Nacl—Bacl2—Srcl2三元熔盐相图的计算

本文运用作者提出的从三个对应的二元系的热力学性质预示三元溶液的热力学性质的新对称几何模型,推导得到三元溶液中三个组元的偏摩尔热力学性质的数学表达式。进而将这一结果应用于NaCl-BaCl_2-SrCl_2三元熔盐相图的计算中,得到此三元系的液相析出面及若干等温截面。计算所得结果与实测结果偏差小于5℃,说明此模型在一些熔盐体系中有较好的适用性。     

CO还原CaO－SiO_2－Al_2O_3－Fe_tO渣系研究

研究了在１７２３Ｋ下ＣＯ还原ＣａＯ－ＳｉＯ_２－Ａ１_２Ｏ_３－Ｆｅ_ｔＯ渣系。根据ＣＯ_２红外分析仪测定的出口气体中ＣＯ_２浓度变化，计算了炉渣的表现还原速度常数Ｋ_ａ和还原速度常数Ｋ。结果表明，加入Ａｌ_２Ｏ_３，提高了ＣａＯ－ＳｉＯ_２－Ｆｅ_ｔＯ的Ｋ_ａ和Ｋ值；炉渣碱度不变时，随着Ｆｅ_ｔＯ含量的增加，Ｋ_ａ呈增加趋势，但Ｋ则呈抛物线趋势变化；当ＦｅＯ的光学碱度∧_ＦｅＯ为１．０或０．８７时，Ｋ_ａ随该四元渣系光学碱度的增加而线性增加，而Ｋ则呈递减趋势。用炉渣规则溶液模型计算了ＣａＯ－ＳｉＯ_２－Ａｌ_２Ｏ_３－Ｆｅ_ｔＯ四元渣系的Ｆｅ_ｔＯ活度ａ_Ｆｅ_ｔＯ。     

Calculating models of mass action concentrations for structural units or ion couples in RbCl-H2O binary system and RbCl-RbNO3-H2O ternary system

Thermodynamic models of calculating mass action concentrations for structural units or ion couples in RbCl-H2O binary and RbCl-RbNO3-H2O ternary strong electrolyte aqueous solutions were developed based on the ion and molecule coexistence theory at 298.15 K. A transformation coefficient is needed to compare the calculated mass action concentration and the reported activity because they are obtained at different standard states and concentration units. The results show that the transformation coefficients between the calculated mass action concentrations and the reported activities of the same structural units or ion couples in RbCl-H2O binary and RbCl-RbNO3-H2O ternary strong electrolyte aqueous solutions change in a very narrow range. The transformed mass action concentrations of structural units or ion couples in RbCl-H2O binary system are in good agreement with the reported activities. The transformed mass action concentrations of RbCl and RbNO3 in RbCl-RbNO3-H2O ternary solution are also in good agreement with the reported activities, aRbCl and , with different total ionic strengths as 0.01, 0.05, 0.1, 0.5, 1.0, 1.5, 2.0, 3.0 and 3.5 mol/kg, respectively. All those results mean the developed thermodynamic model of strong electrolyte aqueous solutions can reflect structural characteristics of RbCl-H2O binary and RbCl-RbNO3-H2O ternary strong electrolyte aqueous solutions and the mass action concentration also strictly follows the mass action law.     

MnO-SiO2-Al2O3渣系作用浓度的计算模型

基于炉渣结构的共存理论,建立了MnO-SiO2-Al2O3三元渣系作用浓度的计算模型,考察了影响MnO作用浓度的影响因素。结果表明:模型计算所得的MnO作用浓度值NMnO与文献实测值aMnO(exp)非常吻合,且计算精度要高于正规溶液模型获得的计算值aMnO(cal),说明该模型能够反映该渣系的结构本质。利用此模型可以很好地预测Mn/Si脱氧钢的夹杂物成分,为生产高质量的帘线钢提供热力学参考。     

CALCULATION OF THERMODYNAMIC PROPERTIES AND PHASE DIAGRAM OF TERNARY MOLTEN SALT SYSTEM NaCl-CaCl_2-SrCl_2 BY USE OF COMPUTOR

本文利用 CaCl-SrCl_2相图中,固相有一个溶解间断区(miscibility gap)的信息,用亚正规溶液模型计算了该二元系液相和固相的 Gibbs 自由能.运用 Toop方程的变通式即最近 Hillert.M.提出的新的非对称方法,由组成 NaCl-CaCl_2-SrCl_2三元系的二元系热力学性质预示了该三元系液相的 Gibbs 自由能,进而用计算机计算了三元液相中各组元的偏克分子 Gibbs 自由能和活度系数.由三元液相中组元 NaCl,CaCl_2和 SrCl_2的过剩偏克分子 Gibbs 自由能,根据相平衡原理,用计算机计算了该三元系的相图.计算结果对于钠电解的实践和盐湖资源的综合利用有实际意义.亚正规溶液模型和新的非对称方法可望适合于计算一系列有潜在重要性的电荷不对称熔盐体系的相图.如对 Na,Ti,Mg,Ce 电解及熔融氯化脱水制取无水氯化镁有实际意义的 NaCl-CaCl_2-BaCl_2,NaCl-SrCl_2-BaCl_2,NaCl-CaCl_2-MgCl_2,KCl-CaCl_2-MgCl_2,KCl-NaCl-CeCl_3等三元相图.     

CO还原CaO—SiO2—FetO三元渣系的研究

在1723K进行了CO还原CaO—SiO_2-Fe_(t)O三元渣系的研究根据CO_2红外分析仪测定的出口气体中的CO_2浓度变化,计算了炉渣的表观还原速度常数K_(a)结果表明,K_(a)随炉渣中Fe_1O量增加呈抛物线变化;当炉渣碱度R<1.0,Fe_(t)O为50％和R为1.5,Fe_(t)O为70％时,K_(a)分别出现最小值用炉渣规则溶液模型可计算1723K时的CaO-SiO_2-Fe_tO三元渣系的Fe_1O活度值a_(Fe_1O)。     

Ab Initio Calculated Thermodynamic Properties of Mo5SiB2 Phase and Nb5SiB2 Phase

Due to their attractive high-temperature properties, multiphase Mo-Si-B alloys in the Mo-rich Mo-Si-B ternary system have been identified for high-temperature applications. The ternary intermetallic T₂ (Mo₅SiB₂) phase is a central feature of the phase equilibria within this ternary system. Experimental stability analyses of the T₂ phase shows its broad homogeneous composition ranges that can yield a constitutional defect structure such as vacancies for Mo-rich compositions and antisite defects for Mo-lean compositions. Previous thermodynamic model did not conform to the defect structures as reported in experiments, and thus subsequently a new sublattice thermodynamic model for the T₂ phase is initiated in this study. To support the new sublattice thermodynamic model, ab initio calculations were implemented to compute formation energy data. The calculated formation energy data explain a source for broad compositional homogeneity range of T₂ structure.     

THERMODYNAMIC CALCULATION MODELS FOR TiO_2-BASED SLAG MELTS

1.IntroductionTheincreasingdemandsf0rlownitrogensteelproductsgiveriset0greatenthusiaJsmtouseTiO2-basedfluxfordenitrogeniZationofsteel[1-3].ManyexperimentscondrmedthatTi0z-basedslagshavehighernitridecaPacitiesandaPpeartobeonekind0fthemosteffectivefiuxesf0rdeIiltrogenization.Butasfarastherm0dynamicstudiesareconcerned,littleworkhasbeenreported0nthethermodynamiccalculationm0delsforTiO2-base'slags[4],especiallyf0rmulticomponentslagswithtitania-Inadditi0n,aJsaresultofusingvanadium-bearingtitani…     

ACTIVITIES OF CaO AND La_2O_3 IN LIQUID CaO-SiO_2-La_2O_3 SLAGS AND SLAG STRUCTURE

The activity of CaO and La_2O_3 in the liquid ternary slay CaO-SiO_2-La_2O_3 has been de-termined by equilibrating Sn with the slag phase in a graphite crucible under l arm of CO at1600C.The experimental results ,showed that the activity of CaO and La_2O_3 changes slowlywhile the ratio of mole fraction.x_(CaO)/x_(SiO_2),is less than unit.hut varies sharply while the ra-rio increases from 1 to 1.2.In addition,by equilibrating Sn with the binary slagB_2O_3-La_2O_3 saturated witlt solid La_2O_3 at three different temperatures,the relation betweenIgγ_(La)~0 and I/T is determined as follows:Igγ_(La)~0=-20400/T+11.37(1500-1600C)A random network model of molten silicate structure was applied to CaO-SiO_2-La2O_3.It was found that the experimentally determined activity-composition curve of CaO arequalitatively reproduced by the curves calculated with the model,but the curves of La_2O_3 areconsiderahly different from the calculated ones.It implies that the model used is over-simpli-fied and that the difference in interaction energy between the metal cations of different valenceand silicate anions should be considered.     

Thermodynamic evaluation of phase equilibria in the CaCl2-MgCl2-CaF2-MgF2 system

The phase diagram of the CaCl₂-CaF₂-MgCl₂-MgF₂ reciprocal ternary system was calculated thermodynamically from available data on the common-ion binary subsystems and from available data on the CaCl₂-MgF₂ join. This join is very nearly quasibinary and divides the system into two quasiternary systems: the CaCl₂-MgF₂-CaF₂ system with a ternary eutectic calculated at 724 +-5 °C and the CaC₂-MgF₂-MgCl₂ system with a ternary eutectic calculated at 561 +-5 °C.     

Thermodynamic evaluation of phase equilibria in the CaCl2-MgCl2-CaF2-MgF2 system

The phase diagram of the CaCl₂-CaF₂-MgCl₂-MgF₂ reciprocal ternary system was calculated thermodynamically from available data on the common-ion binary subsystems and from available data on the CaCl₂-MgF₂ join. This join is very nearly quasibinary and divides the system into two quasiternary systems: the CaCl₂-MgF₂-CaF₂ system with a ternary eutectic calculated at 724 +-5 °C and the CaC₂-MgF₂-MgCl₂ system with a ternary eutectic calculated at 561 +-5 °C.     

PREDICTION OF THERMODYNAMIC PROPERTIES OF THE FeO-CaO-SiO_2 MELTS FROM WILSON EQUATION

1.IntroductionIn0rdert0c0mpensateforash0rtc0ming0fclassicaltherm0dynamics,manyempiricalorsemiempiricalmodelsbased0nthethe0ryofregularsolutionshavebeendevel0pedforpredictingthethermodynamicpr0pertiesofternaryandevenmulticomponentmoltenslags[l'2].Ac0mmoncharacteristic0fthemist0usem0reempiricalappr0aches.Ifonlybinarydataareusedtopredictthetherm0dynamicpr0pertiesofaternarysystem,thedeviationsofpredictedvalueswillbelarger;ifthevauesneedtomatchtherequiredaccuracytaporti0n0fexperimentaldataofaternary…     

Thermodynamic calculation of intermetallic compounds in AZ91 alloy containing calcium

1 Introduction Magnesium alloy is regarded as a promising structural material in the 21 century because of its excellent properties such as low density, high specific strength, good castability and machinability[1?5]. The common magnesium alloy AZ91 is, however, unsuitable for using at the temperatures above 120 ℃ because of its poor creep resistance and strength at elevated temperatures[2]. Adding other elements, like calcium, is an important method to improve the mechanical properties of A…     

Critical evaluation and optimization of the thermodynamic properties and phase diagrams of the Al-Mg, Al-Sr, Mg-Sr, and Al-Mg-Sr Systems

All available thermodynamic and phase diagram data were critically assessed for all phases in the Al-Mg, Al-Sr, and Mg-Sr systems at 1 bar pressure from room temperature to above the liquidus temperatures. For these systems, all reliable data were simultaneously optimized to obtain a set of model equations for the Gibbs energy of the liquid alloy and all solid phases as functions of composition and temperature. The modified quasi-chemical model was used for the liquid. The Al-Mg-Sr ternary phase diagram was calculated from the optimized thermodynamic properties of the binary systems. Since no reliable ternary data were available, three assumptions were made: no ternary terms were added to the model parameters for the thermodynamic properties of the liquid, no ternary solid solutions are present in the system, and no ternary compound is present in the system. The calculated ternary phase diagram is thus a first approximation, which can be improved by the addition of new experimental data and can be used as a base for the calculation of phase diagrams of multicomponent systems.     

Critical assessment and thermodynamic calculation of the ternary system boron-hafnium-titanium (B-Hf-Ti)

Experimental work on the ternary system Ti-Hf-B as well as on the two binary boundary systems Hf-B and Ti-Hf is reviewed. The individual phases of these systems are described with thermodynamic models. The models were fitted to the experimental information and the resulting optimized data sets are presented. The calculated thermodynamic properties of the two binary compounds HfB and HfB₂ are compared with experimental measurements. Phase diagrams were calculated for the bi-nary systems Hf-B and Ti-Hf as well as for the ternary Ti-Hf-B system; for the latter, several isother-mal sections, isopleths, and the liquidus surface are included. They are presented and compared with the experimental information. A reaction scheme for the ternary Ti-Hf-B system was constructed.     

Thermodynamic modeling and phase equilibria calculations of the quaternary Al-Ga-In-Sb Sastem

Quasi sub-subregular solution model with additional ternary parameters, used by Sharma et al. to model the thermodynamic properties of the liquid phases in the ternary Al-Ga-Sb, Al-In-Sb, and GaIn-Sb systems, has been extended to predict the thermodynamic properties of the liquid phase in the quaternary Al-Ga-In-Sb system. The (AlGaln)Sb compound phase in the quaternary Al-Ga-In-Sb system is considered a quasi-regular solution of AlSb, GaSb, and InSb compounds. Phase equilibria in the quaternary Al-Ga-In-Sb system are then calculated and compared with the limited experimental data available in the literature. The ternary Al-Ga-In phase diagram, required for the quaternary calculations, has also been modeled and calculated.     

PHASE DIAGRAM OF TERNARY SYSTEM PrCl_2-CaCl_2-MgCl_2

Three surfaces corresponding to the primary crystallization of PrCl_3,CaCl_2 andMgCl_2 respectively,3 univariant curves related to the secondary crystallization and a ternaryeutectic(44.8 wt-% PrCl_3,31.8 wt-% CaCl_2,546℃)were found in systemPrCl_3-CaCl_2-MgCl_2 by means of DTA.A reaction occurs in this system:L=PrCl_3+CaCl_2+MgCl_2.     

Thermodynamic modeling and phase equilibria calculations of the quaternary Al-Ga-In-Sb Sastem

Quasi sub-subregular solution model with additional ternary parameters, used by Sharma et al. to model the thermodynamic properties of the liquid phases in the ternary Al-Ga-Sb, Al-In-Sb, and GaIn-Sb systems, has been extended to predict the thermodynamic properties of the liquid phase in the quaternary Al-Ga-In-Sb system. The (AlGaln)Sb compound phase in the quaternary Al-Ga-In-Sb system is considered a quasi-regular solution of AlSb, GaSb, and InSb compounds. Phase equilibria in the quaternary Al-Ga-In-Sb system are then calculated and compared with the limited experimental data available in the literature. The ternary Al-Ga-In phase diagram, required for the quaternary calculations, has also been modeled and calculated.     

Thermodynamic Modeling of the Ag-Au-Sb Ternary System

A thermodynamic assessment of the Ag-Au-Sb ternary system has been carried out using the CALPHAD method based on new thermodynamic and phase equilibria data that we have recently determined. The Ag-Sb binary system has also been reoptimized. The calculated phase diagram and thermodynamic properties of the ternary system Ag-Au-Sb show satisfactory general agreement with the experimental data. The liquidus projection and monovariant valleys of the ternary system are well reproduced by the optimized thermodynamic model parameters. Additional experiments to confirm the proposed reaction scheme, which involves two ternary transition peritectic reactions, are suggested.