部分含Pt和Ag的贵金属体系相图热力学计算
|
摘要
Pt系和Ag系贵金属催化剂在现代工业中具有广泛的应用前景。为了给Pt和Ag催化剂性能的研究和改进提供理论上的依据,有必要对相关体系进行热力学优化以便获得精确的相图和热力学数据。本文结合第一原理计算,以CALPHAD方法对Pt-Ga-Ge和Ag-Ga-Ge两个三元系进行了热力学优化计算,建立了白洽的热力学数据库。
主要研究工作如下：
1.运用第一原理计算了Pt-Ga-Ge体系中各个二元系的中间相(包括稳定相与可能的亚稳相)的形成焓,获得了合理的计算结果。
2.在第一原理计算结果的基础上,优化和计算了Pt-Ge,Pt-Ga,Ga-Ge三个二元系。结合文献报道的实验数据外推优化了Pt-Ga-Ge二元系,计算了液相面投影图与一系列等温截面。
3.优化和计算了Ag-Ga和Ag-Ge两个二元系。结合本文优化的Ga-Ge二元系,外推计算了Ag-Ga-Ge三元系和液相面投影图及其一系列等温截面。
The precious metals, Pt, Ag and their alloys, have been widely used as catalysts in modern industry. Establishment of the thermodynamic database of Pt and/or Ag alloys is very important to improve the catalyzing capability of related system. In this work, thermodynamic assessments of Pt-Ga-Ge and Ag-Ga-Ge ternary systems were performed by combining First-Principles with CALPHAD.
1. Formation enthalpies of compounds including stable and hypothetical phases in Pt-Ga-Ge system were calculated by First-Principles method.
2. On the basis of the results from First-Principles calculation, the Pt-Ge and Pt-Ga binary system was optimized. Combined with the reassessed parameters of the Ga-Ge binary system in this work, the Pt-Ga-Ge ternary system was extrapolated. The liquid project and several isothermal sections were calculated
3. The Ag-Ga and Ag-Ge binary systems were reassessed. Combined with the optimized parameters of the Ga-Ge binary system in this work, the Ag-Ga-Ge ternary system was extrapolated. The liquid project and several isothermal sections were calculated.
主要研究工作如下：
1.运用第一原理计算了Pt-Ga-Ge体系中各个二元系的中间相(包括稳定相与可能的亚稳相)的形成焓,获得了合理的计算结果。
2.在第一原理计算结果的基础上,优化和计算了Pt-Ge,Pt-Ga,Ga-Ge三个二元系。结合文献报道的实验数据外推优化了Pt-Ga-Ge二元系,计算了液相面投影图与一系列等温截面。
3.优化和计算了Ag-Ga和Ag-Ge两个二元系。结合本文优化的Ga-Ge二元系,外推计算了Ag-Ga-Ge三元系和液相面投影图及其一系列等温截面。
The precious metals, Pt, Ag and their alloys, have been widely used as catalysts in modern industry. Establishment of the thermodynamic database of Pt and/or Ag alloys is very important to improve the catalyzing capability of related system. In this work, thermodynamic assessments of Pt-Ga-Ge and Ag-Ga-Ge ternary systems were performed by combining First-Principles with CALPHAD.
1. Formation enthalpies of compounds including stable and hypothetical phases in Pt-Ga-Ge system were calculated by First-Principles method.
2. On the basis of the results from First-Principles calculation, the Pt-Ge and Pt-Ga binary system was optimized. Combined with the reassessed parameters of the Ga-Ge binary system in this work, the Pt-Ga-Ge ternary system was extrapolated. The liquid project and several isothermal sections were calculated
3. The Ag-Ga and Ag-Ge binary systems were reassessed. Combined with the optimized parameters of the Ga-Ge binary system in this work, the Ag-Ga-Ge ternary system was extrapolated. The liquid project and several isothermal sections were calculated.
引文
[1]张晓梅,杨一昆,石油化学工业中的贵金属催化剂,贵金属,19(1998)54-58
[2]李平,汽车废气净化用贵金属催化剂,贵金属,15(1994)52-58
[3]李文震,孙公权,严玉山等,低温燃料电池担载型贵金属催化剂,化学进展,17(2005)761-772
[4]陈健,王先厚,李仕禄等,钯、铂贵金属催化剂的工业应用,化肥设计,2(2006)44-45
[5]南军,李梅,刘晨光等,连续重整汽油选择性加氢托烯烃用贵金属催化剂的研究,工业催化,1(2005)39-42
[6]唐永良,万惠霖,银催化剂研究进展,杭州化工,36(2006)6-10
[7]葛世培,肖栋然,康秉鑫等,贵金属催化剂用于重整后加氢,燃料化学学报,16(1988)97-102
[8]J. Beltramini, D.L. Trimm, Activity, selectivity and coking over mono-and bi-metallic reforming catalysts, Appl. Catal.,32(1987)71-83
[9]J. Goldwasser, B. Arenas, C. Bolivar, et al., A study of the platinum-germanium catalytic system, J. Catal.,100(1986) 75-86
[10]S.R. Miguel, O.A. Scelza, A.A. Gastro, Nature of the metall phase in platinum-germanium/alumina catalysts, Appl. Catal.,44(1988)23-32
[11]F.N. Rhines, GC.Cater, Application of Phase Diagram in Metallurgy and Ceramic, Washington,1(1978) 142.
[12]Z.P. Jin, A Study of the Range of Stability of σPhase in Some Ternary System, Scand. J. Metall.,10(1981)279-287.
[13]金展鹏,三元扩散偶及其在相图研究中的应用,中南矿冶学院学报,(1984)27-35。
[14]A.A. Kodentzov, S.F.Dunaev and E.M. Slusarenko, Determination of the Phase Diagram of the V-Ni-Cr System Using Diffusion Couples and Equilibrated Alloys, J. Less Comm. Met.,135(1987) 15-24.
[15]J-C. Zhao and Z.P.Jin, Z.Metallkd., Determination of Phase Equilibria in the Ti-Fe-Co System at 900℃,81(1990) 247-250.
[16]J-C. Zhao, M.R.Jackson and L.A.Peluso, Determination of the Nb-Cr-Si Phase Diagram Using Diffusion Multiples, Acta Mater.,51 (2003) 6395-6405.
[17]J.J. Van Larr.,The computation of phase diagram, Z. Phys.Chem. B.,63(1908) 216-220.
[18]J.L. Meijering., Retrograde Solubility Curves Especially in Alloy Solid Solutions, Philips. Res. Rep.,3(1948) 281-302.
[19]L. Kaufman and H. Bernstein, Computer Calculation of Phase Diagrams, New York:Academic Press,1970.
[20]冯端,师昌绪,刘治国等,材料科学导论[M],北京：化学工业出版社,2001。
[21]A.T. Dinsdale, SGTE data for pure elements, CALPHAD,15(1991) 317-425.
[22]M. Hillert, Phase Equilibria, Phase Diagrams and Phase Transformations:Their Thermodynamic Basis, Cambridge University Press,1998.
[23]O. Redlich, A. Kister, Algebraic representation of thermodynamic properties and the classification of solutions, Ind. Eng.Chem.,40(1948) 345-348.
[24]J.H. Hildebrand, Solubility of Regular Solutions, J. Amer. Chem. Soc.,51(1929) 66-80.
[25]H.K. Hardy, An equation for the solubility surface of ternary'sub-regular' solutions. Acta Metall.,2(1954) 348-349.
[26]M. Hillert, L.I. Staffansson, Regular-solution model for stoichiometric phases and ionic melts. Acta Chem. Scand.,24(1970) 3618-3626.
[27]M. Hillert, B. Jasson, B. Sundman, Application of the Compound-Energy Model to Oxide Systems, Z. Metallkd.,79(1988) 81-87.
[28]M. Hillert, The Compound Energy Formalism, J.Alloys Compds.,320(2001): 161-176.
[29]L.S. Brooks, Vapour pressure of Po (438-745℃), J. Amer. Chem. Soc.,77(1955) 11-12.
[30]储伟,张涛,魏强,孙孝英,载体预处理对贵金属铂系催化剂性质的影响,合成化学,8(2000)428-429.
[31]谢有畅,朱月香,DeNOx催化剂研究进展,化学通报,2(1996)6-7。
[32]李令成,蓝蕴墓,肼分解催化剂进展,工业催化,2(1994)3-4。
[33]高森泉,L.D. Schmidt,载体金属催化剂的氧化-还原处理及其微结构和催化性能—烷烃在Ru, Rh, Ir, Ni, Pt和Pd/SiO2上的氢解,催化学报,10(1989)221-222。
[34]储伟,刘晰,熊国兴等,催化剂载体对天然气催化氧化制合成气反应的影响,天然气化工,119(1998)855-856.
[35]Z.X. Chen, Y.T. Wu, Z.L. Sun, et al., Study of Pt-Ge/Al2O3 reforming catalyst, Petro. Proc. Petro-chem.,36 (2005) 26-28.
[36]J. Goldwasser, B. Arenas, C. Bolivar, et al., A study of the platinum-germanium catalytic system, J. Catal.,100(1986) 75-86.
[37]R. Bouwman and P. Biloen, Valence state and interaction of platinum and germanium on γ-Al2O3 investigated by X-ray photoelectron spectroscopy, J. Catal., 48(1977)209-216.
[38]Y. Diaz, L. Melo, M. Mediavilla, et al., Characterization of bifunctional Pt/H[Ga]ZSM5 and Pt/H[Al]ZSM5 catalysts:II. Evidences of a Pt-Ga interaction, J. Mole cata. A.,227(2005) 7-15.
[39]K. Khalaff and K. Schubert, Constitution of Platinum Gallium and Platinum Gallium Germanium Mixtures, METALL, BERLIN 28 (1974) 1160-1168.
[40]G. Kresse, J. Furthmuller, Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set, Phys. Rev. B.,11169(1996) 54-55.
[41]G. Kresse, J. Furthmuller, Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set, Comput. Mater. Sci., 15(1996)6-7.
[42]K.C. Jain and S. Bhan,The Platiunm-Germanium, Trans. Indian Inst. Met., 19(1966)49-50.
[43]Y. Oya and T. Suzuki, The Pt-Ge Phase Diagram, Z. Metallkd.,78(1987) 295-300
[44]M. Ellner and B. Predel, Durch extrem rasche abkuhlung von schmelzen erzielbare phasen in den systemen Ni-Ge, Pd-Ge und Pt-Ge, J. Less common Met., 76(1980) 181-197.
[45]R. Lbibb and R. Castanet, Thermodynamic investigation of Pt-Ge and Pd-Ge. binary alloys, J. Alloys compds.,189(1992) 23-29.
[46]R. Castanet, Thermodynamic investigation on (a transition metal+germanium) I. (Platinum+germanium) and (palladium+germanium) alloys, J. Chem. Thermodyn., 14(1982)639-640.
[47]O. J. Kleppa, Standard molar enthalpies of formation of Hf3Ge2, MeGe (Me=Ir, Pt) and Pt2Ge, J. Alloys compds.,176(1991) 301-302.
[48]R. Lbibb and R. Castanet, Calorimetric determination of the enthalpies of formation of the solid compounds of the Pt-Ge system, J. Alloys compds.,191(1993) 13-15.
[49]K.C. Jain, S. Bhan, Structure and constitution of platinum-gallium alloys, Trans. Indian Inst. Met.,21(1968) 41-45.
[50]P. Guex, P. Feschotte, The binary systems platinum-aluminium, platinum-gallium and platinum-indium, J. Less Common Met.,46(1976) 101-116.
[51]S. Bhan, K. Schubert, S of the Co-Ge, Rh-Si and its Related Alloys, Z. Metallkd., 51(1960)327-339.
[52]D. Swenson, B. Morosin, On the preparation and crystal structure of a new form of PtGa2, J. Alloys Compds.,243(1996) 173-181.
[53]E. Hellner, F. Laves, Structure of platinum-gallium binary systems, Z. Naturforsch A.,2(1947) 177-183.
[54]T. Chattopadhyay, K. Schubert, Kristallstruktur von Pt3Ga(r) und einigen phasen der mischung Pt-Al, J. Less Common Met.,41(1975) 19-32.
[55]Y. Oya, Y. Mishima, T. Suzuki, The Pt-Ga phase diagram, Z. Metallkd.,78(1987) 485-490.
[56]P. Anres, M. Gaune-Escard, J. Bros., Thermodynamics of the (Pt+Ga) system, J. Alloys Compd.,234(1996) 264-274.
[57]P. Anres, R. Haddad, D. Allam, et al., The limiting molar partial enthalpies of mixing of iron, cobalt, nickel, palladium and platinum in liquid gallium and indium, J. Alloys Compds.,220(1995) 189-192.
[58]W. Vogelbein, M. Ellner, B. Predel., Kalorimetrische untersuchung von binaren legierungen des platins und palladiums mit gallium, indium und thallium, Thermochim. Acta,44(1981) 141-149.
[59]M. Li, C.R. Li, F.M. Wang, W.J. Zhang, Thermodynamic assessment of the Ga-Pt system, Intermetallics,14(2006) 826-831.
[60]W. Klemm, L. Klemm, E. Hohmann, and H. Volk, Z. Anorg. Allg. Chem., 256(1948) 239-252 in German.
[61]P.H. Keck and J. Broder, The Solubility of Silicon and Germanium in Gallium and Indium, Phys. Rev. Lett.,90(1953) 521-522.
[62]E.S. Greiner and P. Breidt, Melting Point of Germa-nium and the Constitution of Some Ge-Ga Alloys, Jr. Trans. AIME,203(1955) 187-188.
[63]N. de Roche, Z. Metallkd., On the Gallium-Germanium System,48(1957) 58-60 in German.
[64]Y.M. Savitskiy, V.V. Baron, and M.A. Tylkina, Phase Diagrams on Properties of Alloys of Gallium and Thallium, Russ. J. Inorg. Chem.,3(1958) 310-327.
[65]F.A. Trumbore, E.M. Porbansky, and A.A. Tartaglia, Solid solubilities of aluminum and gallium in germanium, J. Phys. Chem. Solids,11(1959) 239-245.
[66]C.D. Thurmond and M. Kowalchik, Germanium and Silicon Liquidus Curves, Bell Sys. Tech. J.,39(1960) 169-204.
[67]http://www.accelrvs.com/mstudio/msmodeline/casten.htm
[68]http://www.wiep2k.at/
[69]http://www.abinit.org
[70]http://cms.mpi.univie.ac.at/vasp/
[71]G. Kresse and J. Hafner, Ab initio molecular dynamics for liquid metals, Phys. Rev. B.,47(1993)558-559.
[72]G. Kresse and J. Furthmuller, Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set, Phys. Rev. B.,54(1996) 11169-11170.
[73]G. Kresse and J. Furthmuller, Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set, Comput. Mater. Sci.,6(1996) 15-16.
[74]P.E. Blochl, Projector augmented-wave method, Phys. Rev. B.,50(1994) 17953.
[75]G. Kresse and J. Joubert, From ultrasoft pseudopotentials to the projector augmented-wave method, Phys. Rev. B.,59(1999) 1758-1759.
[76]J.P. Perdew, J.A. Chevary, S.H. Vosko, K.A. Jackson, M. R. Pederson, D. J. Singh and C. Fiolhais, Atoms, molecules, solids, and surfaces:Applications of the generalized gradient approximation for exchange and correlation, Phys. Rev. B., 46(1992)6671-6672.
[77]J.P. Perdew, Accurate and simple analytic representation of the electron-gas correlation energy, Phys. Rev. B.,45(1992) 13244-13245.
[78]H.J. Monkhorst and J.D. Pack, Special points for Brillouin-zone integrations, Phys. Rev. B.,13(1972) 5188-5189.
[79]B. Sundman, J. Agren, A regular solution model for phases with several components and sublattices, suitable for computer applications, J. Phys. Chem. Solids., 42(1981)297-301.
[80]S.V. Meschel, J. Kleppa, Standard enthalpies of formation of some 5d transition metal gallides by high-temperature direct synthesis calorimetry, J Alloys Compds., 311(2000)241-247.
[81]B. Sundman, B. Jansson, J. O. Anderson, The Thermo-Calc databank system, CALPHAD,9(1985) 153-190.
[82]L.L. Xu, J. Wang, H.S. Liu, Z.P. Jin, Thermodynamic assessment of the Pt-Si binary system, CALPHAD,32 (2008) 101-105.
[83]I. Ansara, J.P. Bros, M. Source, et al., Thermodynamic anlysis of the germanium-based ternary systems (Al-Ga-Ge, Al-Ge-Sn, Ga-Ge-Sn), Calphad, 3(1979)225-233.
[84]W. Hume-Rothery, K.W. Andrews, J. Inst. Met., Crystal structure in the Ag-Ga binary system,68(1942) 133-143.
[85]W. Hume-Rothery, K.W. Andrews, Z. Metallkd., Phase equilibria in the Ag-Ga systems,50(1959) 661-662.
[86]B. Predel, D.W. Stein, Bildungsenthalpien binarer verbindungen des galliums mit kupfer, silber und gold sowie analyse der thermodynamischen eigenschaften von 3/2-elektronen-verbindungen. Enthalpies of formation of binary compounds of gallium with copper, silver and gold and the analysis of thermodynamic properties of 3/2-electron-compoundsEnthalpie de formation des composes binaires du gallium avec le cuivre, l'argent et l'or. etude des proprietes thermodynamiques des composes a 3/2electrons, Metallurgica, 20(1972) 681-692.
[87]E. Weibke, L.Wiegels, Z. Anorg. Allg. Chem.,226(1936) 201-209.
[88]A.E. Gunn(?)s, O.B. Karlsen, A. Olsen, P.T. Zagierski, Phase relations and crystal structures in the Ag-Ga system, J. Alloys Compds.,297(2000) 144-155.
[89]Y. Zhang, J.K. Liang, J.B. Li, Q.L. Liu, Y.G. Xiao, Q.Zhang, B.J. Sun, G.H. Rao, Phase relations of the Ag-Ga-N system, J. Alloys Compds.,429(2007) 184-191.
[90]W.D. Hoff, R.P. Stratton, W.J. Kitchingman, The influence of indium and gallium on the lattice spacing of the β' and ζ phases of the silver-zinc alloys, Phil. Mag.,10(1964)979-987.
[91]E. Hellner, The Structure of Mg-Ga2, Forts. Der Miner.,29(1950) 58-61.
[92]H.W. King, T.B. Massalski, Lattice Spacing Relationships and the Electronic Structure of HCP Phases Based on Silver, Phil. Mag.,6(1961) 669-682.
[93]W. Hume-Rothey, P.W. Reynolds, FactorsAffectingthe Formation of 3/2 Electron Compounds in Alloys of Copper, Silver and Gold, G.V. Raynor, J. Inst. Met., 66(1940) 191-207.
[94]K. Moeller, Z. Metallkd., Electronic structure of ζ' based on sliver,31(1939) 19-20.
[95]R.P. Stratton, W.J. Kitchingman, Order in the of the silver-gallium alloys, Acta Crystallogr. A.,17(1964) 1471.
[96]A.E. Gunns, A. Olsen, P.T. Zagierski, Crystal structure determination of Ag2Ga by single crystal X-ray diffraction, Z. Kristallogr.,213(1998) 639-644.
[97]Y. Zhang, Q.L. Liu, J.B. Li, et al, Structures of the ζ and ζ' phases in the Ag-Ga system, J. Alloys Compd.,399(2005) 155-159.
[88]P. Feschotte, P. Bass, Un nouveau compose intermetallique tres timide:AgGa, J. Less Common Met.,171(1991) 157-162.
[99]M.R. Baren, The Ag-Ga phase diagram, Bull. Alloy Phase Diagr.,11(1990) 334-339.
[100]K. Muller, W. Merl, ETA-A,Phase boundaries in Ag-Ga phase diagram, 80(1959)515-520.
[101]E.A. Owen, V.W. Rowlands, Solubility of gallium in copper and in silver, J. Inst. Met.,66(1940) 367-368.
[102]E.A. Owen, D.P. Morris, The Application of X-Ray Methods to the Determination of Phase Boundaries in Metallurgical Equilibrium Diagrams, J. Inst. Met.,76(1949-1950) 145-168.
[103]W. Hume-Rothery, W. Mabbott, K.M. Channet Evans, Containing Papers of a Mathematical or Physical Character, Phyil. Trans. R. Soc. (London) A,233(1934) 1-97.
[104]H. Okamoto, Ag-Ga(silver-gallium), J. Phase Equillb.,13(1992)324-325.
[105]R. Beja, M. Laffitte, enthalpy fo mixing of liquid silver-gallium alloys at 500℃, C.R. Acad. Sci., Paris 267(1968) 123-126.
[106]R. Beja, Ph.D. Thesis, Centre de Recherches de Microcalorimetrie et de Thermochimie du C.N.R.S., Marseille, France,1969.
[107]K. Itagaki, A. Yazawa, Measurements of Heats of Mixing in Liquid Silver Binary Alloys, J. Japan Inst. Met.,32(1968) 1294-1300.
[108]B. Predel, D.W. Stein, Thermodynamische untersuchung der binaren systeme des Galliums mit Kupfer, Silber und Gold. Thermodynamic investigation of the binary systems of gallium with copper, silver and goldInvestigation thermodynamique des systemes binaires du gallium avec le cuivre, l'argent et l'or, Acta Metall..20(1972) 515-522.
[109]V.N. Danilin, S.P. Yatsenko, Thermodynamic properties of silver-gallium alloys, Izv. Akad. Nauk. SSSR, Metally,3(1968) 224-227.
[110]B. Predel, U. Schallner, Investigation of the Thermodynamic Properties of Binary Liquid Alloys of Silver and Gold with Gallium, Indium, and Germanium, Z. Metallkd.,63(1972) 341-347.
[111]G.J. Qi, M. Hino, T. Azakami, Thermodynamic study of liquid Ag-In and Ag-Ga alloys with a Knudsen cell-mass spectrometer, Mater. Trans. JIM,30(1989) 575-582.
[112]T.R. Briggs, R.O. McDuffie, and L.H. Willisford, Germanium. Alloys of Germanium:Silver-Germanium, J. Phys. Chem.,33(1929) 1080-1096.
[113]H. Maucher, On the Systems Copper-Germanium, Silver-Germanium, Forschungsarb. Metallkd. Rontgenmetal.,20(1936) 1-32 in German.
[114]E.A. Owen and V.W. Rowlands, Solubility of germanium in copper and in silver, J. Inst. Met.,66(1940) 368-369.
[115]V.E. Kosenko, Sov. Phys. Solid State,4(1962) 42-43.
[116]R. Castanet and M. Laffitte, Enthalpy of formation at 1280K O liquid alloys silver-germanium, C.R. Acad. Sci.,267(1968) 204.
[117]R. Castanet, Y. Claire and M. Laffitte, Enthalpy of formation of liquid silver-gemanium, silver-tin, and silver-lead alloys at 1280K, J. Chim. Phys.,66(1969) 1276-1277.
[118]U. Gerling, M.J. Pool, B. Predel, contribution to the associate model for binary liquid alloys, Z. Metallkd.,74(1983) 616-619.
[119]O. Redlich, A. Kister, Thermodynamics of nonelectrolytic solutions, algebraic representation of thermodynamic properties and the classification of solutions, Ind. Eng. Chem.,40(1948) 345-348.
[120]P.Y. Chevalier, Thermochim. Acta, Critical assessment of thermodynamic data for the Ag-Ge system,130(1988) 25-32.
[121]J.O. Andersson, T. Helander, L.H. Hoglund, et al., Thermo-Calc & DICTRA, computational tools for materials science, CALPHAD,26(2002) 273-312.
[122]S.L. Chen, S. Daniel, F. Zhang, et al., The PANDAT software package and its applications, CALPHAD,26(2002) 175-188.
[2]李平,汽车废气净化用贵金属催化剂,贵金属,15(1994)52-58
[3]李文震,孙公权,严玉山等,低温燃料电池担载型贵金属催化剂,化学进展,17(2005)761-772
[4]陈健,王先厚,李仕禄等,钯、铂贵金属催化剂的工业应用,化肥设计,2(2006)44-45
[5]南军,李梅,刘晨光等,连续重整汽油选择性加氢托烯烃用贵金属催化剂的研究,工业催化,1(2005)39-42
[6]唐永良,万惠霖,银催化剂研究进展,杭州化工,36(2006)6-10
[7]葛世培,肖栋然,康秉鑫等,贵金属催化剂用于重整后加氢,燃料化学学报,16(1988)97-102
[8]J. Beltramini, D.L. Trimm, Activity, selectivity and coking over mono-and bi-metallic reforming catalysts, Appl. Catal.,32(1987)71-83
[9]J. Goldwasser, B. Arenas, C. Bolivar, et al., A study of the platinum-germanium catalytic system, J. Catal.,100(1986) 75-86
[10]S.R. Miguel, O.A. Scelza, A.A. Gastro, Nature of the metall phase in platinum-germanium/alumina catalysts, Appl. Catal.,44(1988)23-32
[11]F.N. Rhines, GC.Cater, Application of Phase Diagram in Metallurgy and Ceramic, Washington,1(1978) 142.
[12]Z.P. Jin, A Study of the Range of Stability of σPhase in Some Ternary System, Scand. J. Metall.,10(1981)279-287.
[13]金展鹏,三元扩散偶及其在相图研究中的应用,中南矿冶学院学报,(1984)27-35。
[14]A.A. Kodentzov, S.F.Dunaev and E.M. Slusarenko, Determination of the Phase Diagram of the V-Ni-Cr System Using Diffusion Couples and Equilibrated Alloys, J. Less Comm. Met.,135(1987) 15-24.
[15]J-C. Zhao and Z.P.Jin, Z.Metallkd., Determination of Phase Equilibria in the Ti-Fe-Co System at 900℃,81(1990) 247-250.
[16]J-C. Zhao, M.R.Jackson and L.A.Peluso, Determination of the Nb-Cr-Si Phase Diagram Using Diffusion Multiples, Acta Mater.,51 (2003) 6395-6405.
[17]J.J. Van Larr.,The computation of phase diagram, Z. Phys.Chem. B.,63(1908) 216-220.
[18]J.L. Meijering., Retrograde Solubility Curves Especially in Alloy Solid Solutions, Philips. Res. Rep.,3(1948) 281-302.
[19]L. Kaufman and H. Bernstein, Computer Calculation of Phase Diagrams, New York:Academic Press,1970.
[20]冯端,师昌绪,刘治国等,材料科学导论[M],北京：化学工业出版社,2001。
[21]A.T. Dinsdale, SGTE data for pure elements, CALPHAD,15(1991) 317-425.
[22]M. Hillert, Phase Equilibria, Phase Diagrams and Phase Transformations:Their Thermodynamic Basis, Cambridge University Press,1998.
[23]O. Redlich, A. Kister, Algebraic representation of thermodynamic properties and the classification of solutions, Ind. Eng.Chem.,40(1948) 345-348.
[24]J.H. Hildebrand, Solubility of Regular Solutions, J. Amer. Chem. Soc.,51(1929) 66-80.
[25]H.K. Hardy, An equation for the solubility surface of ternary'sub-regular' solutions. Acta Metall.,2(1954) 348-349.
[26]M. Hillert, L.I. Staffansson, Regular-solution model for stoichiometric phases and ionic melts. Acta Chem. Scand.,24(1970) 3618-3626.
[27]M. Hillert, B. Jasson, B. Sundman, Application of the Compound-Energy Model to Oxide Systems, Z. Metallkd.,79(1988) 81-87.
[28]M. Hillert, The Compound Energy Formalism, J.Alloys Compds.,320(2001): 161-176.
[29]L.S. Brooks, Vapour pressure of Po (438-745℃), J. Amer. Chem. Soc.,77(1955) 11-12.
[30]储伟,张涛,魏强,孙孝英,载体预处理对贵金属铂系催化剂性质的影响,合成化学,8(2000)428-429.
[31]谢有畅,朱月香,DeNOx催化剂研究进展,化学通报,2(1996)6-7。
[32]李令成,蓝蕴墓,肼分解催化剂进展,工业催化,2(1994)3-4。
[33]高森泉,L.D. Schmidt,载体金属催化剂的氧化-还原处理及其微结构和催化性能—烷烃在Ru, Rh, Ir, Ni, Pt和Pd/SiO2上的氢解,催化学报,10(1989)221-222。
[34]储伟,刘晰,熊国兴等,催化剂载体对天然气催化氧化制合成气反应的影响,天然气化工,119(1998)855-856.
[35]Z.X. Chen, Y.T. Wu, Z.L. Sun, et al., Study of Pt-Ge/Al2O3 reforming catalyst, Petro. Proc. Petro-chem.,36 (2005) 26-28.
[36]J. Goldwasser, B. Arenas, C. Bolivar, et al., A study of the platinum-germanium catalytic system, J. Catal.,100(1986) 75-86.
[37]R. Bouwman and P. Biloen, Valence state and interaction of platinum and germanium on γ-Al2O3 investigated by X-ray photoelectron spectroscopy, J. Catal., 48(1977)209-216.
[38]Y. Diaz, L. Melo, M. Mediavilla, et al., Characterization of bifunctional Pt/H[Ga]ZSM5 and Pt/H[Al]ZSM5 catalysts:II. Evidences of a Pt-Ga interaction, J. Mole cata. A.,227(2005) 7-15.
[39]K. Khalaff and K. Schubert, Constitution of Platinum Gallium and Platinum Gallium Germanium Mixtures, METALL, BERLIN 28 (1974) 1160-1168.
[40]G. Kresse, J. Furthmuller, Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set, Phys. Rev. B.,11169(1996) 54-55.
[41]G. Kresse, J. Furthmuller, Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set, Comput. Mater. Sci., 15(1996)6-7.
[42]K.C. Jain and S. Bhan,The Platiunm-Germanium, Trans. Indian Inst. Met., 19(1966)49-50.
[43]Y. Oya and T. Suzuki, The Pt-Ge Phase Diagram, Z. Metallkd.,78(1987) 295-300
[44]M. Ellner and B. Predel, Durch extrem rasche abkuhlung von schmelzen erzielbare phasen in den systemen Ni-Ge, Pd-Ge und Pt-Ge, J. Less common Met., 76(1980) 181-197.
[45]R. Lbibb and R. Castanet, Thermodynamic investigation of Pt-Ge and Pd-Ge. binary alloys, J. Alloys compds.,189(1992) 23-29.
[46]R. Castanet, Thermodynamic investigation on (a transition metal+germanium) I. (Platinum+germanium) and (palladium+germanium) alloys, J. Chem. Thermodyn., 14(1982)639-640.
[47]O. J. Kleppa, Standard molar enthalpies of formation of Hf3Ge2, MeGe (Me=Ir, Pt) and Pt2Ge, J. Alloys compds.,176(1991) 301-302.
[48]R. Lbibb and R. Castanet, Calorimetric determination of the enthalpies of formation of the solid compounds of the Pt-Ge system, J. Alloys compds.,191(1993) 13-15.
[49]K.C. Jain, S. Bhan, Structure and constitution of platinum-gallium alloys, Trans. Indian Inst. Met.,21(1968) 41-45.
[50]P. Guex, P. Feschotte, The binary systems platinum-aluminium, platinum-gallium and platinum-indium, J. Less Common Met.,46(1976) 101-116.
[51]S. Bhan, K. Schubert, S of the Co-Ge, Rh-Si and its Related Alloys, Z. Metallkd., 51(1960)327-339.
[52]D. Swenson, B. Morosin, On the preparation and crystal structure of a new form of PtGa2, J. Alloys Compds.,243(1996) 173-181.
[53]E. Hellner, F. Laves, Structure of platinum-gallium binary systems, Z. Naturforsch A.,2(1947) 177-183.
[54]T. Chattopadhyay, K. Schubert, Kristallstruktur von Pt3Ga(r) und einigen phasen der mischung Pt-Al, J. Less Common Met.,41(1975) 19-32.
[55]Y. Oya, Y. Mishima, T. Suzuki, The Pt-Ga phase diagram, Z. Metallkd.,78(1987) 485-490.
[56]P. Anres, M. Gaune-Escard, J. Bros., Thermodynamics of the (Pt+Ga) system, J. Alloys Compd.,234(1996) 264-274.
[57]P. Anres, R. Haddad, D. Allam, et al., The limiting molar partial enthalpies of mixing of iron, cobalt, nickel, palladium and platinum in liquid gallium and indium, J. Alloys Compds.,220(1995) 189-192.
[58]W. Vogelbein, M. Ellner, B. Predel., Kalorimetrische untersuchung von binaren legierungen des platins und palladiums mit gallium, indium und thallium, Thermochim. Acta,44(1981) 141-149.
[59]M. Li, C.R. Li, F.M. Wang, W.J. Zhang, Thermodynamic assessment of the Ga-Pt system, Intermetallics,14(2006) 826-831.
[60]W. Klemm, L. Klemm, E. Hohmann, and H. Volk, Z. Anorg. Allg. Chem., 256(1948) 239-252 in German.
[61]P.H. Keck and J. Broder, The Solubility of Silicon and Germanium in Gallium and Indium, Phys. Rev. Lett.,90(1953) 521-522.
[62]E.S. Greiner and P. Breidt, Melting Point of Germa-nium and the Constitution of Some Ge-Ga Alloys, Jr. Trans. AIME,203(1955) 187-188.
[63]N. de Roche, Z. Metallkd., On the Gallium-Germanium System,48(1957) 58-60 in German.
[64]Y.M. Savitskiy, V.V. Baron, and M.A. Tylkina, Phase Diagrams on Properties of Alloys of Gallium and Thallium, Russ. J. Inorg. Chem.,3(1958) 310-327.
[65]F.A. Trumbore, E.M. Porbansky, and A.A. Tartaglia, Solid solubilities of aluminum and gallium in germanium, J. Phys. Chem. Solids,11(1959) 239-245.
[66]C.D. Thurmond and M. Kowalchik, Germanium and Silicon Liquidus Curves, Bell Sys. Tech. J.,39(1960) 169-204.
[67]http://www.accelrvs.com/mstudio/msmodeline/casten.htm
[68]http://www.wiep2k.at/
[69]http://www.abinit.org
[70]http://cms.mpi.univie.ac.at/vasp/
[71]G. Kresse and J. Hafner, Ab initio molecular dynamics for liquid metals, Phys. Rev. B.,47(1993)558-559.
[72]G. Kresse and J. Furthmuller, Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set, Phys. Rev. B.,54(1996) 11169-11170.
[73]G. Kresse and J. Furthmuller, Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set, Comput. Mater. Sci.,6(1996) 15-16.
[74]P.E. Blochl, Projector augmented-wave method, Phys. Rev. B.,50(1994) 17953.
[75]G. Kresse and J. Joubert, From ultrasoft pseudopotentials to the projector augmented-wave method, Phys. Rev. B.,59(1999) 1758-1759.
[76]J.P. Perdew, J.A. Chevary, S.H. Vosko, K.A. Jackson, M. R. Pederson, D. J. Singh and C. Fiolhais, Atoms, molecules, solids, and surfaces:Applications of the generalized gradient approximation for exchange and correlation, Phys. Rev. B., 46(1992)6671-6672.
[77]J.P. Perdew, Accurate and simple analytic representation of the electron-gas correlation energy, Phys. Rev. B.,45(1992) 13244-13245.
[78]H.J. Monkhorst and J.D. Pack, Special points for Brillouin-zone integrations, Phys. Rev. B.,13(1972) 5188-5189.
[79]B. Sundman, J. Agren, A regular solution model for phases with several components and sublattices, suitable for computer applications, J. Phys. Chem. Solids., 42(1981)297-301.
[80]S.V. Meschel, J. Kleppa, Standard enthalpies of formation of some 5d transition metal gallides by high-temperature direct synthesis calorimetry, J Alloys Compds., 311(2000)241-247.
[81]B. Sundman, B. Jansson, J. O. Anderson, The Thermo-Calc databank system, CALPHAD,9(1985) 153-190.
[82]L.L. Xu, J. Wang, H.S. Liu, Z.P. Jin, Thermodynamic assessment of the Pt-Si binary system, CALPHAD,32 (2008) 101-105.
[83]I. Ansara, J.P. Bros, M. Source, et al., Thermodynamic anlysis of the germanium-based ternary systems (Al-Ga-Ge, Al-Ge-Sn, Ga-Ge-Sn), Calphad, 3(1979)225-233.
[84]W. Hume-Rothery, K.W. Andrews, J. Inst. Met., Crystal structure in the Ag-Ga binary system,68(1942) 133-143.
[85]W. Hume-Rothery, K.W. Andrews, Z. Metallkd., Phase equilibria in the Ag-Ga systems,50(1959) 661-662.
[86]B. Predel, D.W. Stein, Bildungsenthalpien binarer verbindungen des galliums mit kupfer, silber und gold sowie analyse der thermodynamischen eigenschaften von 3/2-elektronen-verbindungen. Enthalpies of formation of binary compounds of gallium with copper, silver and gold and the analysis of thermodynamic properties of 3/2-electron-compoundsEnthalpie de formation des composes binaires du gallium avec le cuivre, l'argent et l'or. etude des proprietes thermodynamiques des composes a 3/2electrons, Metallurgica, 20(1972) 681-692.
[87]E. Weibke, L.Wiegels, Z. Anorg. Allg. Chem.,226(1936) 201-209.
[88]A.E. Gunn(?)s, O.B. Karlsen, A. Olsen, P.T. Zagierski, Phase relations and crystal structures in the Ag-Ga system, J. Alloys Compds.,297(2000) 144-155.
[89]Y. Zhang, J.K. Liang, J.B. Li, Q.L. Liu, Y.G. Xiao, Q.Zhang, B.J. Sun, G.H. Rao, Phase relations of the Ag-Ga-N system, J. Alloys Compds.,429(2007) 184-191.
[90]W.D. Hoff, R.P. Stratton, W.J. Kitchingman, The influence of indium and gallium on the lattice spacing of the β' and ζ phases of the silver-zinc alloys, Phil. Mag.,10(1964)979-987.
[91]E. Hellner, The Structure of Mg-Ga2, Forts. Der Miner.,29(1950) 58-61.
[92]H.W. King, T.B. Massalski, Lattice Spacing Relationships and the Electronic Structure of HCP Phases Based on Silver, Phil. Mag.,6(1961) 669-682.
[93]W. Hume-Rothey, P.W. Reynolds, FactorsAffectingthe Formation of 3/2 Electron Compounds in Alloys of Copper, Silver and Gold, G.V. Raynor, J. Inst. Met., 66(1940) 191-207.
[94]K. Moeller, Z. Metallkd., Electronic structure of ζ' based on sliver,31(1939) 19-20.
[95]R.P. Stratton, W.J. Kitchingman, Order in the of the silver-gallium alloys, Acta Crystallogr. A.,17(1964) 1471.
[96]A.E. Gunns, A. Olsen, P.T. Zagierski, Crystal structure determination of Ag2Ga by single crystal X-ray diffraction, Z. Kristallogr.,213(1998) 639-644.
[97]Y. Zhang, Q.L. Liu, J.B. Li, et al, Structures of the ζ and ζ' phases in the Ag-Ga system, J. Alloys Compd.,399(2005) 155-159.
[88]P. Feschotte, P. Bass, Un nouveau compose intermetallique tres timide:AgGa, J. Less Common Met.,171(1991) 157-162.
[99]M.R. Baren, The Ag-Ga phase diagram, Bull. Alloy Phase Diagr.,11(1990) 334-339.
[100]K. Muller, W. Merl, ETA-A,Phase boundaries in Ag-Ga phase diagram, 80(1959)515-520.
[101]E.A. Owen, V.W. Rowlands, Solubility of gallium in copper and in silver, J. Inst. Met.,66(1940) 367-368.
[102]E.A. Owen, D.P. Morris, The Application of X-Ray Methods to the Determination of Phase Boundaries in Metallurgical Equilibrium Diagrams, J. Inst. Met.,76(1949-1950) 145-168.
[103]W. Hume-Rothery, W. Mabbott, K.M. Channet Evans, Containing Papers of a Mathematical or Physical Character, Phyil. Trans. R. Soc. (London) A,233(1934) 1-97.
[104]H. Okamoto, Ag-Ga(silver-gallium), J. Phase Equillb.,13(1992)324-325.
[105]R. Beja, M. Laffitte, enthalpy fo mixing of liquid silver-gallium alloys at 500℃, C.R. Acad. Sci., Paris 267(1968) 123-126.
[106]R. Beja, Ph.D. Thesis, Centre de Recherches de Microcalorimetrie et de Thermochimie du C.N.R.S., Marseille, France,1969.
[107]K. Itagaki, A. Yazawa, Measurements of Heats of Mixing in Liquid Silver Binary Alloys, J. Japan Inst. Met.,32(1968) 1294-1300.
[108]B. Predel, D.W. Stein, Thermodynamische untersuchung der binaren systeme des Galliums mit Kupfer, Silber und Gold. Thermodynamic investigation of the binary systems of gallium with copper, silver and goldInvestigation thermodynamique des systemes binaires du gallium avec le cuivre, l'argent et l'or, Acta Metall..20(1972) 515-522.
[109]V.N. Danilin, S.P. Yatsenko, Thermodynamic properties of silver-gallium alloys, Izv. Akad. Nauk. SSSR, Metally,3(1968) 224-227.
[110]B. Predel, U. Schallner, Investigation of the Thermodynamic Properties of Binary Liquid Alloys of Silver and Gold with Gallium, Indium, and Germanium, Z. Metallkd.,63(1972) 341-347.
[111]G.J. Qi, M. Hino, T. Azakami, Thermodynamic study of liquid Ag-In and Ag-Ga alloys with a Knudsen cell-mass spectrometer, Mater. Trans. JIM,30(1989) 575-582.
[112]T.R. Briggs, R.O. McDuffie, and L.H. Willisford, Germanium. Alloys of Germanium:Silver-Germanium, J. Phys. Chem.,33(1929) 1080-1096.
[113]H. Maucher, On the Systems Copper-Germanium, Silver-Germanium, Forschungsarb. Metallkd. Rontgenmetal.,20(1936) 1-32 in German.
[114]E.A. Owen and V.W. Rowlands, Solubility of germanium in copper and in silver, J. Inst. Met.,66(1940) 368-369.
[115]V.E. Kosenko, Sov. Phys. Solid State,4(1962) 42-43.
[116]R. Castanet and M. Laffitte, Enthalpy of formation at 1280K O liquid alloys silver-germanium, C.R. Acad. Sci.,267(1968) 204.
[117]R. Castanet, Y. Claire and M. Laffitte, Enthalpy of formation of liquid silver-gemanium, silver-tin, and silver-lead alloys at 1280K, J. Chim. Phys.,66(1969) 1276-1277.
[118]U. Gerling, M.J. Pool, B. Predel, contribution to the associate model for binary liquid alloys, Z. Metallkd.,74(1983) 616-619.
[119]O. Redlich, A. Kister, Thermodynamics of nonelectrolytic solutions, algebraic representation of thermodynamic properties and the classification of solutions, Ind. Eng. Chem.,40(1948) 345-348.
[120]P.Y. Chevalier, Thermochim. Acta, Critical assessment of thermodynamic data for the Ag-Ge system,130(1988) 25-32.
[121]J.O. Andersson, T. Helander, L.H. Hoglund, et al., Thermo-Calc & DICTRA, computational tools for materials science, CALPHAD,26(2002) 273-312.
[122]S.L. Chen, S. Daniel, F. Zhang, et al., The PANDAT software package and its applications, CALPHAD,26(2002) 175-188.