Ni-Ga二元系的热力学计算

采用CALPHAD技术评估了Ni-Ga二元系的相图和热力学性质.用双亚晶格模型描述2个有序相(L1₂-Ni₃Ga和B₂-NiGa)的热力学行为,并在优化过程中考虑了fcc-(Ni)和L1₂Ni₃Ga相的有序-无序转变.溶液相(液相、fcc-(Ni)固溶体)的热力学模型采用Redlich-Kister方程,其余5个中间化合物被视为整比化合物.     

FeS-PbS和PbS-ZnS二元系的热力学优化

采用ＲｅｄｌｉｃｈＫｉｓｔｅｒ多项式描述体系液相的过剩自由焓,根据试验相图和已知的热力学数据优化得到了ＦｅＳＰｂＳ和ＰｂＳＺｎＳ二元系的热力学参数。用优化结果计算的相图与试验测量值吻合较好。     

Fe—Ga—C三元系熔体热力学初探

通过计算和实验测定，求得了为进行提镓热力学分析计算所必要的势力学参数△Ｇ＾ｏＧａ→［Ｇａ］％，ｅ＾ＧａＧａ和ｅ＾ＣＧａ。     

三元硅酸盐系热力学模型

已经开发出三元液相硅酸盐系SiO2-AO-BO的热力学模型，其中A和B是如Ca、Fe、Mn等的金属。它是在一个假定每种金属氧化物随自由能变化产生解聚作用O^0 O^2-=20^-的结构模型基础上得到的。模型能从二元子系中的数据计算三元系中的参数，不需要三元条件。模型用来计算复合硅酸盐如SiO2-FeO-CuO系中各组分的活度，其中Fe^2 行为与硅酸盐中的Ca^2 不同。这个模型也用来计算SiO2-MgO-FeO，SiO2-MgO-CaO,SiO2-MgO-MnO,SiO2-Na2O-MgO和SiO2-Na2O-CaO系中的活度，计算结果与试验结果一致。     

Fe—Bi—j三元溶液体系热力学参数的测定与模型计算

利用气液平衡实验方法和三元系液态合金元组间相互作用系数的计算模型，测定和计算了Ｆｅ－Ｂｉ－ｊ三元溶液体系在１８７３Ｋ时第三组合组元Ｃｒ，Ｃｕ，Ｃ，Ａｌ和Ｓｉ对Ｂｉ的活度相互作用系数以及ｌｎγ＾０值。实验值与模型计算值符合良好。     

FeS—PbS和PbS—ZnS二元系的热力学优化

采用Ｒｅｄｌｉｃｈ－Ｋｉｓｔｅｒ多项式描述体系液相的过剩自由焓，根据试验相图和已知的热力学数据优化得到了ＦｅＳ－ＰｂＳ和ＰｂＳ－ＺｎＳ二元素的热力学参数。用优化结果计算的相图与试验测量值吻合较好。     

金—锡—锌三项合金体系热力学研究

在金，锡比例分别为恒定的９：１，３：１，１：１，１：３的四种情况下，采用电动势方法可测出液态金－锡－锌三项合金体系的热力学特性，在金，锡比例分别为恒定的３：１，１：１，１：３这三种情况下，采用量热测定法可以把直接测量法所得出的混合总热焓与Ｇｉｂｂｓ－Ｄｕｈｅｍ（吉布斯－杜霍姆）方程推导出的电动势测量法所得出的数据进行比较。     

Cu-In体系的热力学优化

评估了Cu-In体系的相平衡和热力学实验结果,并对体系进行了热力学优化。采用替代模型描述体系的液相和富铜固溶体相,双亚晶格模型描述线性化合物相,三亚晶格模型描述非线性化合物相,结合选取合理的实验数据,优化得到Cu-In体系各相的热力学参数,用优化结果计算的相图以及热力学性质与实验结果吻合。     

C—Fe—P,C—Fe—Co熔体热力学性质研究

通过拟合过剩偏摩尔自由能与组元浓度的关系式需要的参数，建立起可应用于整个液相区的组元活度解析式。应用此结构计算铁基含磷、然三元系的活度，其结果与报道的数据基本一致。并对报道的方法进行了部分修正。     

Thermodynamic Modeling of the Al-Ti-V Ternary System

The sub-binary systems Al-Ti, Ti-V, and Al-V are reviewed and adopted from the previous assessments, the thermodynamic analysis of the Al-Ti-V ternary system is performed by the CALPHAD approach, and a set of self-consistent thermodynamic parameters of the ternary system are obtained. Furthermore, the isothermal sections of this system at 1073 K, 1173 K, 1273 K, 1373 K, and 1473 K (800 °C, 900 °C, 1000 °C, 1100 °C, and 1200 °C) and the ternary invariant equilibria are calculated and compared with the corresponding experimental data, and all are in good agreement with most of the experimental results. Thus, the optimized thermodynamic parameters in this study may provide more accurate guidance to develop the new alloys involving it.     

Experimental Study and Thermodynamic Optimization of the FeO-V203 System

Optimization of the phase diagram of FeO-V20a system is a part of an on-going research project to develop a self-consistent multi-component thermodynamic database for vanadium slag from hot metal. Due to the lack o{ ex- perimental data for optimization, a novel experimental investigation has been carried out by thermal analysis （DSC） with a series of slags on different V2 03 contents （i. e. 3mass%- 12mass%）. All available thermodynamic and phase diagram data for the binary systems have been simultaneously optimized with CALPHAD （Calculation of Phase Dia- grams） methods to give one set of model equations for the Gibbs free energy of the liquid slag as functions of compo- sition and temperature. The modified quasi-chemical model was used to describe the binary slag system. It was dem- onstrated that the calculated phase diagram with the optimized parameters was in good agreement with the experi- mental data.     

预示三元系热力学性质的不对称模型

本文提出一种预示三元系热力学性质和用于相图计算的新几何不对称模型。该模型在现有不对称模型中数学解析式最简洁,计算精度较高。它应用于Bi-Ga-Sn、An-Ag-Sn和NaCl-KCI-CaCl₂ 3个三元系,计算值与实验结果吻合较好。文中还阐明了在不对称模型中选取不对称组元的热力学准则。     

A Critical Evaluation and Thermodynamic Optimization of the CaO-CaF2 System

A critical evaluation and thermodynamic optimization of all the available literature experimental data of the CaO-CaF₂ system was conducted to obtain a set of thermodynamic functions which can reproduce all available and reliable experimental phase diagrams and thermodynamic data. The liquid solution was described using the Modified Quasichemical Model which assumes the mixing of O² and F^? in the pseudo anionic sublattice and CaF₂ solid solution was described using the compound energy formalism. The discrepancies in the CaO and CaF₂ liquidii among the available experimental data were resolved. The recent experimental data on the solubility of CaO in solid CaF₂ phase were well reproduced, which is critical to explain the eutectic temperature of the system.     

Solution and Thermodynamic Studies on Binary and Ternary Complexes of Lanthanides

The interactions of La(Ⅲ), Pr(Ⅲ), Nd(Ⅲ), Sm(Ⅲ), Eu(Ⅲ), Gd(Ⅲ), Dy(Ⅲ), and Yb(Ⅲ) with cytosine, 5-bromocytosine, 5-azacytosine and 5-flurocytosine as primary ligands (L) and guanine (A) as secondary ligand for both binary (1:1) as well as ternary (1:1:1) systems were investigated by potentiometric equilibrium measurements at 25, 35 and 45 ℃ in aqueous solution (ionic strength, μ=0.1 mol·dm-3 NaNO3). The stability constants of the binary (1:1) and ternary (1:1:1) metal-ligand complexes follow the following order La＜Pr＜Nd＜Sm＜Eu＞Gd＜Dy＞Yb. Results also indicate that the ternary lanthanide complexes of La(Ⅲ), Pr(Ⅲ), Nd(Ⅲ), Sm(Ⅲ), Eu(Ⅲ), Gd(Ⅲ), Dy(Ⅲ), and Yb(Ⅲ) are more stable than corresponding binary lanthanide complexes. The enthalpy (Δhof) and entropy (Δsof) changes for the formation of binary and ternary complexes were calculated from temperature coefficient data. The ΔΔSof values are positive for all the metal ligand systems. The negative ΔΔHof values indicate the extra stability of the ternary complexes by the exothermic enthalpy changes (ΔΔSof=ΔTSof-ΔBSof and ΔΔHof=ΔTHof-ΔBHof where ΔTSof, ΔTHof and ΔBSof, ΔBHof are the entropy and enthalpy values associated with the ternary and binary complexes, respectively). It was also proposed that the guanine is bonded to metal ions through N1/C6=O and N7 whereas cytosine and its derivatives are bonded through N3 atoms in ternary complexes.     

Fe－Bi－j三元溶液体系热力学参数的测定与模型计算

利用气液平衡实验方法和三元系液态合金组元间相互作用系数的计算模型，测定和计算了Ｆｅ－Ｂｉ－ｊ三元溶液体系在１８７３Ｋ时第三组元Ｃｒ，Ｃｕ，Ｃ，Ａｌ和Ｓｉ对Ｂｉ的活度相互作用系数以及ｌｎγ~０值。实验值与模型计算值符合良好。     

Experimental Study and Thermodynamic Optimization of the FeO-V_2O_3 System

Optimization of the phase diagram of FeO-V2O3 system is a part of an on-going research project to develop a self-consistent multi-component thermodynamic database for vanadium slag from hot metal.Due to the lack of experimental data for optimization,a novel experimental investigation has been carried out by thermal analysis(DSC)with a series of slags on different V2O3 contents(i.e.3mass%-12mass%).All available thermodynamic and phase diagram data for the binary systems have been simultaneously optimized with CALPHAD(Calculation of Phase Diagrams)methods to give one set of model equations for the Gibbs free energy of the liquid slag as functions of composition and temperature.The modified quasi-chemical model was used to describe the binary slag system.It was demonstrated that the calculated phase diagram with the optimized parameters was in good agreement with the experimental data.