合金熔体结构和原子- 分子热力学模型

对金属熔体结构的研究证实熔体中存在短程有序结构,而含金属间化合物的合金熔体中发现了原子- 分子结合的团簇结构,即固态下的金属间化合物在熔体中并没有消失,而是以团簇结构（实际上就是液态的分子）存在,并与熔体中的自由原子存在化学平衡。从熔体结构出发,提出了适用于合金熔体的原子- 分子热力学模型。然后以Ca- Mg合金熔体为例,介绍了该模型的构建和求解方法,并计算了1010K下的Ca- Mg合金熔体中各物质的摩尔分数。最后,将计算得到的钙、镁摩尔分数与各自的实测活度值进行比较,发现两者吻合得较好。这从计算上证明了合金熔体中同时存在着金属原子和金属间化合物分子,两者处于动态化学平衡之中。且达到平衡时,金属原子的摩尔分数实际上就是各自的活度。因此,对于合金熔体而言,活度并不存在。     

Al—Si—Fe三元合金熔体组元活度的解析

将Ａｌ－Ｓｉ－Ｆｅ三元合金熔体中组元Ａｌ的过剩偏摩尔自由能表达成多项式函数的形式,再由组成该三元系的三个二元子系以及三元系部分实验结果作为边界条件确定多项式中的参数Ａｊｋ值。根据Ｇｉｂｂｓ－Ｄｕｈｅｍ方程导出了计算体系过剩摩尔自由能多项式中的参数Ｆｊｋ值,由Ａｊｋ和Ｆｊｋ值求得组元Ｓｉ、Ａｌ的过剩偏摩尔自由能的表达式,并用上述解析表达式计算出了整个液相区域内各组元的等活度线     

探索CaO-Fe2O3系相互作用参数与体系熔化温度变化的关系

将CaO-Fe2O3系拆分成CaO-Ca2F2O5(C2F)与C2F-FeOn两个二元系,借用周国治等人推导出的从二元系相图中提取活度关系式,分别对这两个二元系计算得到,CaO,C2F和Fe3O组元的活度值,并成功提取出了组元间的相互作用参数。结合相互作用参数与原相图液相线分析得到,当温度高于体系最高熔点时,则相互作用参数稳定不变;当体系温度降低时,单一液相产生不同相分离,对应的相互作用参数值也会发生相应的变化,且生成不同的相,对相互作用参数变化影响也不同。     

EuCl3-BaCl2二元系相图的研究

利用差热分析法研究了EuCl3-BaCl2二元系相图,发现该体系有一个固液同组成化合物3EuCl3·2BaCl2,体系相变点为950℃,EuCl360%(摩尔分数);一个异份熔化化合物2EuCl3·3BaCl2,转熔点为630℃,EuCl3 43.6%(摩尔分数);2个低共熔点分别为320℃,EuCl3 51%(摩尔分数)和330℃,EuCl3 79%(摩尔分数).同时探讨了相图的某些规律.     

Fe—C—P,Fe—Mn—P,Fe—Si—P三元金属熔体作用浓度计算模型

根据含化合物的金属熔体结构的共存理论，推导了１６７３Ｋ下Ｆｅ－Ｃ－Ｐ、Ｆｅ－Ｍｎ－Ｐ、Ｆｅ－Ｓｉ－Ｐ三元金属熔体作用浓度计算模型。计算的磷的作用浓度与相应的实测磷活度相符合，从而证明所得模型可以反映Ｆｅ－Ｃ－Ｐ、Ｆｅ－Ｍｎ－Ｐ、Ｆｅ－Ｓｉ－Ｐ三元熔体的结构本质。同时模型揭示了Ｃ、Ｍｎ、Ｓｉ的摩尔分数对磷的转换系数的影响规律。     

含钡二元合金熔体热力学性质的计算

根据Miedema二元合金生成热模型，结合相关热力学数据，对Si-Ca二元合金熔体在1623K时的组元活度进行了计算，计算结果与实测结果吻合较好。并进一步对Ba-Si、Ba-Al和Ba-Ca3种二元含钡合金熔体的生成热△H及1873K时的过剩熵S^E、过剩自由能G^E以及不同温度下各组元的活度等热力学性质进行了计算。结果表明：3种合金的△H、S^E和G^E均为负值，且S^E绝对值的最大值为4．424J／mol，可以近似认为3种合金熔体的S^E为零；Ba-Si和Ba-Al合金熔体的活度相对于理想溶液存在较大负偏差，而Ba-Ca合金熔体的活度与理想溶液偏差较小。     

Al-Si-Fe合金熔体质量作用浓度的热力学模型

基于原子分子共存理论(AMCT)建立了计算Al-Si二元熔体及Al-Si-Fe三元熔体结构单元质量作用浓度的热力学模型.针对Al-Si二元系熔体,根据FactSage热力学软件计算的活度得到生成复杂分子Al2Si和AlSi的反应的标准摩尔吉布斯自由能的表达式,进而获得了 Al-Si二元熔体中标准摩尔溶解吉布斯能变的表达...     

基于原子-分子理论的二元合金熔体热力学计算

分别使用Miedema、MIVM、NRTL、Wilson二元合金系热力学模型及FactSage热力学软件计算Bi-Pb、Bi-Sn、Cd-Pb、Pb-Sn 4个二元合金系的活度值,并与实验值进行比较.结果表明:Miedema、MIVM、NRTL、Wilson模型计算不同体系活度的效果不同,每种模型都有其适用的体系.而FactSage热力学软件计算的活度均与实验值吻合较好,文中使用FactSage分别计算Bi-Pb、Bi-Sn、Cd-Pb、Pb-Sn 4个二元系不同温度下的活度值.同时利用原子-分子理论计算Bi-Pb二元系质量作用浓度,给出生成金属间化合物BiPb反应的标准吉布斯自由能的表达式.      

电渣重熔六元渣系FeO活度的研究

利用熔渣分子—离子共存理论,研究了电渣重熔20%CaO-20%Al_2O_3-60%CaF_2渣系在冶炼过程中,由于吸收MgO、FeO、SiO_2等夹杂物后,在渣中形成了一定浓度的FeO,而使渣系具有向钢液传递[O]的能力,考察了1 550℃下FeO、MgO质量分数以及二元碱度w(CaO)/w(SiO_2)对FeO活度的影响;分析了该渣系在1 550、1 600、1 650、1 700、1 750和1 800℃下FeO活度随温度的变化情况,构建了20%CaO-20%Al_2O_3-60%CaF_2为基础渣系的六元渣系的FeO活度的模型.研究表明:FeO活度随二元碱度w(CaO)/w(SiO_2)的增加而先增大至趋于平缓后略微减小,在碱度为3.8达到最大;FeO活度随FeO质量分数增加而线性增加,高碱度时,随FeO质量分数增加FeO活度相近;碱度为1时,FeO的活度随MgO的质量分数增加而增大,随温度升高而增加,且MgO含量越高,FeO活度越大;当碱度增加到4、7、10时,FeO的活度随MgO的质量分数增加而减小,相同质量分数的MgO时,碱度越大,FeO活度值越小;碱度为4,MgO的质量分数为1%时,FeO活度达到最大值,高碱度时,温度升高,FeO活度基本保持不变,且同一温度下,碱度越大,FeO活度反而降低.工业试验表明,该模型可以直接利用渣系对金属熔体中氧含量变化进行预测,并对减小钢液中氧含量具有指导意义.     

Bi-Te二元体系的热力学优化

在综合评估Bi-Te体系实验数据的基础上,结合第一性原理方法计算的各中间化合物的摩尔形成焓,采用CALPHAD方法优化和计算该二元合金体系的平衡相图。液相采用置换式溶体溶液模型,对于化学计量比中间化合物Bi_7Te_3、Bi_2Te_3以及具有较大固溶度的中间相Bi_2Te、BiTe,分别采用Neumann-Kopp规则以及双亚点阵模型描述其热力学函数。通过优化,得到一组合理自洽的热力学参数,并利用该热力学参数计算相图。计算的相图与文献报道的实验信息吻合较好,计算的863 K下液相Bi的活度以及混合焓也与已有的热化学数据符合良好。     

Crystallization behavior of iron-containing intermetallic compounds in 319 aluminum alloy

The crystallization behavior of iron-containing intermetallic compounds in industrial grade 319 aluminum alloy has been investigated by means of thermal analysis and metallography. In the absence of manganese, the iron compound crystallizes in theβ phase, at all cooling rates ranging from 0.1 °C/s to 20 °C/s under normal casting temperatures (750 °C). However, when the melt is superheated to a high temperature (about 200 to 300 degrees above the liquidus temperature), the iron compound crystallizes in the α phase at high cooling rates. This is due to the fact that γ alumina, which forms at low melt temperatures (≤750 °C), acts as a nucleus for crystallization ofβ phase. When the melt is superheated to high temperature (≥85O °C), the γ alumina transforms to a alumina. This is a poor nucleus for the β-phase crystallization, and as a result, a phase forms. The importance of nucleation and growth undercooling for the crystallization of iron compounds is highlighted. In the presence of manganese, the iron compound crystallizes in a phase at low cooling rates and in both the α andβ phases at high cooling rates. This reverse crystallization behavior is explained in terms of phase diagram relationships.     

Melting equilibria in the iron-rich corner of the Fe-Ni-Cr system

Isothermal holding tests were carried out on the Fe-Ni-Cr system in the two-phase region between the melt and crystal in order to determine the γ and δ liquidus surfaces in the iron-rich corner, to establish the position of the peritectic line running between them, and to compare the results with those contained in relevant literature. The initial contents of the 13 test series were staggered in roughly equal intervals from 29.6% Ni and 12.9% Cr to 18.7% Ni and 28.4% Cr. They were held between the temperatures of 1450 and 1530 °C at intervals of 10 °C for 40 minutes in each case, so that 93 liquidus concentrations and temperatures were determined. Both liquidus surfaces can be described very accurately with corresponding mathematical equations and mathematically intersected in order to determine the course of the peritectic line. The results enable sufficiently accurate development of the melting equilibria of the entire ternary system, building on the basis provided by the known γ and δ liquidus lines of the three binary systems.     

Gravity segregation of complex intermetallic compounds in liquid aluminum-silicon alloys

Primary crystals of intermetallics that are rich in iron, manganese, and chromium form at temperatures above the liquidus, and because their density is higher than that of liquid alumi-num, they cause gravity segregation in the melt. Segregation may occur either in the mold at slow cooling rates or in the bulk liquid in furnaces or ladles. The kinetics of settling of these intermetallic compounds in a melt of Al-12.5 pct Si having 1.2 pct Fe, 0.3 pct Mn, and 0.1 pct Cr has been studied. Sedimentation was investigated at 630 ‡C for settling times of 30, 90, and 180 minutes in an electric resistance furnace. The effect of settling time and height of melt on the volume percent, number, and size of intermetallic compounds was studied by image anal-ysis. The volume percent of intermetallics increases with distance from the melt surface. Both the number of particles and the average size increase during sedimentation. The rate of settling varies with position in the melt due to depletion of intermetallics near the surface and an increase near the bottom. The settling velocities obtained experimentally were compared with terminal velocities calculated by Stokes’ law. Good agreement was generally found. The settling speed of intermetallics reaches the terminal velocity at very short times and very close to the liquid surface. Stokes’ law is therefore applicable to virtually all locations within the melt.     

Thermodynamics of liquid Fe-C solutions

The activity of carbon in liquid iron has been determined at low concentrations by means of the CO-CO₂ equilibrium and at high concentrations by the solubility of graphite. At intermediate concentrations there is a broad region in which measurements have not been made because of thermal instability of gas mixtures high in CO. Because of this phenomenon it is suggested that the reported activity coefficients at low concentrations may be in error and are only useful in determining a limiting value at infinite dilution. At temperatures below the melting point of iron, activity coefficients at intermediate concentrations along the liquidus line are calculated from recent measurements of the activity in austenite and of the solidus and liquidus lines of the phase diagram. The results agree fairly well with the data of Richardson and Dennis at higher temperatures. Several interpolation formulae are investigated. Equations are presented which describe the thermodynamic properties of the binary liquid solution at all compositions between the eutectic and 1760°C.     

Phase-Field Simulation of Fusion Interface Events during Solidification of Dissimilar Welds: Effect of Composition Inhomogeneity

We investigate the events near the fusion interfaces of dissimilar welds using a phase-field model developed for single-phase solidification of binary alloys. The parameters used here correspond to the dissimilar welding of a Ni/Cu couple. The events at the Ni and the Cu interface are very different, which illustrate the importance of the phase diagram through the slope of the liquidus curves. In the Ni side, where the liquidus temperature decreases with increasing alloying, solutal melting of the base metal takes place; the resolidification, with continuously increasing solid composition, is very sluggish until the interface encounters a homogeneous melt composition. The growth difficulty of the base metal increases with increasing initial melt composition, which is equivalent to a steeper slope of the liquidus curve. In the Cu side, the initial conditions result in a deeply undercooled melt and contributions from both constrained and unconstrained modes of growth are observed. The simulations bring out the possibility of nucleation of a concentrated solid phase from the melt, and a secondary melting of the substrate due to the associated recalescence event. The results for the Ni and Cu interfaces can be used to understand more complex dissimilar weld interfaces involving multiphase solidification. This article is based on a presentation given in the symposium entitled “Materials Behavior: Far from Equilibrium” as part of the Golden Jubilee Celebration of Bhabha Atomic Research Centre, which occurred December 15–16, 2006 in Mumbai, India.     

The high temperature phase diagrams for zirconium-molybdenum and hafnium-molybdenum

The high temperature regions of the Zr−Mo and Hf−Mo binary phase diagrams have been constructured from temperature-composition data obtained by gravimetric and pyrometric methods. The liquidus curves were obtained directly from the measurements of saturation solubilities of molybdenum (single crystal) in liquid Zr and Hf. The solubility results are supported by electron microprobe analyses which identify the formation of thin (∼10 μm) layers of nearly stoichiometric compounds ZrMo₂ and HfMo₂ on the surface of the single crystal molybdenum below the respective peritectic temperatures 1918±5 and 2206±5°C. These thin layers and the negligible diffusion zones of Zr and Hf in single crystal molybdenum do not significantly affect the measured solubilities. The diffusion coefficient of Hf in Mo-single crystal at 2080°C is ∼5×10⁻¹² m² s⁻¹. The melting, solidus, liquidus, eutectic and peritectic temperatures were directly measured by pyrometrically observing the partial or complete destruction of “black-body” conditions inside an effusion cell with the appearance of a liquid phase that forms a highly reflecting mirror. The melting points of Zr and Hf metals, 1860±3 and 2228±3°C, respectively, are in good agreement with previously assessed values. The respective eutectic temperatures peratures and compositions 1551±2°C, 29.0±0.5 at. pct Mo and 1896±3°C, 40.5 at. pct Mo, are considerably more precise and only in fair agreement with previously measured or estimated values. The liquidus composition at the peritectic temperature for the Zr−Mo binary is precisely fixed at 54.0±1.0 at. pct Mo and that for the Hf−Mo binary is 61 ±3 at. pct Mo. The thermodynamic activities of molybdenum in the liquid Zr−Mo alloy indicate positive deviations from Raoult's Law. temporarily attached to the Chemistry Division, Argonne National Laboratory, Argonne IL 60439 This work was performed at Argonne National Laboratory under the auspices of the U.S. Energy Research and Development Administration     

A reinvestigation of phase equilibria in the system Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript>-ZnO

The phase equilibria and liquidus temperatures in the binary SiO₂-ZnO system and in the ternary Al₂O₃-SiO₂-ZnO system at low Al₂O₃ concentrations have been experimentally determined using the equilibration and quenching technique followed by electron probe X-ray microanalysis. In the SiO₂-ZnO system, two binary eutectics involving the congruently melting willemite (Zn₂SiO₄) were found at 1448±5 °C and 0.52±0.01 mole fraction ZnO and at 1502±5 °C and 0.71±0.01 mole fraction ZnO, respectively. The two ternary eutectics involving willemite previously reported in the Al₂O₃-SiO₂-ZnO system were found to be at 1315±5 °C and 1425±25 °C, respectively. The compositions of the eutectics are 0.07, 0.52, and 0.41 and 0.05, 0.28, and 0.67 mole fraction Al₂O₃, SiO₂, and ZnO, respectively. The results of the present investigation are significantly different from the results of previous studies.     

Activities of boron in the binary Fe-B,Co-B,and Cu-B melts

Activities of boron in the binary Fe-B, Co-B, and Cu-B melts have been directly determined by the electromotive force (emf) measurement. Boron-saturated liquid Cu-B alloy was used as the reference electrode and a ternary 28 wt pct Al₂O₃-29 wt pct B₂O₃-43 wt pct CaO oxide melt was used as the electrolyte. Deviations of the boron activities from Raoult's law have been found largely negative for the Fe-B and Co-B systems but largely positive for the Cu-B system. Boron activities calculated from the literature data have not been in good agreement with the measured data. Activities of iron, cobalt, and copper have been calculated from the obtained boron activities by means of the Gibbs-Duhem equation. Some modifications to the liquidus curves on the Fe-B and Co-B phase diagrams have been presented. M. YUKINOBU, formerly Graduate Student, Department of Metallurgy, The University of Tokyo S. GOTO, Professor, formerly with the Department of Metallurgy, The University of Tokyo     

The liquidus surfaces of ternary systems involving compound semiconductors: II. Calculation of the liquidus isotherms and component partial pressures in the Ga−As−Zn and Ga−P−Zn systems

The previously derived liquidus equation for anAB compound (GaAs or GaP) incorporating a dilute solute (zinc) in equilibrium with a ternary regular melt was applied to the available liquidus data in the Ga?As and Ga?As?Zn and in the Ga?P and Ga?P?Zn systems. The ternary interchange energies for both systems were computed by the method of multidimensional leastsquares. Utilizing these interchange energies, the liquidus isotherms in the Ga?As?Zn and Ga?P?Zn systems were calculated over a wide temperature range from the nonlinear liquidus equation by a numerical method. By a combination of the ternary regular activity coefficients with the vapor pressures of the pure components and the liquidus isotherms, the component partial pressures along the liquidus isotherms were determined. The ternary liquidus and partial pressure isotherms are in good agreement with the experimental data of Panish, Koster and Ulrich, and Shihet al. It is further shown that in the binary limit, the results of these calculations are also in accord with liquidus and partial pressure measurements for the Ga?As and Ga?P systems.