MIVM对FeO-MgO-SiO2-V2O3四元熔渣体系组元活度的预测

应用分子相互作用体积模型(MIVM)及其伪多元法对FeO-MgO-SiO2和CaO-MgO-FeO-SiO2熔渣中FeO组元的活度进行了验证性预测研究.结果表明:MIVM伪多元法预测值与实验值吻合良好.在此基础上,利用MIVM建立了FeO-MgO-V2O3-SiO2和CaO-FeO-V2 O3-SiO2四元熔渣组元活度的计算式,并计算了该熔渣中V2O3、CaO、MgO、FeO和SiO2的活度;分析了用CaO取代MgO时,FeO含量的变化对其各组元活度的影响,当用CaO取代MgO时,熔渣中各组元的活度都明显减小.     

An Estimation of Component Activity of Vanadium-bearing Liquid Iron and Transition Temperature of Vanadium Oxidization Using MIVM

The component activity of Mn in Fe-C-Mn system as well as the component activities of C and Si in Fe-C-Si system was predicted by applying the pseudo-multicomponent approach of the molecular interaction volume model(MIVM)and the Wagner interaction parameter formalism(WIPF)respectively.The average relative errors between the predicted values of MIVM and the experimental data for the three components were 4.5%,17.0% and 13.0%,respectively,and those between the calculation results of the WIPF and the experimental data were 18.0%for Mn,9.0%for C and 27.0%for Si.The results indicated that the MIVM method could better predict the component activity of carbonaceous iron-based solution.Based on the data in an actual blowing process,the MIVM method was applied to predict the component activities of C and V as well as the transition temperature of vanadium oxidization(TTVO)in Fe-C-V-Si quaternary iron-based solution,and a comparative analysis of the predictions against the experimental data was carried out,with their average relative errors being 24.0% for C,7.3% for V and 1.0% for TTVO respectively.On that basis,the TTVO at Panzhihua Iron and Steel(Group)Co.,Ltd.was estimated by the MIVM method and an expression that the TTVO changed with composition and temperature of iron solutions was obtained by multiple linear regression method.The research results showed that the estimated values were in good agreement with the practical data.     

MIVM对含V2O3多元熔渣体系组元活度的预测

 为了研究钒在攀钢转炉中的热力学行为及分配,根据钒渣的成分对CaO-MgO-Al2O3-V2O3-SiO2熔渣中各组元的活度进行研究。应用分子相互作用体积模型（MIVM）及其伪多元法预测MgO-Al2O3-SiO2、CaO-V2O3-SiO2、CaO-MgO-Al2O3-SiO2渣系中某组元的活度值,并与试验值对比。结果表明,MIVM伪多元法预测值与试验值吻合良好,MgO-Al2O3-SiO2渣系中Al2O3的平均相对误差为15%;CaO-V2O3-SiO2渣系中V2O3的平均相对误差为33%;CaO-MgO-Al2O3-SiO2渣系中SiO2的平均相对误差为13%。在此基础上,利用MIVM预测CaO-MgO-Al2O3-V2O3-SiO2熔渣中各组元的活度,并将V2O3的预测值与试验值对比分析,结果表明,预测值与试验值吻合良好,都呈正偏差,平均相对误差为44%,V2O3的活度随碱度的提高而下降。     

Prediction of activities of three components in the ternary molten slag CaO-FeO-SiO2 by the molecular interaction volume model

In this article, a novel thermodynamic model—the molecular interaction volume model (MIVM)—was employed to predict the activities of three components in the ternary molten slag CaO-FeO-SiO₂ at different temperatures. The results show that the predicted values of activity of CaO and SiO₂ are in reasonable agreement with the experimental data in a range of lower concentrations, which are about x _CaO<0.2 for CaO and about x _{SiO 2}=0.15 to 0.50 for SiO₂ at 1823 K, respectively, and that the predicted values of activity of FeO are in good agreement with the experimental data in a range of entire concentrations at 1623, 1823, and 1873 K. This shows that MIVM is an alternative for the estimation of activity coefficients of all components in a ternary molten slag, where its activity data are absent or their accuracies are questionable only when its sub-binary activities are known and reasonably reliable.     

钛微合金钢炉外精炼相平衡研究与热力学分析

摘要：为了解钛微合金钢炉外精炼过程中Ti元素在渣 钢间的平衡分配行为及走向,应用分子相互作用体积模型（MIVM）,通过规范子二元系活度标准态和优化模型参数,建立了CaO-Al2O3-FeO-TiO2熔渣活度计算模型,并预测渣中各组元活度;在含钛钢炉外精炼条件下,应用MIVM和Wagner公式研究了Ti在精炼渣CaO-Al2O3-FeO-TiO2与含钛钢液Fe-Al-Ti O间的平衡分配及影响因素。研究结果显示：渣中FeO的活度预测值与实验值符合较好,平均相对误差为9%;Ti在渣-钢两相间平衡分配比的计算值与工业数据符合较好;分配比随钢液中Al含量的降低、温度的升高和渣中CaO与Al2O3质量比的增加而增大,该规律与实际生产相一致。因此MIVM对多元含钛熔渣体系组元活度具有较好的预测效果,所设计的相平衡研究方法合理可行。本研究可为含钛合金钢化学冶金的基础理论研究提供一定的参考。     

Application of MIVM for Pb-Sn System in Vacuum Distillation

The activity coefficients of components of the Pb-Sn binary alloy system were calculated based on the molecular interaction volume model (MIVM). A significant advantage of this model lies in its ability to predict the thermodynamic properties of liquid alloys using only two binary infinite activity coefficients. Based on the MIVM, the vapor-liquid phase equilibrium of the Pb-Sn alloy system in vacuum distillation has been predicted using the activity coefficients of Pb and Sn. The results showed that the content of tin in the vapor phase was 0.008?wt?pct, while in the liquid phase, it was 83?wt?pct at 1173?K (900?°C); it reached 0.022?wt?pct in the vapor phase, while in the liquid phase, it was 92?wt?pct at 1223?K (950?°C); and it was 0.052?wt?pct in the vapor phase, while in the liquid phase, it was 97.88?wt?pct at 1273?K (1000?°C). The content of tin in the vapor phase increased with the distillation temperature increasing. Experimental investigations into the separation of Pb and Sn from the Pb-Sn alloy by vacuum distillation were carried out for the proper interpretation of the results of the model. The influence of the distillation time (20 to 80?minutes) and the distillation temperatures of 1173?K, 1223?K, and 1273?K (900?°C, 950?°C, and 1000?°C) on the separating effect was also studied. The experimental results showed that the content of tin in the vapor phase was 0.085?wt?pct, while in liquid phase, it was 83?wt?pct under the operational conditions of distillation temperature of 1173?K (900?°C), evaporation time of 20?minutes, and chamber pressure of 20?Pa; it reached 0.18?wt?pct in the vapor phase, while in the liquid phase, it was 92?wt?pct at 1223?K (950?°C), 20?minutes, and 20?Pa; and it was 0.35?wt?pct in the vapor phase, while in the liquid phase, it was 97.88?wt?pct at 1273?K (1000?°C), 20?minutes, and 20?Pa. In all these experiments, it was observed that the content of tin in the vapor phase increased as the distillation time and temperatures were increased. The experimental results are in good agreement with the predicted values of the MIVM for the Pb-Sn binary system.     

On the influence of coarsening on microsegregation

An analytical treatment of the influence of coarsening by ripening on microsegregation is presented. Comparison of results from the model with data on Al-4.5 wt pct Cu and Sn-Bi alloys indicates that an overestimation of the reduction in microsegregation results if it is assumed that ripening proceeds throughout the solidification range. This is attributed to the changing nature of coarsening processes, in which coalescence processes predominate over ripening at higher volume fractions solid.     

A comparison of the molecular interaction volume model with the subregular solution model in multicomponent liquid alloys

The molecular interaction volume model (MIVM) is a two-parameter model, meaning it can predict the thermodynamic properties in a multicomponent liquid alloy system using only the coordination numbers calculated from the ordinary physical quantities of pure liquid metals and the related binary infinite dilute activity coefficients, γ _∞ ⁱ and γ _∞ ^j , which avoids somewhat adjustable fitting for the binary parameters of B _ji and B _ij. In comparison with the subregular solution model (SRSM), the prediction effect of the MIVM is of better stability and safety because it has a good physical basis.     

应用M-MIVM预测含钛渣系组元活度

 在钢铁冶炼过程中,随着护炉钛材料和含钛铁矿石的应用,大量的含钛炉渣被生产出来。由于缺少多元含钛渣系的热力学数据,限制了钛资源综合利用技术的深入发展。因此,应用改进的分子相互作用体积模型(M-MIVM(FII)),预测了基础渣系Al₂O₃-CaO-SiO₂、FeO-MnO-SiO₂和含钛渣系FeO-MnO-TiO₂、FeO-SiO₂-TiO₂、MnO-SiO₂-TiO₂、Al₂O₃-CaO-FeO-TiO₂中各组元活度,并与试验值比较。结果表明,M-MIVM(FII)的预测值与试验值符合较好,6个体系总的平均相对误差为11%,该精度处于Turkdogan提出的30%以内的试验误差范围; M-MIVM(FII)在参数拟合与活度预测能力方面均优于MIVM,该模型对多元含钛熔渣体系组元活度具有更好的预测效果。在此基础上,应用M-MIVM(FII)预测Al₂O₃-CaO-SiO₂-TiO₂熔体中TiO₂活度,并分析其影响因素。结果表明,TiO₂活度预测值与试验值吻合良好,且随炉渣碱度、Al₂O₃含量的增加而降低,该规律与试验规律相一致。M-MIVM(FII)仅通过拟合子二元系活度或者直接由无限稀活度系数就能够预测多元熔体的热力学性质。     

A mathematical model describing carburization in multielement alloy systems

Previously, a finite difference model was set up describing the diffusion of carbon in high-temperature model alloys and its chemical reaction with one of the alloy components. The model described the formation of up to three different chromium carbides, two of which could coexist. This paper describes the further development of the model for application to commercial alloys. The model was extended to enable treatment of an arbitrary number of (a) metallic carbide-forming components in the alloys, (b) carbides which may form, (c) components out of which each carbide may be composed, and (d) carbides which may coexist. With this model, carbon concentration profiles and distribution profiles of precipitated carbides occurring during carburization of binary, ternary, and quaternary Ni-based alloys were calculated. Kinetic and thermodynamic data needed for the calculations were obtained by combining literacture data with experimental results and by fitting measured with calculated concentration profiles. The resulting calculated carbon profiles and carbide distributions were in good agreement with the experimental results. R. Supchulten, formerly with Kernforschungsanlage Jülich     

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.      

航空发动机阻燃钛合金力学性能预测及成分优化

采用支持向量机算法,在实验数据的基础上,建立航空发动机阻燃钛合金的合金化元素与力学性能关系模型,分析合金化元素对力学性能的影响规律。模型的输入参数为V、Al、Si和C元素,输出参数为室温拉伸性能（抗拉强度、屈服强度、延伸率和断面收缩率）。结果表明:各个力学性能支持向量机模型的线性相关系数均在0.975以上,具有较高的预测能力;各个力学性能测试样本实验值与模型预测值的绝对百分误差均在5%以内,具有良好的泛化能力,能够有效地反映出阻燃钛合金的合金化元素与力学性能之间的定量关系,进而实现对该合金的成分优化。对于Ti?35V?15Cr阻燃钛合金,可以通过加入质量分数为0～0.1%的Si元素和质量分数为0.05%～0.125%的C元素,并减少质量分数为2%～5%的V元素,来提高力学性能;对于Ti?25V?15Cr阻燃钛合金,可以通过加入质量分数为1.5%～1.8%的Al元素和质量分数为0.15%～0.2%的C元素,来提高力学性能。      

Prediction Expressions of Component Activity Coefficients in Si-Based Melts

Prediction expressions of component activity coefficients of the molecular interaction volume model (MIVM) are suggested for making up for absence of Wagner interaction parameters in Si-based melts. Their effectiveness is verified in liquid Fe-Si-B system at 1823 K (1550 °C). In comparison with experimental data, all errors of ±22 to 56 pct and deviations of ±0.0132 to 0.0318 predicted by MIVM are smaller than those (±53 to 94 pct and ±0.0759 to 0.1010) by the unified interaction parameter formalism. This indicates that the former is better than the later in the system. Accordingly, some interested thermodynamic diagrams and parameters at 1687 K and 1823 K (1414 °C and 1550 °C) are predicted in liquid Si-Al-Fe system, for instance, $ \varepsilon_{\text{Al}}^{\text{Al}} = 2.318 $ , $ \varepsilon_{\text{Fe}}^{\text{Fe}} = 4.297 $ , and $ \varepsilon_{\text{Fe}}^{\text{Al}} = \varepsilon_{\text{Al}}^{\text{Fe}} = - 2.443 $ in the dilute solution at 1687 K (1414 °C). The method of MIVM is able to expand to Si-based multicomponent melt if its sub-binary activity data are available. The reliability of predicted results for the melt is closely dependent upon that of component activities or infinite dilute activity coefficients in its sub-binary systems.     

铁基非晶合金的辐照性能

铁基非晶合金由于成本低较、易制备、较好的温度稳定性等优点,并具优异的机械性能、磁性能和耐腐蚀性能而被广泛研究.并且其固有的无序结构有助于抵抗辐照导致的损伤,使得铁基非晶合金可作为抗辐照材料使用.辐照既可以试验铁基非晶合金的性能也是优化铁基非晶合金结构和性能的有效方法.本文综述了铁基非晶合金中子辐照、离子辐照和电子辐照性能的研究进展,探讨了铁基非晶合金的结构和性能与非晶合金的成分以及辐照粒子的类型、能量、注量之间的关系,以及辐照晶化的机制,为进一步促进高性能铁基非晶合金的研究提供了有价值的参考.      

Computer-Aided Design of Manufacturing Chain Based on Closed Die Forging for Hardly Deformable Cu-Based Alloys

Two copper-based alloys were considered, Cu-1 pct Cr and Cu-0.7 pct Cr-1 pct Si-2 pct Ni. The thermal, electrical, and mechanical properties of these alloys are given in the paper and compared to pure copper and steel. The role of aging and precipitation kinetics in hardening of the alloys is discussed based upon the developed model. Results of plastometric tests performed at various temperatures and various strain rates are presented. The effect of the initial microstructure on the flow stress was investigated. Rheologic models for the alloys were developed. A finite element (FE) model based on the Norton–Hoff visco-plastic flow rule was applied to the simulation of forging of the alloys. Analysis of the die wear for various processes of hot and cold forging is presented as well. A microstructure evolution model was implemented into the FE code, and the microstructure and mechanical properties of final products were predicted. Various variants of the manufacturing cycles were considered. These include different preheating schedules, hot forging, cold forging, and aging. All variants were simulated using the FE method and loads, die filling, tool wear, and mechanical properties of products were predicted. Three variants giving the best combination of forging parameters were selected and industrial trials were performed. The best manufacturing technology for the copper-based alloys is proposed.     

Investigation of Optimal Megnetic Properties in NdFeB Magnets by Artificial Neural Network

In order to study the effect of alloy component on magnetic properties of NdFeB magnets, the experiment schemes are carried out by the uniform design theory, and the relationship between the component and the magnetic properties is established by artificial neural network(ANN) predicting model.The element contents of alloys are optimized by the ANN model.Meanwhile, the influences of mono-factor or multi-factor interaction on alloy magnetic properties are respectively discussed according to the curves ploted by ANN model.Simulation result shows that the predicted and measured results are in good agreement.The relative error is every low, the error is not more than 1.68% for remanence Br, 1.56% for maximal energy product (BH)m, and 7.73% for coercivity Hcj.Hcj can be obviously improved and Br can be reduced by increasing Nd or Zr content.Co and B have advantageous effects on increasing Br and disadvantageous effects on increasing Hcj.Influence of alloying elements on Hcj and Br are inverse, and the interaction among the alloying elements play an important role in the magnetic properties of NdFeB magnets.The ANN prediction model presents a new approach to investigate the nonlinear relationship between the component and the magnetic properties of NdFeB alloys.     

Simulation of Stresses during Casting of Binary Magnesium-Aluminum Alloys

A viscoplastic stress model is used to predict contraction forces measured during casting of two binary Mg-Al alloys. Force measurements from castings that did not hot tear, together with estimates from data found in the literature, are used to obtain the high-temperature mechanical properties needed in the stress model. In the absence of hot tearing, the simulation results show reasonably good agreement with the measurements. It is found that coherency of the semisolid mush starts at a solid fraction of about 0.5 and that the maximum tensile strength for the Mg-1 and 9 wt pct Al alloys at their final solidification temperatures is 1.5 and 4 MPa, respectively. In the presence of hot tearing, the measured stresses are generally overpredicted, which is attributed to the lack of a fracture model for the mush. Based on the comparison of measured and predicted stresses, it is also shown that coupling of the stress model to feeding flow and macrosegregation calculations is needed in order to accurately predict stresses in the presence of hot tearing.     

Modification of AZ91?Mg Alloys for High Temperature Applications

The good specific strength and specific modulus of magnesium alloys had drawn the attention of the automotive manufacturers for use in fuel efficient vehicles. Among the cast magnesium alloys, AZ91 (Mg?C9Al?C1Zn) is the most sought alloy because of its good casting properties. However, this alloy loses its strength and creep resistance properties above 120?°C due to softening of the ?? phase (Mg₁₇Al₁₂). Hence, this alloy cannot be used for making heavier engine components (power train), which require the thermal stability up to about 250?°C. The paper discusses the approach of modifying the AZ91 alloy by minor alloying additions to improve the high temperature withstanding capability without significantly affecting its casting properties. Additions of Ca to AZ91 alloy to the levels of about 0.4?wt% increased the ambient and high temperature strength of the base alloy. Additions of other minor alloying elements such as Sb, Pb, rare earths etc. can also increase the high temperature capability of the AZ91 by further modifying the ?? phase structure. The paper overviews the work carried out by the authors on the role of different alloying additions on the microstructure and mechanical properties of AZ91 magnesium alloys.     

Solidification of undercooled Sn-Sb peritectic alloys: Part II. Heterogeneous nucleation

The undercooling behavior of fine droplet samples of Sn-rich, Sn-Sb alloys was investigated using differential thermal analysis (DTA). Undercooling levels measured during cooling from the liquid state follow the trend of the intermetallic phase liquidus, suggesting that solidification of all droplet samples (even those which solidify to yield a supersaturatedβ-tin product) was probably initiated with formation of primary intermetallic phase. Heterogeneous nucleation thermal cycling treatments were then used to measure the relative catalytic potency of primary intermetallic phases in this system for nucleation ofβ-tin during cooling. Crystallization reactions below the equilibrium peritectic temperature of 250 °C, at 187 °C and 230 °C, have been interpreted as corresponding to nucleation ofβ on Sn₃Sb₂ and SnSb substrates, respectively. The behavior observed in the Sn-Sb system can be generalized to guide the interpretation of heterogeneous catalysis and the analysis of solidification pathways in other peritectic alloy systems. Formerly Graduate Student, Department of Materials Science and Engineering, University of Wisconsin-Madison