界面热力学与晶界相图的研究进展

晶界作为微观结构的重要组成部分,对材料的性能起着关键性的影响.晶界相变是准确阐述众多材料现象的重要信息.然而,由于晶界结构复杂、晶界相变观测困难等原因,迄今为止仍缺乏对这些材料现象的直接证据和机理解释.随着先进表征设备特别是球差校正透射电镜的发展,再加上功能强大的计算机模拟,建立界面热力学模型并构建不同类型的晶界相图,为晶界结构及晶界相变的研究提供了广阔的前景.本文从晶界与晶界相变的分类、表征、界面热力学模型、晶界相图的构建等方面,综述了界面热力学与晶界相图的研究进展,展望了该研究领域未来发展的重点及趋势.     

基于CALPHAD的高温高压相图建模

高温高压相图在物理化学、矿物学、地球科学和极端条件下的材料科学中都具有重要的地位和应用价值，相图计算方法(alculation of phase diagram, CALPHAD)是建立温度-压强热力学相图和热力学数据库的主要方法，可以计算材料体系的相平衡、组成相的相分数和相成分、热力学性质，一定程度上解决单一实验建立高温高压相图的困难。本文对基于CALPHAD的高温高压相图建模方法进行了详细介绍，并总结其当前面临的问题和下一步研究方向，为极端条件下材料设计和性能评估奠定基础。     

硬质合金及耐磨涂层：理论设计及产品开发（Ⅲ）

热力学和第一性原理计算在材料设计方面发挥着重要的作用,通过这些理论预测能够快速确定材料工艺-成分-结构-性能之间的关系。本文主要介绍了热力学计算在化学气相沉积(Chemical Vapor Deposition,简称CVD)涂层以及第一性原理计算在物理气相沉积(Physical Vapor Deposition,简称PVD)涂层设计开发方面的应用,并以CVD TiSiN和PVD纳米多层TiAlN/ZrN新型涂层开发为例,详细阐述了热力学和第一性原理计算的具体作用。理论计算与关键实验验证相结合是提高耐磨涂层研发效率与质量的有效途径,同时也是未来新型耐磨涂层开发的发展趋势。     

硬质合金及耐磨涂层：理论设计及产品开发（Ⅰ）

随着计算机技术与热力学动力学数据库的发展,把材料计算模拟和关键实验结合在一起,集成、优化、应用到硬质合金产品设计开发的全过程,通过成分–工艺–结构–性能的关联分析,能够把硬质合金及耐磨涂层的研发由传统经验或者半经验方式提升到科学的顶层/底层设计,加快研发速度,降低研发成本。本文阐述了第一性原理计算、CALPHAD方法(相图计算方法)、相场模拟和有限元模拟等计算模拟方法,论述了它们在硬质合金及耐磨涂层研发中所发挥的具体作用,从用户需要、设计制备和工业生产3个层面探讨并建立了基于集成计算材料工程进行产品开发的框架。     

Nd-Fe-B-Dy四元系热力学数据库的建立及其合金设计

本研究利用CALPHAD方法,采用合理的热力学模型,热力学优化和计算了Nd-Dy、Dy-B二元系和Fe-B-Dy、Dy-Fe-Nd、B-Dy-Nd三元系的相图,并利用文献报道的其他子二元系和三元系的热力学参数,充分考虑了热力学模型的统一性和参数的兼容性,建立了Nd-Fe-B-Dy四元系合金的热力学数据库,并应用该数据库,预测了Nd-Fe-B-Dy四元合金Nd16-xDyxFe77B7 (x≤5 at.%)的纵截面相图;同时还分析了一系列不同Dy含量的永磁合金在平衡凝固下各相相分数随温度的变化情况。这些计算信息对掺镝NdFeB永磁合金的组织设计以及制备工艺参数的选择具有重要的指导意义。     

Mg-Pr二元体系热力学优化（2）

相图热力学优化是材料设计理论和方法最重要的组成部分，是新材料的开发和应用的重要依据之一。相图计算即CALPHAD技术，主要是依据化学热力学原理和基本关系，计算热力学体系的平衡性质。一个物质体系的热力学特征函数确定以后，这个物质体系的全部热力学性质都可以计算出来，其中包括相图。镁合金是最轻的一种金属结构材料，广泛应用于航空航天、汽车、电子工业等许多领域。镁一镨合金作为镁合金的一种，也具有非常广阔的应用前景。本工作采用瑞典皇家工学院开发的相平衡计算软件Thermo-Calc系统，利用CALPHAD技术，通过选择或建立合理的热力学模型，将相图和热力学数据联系起来，对镁-镨二元合金体系相图和热力学数据进行热力学优化和评估，获得自洽的Mg-Pr体系的热力学描述即体系中所有物相，包括溶体相和金属间化合物的Gibbs自由能，为相关材料的设计和工艺制定服务。     

Mg—Pr二元体系热力学优化（1）

相图热力学优化是材料设计理论和方法最重要的组成部分，是新材料的开发和应用的重要依据之一。相图计算即CALPHAD技术，主要是依据化学热力学原理和基本关系，计算热力学体系的平衡性质。一个物质体系的热力学特征函数确定以后，这个物质体系的全部热力学性质都可以计算出来，其中包括相图。镁合金是最轻的一种金属结构材料，广泛应用于航空航天、汽车、电子工业等许多领域。镁-镨合金作为镁合金的一种，也具有非常广阔的应用前景。本工作采用瑞典皇家工学院开发的相平衡计算软件Thermo—Calc系统，利用CALPHAD技术，通过选择或建立合理的热力学模型，将相图和热力学数据联系起来，对镁-镨二元合金体系相图和热力学数据进行热力学优化和评估，获得自洽的Mg—Pr体系的热力学描述即体系中所有物相，包括溶体相和金属问化合物的Gibbs自由能，为相关材料的设计和工艺制定服务。     

高性能铜合金热力学数据库的开发及其在材料设计中的应用

利用相图计算(CALPHAD)方法,采用亚规则溶体模型描述溶体相的吉布斯自由能,采用亚点阵模型描述金属间化合物和有序相的吉布斯自由能,并结合相平衡和热力学性质的实验数据,优化与计算Cu-X二元系以及Cu-Fe、Cu-Ni、Cu-Cr、Cu-Co、Cu-Mo和Cu-W基各三元系的相图,获得自洽性良好的热力学参数,并建立铜合金热力学数据库。该数据库可以提供稳定和亚稳的相图计算、相分数计算、液相面计算、热力学性质的计算等多种信息,为外推计算铜基多元合金系的相平衡提供理论基础,并为高性能铜合金材料的设计及制备提供重要的理论指导。     

合金元素对V(110)表面O吸附影响的第一性原理研究

采用第一性原理方法研究了V(110)表面的氧吸附行为以及Al、Ti、Cr等合金元素的影响,并结合热力学原理构建了钒合金表面氧化相图,分析了钒合金表面氧化的微观机制。结果表明,Al和Ti倾向于在V(110)表面偏析,Cr不会在V(110)表面偏析。在V(110)表面会发生Al和Ti的选择性氧化,而Cr不会发生选择性氧化。对钒合金表面氧化机制的研究结果可以很好地解释钒合金的氧化行为,并可预测V-Al合金的选择性氧化行为,从而为钒合金表面氧化物阻氚涂层的制备提供指导。     

表面科学与工程在纳米技术发展与应用中的直接作用

表面科学与工程在纳米技术的发展与应用中发挥着特殊的作用，尤其在纳米尺度材料的制备和纳米制造等领域。在纳米材料领域，纳米晶块材料的界面问题和纳米尺度的分子自组装的表面与界面问题是极富挑战性的前沿工作。在纳米制造领域，微机械部件的微纳米尺度的操作手设计和运动副表面的微观失效、摩擦磨损和润滑等问题也将开辟表面科学与工程新的研究领域。     

A thermogravimetric investigation of the Fe-Ni-S system from 700 to 900°C

A thermogravimetric method employing H₂-H₂S-Ar gas mixtures was used to measure the thermodynamic properties and phase equilibria of the Fe-Ni-S system. The equilibrium sulfur pressures in the ternary monosulfide phase and an adjacent two-phase region were measured between 700 to 900°C. Isothermal sections at 700, 750, 800, and 850°C are constructed as well as stability diagrams for the same temperatures.     

Thermodynamic assessment of ZnO-SiO2 system

ZnO-containing slags are common in pyrometallurgical processing of the base metals and steel. This caused the interest to the thermodynamics of the ZnO-SiO₂ system. A complete literature survey, critical evaluation of the available experimental data and a thermodynamic optimization of the phase equilibria and thermodynamic properties of the system ZnO-SiO₂ at 1.013×10⁵ Pa are presented. The molten oxide was described as an associate solution. The properties of liquid were reassessed and enthalpy term of the Gibbs energy of solid Zn₂SiO₄ was re-fitted to be compatible with the new data in the willemite primary phase field. The thermodynamic data set agrees well with the recent experimental observations. It can be used for predicting, e.g., the thermodynamic properties and the domains of the phase diagram, like critical point of the liquid miscibility gap, with a better accuracy than using the previous assessments. A set of optimized model parameters were obtained, reproducing the reliable thermodynamic and phase equilibrium data within their experimental errors from 298 K to liquidus temperatures, over the entire composition range. The created database can be used in a Gibbs energy minimization software to calculate the thermodynamic properties and the phase diagram sections of interest.     

AuCu3-亚格子系统的合金基因Gibbs能配分函数和平衡全息网络相图（英文）

以AuCu3-亚格子系统为例,介绍3项发现:第一,迄今阻碍金属材料科学进步的第三大障碍是研究者们习惯用平衡均匀转变的思维方式认识温度极其缓慢变化的合金相变实验现象,然后以实验现象的错误认识为选择信息,建立Gibbs能函数和所谓的"平衡相图";第二,AuCu3-型亚格子系统的平衡全息网络相图可用来描述与成分和温度有关的合金基因排列结构和各种热力学性质的系统相关性;第三,每个合金的平衡转变都是均匀的单相转变,不是非均匀的双相转变,存在一条没有有序相和无序相共存区的单相相界线,相界线顶点成分和温度远偏离AuCu3化合物临界点的计量成分和温度。     

Vertical section phase diagrams of La−Fe−B ternary system

The vertical sections of the La?Fe?B system were investigated using electron probe microanalysis and differential thermal analysis. Based on the microstructures and phase compositions of the as-cast and equilibrium alloys, together with their heat flow?temperature curves, phase diagrams for three vertical sections were drawn: La_xFe₈₂B_y (x+y=18), La_xFe₇₀B_y (x+y=30) and La_xFe₅₃B_y (x+y=47), where x and y represent mass fraction of La and B, respectively, % . Additionally, according to the phase diagrams, the compound La₂Fe₁₄B was identified as a stable phase at high temperatures. It was found to be stable between 926.2 and 792.6 °C; at low temperatures, however, it decomposed into α-La, α-Fe and LaFe₄B₄, according to the reaction La₂Fe₁₄B→α-Fe+α-La+LaFe₄B₄.     

Modern thermodynamics in CVD of hard materials

The diamond growth together with the graphite etching under low pressure had often been regarded as a “thermodynamic paradox” maybe “violating the second law of thermodynamics”, since the success of the activated chemical vapor deposited (CVD) diamond processes in 1970. After quantitative verification of reaction coupling, a series of nonequilibrium phase diagrams for the activated diamond processes have been quantitatively calculated. These nonequilibrium phase diagrams agree excellently with experiments. However, there is no room for the nonequilibrium phase diagram in both classical equilibrium thermodynamics and traditional nonequilibrium thermodynamics. Therefore, the systematization of modern thermodynamics has been drastically changed and a new field for nonequilibrium phase diagrams emerges. Nonequilibrium phase diagrams for activated CVD cubic boron nitride processes have also been calculated in this paper.     

Thermodynamic Optimization and Calculation of the HoCl3-MCl (M = Na, K, Rb, Cs) Systems

According to measured experimental phase diagram data and thermodynamic data, the HoCl₃-MCl (M = Na, K, Rb, Cs) phase diagrams were determined by the CALPHAD technique. The Gibbs energies of liquid phases in these systems have been optimized and calculated by the modified quasi-chemical model in the pair-approximation for short-range ordering. A series of thermodynamic functions have been optimized and calculated on the basis of an interactive computer-assisted analysis. The results show that the thermodynamic properties and phase diagrams are self-consistent. The optimized results for the systems are discussed.     

CONTACT MATERIALS FOR GaSb AND InSb: A PHASE DIAGRAM APPROACH

1. IntroductionAmong the III-V compound semiconductors, GaSb and InSb, belong to the narrowbandgap materials which gained increasing interest during the last yearsIl,2l due to theirhigh potentiality for many electronic and optoelectronic aPplications. The…     

Thermodynamics of equilibrium and partitionless solidifications in glass forming binary eutectic alloys

T₀ curves in the phase diagrams have been proven useful to understand thermodynamically glass formation in metallic alloys, emphasizing the importance of the metastable solid solutions crystallized partitionlessly. Here we focus on four typical binary eutectic alloys with distinct glass-forming abilities and interatomic interactions, Ag₆₀Cu₄₀, Sb_17.5Pb_82.5, Au_81.4Si_18.6, and Ni₂₄Zr₇₆. The thermodynamics involved in the liquid–solid solution transition at T₀ temperatures for the alloys of eutectic compositions are quantified, and the validity of the thermodynamic properties is evaluated. The comparison of the melting entropies for the equilibrium and partitionless solidifications reveals a basic relation. Based on the thermodynamics of the equilibrium phases and the solid solutions, an understanding of the glass formation of metallic alloys is proposed.     

MOLTEN SALT PHASE DIAGRAMS CALCULATION USING ARTIFICIAL NEURAL NETWORK OR PATTERN RECOGNITION-BOND PARAMETERS PART 3.ESTIMATION OF LIQUIDUS TEMPERATURE AND EXPERT SYSTEM

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