Estimation of the Viscosities of Binary Metallic Melts Using Gibbs Energies of Mixing

S. SEETHARAMAN and DU SICHEN In the present work, information on the integral molar Gibbs energies of mixing is employed to calculate the viscosities of binary substitutional metallic melts. A correlation has been established between the second derivative of the integral molar Gibbs energy of mixing with respect to composition and the corresponding function for the Gibbs energy of activation for viscosity. The viscosities predicted from available thermodynamic data in the case of a number of binary metallic systems using this correlation show satisfactory agreement with the values reported from experimental measurements. The value of this correlation in predicting the viscosities of complex metallic melts is also examined.

I.

INTRODUCTION

R E L I A B L E viscosity data of high-temperature metallic as well as ionic melts are important for the modeling and design of metallurgical processes. For example, a knowledge of the viscosities of metallic melts and slags is essential in understanding the kinetics of reactions relevant to process metallurgy as well as for processes like casting and welding. Although a number of experimental measurements have been carried out, the amount of data available on viscosity is still scarce compared to the needs of today's technology. This is particularly true when complex melts are involved. In the case of metallic systems, where the viscosities of many pure liquid metals have been reported, the available viscosity data for binary alloys are limited to a few systems. To the knowledge of the present authors, no systematic measurement has been carried out for higher-order metallic systems. The viscosities of liquids depend, to a great extent, on the movements of species (atoms, molecules, or ions) and thus on the bonding and on the configuration of the species in the liquid. On the other hand, the thermodynamic properties such as molar Gibbs energy, enthalpy, entropy, and volume of mixing are also related to the nature and strength of the bonds of the species and the distribution of the same in the liquid with reference to order-disorder phenomena, It could thus be expected that there are natural correlations between viscosity and the thermodynamic properties. In fact, evidence of the existence of such correlations has been observed earlier. For example, it has been shown tlJ that viscosities may vary substantially with the composition and trends of the viscosity isotherms, and the liquidus in both Ag-Sn and A1-Cu systems exhibit similarities. The dependence on the binding and the arrangement of the species in the liquids shared by both viscosity and Gibbs energy of mixing open up the possibility of establishing mathematical relationships between these two properties. Since the thermodynamic properties of complex systems at high temperatures have
S. SEETHARAMAN, Professor, and DU SICHEN, Research Associate, are with the Division of Theoretical Metallurgy, Royal Institute of Technology, 100 44 Stockholm, Sweden. Manuscript submitted July 7, 1993. METALLURGICAL AND MATERIALS TRANSACTIONS B

been studied extensively, the relationship between the viscosity and thermodynamic properties would provide a useful tool for the estimation of the viscosity values using the vast amount of thermodynamic information available.

II.

PREVIOUS WORK

A number of studies have been carried out earlier to relate the viscosities of liquid alloys to the thermodynamic properties. Among them, Kucharski's model tz~ still requires directly measured viscosity data for the binary system. Hence, it cannot be employed to predict the viscosities purely from thermodynamic properties, Moelwyn-Hughes t31 proposed the following equation to calculate the viscosities of binary liquid mixtures using the values for enthalpies of mixing: ~7=(XIrh +X2~2) 1 -2 [1]

where r/l and '12 are the viscosities of the pure components 1 and 2, H E U" mol l) represents the integral molar enthalpy of mixing, R is the gas constant in J" K -~ 9mol-', and T is temperature in kelvin. Equation [1] indicates that the sign of deviation of the viscosity from linearity depends only on the sign of the enthalpy of mixing, which appears to be true in a number of binary metallic melts. While the equation is simple, its application has not been found to be particularly satisfactory. 14,51 It is interesting to note that Iida and Guthrie ISJ point out that viscosities could not be formulated in terms of thermodynamic properties alone. Iida et al.E6] proposed an equation relating the viscosity of a binary system to the diameters and masses of different atoms as well as to the integral molar enthalpy of mixing. A similar equation was later suggested by Morita et al.ITJ Instead of the integral molar enthalpy of mixing, these authors introduced activity coefficients. Both these approaches have been applied to some binary metallic systems. Good agreement between the calculations and the experiments has been reported for regular or nearly regular solutions. Recently, Hirai IS1reported that the viscosities of liquid
VOLUME 25B, AUGUST 1994--589

metals could be estimated using temperatures of the liquidus of the corresponding phase diagram. This approach was stimulated by the study of Andrade,tgJ who derived a formula for viscosities of pure liquid metals at their melting points based on the quasi-crystalline theory. Andrade's formula has been found to be very successful in predicting the viscosities of pure liquid metals in the neighborhood of their melting points. Hirai tSI extended Andrade's equations, suggesting that the viscosities o f liquid alloys could be calculated by the following equations: [2a] 1.7 lO-7p2/3Tlm/2M 1/6 A = (Pa- s) [2b]

,/ = A exp \ - ~ - / with A = -M

(AG*~

hNp

[4]

where p is the density of the melt, h is Planck's constant, N is Avagadro's number, M is the molecular weight, and AG* is the Gibbs energy of activation per mole.*
*Throughout the present article, AG* refers to the Gibbs energy of activation for viscosities, while AmGm~,refers to the relative integral molar Gibbs energy of mixing.

In the case of unary systems, the Gibbs energy of activation is a function of temperature and can be expressed as AG* = a + b T + c T l n T + . . . [5]

B = 2.65T~ 27 (J'mo1-1)

[2c]

The application of this method to the calculation of the viscosities of several binary systems shows reasonable agreement between the calculated and experimental results. Hirai's tS] approach implies that the viscosity isotherm would always follow the trend of the liquidus. However, this is not true in cases like the Bi-Sn binary system, where positive deviation in the viscosity isotherm has been observed tSl while the system is eutectic. A mathematical model( 1~ for estimation of viscosities of complex metallic and ionic melts has been developed earlier. The model is based on the absolute reaction rate theory for the description of flow process. The viscous flow is described by the equation

where a, b, and c are model parameters. It is usually sufficient to use the first two or three terms on the righthand side of Eq. [5]. In the case of high-order metallic systems, the molecular weight of the melt can be calculated by the equation

M = EXi" Mi

[6]

where Xs and Ms represent the mole fraction and the molecular weight of component i in the solution, respectively. In a similar way, the density of the melt may be estimated, as a first approximation, by p = EXs" Ps [7]

rl=aexp(AG*~

where Pi is the density of the pure component i in liquid state. The Gibbs energy of activation is expressed as AG* = ZX i- AG* + AG*ix [8]

\ RT /

[3]

The Gibbs energy of activation, AG*, is considered to be a function of both temperature and composition of the melt. The model has been applied successfully to various metallic as well as ionic systems. The present work aims at establishing correlations between the aforementioned description of viscosities and thermodynamic properties, enabled by the similarity in their model formulations. In this article, the correlations will be restricted to metallic melts and will subsequently be extended to ionic melts.

The subscript i stands for component i. The first term on the right-hand side of Eq. [8] represents the "linear" variation of the Gibbs energy of activation from the pure components in the absence of interaction between different components. The AG* is the Gibbs energy of activation of pure component i in liquid state. The second term in Eq. [8] represents the part due to the mutual interactions between different species.

B. Relationship between AG* and the Gibbs Energy of Mixing, A"Gm,x

The difference between the Gibbs energy of activation, AG*, and the Gibbs energy of mixing in a solution, AmGmix, c a n be expressed by the following equation: AG*
AmGmix -

III.

MODEL CONSIDERATION

For the sake of clarity, the viscosity model o~ for metallic systems is briefly outlined here before considering the correlations with the Gibbs energy of mixing.

Xi" AG* - AmGmix+

+

AGm*ix

[9]

By rearranging Eq. [9], one can arrive at the relationship

A. The Viscosity Model

According to the absolute reaction rate theory by Glasstone et al.,ln] the viscosity of viscous flow, r/, can be expressed by Eq. [3]:
590--VOLUME 25B, AUGUST 1994

A G * = A'nGmix 4- E X i 9 AG*

(Aam*ix - AmGmix)

[10]

If the difference between AG*ix and A'G,~ix could be estimated, the Gibbs energy of the activation for the multicomponent melt could be calculated from the Gibbs
METALLURGICAL AND MATERIALS TRANSACTIONS B

energies of activation for the pure components and the Gibbs energy of mixing. In order to arrive at an optimum correlation between Gibbs energy of mixing and the Gibbs activation energy for viscosity, it is necessary that the Gibbs energy of mixing be altered to a suitable form where it has maximum sensitivity to the degree of order. Darken t12~ observed that the second derivative of the integral molar excess Gibbs energy with respect to composition (excess stability) is a function that is quite sensitive in reflecting the interatomic attractive or repulsive forces. This has been well illustrated u2~ in the case of Ag-A1 liquid alloys, where the plot of excess stability as a function of composition at 1173 K shows a peak corresponding to XA~ = 0.25. This may be attributed to the residual ordering that may exist corresponding to the /x phase in the solid state, which decomposes at 721 K. In view of the advantages of this function, it was proposed in the present work to correlate this function to the second derivative of the Gibbs energy for activation for viscous flow. The difference between the two, viz., the factor for thermal motion, has been pointed out t131 to be based on the transfer of momentum of atomic vibration from one layer to another. From an examination of a number of binary metallic systems, this factor was estimated as

Table I. The References for the Binary and Co-Fe-Ni Systems

System In-Sn Ag-Au Ag-Sn Ag-Sb Ag-ln Bi-Sn Co-Fe Bi-Cu Co-Fe-Ni

References for the Thermodynamic Data (Gibbs Energy of Mixing) 15 14 14 15 15 14 14 14 14

References for the Viscosity Data 17 18 19 6 20 21 22 16 --

[d2(amCmix ]
[ dX Je,r L dX2
Je.T-6RT [11] where R is the gas constant in J. K -~. tool -~ and T is the temperature of the melt in kelvin. This, upon integration, leads to the expression

AeG *

AEGmix :

3RT'X~ "Xz

[12]

for a binary system 1-2, where X~ and X2 are the respective mole fractions. Combining Eqs. [ 12] and [10], the following general expression is arrived at for the Gibbs activation energy for the viscosity:

AG* = ~,Si. AGi* +

AmGmix -1-

3RT'X1 "X2

[13]

most accurate unary data, especially when there are discrepancies in the reported values between different viscosity measurements. The experimental results are frequently inconsistent.t~J Even in the case of binary liquid alloys, there are anomalies, The authors' choices of Gibbs activation energies for unary viscosities are listed in Table II in the form of the equation a + bT, along with the sources for these values. In the testing of Eq. [13], it is also important that the Gibbs energies of mixing chosen from literature are reliable. In the present work, the main sources of thermodynamic data for liquid metals were SGTE ~141 and Hultgren et al. u51 In the case of density values for pure liquid metals necessary for using Eq. [4], the values were assumed to be the same as at their melting points. The viscosities for binary alloys calculated using Eq. [13] are presented in Figures 1 through 8. It should be mentioned that in the case of using the thermodynamic data by Hultgren et al.,[15) the viscosity values were calculated only for the compositions for which the Gibbs energies of mixing were available. The predicted values are compared with the available experimental data in these figures. It can be seen that the agreement between the two in most of the cases is satisfactory.

Equation [ 13] enables the computation of the viscosities of binary substitutional metallic melts from unary values with a knowledge of the Gibbs energy of mixing for the system at the relevant temperatures.

A. System ln-Sn
Among the systems examined in the present work, the In-Sn binary exhibits a eutectic at 393 K. uSj Two intermediate phases, /3 (In3Sn) and y (InSn4), are formed in the system, indicating attractive forces between In and Sn. The viscosity values of the pure unaries are somewhat close to each other. As can be seen in Figure 1, the predicted viscosity curve for the binary shows a slight negative deviation from linearity, a trend that seems to be in accordance with the negative deviation from Raoult's law exhibited by the system. The experimental results are somewhat scattered. Despite this, the agreement with the prediction can be considered reasonable.

IV.

APPLICATIONS OF THE MODEL

Equation [13] has been applied to eight different binary substitutional metallic solutions. These systems were chosen so that the corresponding phase diagrams show variations from complete miscibility in the solid state (Ag-Au) to systems with intermediate phases in the solid state (Ag-Sn). The system Fe-Co was included among those studied to see if the unfilled d-electron levels have any influence on the viscosity behavior. In the case of some of the systems, the unary viscosities were somewhat similar (for example, Sn-Bi), while in other cases, the difference was significant (Cu-Bi). A list of the systems examined is presented in Table I. In the evaluation of the binary viscosities using the unary values and Eq. [13], there is the problem of selecting the
METALLURGICAL AND MATERIALS TRANSACTIONS B

B. System Ag-Au
This system shows complete miscibility in both solid and liquid states. The enthalpies of mixing in this system
VOLUME 25B, AUGUST 1994--591

Table II. The Gibbs Activation Energies of Viscosities and the References of the Viscosity Data for the Pure Liquid Metals

System Ag Au Bi Co Cu Fe In Ni Sb Sn

AG* = a + bT a b 20,340 22.506 17,620 28.889 6437 25.836 66,745 0 24,812 16.480 52,719 9.0262 5480 23.655 34,983 17.395 11,670 21.874 6780 24.013

References 23 24 16 22 16 22 25 26 20 20

0.0025

- 0.0020

Calculated by the present work (573K) Experimental data [171 (573K)

[]

viscosity values are significantly different from each other. In spite of these complications, the predictions of the binary viscosities using the present model are in good agreement with the experimental data. In the case of the Ag-Sn system, experimental viscosity values are available for 1273 and 1573 K (Figure 3). Hence, the calculations were carried out in the present work for both these temperatures. It is seen that the experimental values fall on the predicted lines for both the temperatures. Calculations were carried out to see whether the model put forward by Hirai lSl in the case of systems Ag-Sn and Ag-Sb could give satisfactory predictions. These values have also been incorporated in Figures 3 and 4. Hirai's model shows deviation in both cases, which is significant in the case of high Sb alloys, as can be seen in Figure 4. Another interesting aspect is the predictions in the case of the Ag-In system at 900 K (Figure 5). This temperature is 334 K lower than the melting point of pure Ag. The capability of the present model to predict binary viscosity values at temperatures much below the melting point of the pure metal is well illustrated in this case.
D. System Bi-Sn

.'p r

0.0015

n
0.0010

[] r l ~ l - l u ~
cb Q ~ o

-~ >

The system Bi-Sn exhibits a simple eutectic at 412 K and XBi = 0.43. Hirai's tm model, which is based on the liquidus temperature, should, in fact, predict negative deviation for binary viscosities in this system. On the other hand, the experimental viscosity data show a positive deviation in the central region, as shown in Figure 6. The predictions by the present model describe binary viscosities very well in this system.
E. System Co-Fe

0.0005

0.0000
0.0

0.2

0.4

06

0.8

1.0

In

Xs n

Sn

Fig. 1 - - A comparison of the model predictions and experimental viscosities in the ln-Sn system at 573 K.

While the binary system exhibits complete solid and liquid miscibilities at higher temperatures, the prevalence of slight attractive forces is indicated by the formation of a' phase at lower temperatures. The enthalpies are slightly negative. The present model predictions are compared with the experimental values for three different temperatures in Figure 7. Even in this case, the trends shown by the predicted values are in accordance with the experimental results.
F. System Bi-Cu

are negative. This would mean that, according to the relationship put forward by Eq. [1], the binary viscosities should exhibit a negative deviation. On the other hand, the experimental viscosity values of Kazlov et al. t~m for this binary show a positive deviation over a large composition range, as can be seen in Figure 2. The present approach is able to predict the viscosities quite accurately.
C. Systems Ag-Sn, Ag-Sb, and Ag-In

The phase diagrams for these systems are somewhat similar and indicate strong compound-formation tendencies at the Ag end. Correspondingly, these systems show negative enthalpies of mixing for high Ag alloys in the liquid state. In the case of Ag-Sb and Ag-Sn, there is a sign change in enthalpy in the low Ag region. The unary
592--VOLUME 25B, AUGUST 1994

The mutual solid solubility of Bi and Cu are less than 0.5 at. pet. The repulsive interactions between Bi and Cu are well illustrated by the high positive enthalpies of mixing in the liquid state. The viscosities in this system at 1473 K have been predicted by both the present model and that of Hirai Im and are compared with the experimental viscosity data in Figure 8. It is seen that while the present approach is closer to the experimental data than Hirai's, the agreement is still not satisfactory. This can be due to the uncertainties in the thermodynamic data or the experimental viscosity data, or both. It is also not certain whether the deviations from the model could be attributed to the strong clustering effect that could be prevailing in the system, thereby requiring an additional term in the model. Unless the reliability of the experimental data is well established, it is difficult to make
METALLURGICAL AND MATERIALS TRANSACTIONS B

0.0070 0.0065 0.0060

0.005

1273K: . . . . .

Calculated by the present work

......... Calculated using Hirai's model [8]

Calcuated by the present work (1473K) 13 Experimental datal~l (1473K)

9 0.004 1573K: O
'J'.~ll 9

Experimental data [191 Calculated by the present work Calculated using Hirai's model [~1 Experimental data [tgl

0.0055

.m

0.0050 [] ga,

0.003

. ~ 0.0045
O

~; 0.0o4o
0.0035 0.0030 0.0025
0.0020 I I I o I I

>

0002

~o ".',, "...'m, "",. 6 -".'-,,

2,

0.001

0.0

0.2

0.4
XAg

0.6

0.8

1.0

0.000

Au

Ag

0.0

0.2

0.4

0.6

0.8

1.0

Ag
Fig. 2 - - A comparison of the model predictions and experimental viscosities in the A g - A u system at 1473 K.

Xsn

Sn

Fig. 3 - - A comparison of the model predictions and experimental viscosities in the Ag-Sn system at 1273 and 1573 K.

any modification in the present model for such extreme effects.

G. Viscosity Predictions in the Case of Higher-Order Systems

To the knowledge of the present authors, no systematic experimental study of ternary and higher-order viscosities has been carried out. The lack of data makes any thermodynamic correlation uncertain. However, in the present work, an attempt was made to put forward an empirical correlation for the ternary systems on the basis of the expression for the binary systems, viz., Eq. [13]. This would be represented as AG* = EXi" AG* +
"(X 1

0.006

0.005

--r-I.. Calculaled by the present work (1273K) - - Calculated using Hirai's model 181 (1273K) O Expenmenlal Dala [2~ (1273K)

AmGmix +

3RT
[14] t~

0.0041

"X2 q- X 1 " X 3 Jr X 2 - X 3 )

where subscripts 1, 2, and 3 stand for the three components. Equation [14] was used in the present work to predict the viscosities in the ternary Co-Fe-Ni system at Xco = 0.2 at different temperatures. The calculated viscosity isotherms are presented in Figure 9. Equation [ 14] can also be extended to higher-order systems, viz., AG* = EXi'AGi* + mmGmix+ 3 R T ' E ~Xi'X~ [15]

. ~ 0.003

".i\
9 , "-.Q "~...
" " 0 - . . . . . . . . ::=El=..--.. . . . . . . . . .
"'1-1....

> 0.002

[] ..... rl . 0

It is, however, to be remembered that the correlation between [(O=AG*ix)/(OX2)]e.r and [(O2A~Gmix)/(OX2)]e.r, when integrated for multicomponent melts, would lead to a complex relationship. Equation [15] should be considered only as an empirical relationship. In the case of the application of the present model to unknown systems, it is quite possible that the data for unary melts may be lacking. In such cases, these values can be estimated with a reasonable degree of accuracy
METALLURGICAL AND MATERIALS TRANSACTIONS B

ooo!

"

[ ] ..... ~ ..... I

0.000 0.0

0.2

0.4 Xsb

0.6

0.8

1.0

Ag

Sb

Fig. 4 - - A comparison of the model predictions and experimental viscosities in the Ag-Sb system at 1273 K. VOLUME 25B, AUGUST 1994--593

0,0045

"

,"

- ~

0.012

0.0040

--- []---Calculated by the present work (900K) O Experimental data [211(900K)

1813K:
0.010 9

Calculated by the present work Experimental data [231 Calculated by the present work Experimental data [23] Calculated by the present work Experimental data [231

0.0035
0.008 0.0030 0-, 0.0025 o ;;> 0.0020
~ ~

1893K: . . . . .
9

O
t:r ~

2023K: . . . . 9

.El

.~ 0.0o6
9
0.004

i-------J

Jt

.~5
.o

0.0015
O .+'" ~ 1 7 6 t~

.El
0.002

0.0010
..-

. [].~

0.0005

0.000

..

0.0

0.2

0.4

0.6

0.8

0.0

0.2

0.4

0.6

0.8"

1.0

In

XAg

Fe

)(Co

Co

Fig. 5 - - A comparison o f the model predictions and experimental viscosities in the Ag-In system at 900 K.

Fig. 7 - A comparison of the model predictions and experimental viscosities in the Co-Fe system at 1913, 1993, and 2023 K.

0.0024 0.0022 0.0020

0.005

Calculated by the present work (673K) . . . . Calculated using Hirai's model181(673K) [] Experimental dataI221(673K)

0.004

.... []

Calculated by the present work (1473K) Calculated using Hirai's model[gl (1473K) Experimental data[161(1473K)

0.0018

0.0016
s

.a.
0.0014 ~ 0.0012 0.0010 0.0OO8 0,0006
I ~ I i l , I

,,p 0.003 [ ",

r

'

>

0.002

0.001

0.0

0.2

0.4 XBi

0.6

0.8

1.0 Bi 0.000 0.0 0.2 0.4 0.6 0.8 1.0

Sn

Fig. 6 - - A comparison of the model predictions and experimental viscosities in the Bi-Sn system at 673 K.

Cu

XBi

Bi

Fig. 8 - A comparison of the model predictions and experimental viscosities in the Bi-Cu system at 1473 K.

from Hirai's equations, tSl as has been tested by the present authors.

H. Viscosity Predictions in Dilute Alloys and Ionic Melts

It has been pointed out by Iida and Guthrie tS~ that, despite the number of experimental studies carried out on
594--VOLUME 25B, AUGUST 1994

the viscosities of dilute liquid alloys, especially Fe-based alloys, the great majority of data are not reliable and are often inconsistent. Hence, no attempt was made in the present work to test the predictive ability in the case of dilute alloys, especially those with interstitial solutes.
METALLURGICAL AND MATERIALS TRANSACTIONS B

0004[
1973 K ...... 2073 K

ACKNOWLEDGMENTS
The authors are grateful to Professors M. Hillert, S.K. Saxena, and H. Fredriksson for their comments on the manuscript. Financial support for this work from the Swedish Council for Technical Sciences (TFR) is gratefully acknowledged.

'-- ----- 2173 K

0.003

"'"..(

REFERENCES
1. F.D. Richardson: Physical Chemistry of Melts in Metallurgy, Academic Press, Inc., London, 1974, vol. 1, pp. 1-27. 2. M. Kucharski: Z. Metallkd., 1986, vol. 77, pp. 393-96. 3. E.A. Moelwyn-Hughes: Physical Chemistry, Pergamon Press, Oxford, 1961. 4. A.F. Crawley: Metall. Trans., 1972, vol. 3, pp. 971-75. 5. T. lida and R.I.L. Guthrie: The Physical Properties of Liquid Metals, Claredon Press, Oxford, 1993, pp. 147-98. 6. T. lida, M. Ueda, and Z. Morita: Tetsu-to-Hagan(, 1976, vol. 62, pp. 1169-78. 7. Z. Morita, T. lida, and M. Ueda: Liquid Metals, Inst. Phys. Conf. Ser. No. 30, Institute of Physics, Bristol, 1976, pp. 600-06. 8. M. Hirai: Iron SteelInst. Jpn. Int., 1993, vol. 33 (2), pp. 251-58. 9. E.N. daC. Andrade: Phil. Mag., 1934, vol. 17, pp. 49%732. 10. Du Sichen, J. Bygdrn, and S. Seetharaman: Metall. Mater. Trans. B, 1994, vol. 25B, pp. 519-25. ll. S. Glasstone, K.J. Laidler, and H. Eyring: The Theory of Rate Process, McGraw-Hill Book Co., New York, NY, 1941. 12. L S . Darken: TMS-AIME, 1967, vol. 239, pp. 80-89. 13. M. Born and H.S. Green: A General Kinetic Theory of Liquid, Cambridge University Press, London, 1949. 14. Scientific Group Thermodata Europe: SGTE SOLUTION DATABASE. 15. R. Hultgren, P.D. Desai, D.T. Hawkins, M. Gleiser, and K.K. Kelley: Selected Values of the Thermodynamic Properties of Binary Alloys, ASM, Metals Park, OH, 1973. 16. M.G. Frohberg and K. I)zbagi: Z. Metallkd., 1981, vol. 72, pp. 630-36. 17. H. Walsdorfer, I. Alpshofen, and B. Predel: Z. Metallkd., 1988, vol. 79, pp. 503-12. 18. L.Ya. Kozlov, L.M. Romanov, and N.N. Petrov: lzv. Vyssh. Uchebn. Zaved. Chem. Metall., 1983, vol. 3, pp. 7-11 (Russian). 19. E. Gebhardt, M. Becher, and E. Tragner: Z. Metallkd., 1953, vol. 44, pp. 379-82. 20. H. Nakajima: Trans. Jpn. Inst. Met., 1976, vol. 17, pp. 403-07. 21. T. Iida: Ph.D. Thesis, Tohthoku University, 1970. 22. N.E. Bodakin, B.A. Baum, and G,V. Tyagunov: lzv. Vyssh. Uchebn, Zaved., Chem. Metall., 1978, vol. 7, pp. 9-13_ 23. T. lida, Z. Morita, and S. Takeuchi: J. Jpn. Inst. Met., 1975, vol. 39, pp. 1169-75. 24. E. Gebhardt and G. Wrrwag: Z. Metallkd., 1952, vol. 43, pp. 106-08. 25. B. Djemili, L. Martin-Garin, R. Martin-Garin, and P. Desrr: J. Less-Common Met., 1981, vol. 79, pp. 29-37. 26. K. Kawai and Y. Shiraishi: Handbook of Physico-Chemical Properties at High Temperatures, Iron and Steel Institute of Japan, Tokyo, 1988.

>
9- .............. ..~

....--"

0.001

0.0

0.2

0.4

0.6

0.8

XFe
Fig. 9--Viscosity values predicted using Eq. [19] in the case of the system Co-Fe-Ni (Xco = 0.2) for the temperatures 1973, 2073, and 2173 K.

The factor of 3RT in Eq. [13] may need to be altered because of the interstitial solute atoms. Similarly, in the case of ionic melts, the authors feel that kinetic energy fluctuations could be quite different. Attempts are currently being made to expand the present model to cover these systems as well.

V.

SUMMARY

A relationship has been suggested to relate the Gibbs activation energy of viscosity to the Gibbs energy of mixing in binary metallic melts. The viscosities of binary substitutional liquid alloys can be evaluated using the values of Gibbs energy of mixing along with the information on viscosities of the corresponding unary systems. The method has been tested for various binary melts. Satisfactory calculated results have been obtained in most of the systems studied. The good agreement between the calculated and experimental viscosity values shows the applicability of the present approach to the evaluation of the viscosities of binary alloys.

METALLURGICAL AND MATERIALS TRANSACTIONS B

VOLUME 25B, AUGUST 1994--595