J. Mater, Sci ‘Technol, Vol18 No, 2002 237 A New Thermodynamic Calculation Method for Binary Alloys: Part Xinggiu CHEN', Hailan LI and Xueyong DING Statistical Calculation of Excess Functions School of Materials and Metallurgy, Northeastern University, Shenyang 110004, China P.Rogl and P.Podloucky Institut fir Physikalische Chemie, Universitit Wien, Wahringorstrage 42, A-1090 Wien, Austria (Manuscript received February 27, 2001, in revised form April 9, 2001] ‘The improved form of calculation formula for the activities of the components in binary liquids and solid alloys has been derived based on the free volume theory considering excess entropy and Miedema’s model for calculating the formation heat of binary alloys. A calculation method of excess thermodynamic functions for binary alloys, the formulas of integral molar excess properties and partial molar excess properties for solid ordered or disordered binary alloys have been developed. The calculated results are in good agreement with the experimental values, KEY WORDS: Binary alloy, Thermodynamic, Excess functions, Enthalpy 1. Introduction, “Tosolve the ficulties and complexities of obtaining ther smodynamie parameters by experiments, researchers had sug troted many models to correlate thermodynamic parameters find concentrations of components, Some empirical formulas ihave also been reported for thertnodyuamie properties in de Ite solid solutions as well as dite quid solutions of binary alloy, but these thermodynamic formulas are rarely valid over the whole concentration ranges fo real igi and sod metal lie solutions, Tho main problems in all ofthe present models on alloy melts area fllows Tn a general way, the excess entropy was neglected in ‘the models. The regular solution modell"!, proposed by H.J-Hildebrand, and then the sub-regular solution model!™!, proposed by LK Hardy, had not taken the problem of ex: Eos entropy SEAD into consideration. However, SE does not tsqal to zero in some molten solutions. It can be ether pos tive or negative. This smainly boca that the mixing of two mmponents can not be completely random, What is more, the mixing entropy i also significantly influenced by the atom profile, dimension direction, and so on”), As a result, the ex- fess entropy may not equal to zero for real solutions. fn order fo solve this problem, E.A.Cuggenteim proposed the sol tion model of standard chemical theory, and provided the texpremion of excess fee energy fr the binary system ‘Then CHP Lapis and J.P Eliot proposed the subvregular sol ‘tion model considering S® is directly proportional to AH"), Although these models have physical background in some de- ire, they stil depend on experimental date The coeficents of each empirical formula were determined by parameter-ftting of the experimental values. So their ap- plications are still limited, and the limitations exist in the ‘whole concentration range, saying nothing of the thermody namics formulas for solid alloys. Although the solution mod- cls suggested by Kubaschewski), Lupis” and Williams! hhave successfully explained the relationship between partial enthalpy of mixing and excess entropy of solution of compo- nent i in infinitely dilute liquid binary alloys of solvent j, it is difficult to decide their coefficients. Recently, T-Tanaka, and N.A.Gokeen ef al. had derived 4 statistical thermodynamic solution model” based on the free volume theory. The main aim is to calculate the excess entropy and excess Gibbs free energy in solid binary alloys through the experimental results of enthalpy of mixing. How- ‘ever, for successful application of the model the experimental results of mixing enthalpy should be known for different con- ‘centration ranges, otherwise the calculation cannot be car F TTp whom correspondence should be addressed E-mail xinggiuttsscunivieac.at, Ph.D. Candidate ried out. It is very important that the effective methods can evaluate thermodynamic data of solid binary alloys without txperimental vals. inthis paper, combining the Miedema’s modell for cal culating the formation heat of binary alloys, an improved cal- ulation formula for activities of components in binary alloy System is proposed using excess configuration entropy” and ‘excess vibration entropy suggested by Tanaka et al) ac- ‘cording to the free volume theory. The new calculation meth fods of excess thermodynamic functions are expected to be valid for solid and liquid binary alloys. The thermodynamic Calculation method has also been established for ordered or disordered solid alloys. 2, Model Basis 24 Derivation vibration ‘The free volume theory assumes that each atom moves in a liquid metal within a restricted rogion in a cell made by its nearest-neighbor atoms. Equations (1)~(6) were derived by ‘T’Tanaka and N.A.Gokcen et al. aevording to the free volume theory!" of excess configuration and Sule @ matsjai, (nr) @ 8/2 Rae, ets AW sg ~ 24 (Vn + Uys) — Wut Uy )® [ Wal, }} where AH, 9%, ASEoxp and ASEip are the enthalpy of mixing, the exchange energy, the excess configuration entropy and the excess vibration entropy, respectively. = is the co- ordination number, Li; Ls) the distance which interatomic potential extends in a cell of liquid pure atom i or j, Ui and Us; the depth of potential energy in a cell of liquid pure atom i and j, respectively. Ni = Noe aie ~ 1440/RT w Lis = 1/2- (vB Vi/No)"/* (i can be changed into j) (5) for liquid alloys Ui = ~685- 477 (F can be changed into j) 6) for solid alloys!) Uys = ~(685- 92 +17.6)Tina (ican be changed into 3) (7) where No, Vi, and Ts are Avogadro's number, molar vol tune of pure atom, the coefficient of pure i to transform the solid state frequency into that of the liquid state at the melt- ing point which can be normally assumed as 0.50! and the melting point of pure metal, respectively238 J. Mater. Sci Teehnol, Vol18 No, 2002 2.2 Model of formation enthalpy for binary alloy”! In the ij binary alloy system, the heat of formation can be calculated from the Miedema et al, equation, shown as follows: I Fstalvl(n = (6; = 6)* = (r/o) ® (nae yet + (nae) In Bq), the 2s and 2) are the mole fractions of elements j and jj Vj and Vj are the molar volumes of i and j in cm’ at room temperature; (Moy): and (iw); are the electron density of i and j in electrons; 4, and; are the electronegativity of f and j in wolts;and p, q, ty, 5 and r/p are the constants empirically derived by Miedema et al. The values, as well as values of all the constants, are obtainable from Miedema et al! For a disordered solution and an ordered solid binary alloy, the term f, in Ea.(8) may be calculated from Eqs.(9) and (10), respectively!) 20 atty = HEUER wile fy = 2) = 2:V2/(aav2!* + 25V3!) (disordered solution) oO) fy = 25[L + 8(z123)?] (ordered solution) (a0) 3. Establishment of Thermodynamic Equations ‘The exchange energy $2 can be calculated from Eqs.(4) and (8). ‘Then, substituting My into Bgp.(2) and (3), the excess configuration entropy A SExy and the excess vibration entropy AS¥iq can be obtained. Combining some basic thermodynamic felationship, the activity coefficients can also be derived. Substituting Eq,(4) into Ea.(1), the following equation can be obtained: My = RT/(2z2;)- {1 = [1 — AH (RTY?} () from Eqs.(11), (2) and (3), ASEoyp and AS¥iy can be calculated, shown as follows: AS8ons = AHy/2P) + (R/A) [1 — 40H, /(REYP ~ Rf 2) Asha = 3/2- Reves[& 5 ee + jar [-(- satay") (as) Substituting Bgs.(12) and (13) into the following Ba.(14), and relating to Ba.(8), the excess entropy Sf can be calculated. SB = ASkowr +4580 (a) In binary alloy systems, there are the following basic thermodynamic relationships, shown as folows: GE = aH, - 15% (1) (8) an) “The following equations can be obtained feom Eqs(8), (15), (16) and (17): GE = AM /2-AyPO~4A Ms / RT)? +12) [0.54 2A (ABMs /RIY"?/RL OAH [82 RT B(1—2,)?+AsT (18) where: Ay = RAE 8/4 ET Us + Us) Oa) Buy = (Lis ~ bys)? [(Laskss) +2 ~ Wie + Uys)? | (Ua ys) for liquid oF disordered sold solution Bally _ wilds = 6) Be, SM Ay m Temes - &) VPM + w(t = 2e)(ds ~ 49 1+ wj(1~ 2215 ~ $0) PRE wll VF PUL + wyeelds — 60) for ordered solid solution OAH 1 wii) ve Bet = Al {2 Ta ane) Baw? av toeiesV VS (ayV 3" — nV) } LVF aN? — 2D) + Bea A) For binary alloy systems, the following relationship between partial excess Gibbs free energy and activity coefficients can be expressed as Bq.(19): Gf =Rriny as) "Therefore, from Eqs.(18) and (19), activity coefficient + can be given as Ea,(20). 4 = exp(AHy/2RT) ~ Ay (1 ~ 4AM /RTYY?/R~3/2- Bis(1 —26)8 + Ay [RE (1-2) 10.5 + 24,j(1 ~ 40.y/RTY- Y/R] 1/(RT) OAH /2.} (20) [According to Eqs.(17), (19) and (20), activity coefficient y of the component j in binary system can be expressed as Eq. (21). 95 = expl(G8 - ei RT In) 2 RT)] (2) It is therefore possible to predict the values of 7 and 7 in the binary system, "According to Bqs.(L1) to (17), itis convenient to ealeulate the integral molar excess thermodynamic functions for liquid and disordered of ordered solid binary alloy aystems using the properties of the pure components,J. Mater. Sci, Technol, Vol18 No.3, 2002 28a a ae a «0 ema fracon a jg. Relation between mole fraction and activity in liquid Ag-Pb at 1273 K sr Yo, i qo acon ‘wn Fig.2. Relation between mole fraction and activity in li Fe-Mn at 1863 K 4, Calculated Results and Discussion 4.1 Parameters of calculation formula In this article, the physical properties necessary for the calculation in each alloy are listed in Table 1 ‘Table 1 Parameters for a part of elements) Elements ni Vn TET ae Ag 3647 45007 1230 Pb «L6T 429 5.45 004 594 Na 082 827 2.70 O14 371 Tl «112 667 390 007 700 Fe «LTT 3.69 4.93 0.04 1808, Mn 161 378 445 0.04 1517 Ge 1.37 460 455 0.04 1210 Au 1ST 47 515 004 1337 Co «175-35 5:10 0.04 1768 Pe__L7e 44 5.65004 _2042 TS When the values of Fare not available, can be approximately 0.5 based on literature [12] 4.2 Calculated results For solid and liquid binary alloy systems, referring to the properties ofthe pure elements, the activity coefficients 7. and 1 in liquid Ag-Pb, Fe-Mn systems and solid Ag-Au, Co-Pt were calculated to discuss the validity of the present formula Eqs. (20) and (21). The calculated results of , and 75 for the above binary alloys are shown in Figs to in which the Calculated results for 3, and 7 are in reasonable agreement with the experimental results!" ‘The integral molar excess thermodynamic functions may be calculated by Eqs.(11)~(17); the partial molar excess 239 o3| Oe 0s 08 a7 08 08 10 Boor oz os “ ‘ele action hu Fig.3 Relation between mole fraction and activity in solid ‘Ag-Au at 800 K 419 oa Soci ono oo be os O60 egal fracion Fig.4 Relation between mole fraction and activity in solid Co-Pt at 1273 K Gibbs free energies are computed by Bq(18). As some ex: amples for the application of Bqs.(11)~(17), and (18), the enthalpy of mixing and the integral molar excess Gibbs free energy, the integral excess entropy, the partial excess Gibbs free energy for the solid binary disordered solution Ag-Aw and for the ordered solution Co-Pt over the whole concentration ranges are calculated, The calculated results and experimen tal values*** for excess functions AGE, TASE, GP and excess enthalpy AH, in the above binary alloys are shown in Tables 2 and 3, respectively. The comparison of the cal- culated results with experimental values! for activity co- ‘ficients functions in these alloys is shown ia Figs3 and 4, respectively. From these tables and figures, the calculated results for these terms are in reasonable agreement with the experimental results"! for ordered of disordered binary al- loys. 4.3 Discussion 43.1 Physical meaning of formula The method was derived ‘through a combination of (a) the atomic cell of free volume and (b) the Wigner-Seitz cell included by Miedema’s model for calculating the formation heat of binary alloy systems. ‘The same as both models the method assumes that the po- tential energy is the minimum at the border of two cells. The structure of the two cells was considered as molten metal in short-range order and in long-range disorder, and the physical parameters of them have also common points. So combining them together and fully considering excess entropy are reason- able. This can be explained by the calculation results, which is indicated in Figs-l~d. Moreover, Miedema method was proved to be successful for binary solid ordered or disordered Solutions and ‘Tanaka et al. successfully applied the free volume theory to solid alloys. As a result, combining them together to calculate thermodynamic quantities is reasonable, ‘This is also explained by the calculation results, indicated in ‘Tables 2 and 3.