热力学优化Bi-Ni二元系

基于文献报导的实验数据,采用相图计算（CALPHAD）方法,热力学优化了Bi-Ni二元系相图。该二元系的液相、fcc_A1（Ni）相和rhombohedral_A7（Bi）相用替换溶液模型来描述,其过剩吉布斯自由能用Redlich-Kister多项式来表达。考虑到晶体结构（NiAs型）以及与多组元体系热力学数据库的兼容性,中间化合物BiNi相采用亚点阵模型：（Bi）（Ni,Va）（Ni,Va）;Bi3Ni相处理为化学计量比化合物。最后,通过优化该二元系实测的相图和热力学数据,获得一组能够表达各相吉布斯自由能的自洽的热力学参数。根据这些热力学参数计算的相图和热力学数据与报导的实验数据吻合良好。     

Thermodynamic assessment of the Ni-Sb binary system

The Ni-Sb binary alloy system was thermodynamically assessed using CALPHAD approach in this article.Excess Gibbs energies of solution phases,liquid and fcc phases,were formulated using the Redlich-Kister expression.The intermediate phases were modeled by the sublattice model with (Ni,Va)0.5(Ni,Sb)0.25(Ni)0.25 for Ni3Sb_HT phase and (Ni,Va)0.3333(Sb)0.3333(Ni,Va)0.3333 for NiSb phase.The other phases including Ni3Sb,Ni7Sb3,and NiSb2 were treated as stoichiometric compound owing to their narrow composition ranges.Based on the reported thermodynamic properties and phase diagram data,the thermodynamic parameters of these phases were optimized,and the obtained values can reproduce the available experimental data well.     

Thermodynamic assessment of the Nb-Ge system

The Nb-Ge binary system has been thermodynamically assessed using the CALPHAD (Calculation of Phase Diagrams) approach on the basis of the experimental data of both the phase equilibria and the thermochemical properties. The reasonable models were constructed for all the phases of the system. The liquid and the terminal solid solution phases, Bcc-(Nb) and Diamond-(Ge), were described as the substitutional solutions with Redlich-Kister polynomials for the expressions of the excess Gibbs free energies. The intermediate phases (Nb₃Ge), (Nb₅Ge₃), (Nb₃Ge₂) and (NbGe₂) with homogeneity ranges were treated as the sublattice models Nb_0.75(Ge,Nb,Va)_0.25, Nb_0.5(Nb,Ge)_0.125(Ge,Va)_0.375, (Nb,Ge)_0.222(Nb,Ge)_0.333Nb_0.333(Ge,Va)_0.111 and (Nb,Ge)_0.333(Nb,Ge)_0.667 respectively based on their structure features of atom arrangements. A set of self-consistent thermodynamic parameters for the Nb-Ge system was obtained. Using the present thermodynamic data, the calculation results can reproduce the experimental data well.     

Bi掺杂Mg2Si的稳定性,弹性性能和电子结构的第一性原理计算

从动力学角度研究合金元素Bi对Mg_2Si的掺杂情况,采用CASTEP中基于密度泛函理论的第一性原理方法分析了合金元素Bi掺杂Mg_2Si的占位情况、结构稳定性、弹性性能和电子结构。计算结果表明:Mg_2Si、Mg-7Si_4Bi、Mg_8Si_3Bi均可稳定存在于体系中,Bi原子优先占据Mg_2Si晶体中Si原子位置,Mg_8Si_4Bi间隙固溶体不稳定存在体系中;Mg_Si、Mg_7Si_4Bi、Mg_8Si_3Bi均为脆性相,掺杂合金元素Bi后可以提高Mg_Si的韧性、合金化能力和导电性;Mg_2Si的成键本质是金属键、共价键和离子键的结合,Bi原子掺杂Mg2Si后产生Bi-Si和Bi-Mg键合作用,有利于提高体系的稳定性。     

Mg-Zn-Si体系的相平衡计算及应用

利用Calphad方法重新评估了Mg-Si二元系的液相,并结合Mg-Zn和Zn-Si二元系热力学数据,外推得到Mg-Zn-Si三元系热力学参数;同时根据Mg2Si-MgZn2伪二元相图实验数据评估了Mg-Zn-Si系的液相三元相交互作用参数,计算相图与实验数据较一致。利用Scheil凝固模型模拟了Mg-2.33Zn-0.9Si(at%)合金的凝固过程,预测了镁合金在铸造冷却过程中的相演变信息,模拟计算结果与实验结果吻合较好     

Thermodynamic optimization of the boron-cobalt-iron system

A thermodynamic optimization of the boron-cobalt-iron ternary system is performed based on thermodynamic models of the three constitutional binary systems and the experimental data on phase diagrams and thermodynamic properties of the ternary system. The liquid, fcc_A1, bcc_A2 and hcp_A3 solution phases are described by the substitutional solution model. The three intermediate line compounds, (Co,Fe)B, (Co,Fe)₂B and (Co,Fe)₃B, are described by the two sublattice model. A set of thermodynamic parameters are obtained. The calculated phase diagram and thermodynamic properties are in reasonable agreement with most of the experimental data.     

Experimental Investigation of the Epsilon Phase in Pb–Bi System

The Pb–Bi (Lead–Bismuth) binary system has gained some prominence in recent years due to the possible use of eutectic alloys as primary-circuit coolant in generation IV nuclear reactors. Apart from the terminal solid solutions A1-Pb and A7-Bi, the system presents also one intermetallic phase with the hexagonal close-packed structure (A3), usually denoted ε phase. Due to the low temperatures involved in this system, attainment of equilibrium is difficult, and in addition, the proximity of x-ray scattering factors for both elements raises questions about a possible polymorphic transition. In the present work, three samples with compositions Pb–29 wt.%Bi, Pb–31 wt.%Bi and Pb–33 wt.%Bi were prepared and characterized by x-ray diffraction. The lattice parameters of ε are consistent with those reported in the literature, and their dependence on Bi content was determined as well. Only the hexagonal phase was identified in the 29 wt.%Bi sample, although the currently assessed Pb–Bi phase diagram predicts the presence of the Pb-rich A1 terminal solid solution in this composition. A 2-year annealing at room temperature was performed and the XRD characterization results for these samples are compared with the original data.     

Thermodynamic assessment of the Mo–Re binary system

The existing Mo–Re phase diagrams are reviewed and a thermodynamic calculation of the Mo–Re binary system is undertaken. The Gibbs energies are estimated for liquid, bcc (Mo), hcp (Re), σ and χ phases. The liquid, bcc (Mo) and hcp (Re) phases are described by a regular solution model, whereas the σ and χ phases are described respectively by three-sublattice models. For the σ phase, two thermodynamic models are used for calculations and the results are compared. The models take into account the crystallographic structure and similarity between the σ and χ phases. The calculated results remove the ambiguity of the existing phase diagram data and are compared with the experimental data in the literature.     

Thermodynamic modeling of the Ag–Sr system

The CALPHAD method was employed to model thermodynamic properties of the Ag–Sr system. The liquid phase was treated as a substitutional model (Ag,Sr), with the excess molar Gibbs free energy expressed by the Redlich–Kister formula. All the intermetallic phases were modeled as stochiometric compounds. The solubilities of Ag and Sr in the terminal solid phases were not considered due to their negligible values. Calculated results were then compared with available data from existing literatures. A set of self-consistent thermodynamic parameters of the Ag–Sr binary system was obtained.     

Thermodynamic Assessment of the Ti-Ir System

The thermodynamic assessment of the binary system Ti-Ir has been carried out by modeling the Gibbs energy of all individual phases using the calculation of phase diagrams approach based on the available literature data including the phase equilibria and thermodynamic properties. The Gibbs free energies of the liquid, bcc, fcc and hcp phases were described by the subregular solution model with Redlich-Kister formula, and those of the intermetallic compounds (Ti₃Ir, γTiIr, βTiIr and TiIr₃) in the Ti-Ir binary system were described by the two-sublattice model. The calculations are in good agreement with the literature data on both phase equilibria and thermodynamic properties in the Ti-Ir system.     

Experimental Investigation and Thermodynamic Calculation of the Phase Equilibria in the Al-Bi-Sn Ternary System

This work first deals with the experimental investigation and thermodynamic calculation in the Al-Bi-Sn ternary system. The phase equilibria at 400 and 500 °C in the Al-Bi-Sn ternary system have been experimentally determined by electron probe microanalysis (EPMA) on the equilibrated alloys. Based on the experimental data determined in the present work, the phase equilibria in the Al-Bi-Sn ternary system have been thermodynamically assessed by using the CALPHAD (CALculation of PHAse Diagrams) method, and a consistent set of thermodynamic parameters leading to reasonable agreement between the calculated results and experimental data was obtained. The additions of Sn can effectively reduce the stable liquid miscibility gap in the Al-Bi binary system and gradually decrease its critical temperature. And the additions of Bi can significantly stabilize the metastable liquid miscibility gap in the Al-Sn binary system. This is shown by an initial decrease in critical temperature with increasing Bi additions.     

Thermodynamic optimization of Mg-Nd system

Based on the reported experimental data,the phase diagram of Mg-Nd binary system was optimized using the CALPHADapproach.Gibbs energies of the disordered BCC_A2 and ordered BCC_B2 phases were modeled with a single expression based on a2-sublattice model.Liquid and terminal solutions,such as dHCP and HCP,were modeled as substitutional solutions.Intermediatephases Mg2Nd,Mg3Nd and Mg41Nd5 were treated as stoichiometric compounds.The optimization was carried out in theThermo-Calc package.A set of thermodynamic parameters is obtained.Calculated phase diagram,enthalpies of formation and Gibbsenergies of formation are in reasonable agreement with the experimental data.     

Thermodynamic assessment of the Gd–Sb system

A thermodynamic assessment of the binary Gd–Sb system was performed through the CALPHAD approach (CALculation of PHAse Diagram) based on the evaluation of all phase diagram data and available thermodynamic data in the literature. The liquid, hcp-A3 (αGd) and bcc-A2 (βGd) phases were described by a substitutional solution model. All the intermediate phases, Gd₅Sb₃, Gd₄Sb₃, βGdSb, αGdSb and Gd₁₆Sb₃₉, were treated as stoichiometric compounds. A set of self-consistent thermodynamic parameters of the Gd–Sb system has been obtained. A good agreement is obtained between the experimental and the calculated phase diagrams.     

Ni—Zr二元相图计算

优化和计算了ＮｉＺｒ二元相图。液相用缔合物模型、端际固溶体用替换溶液模型描述，Ｎｉ５Ｚｒ和Ｎｉ１０Ｚｒ７则分别选用了（Ｎｉ）１（Ｎｉ，Ｖａ）４（Ｎｉ，Ｚｒ）１和（Ｎｉ，Ｚｒ）１０Ｚｒ７的亚点阵模型。计算结果与大部分相图和热力学数据相吻合     

Assessment of the Te-Tl (tellurium-thallium) system

The optimized thermodynamic data for the Te- TI binary system have been obtained by the computer operated least squares method from measured data. The Gibbs energy of the liquid phase was modeled as a two- sublattice model for ionic melt after Hillert.³¹ The intermediate compounds, Te₃Tl{2}and TeTl, were treated as stoichiometric phases, and the nonstoichiometric γ phase was expressed as a sublattice model. A strong tendency for chemical short- range order in the liquid state at the composition close to TeTh was confirmed by calculated results, but the existence of the TeTh phase was not justified. The experimental thermodynamic and phase diagram data were closely reproduced by the optimized thermodynamic data. Parameters describing the Gibbs energies of all the phases in this calculation and the calculated phase diagram and thermodynamic functions are presented and compared with experimental information.