SCIENCE CHINA

Physics, Mechanics & Astronomy

Research Paper

January 2010

Vol. 53 No.1: 7680

doi: 10.1007/s11433-010-0080-7

Thermodynamic properties of under-cooled silver melts

ZHU YuYing1, LI Qiang1,2,3*, WANG Ge1, JING Qin2, WANG Xu1, GAO Ying3 & GAO JingNa3
Department of Mechanical Engineering, Yanshan University, Qinhuangdao 066004, China; Key Laboratory of Metastable Materials Science & Technology, Yanshan University, Qinhuangdao 066004, China; 3 Department of Materials Science & Engineering, Hebei University of Science and Technology, Shijiazhuang 050018, China
2 1

Received April 2, 2009; accepted July 21, 2009

Differential scanning calorimeter technique combined with the traditional fluxing treatment was used to investigate the specific heat and related thermodynamic properties of under-cooled pure silver melts. The specific heat of the under-cooled melt showed a linear dependence on the temperature in the range of the obtained under-cooling from 0 to 198 K. The related thermodynamic properties of silver, such as the entropy change, the enthalpy change and the Gibbs free energy difference between the under-cooled melt and the solid phase, were derived from the measured specific heat. The relations between the temperature and the thermal diffusion or the thermal conductivity of the under-cooled melt were analyzed respectively. under-cooled silver melts, specific heat, thermodynamic properties

Specific heat and related thermodynamic properties of under-cooled liquid melts are very important parameters to further research on the mechanism of non-equilibrium solidification and formation of new metastable materials, and these properties are also essential for describing the nucleation and growth phenomena in under-cooling melts [16]. In the past several decades, the specific heat and related thermodynamic properties of under-cooled metals, alloys and oxides have been investigated, by electromagnetic [715] and electrostatic [16, 17] levitation, whose techniques can easily realize the deep under-cooling of melts. But the heat transmission in the process of levitation lacks accurate control and measurement, and the techniques can measure only the average specific heat of under-cooled melts, which does not accurately show the relation between specific heat and temperature. During repeated melting and solidification, the sample in a suitable flux can be purified and the container wall effects on heterogeneous nucleation can be suppressed. As a result, deep under-cooling can be obtained [18, 19]. When combined with the DSC technique,
*Corresponding author (email: liqiang@ysu.edu.cn) Science China Press and Springer-Verlag Berlin Heidelberg 2010

accurate measurement of the specific heat of the deeply under-cooled melts is realized [2023]. Studies on the measurement of the specific heat of deep under-cooled metal liquids and alloys have been reported recently [2428], but the accurate experimental data on the specific heat and related thermodynamic properties of the under-cooled melts are still very scarce, for high-melting metals and alloys in the temperature range above 1200 K in particular. The recent literature covers only the measurements of some pure metals and simple binary alloys. In this paper, fluxing treatment is used within a DSC facility to investigate pure silver, a high-melting metal with the melting point temperature of 1233.6 K. The related thermodynamic properties including the enthalpy change, the entropy change, the Gibbs free energy difference, thermal diffusivity and thermal conductivity, are derived on the basis of the experimental results. And their temperature dependence is discussed, respectively. The experimental results are compared with several traditional approximate models based on different assumptions [2933] in order to find the most accurate model for describing the non-equilibrium solidification of deep under-cooled silver melts.
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1 The experimental procedure

Silver samples (about 11.5 mg) were cut from high purity (99.999%) material. Under-cooling and the specific heat were measured with sapphire as the reference standard in a differential heat flow calorimeter (Nestzsch STA449C). The sample was put into the Al2O3 crucible together with dehydrated B2O3 flux (about 1015 mg). The chamber containing the crucible was filled with pure argon gas, and the specimens were heated to the melting temperature and then overheated. The temperature was held constant at 1400 K for a period of time and then decreased with a cooling rate between 5 to 40 K/min. By repeatedly overheating and solidifying treatment, deep under-cooling was achieved. Every integrated experiment includes three operations in order to obtain baseline, sample line and standard line. The DSC facility was calibrated by using such pure elements as In, Sn, Zn, Al, Au and Ni.

measured enthalpy of fusion is (1062) J/g. This matches the literature values [34]. The highest under-cooling obtained in this work is 198 K. The measured specific heat of liquid silver through the entire experimental temperature range, including the overheated liquid and the deeply under-cooled liquid, shows an almost linear dependence on temperature. Even at the deepest under-cooling in the present experiment, no obvious deviation is observed. The data fits the following linear expression
l CP = 0.323 9.924 106 T J g 1 k 1 .

(1)

The experimental excessive specific heat between the under-cooled liquid and the corresponding solid phase of l s is computed as a function of temperature silver, CP
l s CP = 0.123 8.59 105 T J g 1 k 1 .

(2)

2 Results and discussion

2.1 Specific heat Figure 1 shows the measured specific heat of the solid phase, overheated liquid, and under-cooled liquid. The literature data [34] of the solid phase and the overheated liquid are marked with black squares in Figure 1. These two regions overlap, with the accuracy of the measurements within 2.5%, which demonstrates the applicability and accuracy of the applied experimental technique even at high temperatures. In addition, for the first time the present experiment can be extended to the deep under-cooled regime of pure silver. The melting point obtained in this work is 1240 K, which contains a positive error of 0.48%, compared with the literature data [34]. The specific heat of the melt was measured and its fusion enthalpy Hm was obtained. The

2.2 Comparison with specific heat obtained by several models Without specific heat data of the under-cooled liquid, the specific heat and related thermodynamic properties of under-cooled liquids are generally estimated from easily obtained parameters, such as the specific heat of the solid phase and the melting point temperature. Several models based on different assumptions have been developed previously to describe the relationship between specific heat and under-cooling. One of them is the well-known model of Turnbull [29], who proposed that the specific heat of under-cooled melt is approximately equal to that of crystalline solid at the same temperature, and who neglected the difference in specific heat between the liquid and the solid phase. This results in a linear approximation between the Gibbs free energy difference and the under-cooling. The excessive specific heat C lp s is, then, equal to zero
l s CP = 0.

(3)

Jones and Chadwick [30], assuming the excessive specific heat is constant, recommend using a suitable value, m , usually the difference at the melting temperature, C p which is equal to the ratio of fusion enthalpy Hm divided by the melting point temperature Tm. This yields the relations
l s CP = H m / Tm .

(4)

Battezatti and Garron [31] by revising the model of Jones and Chadwick, gave another equation to calculate the excessive specific heat
Figure 1 Measured specific heat of pure silver compared with the literature data by Hultgren et al. [34].
l s CP = 0.8H m / Tm .

(5)

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Dubey and Ramachandrarao [32] proposed a further model, on the basis of the hole theory of liquids
2T 3 + 3T 2 T T 3 l s CP = ( H m / T ) , 2T 3

(6)

where the T is under-cooling. Singh and Holz [33] recommended that the excessive specific heat should be expressed as a linear function of temperature
C
l s P

enthalpy change Hls(T), the entropy change Sls(T) and the Gibbs free energy difference Gls(T), etc. can be calculated. The thermodynamic properties, especially the Gibbs free energy difference, are very important to further research on the mechanism of the non-equilibrium solidification, crystal nucleation and growth and formation of new meta-stable materials. After the specific heat is determined, the properties can be calculated according to the following equations:
H l s (T ) = H m
Tm T l s CP (T )dT ,

= AT + B,

(7)

(8) (9) (10)

where A and B represent unknown constants. The experimental excessive specific heat shows a linear dependence on temperature, as shown in Figure 2. The results derived from some traditional models are included in the figure. The calculated results by Turnbull, Thompson, and Battezatti are all constants and equal to 0, 0.085 J g1 K1 and 0.068 J g1 K1, respectively. The results suggest that none of the three models can correctly describe the specific heat of the under-cooled silver. The data from Dubey become increasingly larger with the increase of under-cooling. Although there exists a positive deviation of about 0.074 J g1 K1 from the experimental data, the increasing tendencies with under-cooling are consistent. Figure 2 does not include the result from the Singh model, as a result of the two unknown constants, A and B. But the experimental data coincide with Singh, an approximate model assuming that Cp can frequently be expressed as a linear function of temperature. 2.3 Related thermodynamic properties From the measured excessive specific heat between the under-cooled liquid and the solid phase, the relevant thermodynamic properties of under-cooled silver, such as the

Sl s (T ) =

Tm C l s (T ) H m P dT , T Tm T

Gl s (T ) = H l s (T ) Sl s (T ) T .

According to the experimental excessive specific heat, following eqs. (8)(10), the enthalpy change, the entropy change, and the Gibbs free energy difference are calculated as functions of under-cooling, indicated by the solid line shown in Figure 3. Dubey is selected for comparison with the experimental thermodynamic properties, based on the analysis of the excessive specific heat. The results are given in Figure 3. It can be seen that Hls(T) and Sls(T) decrease with the under-cooling increasing, whereas Gls(T) increases. This reveals that the thermodynamic driving force of phase transformation, Gls(T), becomes larger and larger when the under-cooling increases from 0 K to the maximum under-cooling of 198 K. The deviations between the experimental line and the results derived from Dubey increase with the under-cooling increasing. For Hls(T) and Sls(T), the deviations of Dubey are rather remarkable and is far greater than that of Gls(T). This suggests that the Dubey model, assuming that the excessive specific heat is a complicated polynomial of temperature, cannot reflect the actual

Figure 2 Excessive specific heat between under-cooled liquid and solid phase versus under-cooling.

Figure 3 Thermodynamic properties versus under-cooling. (a) Difference of enthalpy; (b) difference of entropy; (c) difference of Gibbs Free Energy.

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situation of the change in enthalpy and entropy during solidification. Although there seems to be only a little difference, the Gls(T) has a remarkable effect on the nucleation kinetics. Yet, Dubey still shows a noticeable deviation with the increase of under-cooling. This indicates that the model of Dubey can only describe the solidification process under low under-cooling conditions. Both thermal conductivity and thermal diffusivity are necessary thermodynamics properties for investigating the process of non-equilibrium solidification of under-cooled liquids, which are very difficult to measure directly. The well-known law of Wiedemann-Franz-Lorenz (WFL) [35] describes the relationship between thermal conductivity, and electrical resistivity, e, which reads

, l Cp

(14)

where is the density of under-cooled liquid, which can be calculated from the following experiential formula

= m + (T Tm ),

(15)

where m is the density of melting point, and is the temperature coefficient. According to the literature [35], for silver, m is 9.33 g cm3 and is 9.1104 g cm3 K1. The density of under-cooled silver can be expressed as

= 9.33 9.1 104 (T Tm ) g cm 3 .

(16)

e / T = 2.45 108 W K 2 ,

(11)

where e is the electrical resistivity of under-cooled silver melt that can be derived from the following experiential formula [35]

In terms of the results of eqs. (1), (13) and (16), the thermal diffusivity is calculated and presented in Figure 4. A linear relationship yields

= 2.78 105 + 2.62 108 T m 2 s 1 .

(17)

e = 0.009T + 6.2 cm.

(12)

According to eqs. (10) and (11), the thermal conductivity can be derived, and expressed as

2.45 T W K 1 m 1 . 0.009T + 6.2

(13)

The thermal conductivity can be calculated on the basis of eq. (13), and the results are shown in Figure 4. The thermal conductivity shows an approximately linear dependence on temperature, and increases with the increase of temperature. Based on the experimental measurements, the thermal diffusivity, , can be predicted from the measured specific heat of under-cooled liquid and the calculated thermal conductivity. As a function of temperature, can be indirectly obtained by the following relations [35]:

The thermal diffusivity is always taken as a constant in the investigations of rapid solidification. However, it is actually a function of temperature for under-cooled silver according to Figure 4, and it increases with the increasing temperature. Therefore, it is essential to determine thermodynamic properties for theoretical investigations. Owing to the lack of experimental data in the under-cooled regime, as well as the difficulty in measuring the thermal diffusivity in the laboratory, a comparison of the present study with other investigations is not available.

3 Conclusions
Combined traditional flux (dehydrated B2O3) treatment with the DSC technique, the specific heat and related thermodynamic properties of under-cooled silver are precisely measured. It is found that the specific heat of under-cooled silver shows a linear dependence on temperature and increases with the increase of temperature. The excessive specific heat between the under-cooled liquid and the corresponding solid phase is investigated, and compared with five traditional models including Singh-Holz. The excessive specific heat is a linear function of temperature. The enthalpy change, the entropy change and the difference of Gibbs free energy are calculated and compared with the data calculated from Dubey, which is usually used in the theoretical investigation in the process of solidification. The results show that the model can only reveal the reality of the non-equilibrium solidification accurately when the under-cooling is small, and the deviation is greater when the under-cooling increases. The thermal conductivity and thermal diffusivity, calculated at the end of this report, are functions of temperature and increase with the increase of temperature.

Figure 4 Thermal conductivity and thermal diffusivity coefficient versus under-cooling.

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Supported by the National Natural Science Foundation of China (Grant No. 50731005/50821001), the National Basic Research Program of China (Grant Nos. 2009CB626603 and 2007CB616915), PCSIRT (Grant No. IRT0650), and the Hebei Technology Department Foundation (Grant No. 08965109D). 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 Herlach D M, Holland-Moritz D, Wilde G, et al. Undercoolability of pure Co and Co-based alloys. J Non-Cryst Solids, 1999, 250-252: 271276 Yan X Q, Song X Y, Zhang J X. Review on development of bulk amorphous alloys. Rare Metal Mat Eng, 2008, 37: 931935 Herlach D M, Galenko P K. Rapid solidification: In situ diagnostics and theoretical modeling. Mater Sci Eng A, 2007, 449-451: 3441 Panofen C, Herlach D M. Solidification of highly undercooled Si and Si-Ge melts. Mater Sci Eng A, 2007, 449-451: 699703 Liu R P, Herlach D M, Vandyoussefi M, et al. Morphologies of silicon crystals solidified on a chill plate. Metal Mater Trans A, 2004, 35: 10671073 Liu R P. Thermodynamic analyses of the solid-liquid interface and growth mode transition in undercooled melts. Chin Phys Lett, 2003, 20: 16221625 Wang H P, Wei B. Theoretical prediction and experimental evidence for thermodynamic properties of metastable liquid Fe-Cu-Mo ternary alloys. Appl Phys Lett, 2008, 93: 171904, 10.1063/1.3009209 Wang H P, Wei B B. Surface tension and specific heat of liquid Ni70.2Si29.8 alloy. Chin Sci Bull, 2005, 50: 945949 Wang Q, Liu R P, Qian Y Q, et al. Metal-like growth of silicon during rapid solidification by quenching undercooled droplets on a chill plate. Scr Mater, 2006, 54: 3740 Ge L L, Liu R P, Li G, et al. Solidification of Al-50at.%Si alloy in a drop tube. Mater Sci Eng A, 2004, 385: 128132 Liu R P, Herlach D M, Vandyoussefi M, et al. Undercooling and solidification of Al-50at.%Si alloy by electromagnetic levitation. Metall Mater Trans A, 2004, 35: 607612 Liu R P, Volkmann T, Herlach D M. Undercooling and solidification of Si by electromagnetic levitation. Acta Mater, 2001, 49: 439444 Liu R P, Wang W K, Li G, et al. Transition from continuous to lateral growth for ge crystal in undercooled Ge74Ni26 alloy melts. Scr Mater, 1999, 41: 855860 Wang Q, Ma M A, Jing Q, et al. Undercooling and unidirectional solidification of CuNi alloy melts. Chin Phys Lett, 2008, 25: 3808 3810 Qi L, Dong L F, Zhang S L, et al. Cluster evolution in the rapid cooling process of Cu-Ag melts under high pressure: Molecular-dynamics simulation. Comput Mater Sci, 2008, 43: 732735 Hu L, Lu X Y, Hou Zh M. Progress in electrostatic levitation technology (in Chinese). Physics, 2007, 36: 449455 Sung Y S, Takeya H, Togano K. Deriving thermophysical properties of liquid Nb by containerless electrostatic levitation. Appl Phys Lett,

18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35

2002, 92: 65316536 Li Q, Zhu Y Y, Liu R P, et al. Specific heat and related thermodynamic properties of undercooled germanium melt. J Appl Phys, 2004, 85: 558560 Li Q, Zhu Y Y, He Y H, et al. Undercooling and solidification of germanium melts studied by differential scanning calorimeter. Sci China ser G-Phys Mech Astron, 2004, 47: 581587 Rodrguez-Aseguinolaza J, Ruiz-Larrea I, N M L, et al. A new quantitative approach to the thermoelastic martensitic transformation: The density of elastic states. Acta Mater, 2008, 56: 62836290 Liu N, Liu F, Yang C L, et al. Peritectic solidification of undercooled Fe-Co alloys. J Alloys Compd, 2008, 465: 391395 Wang P, Liu F, Lu Y P, et al. Grain refinement and coarsening in hypercooled solidification of eutectic alloy. J Cryst Growth, 2008, 310: 43094313 Kaushal A M, Bansal A K. Thermodynamic behavior of glassy state of structurally related compounds. Eur J Pharm Biopharm, 2008, 69: 10671076 Wilde G, Sebright J L, Perepezko J H. Bulk liquid undercooling and nucleation in gold. Acta Mater, 2006, 54: 47594769 Benjamin A, Jan Schroers L, Busch R. Thermodynamics, kinetics and crystallization of Pt57.3Cu14.6Ni5.3P22.8 bulk metallic glass. Acta Mater, 2007, 55: 11091116 Fiore G, Battezzati L. Thermodynamic properties of the Pd77.5Cu6Si16.5 undercooled liquid. J Alloys Compd, 2009, 483: 5456, doi:10.1016/j.jallcom.2008.07.170 Hua R X, Nash P L, Chen Q, et al. Heat capacities of several Al-Ni-Ti compounds. Thermochim Acta, 2009, 486: 5765 Battezzati L, Mortarino G M. On thermophysical and mechanical properties of glass-forming alloys. J Alloys Compd, 2009, 483: 222226, doi: 10.1016/j.jallcom.2008.08.099 Turnbull D. Formation of crystal nuclei in liquid metal. J Appl Phys, 1950, 21: 10221028 Jones D R H, Chadwick G A. An expression for the free energy of fusion in the homogeneous nucleation of solid from pure melts. Philos Mag, 1971, 24: 995998 Battezzati L, Garrone E. On the approximation of the free energy of undercooled glass-forming metallic melts. Z Metallkd, 1984, 75: 305310 Dubey K, Ramachandrarao P. On the free energy change accompanying crystallization of undercooled melts. Acta Metal, 1984, 32: 9196 Singh H, Holz A. Stability limit of supercooled liquids. Solid State Commun, 1983, 45: 985988 Hultgren R, Dessai P D, Hawkins D T. Selected Values of the Thermodynamic Properties of the Elements. Metals Park, OH: American Society for Metals, 1973. 22 Iida T, Guthrie R I L. The Physical Properties of Liquid Metals. Oxford: Clarendon Press, 1993. 24