Be-Cr二元体系热力学优化

在评估现有文献实验相图数据的基础上,采用Calphad技术优化和计算了Be-Cr二元合金体系平衡相图.液相和端际固溶体相采用替换式溶体溶液模型,化学计量比中间化合物CrBe₂和CrBe₁₂采用Neumann-Kopp规则描述它们的热力学函数.利用优化所得的热力学参数计算相图,结果能很好地解释大部分实验数据.本工作还采用Miedema模型估算了中间化合物CrBe₂和CrBe₁₂的摩尔生成焓,并与热力学计算值比较,所得结果符合良好.      

Mg-Gd-Zn系合金显微组织与相分析

为了研究Mg-Zn-Gd系合金中的相组成,采用热力学计算软件Pandat和Mg热力学数据库,外推计算了Mg-Gd-Zn系合金富镁角的水平截面图与垂直截面图,用Mg-6Gd-2Zn和Mg-6Gd-4Zn两种合金对该外推相图进行验证和修正,并在200℃下对该铸态合金保温480 h进行平衡处理,用光学显微镜(OM)、扫描电子显微镜(SEM)、X射线衍射仪(XRD)及差热分析(DSC)对该平衡处理后的合金的平衡相组成及凝固过程的相变温度点进行分析。通过计算相图可知Mg-Gd-Zn系合金富镁角的平衡组织为α-Mg,Mg5Gd,MgZn三种平衡相;通过XRD可知该系合金中主要有α-Mg,Mg5Gd,MgZn 3种平衡相;通过DSC可知,Mg-6Gd-2Zn与Mg-6Gd-4Zn合金的液相线、固相线及过饱和固溶体析出相的相变温度的实验测定值与计算值误差分别为1.92%,4.99%,3.68%和0.05%,3.67%,0.16%,说明计算相图得到的相与XRD,DSC实验结果测得的相相符,证明此数据库外延计算相图可以使用;通过SEM照片及EDS分析可知Mg-Zn-Gd合金晶界处有板块状的Mg5(Gd,Zn)化合物与颗粒状Mg(Gd,Zn)化合物;通过计算得到的Mg-Gd-Zn系平衡相图的平衡组织为α-Mg+Mg5Gd+MgZn,而修正后的平衡组织为α-Mg+Mg5(Gd,Zn)+Mg(Gd,Zn)。     

Zr-Nb-O三元系的热力学优化

综合评估了文献报道的Zr-Nb-O三元系及其子二元系的相图及热力学信息。液相的Gibbs自由能采用离子亚晶格模型描述,固溶体相(α,β)和所有化合物(αZrO2,βZrO2,γZrO2,NbO,NbO2和Nb2O5)的Gibbs自由能都采用双亚晶格模型描述。用CALPHAD(CALculation ofPHAse Diagrams)技术,使用Pandat软件中的PanOptimizer优化模块,对Zr-O二元系进行了热力学优化,计算得到的相图和热力学性质与实验结果相吻合。应用优化的Zr-O二元系模型参数,结合Zr-Nb、Nb-O已有的热力学评估结果,对Zr-Nb-O三元系进行了热力学优化,得到了该体系的一套热力学模型参数。计算了Zr-Nb-O三元系在1273,1473和1773 K温度下的等温截面,与实验数据符合得较好。计算了若干该体系在富Zr区α+ββ的相转变温度,结果和实验测量也能较好地吻合。研究结果对建立多元锆合金热力学数据库,以及指导新型锆基合金材料的成分设计具有重要意义。     

高氧化铝高炉渣成分优化的研究

针对高氧化铝高炉渣的成分优化问题进行了理论计算和实验室研究。运用FactSage热力学软件绘制了氧化铝含量为20%的SiO2-CaO-MgO-Al2O3四元系相图,分析了炉渣熔点随二元碱度和氧化镁含量的变化规律。运用数学模型计算了四元渣系在1450℃下的黏度值。根据通过理论计算所确定的成分范围,选取了黏度试验样品的化学成分。研究结果表明,对于(Al2O3)=20%的高炉渣,二元碱度宜控制在1.20~1.30范围,MgO含量不宜超过12%。当今世界铁矿石市场上价格及性能波动频繁,本文采用的研究方法有助于根据市场情况的变化及时调整炉渣成分,保证高炉稳定顺行。     

CaO-SiO2-FeOx-MgO氧化物体系液相区及相关系计算

焚烧垃圾底灰的主要氧化物组分为SiO2、CaO、Al2O3、Fe2O3、Na2O和MgO,该六元体系相关系和热力学性质对于焚烧底灰渣化处理中玻璃相形成以及重金属低浸出具有重要影响.本文运用计算热力学理论及相图计算方法,对CaO-SiO2-FeOx-MgO四元氧化物体系的热力学性质进行了研究,获得了描述该四元系液相吉布斯自由能的模型参数,并依此计算了不同温度及氧分压下SiO2-FeOx-MgO、CaO-SiO2-FeOx和CaO-SiO2-FeOx-MgO体系液相区和高铁区域的相关系.计算结果表明温度及氧分压对上述3个氧化物体系的液相区及高FeOx区域的相平衡关系具有较大影响     

高炉炉渣熔化温度及液相生成热力学分析

为了研究温度、二元碱度、Al2O3含量和MgO含量对高炉渣熔化温度和液相生成特性的影响,结合炼铁生产中典型的高炉渣成分,利用Factsage集成热力学数据计算系统计算并绘制出了不同组分高炉渣渣系四元相图,并根据试验计算所得结果,分别分析了温度、二元碱度、Al2O3含量和MgO含量这4种因素对高炉渣熔化温度及炉渣液相区变化的作用规律,并结合生产实际给出了高炉冶炼中适宜的炉渣碱度、炉渣中合理的MgO及Al2O3含量。     

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。     

Al-V系二元相图的计算、评估及其活度

利用最新版本的Pandat热力学计算软件,采用最新的Ti合金数据库和合理的热力学模型,计算出了Al-V系二元相图.研究发现:从相率和相图的特殊点对其进行了详细的热力学评估,最大误差为1.14%,说明计算相图与试验相图吻合较好;在Al-V二元相图的基础上,提取了Al和V在不同物质的成分和温度下的活度;拟合了恒温下其活度的计算公式,其线性相关度R趋近于1;作出了V的活度-成分-温度关系曲线,有效地解决了"试验测活度难"的问题.     

从弱酸高铁的镍钴溶液中分离杂质

通过热力学计算和E-pH图,以及不同温度下的Fe-SO_3—H_2O系相图,讨论了从高铁镍钻溶液中分离铁等杂质的过程。并提供了可供生产应用的试验数据。     

MNO_3–Ca(NO_3)_2 (M=Li,Na,K)二元相图的热力学优化

基于CALPHAD方法对MNO3-Ca(NO3)2(M=Li,Na,K)二元相图的试验数据首次进行了热力学优化拟合,得到了3个二元相图的过量混合热力学性质的参数及Ca(NO3)2的熔化吉布斯自由能随温度变化的函数表达式,并用拟合的参数计算了3个二元相图,最后将计算得到的相图与试验相图进行了比较。     

Isothermal section of Nd-Zr-Si ternary system at 773 K

Phase diagram is an important basis for materials research and materials application.The phase relations of the Nd-Zr-Si ternary system at 773 K were investigated by X-ray powder diffraction analysis,metallographic analysis and scanning electron microscopy with en-ergy dispersive analysis.The isothermal section of the phase diagram of the Nd-Zr-Si ternary system at 773 K was determined.The isother-mal section of the system consisted of 13 single-phase regions,23 two-phase regions and 11 three-phase regions.The homogeneity range of α-NdSix was from 63 at.% to 66 at.% Si(with x=1.70-1.94).The maximum solid solubilities of Nd in Zr-Si binary compounds and Zr in the Nd-Si binary compounds were observed less than 1 at.% at 773 K.     

Phase relationships in the Yb-Fe-Sb system at 530℃

Phase relationships in the Yb-Fe-Sb ternary system at 530℃ were investigated mainly by powder metallurgy and X-ray powder diffraction. Nine binary compounds (Yb6Fe23, Yb2Fe17, FeSb, FeSb2, YbSb2, YbSb, Yb11Sb10, Yb4Sb3, and αYb5Sb3) and one ternary compound (Fe4YbSb12) were confirmed in this system at 530℃. The homogeneity range of FeSb phase extended from approximately 43at.%Sb to 45at.%Sb, the maximum solid solubility of Sb in Fe phase and Yb in FeSb phase was approximately 3at.%Sb and 1at.%Yb at 530℃, respectively. Isothermal section of the phase diagram of the Yb-Fe-Sb ternary system at 530℃ consisted of thirteen single-phase regions, twenty-four two-phase regions, and twelve three-phase regions.     

Experimental investigation and thermodynamic calculation of the phase equilibria in the Cu-Sn and Cu-Sn-Mn systems

The phase equilibria in the Cu-rich portion of the Cu-Sn binary and Cu-Sn-Mn ternary systems have been determined using the diffusion-couple method, differential scanning calorimetry (DSC), high-temperature electron diffraction (HTED), and high-temperature X-ray diffraction (HTXRD) techniques. The present experimental results on the binary Cu-Sn system show the presence of the two-stage, second-order reaction A2 → B2 → D0₃ in the bcc-phase region, rather than a two-phase equilibrium between the disordered bcc (A2) and the ordered bcc (D0₃) phases, as reported before. Phase equilibria in the Cu-Sn-Mn ternary system in the composition range of 0 to 30 at. pct Sn and 0 to 30 at. pct Mn at 550 °C, 600 °C, 650 °C, and 700 °C have been determined, and a ternary compound (Cu₄MnSn) with a very small solubility has been detected. A thermodynamic analysis of the Cu-Sn-Mn ternary system including the Cu-Sn and Mn-Sn binary systems has also been carried out by the CALPHAD (Calculation of Phase Diagrams) method, in which the Gibbs energy of the bcc phase is described by the two-sublattice model in order to take into account the second-order A2/B2 ordering reaction. A consistent set of optimized thermodynamic parameters for the Cu-Sn-Mn system for describing the Gibbs energy of each phase results in a better fit between calculation and experiment.     

Investigation of the phase equilibria in the Sn-Bi-In alloy system

This article presents an investigation of the phase equilibria in the Sn-Bi-In ternary alloy system, performed both by theoretical and experimental methods. Following the regular solution model and a standard thermochemical calculation, a theoretical evaluation of the phase equilibrium in the entire ternary system is conducted. The thermodynamic parameters required for the calculation are initially obtained by fitting the model to existing data available from prior studies. The theoretical results are then validated and further improved by experimental work in which alloys with several critical compositions were chosen and examined. In the experimental work, differential scanning calorimetry (DSC), X-ray diffraction (XRD), and energy-dispersive X-ray (EDX) spectroscopy were jointly used to identify the transition temperatures and the phases in the microstructure. The resulting phase diagram agrees well both with the existing data and with the data from the current experiments. However, different from previous findings, this study finds a nonbinary nature of the Sn-BiIn and Sn-BiIn₂ quasi-binaries and nine invariant reactions, one eutectic, six peritectic and two peritectoid. The phase-reaction scheme (Scheil diagram), the liquidus projection, and the phase diagram, covering entire compositional ranges, are established.     

Experimental Investigation of the Ce-Mg-Mn Isothermal Section at 723 K (450 °C) via Diffusion Couples Technique

The isothermal section of the Ce-Mg-Mn phase diagram at 723 K (450 °C) was established experimentally by means of diffusion couples and key alloys. The phase relationships in the complete composition range were determined based on six solid–solid diffusion couples and twelve annealed key alloys. No ternary compounds were found in the Ce-Mg-Mn system at 723 K (450 °C). X-ray diffraction and energy-dispersive X-ray spectroscopy spot analyses were used for phase identification. EDS line-scans, across the diffusion layers, were performed to determine the binary and ternary homogeneity ranges. Mn was observed in the diffusion couples and key alloys microstructures as either a solute element in the Ce-Mg compounds or as a pure element, because it has no tendency to form intermetallic compounds with either Ce or Mg. The fast at. interdiffusion of Ce and Mg produces several binary compounds (Ce _x Mg _y ) during the diffusion process. Thus, the diffusion layers formed in the ternary diffusion couples were similar to those in the Ce-Mg binary diffusion couples, except that the ternary diffusion couples contain layers of Ce-Mg compounds that dissolve certain amount of Mn. Also, the ternary diffusion couples showed layers containing islands of pure Mn distributed in most diffusion zones. As a result, the phase boundary lines were pointing toward Mn-rich corner, which supports the tendency of Mn to be in equilibrium with all the phases in the system.     

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.     

Liquidus Projection of the B-Fe-U Diagram: The Boron-Rich Corner

The liquidus projection at the boron-rich corner of the B-Fe-U phase diagram is proposed based on powder X-ray diffraction measurements, heating curves, and scanning electron microscopy observations, complemented with both energy dispersive X-ray spectroscopy and electron probe microanalysis. Evidence for six ternary reactions is presented, the corresponding 12 monovariant lines are drawn, and the nature and location of the ternary reactions are given. The ternary compounds existing in this region of the B-Fe-U ternary phase diagram, UFeB₄ and UFe₂B₆, were confirmed to be formed by ternary peritectic reactions, yet UFeB₄ has a considerably larger primary crystallization field, which points to an easier preparation of single crystals of this compound, when compared with UFe₂B₆.     

Phase diagram of Er-Sn-Te system for diluted magnetic semiconductor developments

Phase diagrams of the RE (rare earth)-IV-VI systems are very important for the design of rare earth doped diluted magnetic semiconductors (DMSs), but related information is very limited. In this work, ...     

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.     

Phase equilibria in low basicity region of CaO-SiO_2-Nb_2O_5-(5 wt%,10 wt%,15 wt%) La_2O_3 system

The lack of thermodynamic information,such as primary phase fields and liquidus temperatures,in the CaO-SiO_2-Nb_2O_5-La_2O_3 quaternary system phase diagram has restricted the comprehensive utilization of the niobium(Nb) and rare earth(RE) resources.In this work,the phase equilibria in low basicity region(w(CaO)/w(SiO_2)1) of CaO-SiO_2-Nb_2O_5-(0-15 wt%)La_2O_3 system at 1373-1873 K were experimentally studied by thermodynamic equilibrium experiment,and then,the results were analyzed by X-ray diffraction(XRD),scanning electron microscopy(SEM),and energy dispersive spectrometry(EDS).Additionally,an optimized method was proposed to process the compositions of equilibrium liquid phases at different temperatures.According to the experimental results,the univariate line between CaNb_2O_6,SiO_2 and LaNbO_4 primary phase fields,interface between CaNb_2O_6 and SiO_2 primary phase fields and isothermal liquidus surfaces in SiO_2 primary phase field were determined.Finally,the spatial phase diagram of CaO-SiO_2-Nb_2O_5-La_2O_3 within specific region was constructed,and furthermore,the phase diagram was also presented in CaO-SiO_2-Nb_2O_5 pseudo-ternary system with w(La_2O_3)=5 wt%,10 wt% and 15 wt%.The research results have guiding significance for the improvement of related phase diagram and the comprehensive utilization of Nb and RE resources.