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.     

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.     

LiF-NaF-KF体系的相图计算

基于CALPHAD技术首先评估了LiF-NaF和LiF-KF两个二元熔盐体系,液相和端际固溶体Halite相均采用Redlich-Kister多项式置换熔体模型描述,模型参数的优化选取实验相平衡数据和热化学数据以及本文根据第一性原理预测的数据.结合文献中已报道的NaF-KF体系的热力学参数,用Muggianu模型扩展至LiF-NaF-KF三元体系,根据三元共晶点的实验数据调整三元交互参数.最终的相图计算结果与绝大部分实验数据和第一原理计算数据吻合较好,由此获得了一套自洽且可靠的热力学参数,其能够准确描述LiF-NaF-KF体系的相平衡与热力学性质.      

Thermodynamic modeling of lead distribution among matte, slag, and liquid copper

Recently, a thermodynamic database was developed for the calculation of equilibria involved in the production of copper. The present study is concerned with the further development of the thermodynamic models and the database of model parameters for the matte, slag, and blister copper phases with a view to including Pb in the database and permitting calculations in the seven-component system Pb-Cu-Ca-Fe-Si-O-S. Thermodynamic and phase equilibrium data available in the literature are reviewed, critically assessed, and optimized with the modified quasi-chemical model. When used with the Gibbs energy minimization software and other databases of the FACT thermodynamic computing system, the database developed in the present study can be used for the calculation of matte-slag-copper-gas phase equilibria during copper smelting and converting. The distribution of lead among these phases can be computed. For example, the distribution of lead among matte, silica-saturated slag, and copper has been calculated at metal saturation, or under fixed partial pressure of SO₂, and has been compared with the available experimental data. The Pb distributions among the equilibrium phases have been calculated under various conditions, which are difficult to study experimentally, such as at magnetite saturation or under various oxygen partial pressures and iron to silica ratios in the slag.     

LiBr-TbBr3体系相图热力学评估

采用CALPHAD技术热力学评估、计算了LiBr-TbBr3体系在整个成分范围内的平衡相图,其中组元LiBr和TbBr3的热力学性质分别采用SGTE热力学数据库和作者近期的评估结果,LiBr-TbBr3体系的热力学数据则通过对已有相图、热力学实验数据的精确评估优化获得.计算结果与实验数据的比较表明,本工作建立的热力学数据能够很好地解释现有实验结果、具有较好的物理意义.     

A thermodynamic database for copper smelting and converting

The thermodynamic properties of the slag, matte, and liquid copper phases in the Cu-Ca-Fe-Si-O-S system have been critically assessed and optimized over the ranges of compositions of importance to copper smelting/converting based on thermodynamic and phase equilibria information available in the literature and using the modified quasichemical model. A thermodynamic database has been developed, which can be used for the calculation of matte-slag-copper-gas phase equilibria of interest for the production of copper. The model reproduces within experimental error limits all available experimental data on phase diagrams, matte-alloy miscibility gap and tie-lines, enthalpies of mixing, and activities of Cu and S in the matte and liquid alloy. The calculated solubilities of Cu in both S-free slag and slag equilibrated with matte are also in good agreement with experiment under all studied conditions, such as at SiO₂ saturation, in equilibrium with Fe, Cu, or Cu-Au alloys, at fixed oxygen or SO₂ partial pressures and at different contents of CaO in the slag. Sulfide contents (sulfide capacities) of the slags are predicted within experimental error limits from the modified Reddy-Blander model, with no adjustable parameters. As an example of the application of the database, the stability field of matte/slag equilibrium is calculated, and the matte and slag compositions are plotted vs iron to silica ratio in the slag at various SO₂ pressures over this field. The matte-slag two-phase field is limited by the calculated lines corresponding to precipitation of copper, silica, and magnetite.     

An experimental and thermodynamic study of the Fe-Cr-C-N system at 1273 K

The thermodynamic properties of the Fe-Cr-C-N system at 1273 K (1000 °C) have been evaluated using old and new information. The binary systems are well established. The Fe-Cr-C system is fairly well established, but some experiments were performed in this study in order to establish theα/γ/M₂₃C₆ equilibrium. The Fe-Cr-N system was evaluated in a parallel study. In the Fe-C-N system the properties of theα andγ phases are well established. No direct information from the Cr-C-N system was used. In order to establish the properties of the quaternary system some experiments were made by equilibrating a set of Fe-Cr-C-N alloys at 1273 K, using a sealed capsule technique. After quenching, the carbon and nitrogen activities were evaluated by analyzing the specimens, which were completely austenitic. Phase equilibria in other specimens were studied by microprobe measurements and X-ray phase identification. When the quaternary system was evaluated thermodynamically, it was found that all the experimental information could be reasonably well accounted for without introducing new parameters for the quaternary system. However, it was necessary to evaluate the properties of the metastableε-Cr₂C phase in order to fit the quaternary experimental information. The phase diagram was calculated from the evaluated thermodynamic properties. A number of sections are presented for direct comparison with the experimental data. Formerly with Royal Institute of Technology, Stockholm.     

Co-Cr系相平衡的热力学计算和fcc相的磁性诱导相分离

Two-phase equilibria between the ferromagnetic fcc and the paramagnetic fcc phase from 800 ℃ to 900 ℃ in the Co-rich region have been detected by the diffusion couple technique. Two phase separation region of the fcc has been confirmed along the Curie temperature. The phase equilibria including the present results and the thermodynamic data of the Co-Cr system reported in the literature were analyzed on the basis of the thermodynamic evaluation. A set of thermodynarnic values for the liquid, fcc, hcp, bcc, sigma phases was obtained. The calculated phase equilibria were in good agreement with most of the experimental data.     

Phase Stability in the Mo-Ti-Zr-C System via Thermodynamic Modeling and Diffusion Multiple Validation

Alloys in the Mo-rich corner of the Mo-Ti-Zr-C system have found broad applications in non-oxidizing environments requiring structural integrity well beyond 1273 K (1000 °C). Alloys such as TZM (Mo-0.5Ti-0.08Zr-0.03C by weight %) and TZC (Mo-1.2Ti-0.3Zr-0.1C by weight) owe much of their high temperature strength and microstructural stability to MC and M₂C carbide phases. In turn, the stability of the respective carbides and the subsequent mechanical behavior of the alloys are strongly dependent on the alloying additions and thermal history. A CALPHAD-based thermodynamic modeling approach is employed to develop a quaternary thermodynamic database for the Mo-Ti-Zr-C system. The thermodynamic database thus developed is validated with diffusion multiple experiments and the validated database is exercised to elucidate the effects of alloying and thermal history on the phase equilibrium in Mo-rich alloys.     

Thermodynamics and phase relationships of transition metal-sulfur systems: Part V. A reevaluation of the Fe-S system using an associated solution model for the liquid phase

The relevant thermodynamic and phase equilibrium data for the Fe-S binary system have been reevaluated in light of more recent data. An associated solution model is used to describe the thermodynamic properties of the liquid phase as a function of composition and temperature. For the pyrrhotite phase, a statistical thermodynamic model based on the formation of Frenkel defects in the lattice is used. For the austenite and ferrite phases, the solute is assumed to follow Henry’s law, and pyrite is taken to be a stoichiometric compound. The model parameters for the various phases are obtained by evaluating all relevant experimental data reported in the literature. The calculated phase diagram is in good agreement with the experimental data. The calculated sulfur activity values for the liquid phase agree well with experimental values including those at higher sulfur concentrations. This is an improvement of an earlier evaluation by Sharma and Chang using the same model with the same number of parameters.     

A thermodynamic evaluation of the Cr-Fe-N system

The thermodynamic properties of the Cr-Fe-N system have been analyzed using thermodynamic models describing the Gibbs energy of the individual phases. A two-sublattice model has been used for the interstitial solution phases and a substitutional solution model for the liquid phase. The analysis involves a combination of predictions from recent assessments of the binary sides with computerized optimization of new ternary parameters. A set of parameters describing the Gibbs energy of the body-centered cubic (bcc), face-centered cubic (fcc), ∈, CrN, Fe₄N, and liquid phases is given. Using this set of parameters, any type of phase equilibria can be calculated. A number of diagrams are presented comparing the results from the calculations with available experimental data, and the agreement is discussed. Most experimental data are well accounted for. The present study is also compared with a previous evaluation.     

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.     

A thermodynamic evaluation of the Ti-Mo-C system

A thermodynamic assessment of the Ti-Mo-C system has been made, employing a two-sublattice regular solution model for the solid solution and carbide phases and an ordinary subregular solution model for the liquid phase. A set of thermodynamic parameters describing the Gibbs energy of each individual phase in the Ti-Mo-C as well as the Ti-Mo systems was evaluated from thermochemical and phase equilibria information available in the literature through a computer-aided optimization procedure called the CALPHAD method. The comparison between the calculated and experimental results was made and practically important phase diagrams are also presented.