CuGe alloys is lower than those calculated by Neumannkopps rule. The maximum undercoolings of liquid CuGe alloys in which the a(Cu) and (Ge) phases nucleate preferentially are 73 and 71 K respectively in the DSC experiments. By contrast, the undercoolings of those liquid alloys in which intermetallic compounds nucleate as the primary phases are only around 20 K. Their relatively weak undercoolability is due to the low activation energy for nucleation of intermetallic compounds as compared with that of a(Cu) and (Ge) phases. Microstructural observation reveals that a(Cu) phase forms well-developed dendrites, whereas the (Ge) phase exhibits faceted growth in the form of polygonal blocks. The n, e and e1 intermetallic compounds are also found to display non-faceted growth manner. Furthermore, in eutectic CuGe alloys, the e phase grows cooperatively with the n phase into lamellar structure, whereas the e2 and (Ge) phases tend to form irregular eutectic structure. The peritectic reactions can rarely be completed, and the solidication microstructures of peritectic CuGe alloys consist of both the primary and peritectic phases. Acknowledgements This work was supported by the National Natural Science Foundation of China (Nos. 50971105 and 51101123) and Fundamental Research Fund of Northwestern Polytechnical University (Nos. JC201050 and JC20110280). References
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Fig. 9. The measured undercoolings of CuGe alloys versus composition.

Table 4 Liquid/solid interfacial energy of various phases in binary CuGe system. Phase
a

Composition (at.% Ge) 4.4 26.1 100

am
0.71 0.71 0.86

Interfacial energy (Jm2) 0.347 0.084 0.283

e
(Ge)

Fig. 10. Activation energy for nucleation of different phases versus undercooling.

the activation energy for homogeneous nucleation of the three solid phases follows the relation:

DGe < DGGe < DGaCu

11

It is reasonable to assume that inequality (11) is also valid in the heterogeneous nucleation processes of CuGe alloys in the DSC calorimeter. The activation energy for heterogeneous nucleation of intermetallic compounds is lower than that of a(Cu) and (Ge) phases, suggesting that the intermetallic compounds are easier to nucleate. This accounts for the weak undercoolability of those liquid alloys in which intermetallic compounds nucleate as the primary phases, and reveals the fact that the activation energy for primary phase nucleation determines the undercoolability of liquid CuGe alloys.

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