Calphad-computer Coupling of Phase Diagrams and Thermochemistry最新文献_第6页

aiMP and aiOQ databases in FactSage: Materials informatics relying on ab initio, machine learning and CALPHAD data FactSage中的aiMP和aiOQ数据库：基于从头算、机器学习和CALPHAD数据的材料信息学

IF 1.9 3区材料科学 Q4 CHEMISTRY, PHYSICAL

Calphad-computer Coupling of Phase Diagrams and Thermochemistry

Pub Date : 2025-07-10 DOI: 10.1016/j.calphad.2025.102838

C. Frueh, C. Aras, Ö. Büyükuslu, M. to Baben

aiMP and aiOQ are databases derived from the 0 K density functional theory (DFT) calculations data stored in the Materials Project and Open Quantum Materials Database (OQMD) repositories, respectively. aiMP and aiOQ databases rely on methods to process 0 K DFT data using machine learning models trained on thousands of compounds. These models adjust formation enthalpies to improve consistency with existing CALPHAD (CALculation of PHAse Diagrams) databases and predict thermodynamic properties such as entropy and heat capacity as functions of temperature.

This work demonstrates three Materials Informatics applications of large-scale CALPHAD-compatible databases enabled by automated workflows.

First, a comparison was made between the SGTE Pure Substance database (SGPS), containing 3927 compounds, and the aiMP database, which includes overlapping entries for 1519 compounds. For these overlapping compounds, the enthalpy of formation, entropy at 298 K, and heat capacity at 298 K were analyzed. Any discrepancies exceeding the inherent error of the machine learning models were flagged. A literature survey was then conducted for compounds with larger discrepancies and erroneous data was confirmed in approximately 0.7% of the SGPS data.

Second, the aiMP database was used to estimate phase diagrams and identify potential new coating materials for SiC/SiC composites, which are under investigation as accident-tolerant fuel cladding materials.

Finally, it is shown that aiMP can serve as a starting point for both traditional and automated CALPHAD modeling. Three examples were explored Al-Ca, Mg-Si, and Ca-Li. These examples highlight the versatility of machine learning-enhanced thermodynamic databases in accelerating material discovery and improving database reliability.

aiMP和aiOQ数据库分别来源于存储在材料项目和开放量子材料数据库（OQMD）存储库中的0 K密度泛函理论（DFT）计算数据。aiMP和aiOQ数据库依赖于使用数千种化合物训练的机器学习模型来处理0 K DFT数据的方法。这些模型调整地层焓，以提高与现有CALPHAD（相图计算）数据库的一致性，并预测热力学性质，如熵和热容作为温度的函数。这项工作演示了三种材料信息学应用程序的大规模calphad兼容数据库启用自动化工作流程。首先，我们比较了包含3927种化合物的SGTE纯物质数据库（SGPS）和包含1519种化合物重叠条目的aiMP数据库。对这些重叠化合物的生成焓、298k时的熵和298k时的热容进行了分析。任何超出机器学习模型固有误差的差异都会被标记出来。然后对差异较大的化合物进行文献调查，在大约0.7%的SGPS数据中确认了错误数据。其次，aiMP数据库用于估计相图并确定潜在的SiC/SiC复合材料的新涂层材料，这些材料正在研究作为耐事故燃料包层材料。最后，表明aiMP可以作为传统和自动化CALPHAD建模的起点。以Al-Ca、Mg-Si和Ca-Li为例。这些例子突出了机器学习增强的热力学数据库在加速材料发现和提高数据库可靠性方面的多功能性。

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引用次数: 0

PanEvolution: Integrating CALPHAD, microstructure modeling, and finite element method PanEvolution：整合CALPHAD，微观结构建模和有限元方法

IF 1.9 3区材料科学 Q4 CHEMISTRY, PHYSICAL

Calphad-computer Coupling of Phase Diagrams and Thermochemistry

Pub Date : 2025-07-09 DOI: 10.1016/j.calphad.2025.102851

Weisheng Cao , Fan Zhang , Kamalnath Kadirvel , Shuanglin Chen , Eric Payton , Matthew Krug

This paper introduces PanEvolution, a modeling platform that integrates CALPHAD, microstructure modeling, and finite element method (FEM). This work represents the third generation of Pandat software, designed to simulate the microstructure evolution of metallic materials during conventional manufacturing processes. The key features of PanEvolution include: (1) direct coupling of CALPHAD with various FEM software packages. This enables FEM packages to obtain accurate input of phase information for multi-component alloys and perform simulations of microstructure evolution for technically important metallic alloys, including precipitation, recrystallization, grain growth, and coarsening, during conventional manufacturing processes such as forging and rolling. (2) an open architecture that facilitates the easy replacement and swapping of fast-acting microstructure models. This enables microstructure evolution and property models developed by academia or industry to be easily integrated into the PanEvolution platform to maximize their value in industrial applications.

本文介绍了一个集CALPHAD、微结构建模和有限元法于一体的建模平台PanEvolution。这项工作代表了第三代Pandat软件，旨在模拟传统制造过程中金属材料的微观结构演变。PanEvolution的主要特点包括：(1)CALPHAD与各种有限元软件包的直接耦合。这使FEM软件包能够获得多组分合金的准确相信息输入，并对技术上重要的金属合金的微观结构演变进行模拟，包括在锻造和轧制等传统制造过程中的沉淀、再结晶、晶粒生长和粗化。(2)开放式架构，便于快速作用的微观结构模型的替换和交换。这使得学术界或工业界开发的微观结构演化和属性模型可以轻松集成到PanEvolution平台中，以最大限度地发挥其在工业应用中的价值。

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引用次数: 0

Phase equilibria and thermodynamic assessment of the Co–Cr binary system Co-Cr二元体系的相平衡及热力学评价

IF 1.9 3区材料科学 Q4 CHEMISTRY, PHYSICAL

Calphad-computer Coupling of Phase Diagrams and Thermochemistry

Pub Date : 2025-07-06 DOI: 10.1016/j.calphad.2025.102853

Kazushige Ioroi, Haruhi Kumeta, Xiao Xu, Ryosuke Kainuma, Toshihiro Omori

The phase equilibria of the Co–Cr binary system were experimentally investigated across the whole composition range. Liquidus and solidus temperatures, measured up to 1800 °C using a differential thermal analyzer and differential scanning calorimeter, were slightly higher than those reported in the literature. The equilibrium compositions of two-phase alloys were analyzed using an electron probe microanalyzer, yielding reliable data regarding the γ(Co) + α(Cr) phase boundaries at high temperatures and ε(Co) + σ phase boundaries at low temperatures. Subsequently, a thermodynamic assessment of the Co–Cr binary system was performed using the CALPHAD technique, relying on our experimental data as well as thermodynamic property data from the literatures. The calculated Co–Cr phase diagram accurately reproduced the experimentally determined phase boundaries and thermodynamic properties, including activity, excess enthalpy, and excess Gibbs energy.

在整个组成范围内对Co-Cr二元体系的相平衡进行了实验研究。用差示热分析仪和差示扫描量热计测量的液相和固相温度高达1800°C，略高于文献报道的温度。利用电子探针微量分析仪分析了两相合金的平衡成分，得到了高温下γ(Co) + α(Cr)相界和低温下ε(Co) + σ相界的可靠数据。随后，基于我们的实验数据和文献中的热力学性质数据，使用CALPHAD技术对Co-Cr二元体系进行了热力学评估。计算出的Co-Cr相图精确地再现了实验确定的相边界和热力学性质，包括活度、多余焓和多余吉布斯能。

引用次数: 0

Extension of the modified quasichemical model in the distinguishable-pair approximation to multicomponent solutions via an on-the-fly interpolation framework 利用动态插值框架将可分辨对近似中修正的准化学模型推广到多组分解

IF 1.9 3区材料科学 Q4 CHEMISTRY, PHYSICAL

Calphad-computer Coupling of Phase Diagrams and Thermochemistry

Pub Date : 2025-07-04 DOI: 10.1016/j.calphad.2025.102852

Kun Wang , Patrice Chartrand

The Modified Quasichemical Model in the Distinguishable-Pair Approximation (MQMDPA) was originally developed to describe thermodynamic properties of binary solutions with manifold short-range ordering (SRO) among atoms. This study extends the MQMDPA to multicomponent solutions through the development of an on-the-fly bond-energy formalism (OTFBEF). The OTFBEF employs interpolation functions to dynamically transform bond energy expressions from binary to ternary and higher-order multicomponent systems. By fixing the interpolation functions to specific values, the OTFBEF seamlessly reduces to traditional geometric methods, the generic method, or the hybrid Kohler-Toop loop framework, ensuring compatibility with established approaches, particularly with the widely used MQMPA. The interpolation functions can be optimized using experimental data from ternary systems or theoretically defined through integral and partial methods, providing flexibility for both prediction and calibration. The versatility and generality of the OTFBEF empower the MQMDPA to model multicomponent solutions with complex configurations effectively. Future work will focus on expanding the MQMDPA within a two-sublattice framework to address reciprocal solutions, further enhancing its applicability.

可分辨对近似中的修正准化学模型（MQMDPA）最初是为了描述原子间具有流形短程有序（SRO）的二元解的热力学性质而建立的。本研究通过开发动态键能形式（OTFBEF）将MQMDPA扩展到多组件解决方案。OTFBEF采用插值函数将键能表达式从二元系统动态转换为三元高阶多组分系统。通过将插值函数固定到特定值，OTFBEF可以无缝地简化为传统的几何方法、通用方法或混合Kohler-Toop循环框架，从而确保与现有方法的兼容性，特别是与广泛使用的MQMPA的兼容性。插值函数可以利用三元系统的实验数据进行优化，也可以通过积分和部分方法进行理论定义，为预测和校准提供了灵活性。OTFBEF的多功能性和通用性使MQMDPA能够有效地为具有复杂配置的多组件解决方案建模。未来的工作将侧重于在两个子格框架内扩展MQMDPA，以解决相互解决方案，进一步增强其适用性。

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引用次数: 0

Phase transformation temperatures of the Sn–In–Ni–Zn quaternary system Sn-In-Ni-Zn四元体系的相变温度

IF 1.9 3区材料科学 Q4 CHEMISTRY, PHYSICAL

Calphad-computer Coupling of Phase Diagrams and Thermochemistry

Pub Date : 2025-07-01 DOI: 10.1016/j.calphad.2025.102854

Sinn-wen Chen , Te-Wei Lin , Hsin-Chieh Huang , Cheng-Hsi Ho , Chuan Zhang , Jun Zhu

The Sn–In–Ni–Zn system is an important material system for electronic soldering. Various alloys, such as Sn–In, Sn–Ni, Sn–Zn, and Sn–In–Zn, are frequently used in electronic products. Unexpectedly, it was found that even for these important systems, there are only limited experimental measurements of the liquidus and invariant reaction temperatures. Additionally, there are significant differences between the experimental results and those calculated using the CALPHAD method with various available databases. To tackle these issues, Sn-rich alloys including Sn–Zn, Sn–In, Sn–Ni, Sn–In–Zn, Sn–Ni–Zn, Sn–In–Ni, and Sn–In–Ni–Zn were prepared. Their liquidus temperatures were determined experimentally through thermal analysis combined with holding-quenching experiments, while invariant reaction temperatures were measured using thermal analysis with an internal marker. The uncertainties in the measurements are 3 °C for the liquidus temperatures and 1 °C for the invariant reactions. Although high-quality thermal analysis can determine phase transformation temperatures with an accuracy of up to 1 °C, reliable determination of liquidus temperatures becomes quite challenging when the heat effect is not significant. This may explain why the literature data are inconsistent. These experimental results were subsequently used to refine CALPHAD-type modeling, and phase diagram calculations with better agreement were achieved.

Sn-In-Ni-Zn系统是一种重要的电子焊接材料系统。各种合金，如Sn-In， Sn-Ni， Sn-Zn和Sn-In - zn，经常用于电子产品。出乎意料的是，即使对于这些重要的体系，也只有有限的液相线和不变反应温度的实验测量。此外，实验结果与使用各种可用数据库的CALPHAD方法计算的结果存在显着差异。为了解决这些问题，制备了Sn-Zn、Sn-In、Sn-Ni、Sn-In - zn、Sn-Ni - zn、Sn-In - ni和Sn-In - ni - zn等富锡合金。它们的液相温度是通过热分析结合保温淬火实验来测定的，不变反应温度是通过带内标的热分析来测定的。测量的不确定度为液体温度为3℃，不变反应为1℃。尽管高质量的热分析可以以高达1°C的精度确定相变温度，但当热效应不显著时，液相温度的可靠测定变得相当具有挑战性。这也许可以解释为什么文献数据不一致。这些实验结果随后用于改进calphad型建模，并获得了更一致的相图计算。

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引用次数: 0

Experimental study and thermodynamic assessment of the MgSO4-CaSO4 system MgSO4-CaSO4体系的实验研究及热力学评价

IF 1.9 3区材料科学 Q4 CHEMISTRY, PHYSICAL

Calphad-computer Coupling of Phase Diagrams and Thermochemistry

Pub Date : 2025-06-30 DOI: 10.1016/j.calphad.2025.102855

Amedeo Morsa , Elena Yazhenskikh , Mirko Ziegner , Egbert Wessel , Rhys Dominic Jacob , Michael Müller , Dmitry Sergeev

This work presents a comprehensive experimental investigation into the thermal properties of the binary system MgSO₄-CaSO₄, alongside thermodynamic modelling of its thermodynamic properties, with a focus on enhancing its application in thermal energy storage. The phase diagram and thermodynamic properties of the pure sulphates and intermediate compounds were determined using Differential Thermal Analysis (DTA) and Differential Scanning Calorimetry (DSC). The DSC results led to the refinement of the enthalpy values for phase transitions of MgSO₄, with updated values of 14.6 kJ/mol and 43.4 kJ/mol for the solid-solid and solid-liquid transitions, respectively. High-Temperature X-ray Diffraction (HTXRD) was employed to study the intermediate compounds, leading to the identification of CaMg₂(SO₄)₃. For the first time, the melting temperature and the enthalpy of fusion for this compound were experimentally determined, yielding a value of 145.5 kJ/mol at 1213 ± 5 °C. A novel phase with the composition CaMg(SO₄)₂ was identified using DTA, HTXRD, and Scanning Electron Microscopy (SEM). This phase exhibits a melting temperature of 1309 ± 5 °C, as determined by DTA, and demonstrates thermal stability within a high-temperature range of 1020–1308 °C. These experimental data were used to update the thermodynamic database for the system MgSO₄-CaSO₄ for more accurate thermochemical calculations and predictions.

本文对二元体系MgSO4-CaSO4的热性质进行了全面的实验研究，并对其热力学性质进行了热力学建模，重点研究了其在热能储存中的应用。采用差热分析（DTA）和差示扫描量热法（DSC）测定了纯硫酸盐和中间化合物的相图和热力学性质。DSC结果对MgSO4相变焓值进行了修正，固-固和固-液相变焓值分别为14.6 kJ/mol和43.4 kJ/mol。利用高温x射线衍射（HTXRD）对中间化合物进行了研究，鉴定出了CaMg2(SO4)3。首次通过实验测定了该化合物在1213±5℃时的熔合温度和熔合焓，得到了145.5 kJ/mol。通过DTA、HTXRD和扫描电镜（SEM）鉴定了一种新的相，其组成为CaMg(SO4)2。根据差热分析，该相的熔化温度为1309±5℃，在1020-1308℃的高温范围内表现出热稳定性。这些实验数据被用于更新MgSO4-CaSO4体系的热力学数据库，以获得更准确的热化学计算和预测。

{"title":"Experimental study and thermodynamic assessment of the MgSO4-CaSO4 system","authors":"Amedeo Morsa , Elena Yazhenskikh , Mirko Ziegner , Egbert Wessel , Rhys Dominic Jacob , Michael Müller , Dmitry Sergeev","doi":"10.1016/j.calphad.2025.102855","DOIUrl":"10.1016/j.calphad.2025.102855","url":null,"abstract":"<div><div>This work presents a comprehensive experimental investigation into the thermal properties of the binary system MgSO<sub>4</sub>-CaSO<sub>4</sub>, alongside thermodynamic modelling of its thermodynamic properties, with a focus on enhancing its application in thermal energy storage. The phase diagram and thermodynamic properties of the pure sulphates and intermediate compounds were determined using Differential Thermal Analysis (DTA) and Differential Scanning Calorimetry (DSC). The DSC results led to the refinement of the enthalpy values for phase transitions of MgSO<sub>4</sub>, with updated values of 14.6 kJ/mol and 43.4 kJ/mol for the solid-solid and solid-liquid transitions, respectively. High-Temperature X-ray Diffraction (HTXRD) was employed to study the intermediate compounds, leading to the identification of CaMg<sub>2</sub>(SO<sub>4</sub>)<sub>3</sub>. For the first time, the melting temperature and the enthalpy of fusion for this compound were experimentally determined, yielding a value of 145.5 kJ/mol at 1213 ± 5 °C. A novel phase with the composition CaMg(SO<sub>4</sub>)<sub>2</sub> was identified using DTA, HTXRD, and Scanning Electron Microscopy (SEM). This phase exhibits a melting temperature of 1309 ± 5 °C, as determined by DTA, and demonstrates thermal stability within a high-temperature range of 1020–1308 °C. These experimental data were used to update the thermodynamic database for the system MgSO<sub>4</sub>-CaSO<sub>4</sub> for more accurate thermochemical calculations and predictions.</div></div>","PeriodicalId":9436,"journal":{"name":"Calphad-computer Coupling of Phase Diagrams and Thermochemistry","volume":"90 ","pages":"Article 102855"},"PeriodicalIF":1.9,"publicationDate":"2025-06-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144517238","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Modified polyhedron model for predicting standard enthalpy of formation and entropy of mixed oxides 预测混合氧化物标准生成焓和熵的改进多面体模型

IF 1.9 3区材料科学 Q4 CHEMISTRY, PHYSICAL

Calphad-computer Coupling of Phase Diagrams and Thermochemistry

Pub Date : 2025-06-26 DOI: 10.1016/j.calphad.2025.102848

Jesus A. Arias Hernandez, Elmira Moosavi-Khoonsari

Thermodynamic modeling of oxidic systems is crucial in advancing various fields of science and technology. Polyhedron Model (PM) estimates the standard enthalpy of formation and entropy of mixed oxides via the linear summation of the thermodynamic properties of constituent polyhedra. Each polyhedron consists of a centered cation with neighboring oxygen anions; hence, the model accounts for the interaction between anions and cations. While second-order transitions have been considered in previous iterations of the model, the PM has certain shortcomings, including neglect of variations in polyhedron volume, polyhedron distortion, inter-polyhedron linkage, and second nearest-neighbor or higher-order interactions, which are not negligible. The present work introduces the Modified Polyhedron Model (MPM), which aims to incorporate these contributions through a neural network (NN) model to improve the accuracy of predictions for standard enthalpy of formation (

{Δ H}_{298 K}^{o}

) and standard entropy (

S_{298 K}^{o}

). This is possible by using the residuals from the PM as inputs to the NN model, whose outputs are the calculated thermodynamic properties of compounds. The dataset consists of 155 compounds in the Li-Na-K-Ca-Mg-Mn-Fe-Al-Ti-Si-O system, classified by 20 polyhedra. The MPM considerably reduces the error in predicting enthalpy of formation and entropy, improving the alignment with experimental values across most analyzed compounds in comparison with the PM. These results suggest that the MPM can significantly improve the predictability of thermodynamic properties for mixed oxides.

氧化系统的热力学建模对于推动各个科学技术领域的发展至关重要。多面体模型（Polyhedron Model， PM）通过对组成多面体的热力学性质的线性求和来估计混合氧化物的标准生成焓和熵。每个多面体由一个中心阳离子和邻近的氧阴离子组成；因此，该模型解释了阴离子和阳离子之间的相互作用。虽然在以前的模型迭代中已经考虑了二阶过渡，但PM有一定的缺点，包括忽略多面体体积的变化、多面体畸变、多面体间的连接以及第二近邻或高阶相互作用，这些都是不可忽略的。本研究引入了修正多面体模型（MPM），该模型旨在通过神经网络（NN）模型整合这些贡献，以提高标准生成焓（ΔH298Ko）和标准熵（S298Ko）预测的准确性。这可以通过使用PM的残差作为NN模型的输入来实现，NN模型的输出是计算出的化合物的热力学性质。该数据集由Li-Na-K-Ca-Mg-Mn-Fe-Al-Ti-Si-O体系中的155种化合物组成，按20个多面体分类。与PM相比，MPM大大减少了预测生成焓和熵的误差，提高了大多数分析化合物与实验值的一致性。这些结果表明，MPM可以显著提高混合氧化物热力学性质的可预测性。

{"title":"Modified polyhedron model for predicting standard enthalpy of formation and entropy of mixed oxides","authors":"Jesus A. Arias Hernandez, Elmira Moosavi-Khoonsari","doi":"10.1016/j.calphad.2025.102848","DOIUrl":"10.1016/j.calphad.2025.102848","url":null,"abstract":"<div><div>Thermodynamic modeling of oxidic systems is crucial in advancing various fields of science and technology. Polyhedron Model (PM) estimates the standard enthalpy of formation and entropy of mixed oxides via the linear summation of the thermodynamic properties of constituent polyhedra. Each polyhedron consists of a centered cation with neighboring oxygen anions; hence, the model accounts for the interaction between anions and cations. While second-order transitions have been considered in previous iterations of the model, the PM has certain shortcomings, including neglect of variations in polyhedron volume, polyhedron distortion, inter-polyhedron linkage, and second nearest-neighbor or higher-order interactions, which are not negligible. The present work introduces the Modified Polyhedron Model (MPM), which aims to incorporate these contributions through a neural network (NN) model to improve the accuracy of predictions for standard enthalpy of formation (<span><math><mrow><msubsup><mrow><mo>Δ</mo><mi>H</mi></mrow><mrow><mn>298</mn><mspace></mspace><mi>K</mi></mrow><mi>o</mi></msubsup></mrow></math></span>) and standard entropy (<span><math><mrow><msubsup><mi>S</mi><mrow><mn>298</mn><mspace></mspace><mi>K</mi></mrow><mi>o</mi></msubsup></mrow></math></span>). This is possible by using the residuals from the PM as inputs to the NN model, whose outputs are the calculated thermodynamic properties of compounds. The dataset consists of 155 compounds in the Li-Na-K-Ca-Mg-Mn-Fe-Al-Ti-Si-O system, classified by 20 polyhedra. The MPM considerably reduces the error in predicting enthalpy of formation and entropy, improving the alignment with experimental values across most analyzed compounds in comparison with the PM. These results suggest that the MPM can significantly improve the predictability of thermodynamic properties for mixed oxides.</div></div>","PeriodicalId":9436,"journal":{"name":"Calphad-computer Coupling of Phase Diagrams and Thermochemistry","volume":"90 ","pages":"Article 102848"},"PeriodicalIF":1.9,"publicationDate":"2025-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144489490","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Crystal structure and thermodynamic properties of post-spinel-type CaV2O4 at high temperatures (298.15–1373 K) 后尖晶石型CaV2O4高温（298.15 ~ 1373 K）晶体结构与热力学性质

IF 1.9 3区材料科学 Q4 CHEMISTRY, PHYSICAL

Calphad-computer Coupling of Phase Diagrams and Thermochemistry

Pub Date : 2025-06-21 DOI: 10.1016/j.calphad.2025.102850

Dapeng Zhong , Jie Yu , Xin Jin , Guishang Pei , Wenhao Yu , Qingyun Huang , Changcai Zhou , Xuewei Lv , Wei Lv

We conducted an analysis of the crystal structure and thermodynamic properties of CaV₂O₄ synthesized through high-temperature solid-state calcination under elevated temperature conditions. The XRD analysis indicated that CaV₂O₄ crystallizes in an orthorhombic structure, characterized by unit cell parameters a = 9.21311(10) Å, b = 3.008421(35) Å, c = 10.68206(12) Å, and α = β = γ = 90°. The enthalpy of formation and entropy of CaV₂O₄ at 298.15 K are −1890.56 ± 5.84 kJ/mol J·mol⁻¹ and 129.62 ± 1.09 J·mol⁻¹ K⁻¹, respectively. The heat capacity of CaV₂O₄ at 573–1373 K was determined using drop calorimetry, yielding the expression C_p = 165.7748 + 3.2353 × 10⁻²T - 2.64268 × 10⁶T⁻² (J·mol⁻¹·K⁻¹). Additional thermodynamic data for CaV₂O₄ were derived using the C_p,m expression at elevated temperatures.

对高温固相煅烧合成的CaV2O4的晶体结构和热力学性质进行了分析。XRD分析表明，CaV2O4为正交晶型，晶型参数为a = 9.21311（10） Å， b = 3.008421（35） Å， c = 10.68206（12） Å， α = β = γ = 90°。在298.15 K下，CaV2O4的生成焓和熵分别为−1890.56±5.84 kJ/mol J·mol−1和129.62±1.09 J·mol−1 K−1。用滴量热法测定了573 ~ 1373 K时CaV2O4的热容，得到Cp = 165.7748 + 3.2353 × 10−2T - 2.64268 × 106T−2 （J·mol−1·K−1）。利用Cp，m表达式推导了CaV2O4在高温下的热力学数据。

{"title":"Crystal structure and thermodynamic properties of post-spinel-type CaV2O4 at high temperatures (298.15–1373 K)","authors":"Dapeng Zhong , Jie Yu , Xin Jin , Guishang Pei , Wenhao Yu , Qingyun Huang , Changcai Zhou , Xuewei Lv , Wei Lv","doi":"10.1016/j.calphad.2025.102850","DOIUrl":"10.1016/j.calphad.2025.102850","url":null,"abstract":"<div><div>We conducted an analysis of the crystal structure and thermodynamic properties of CaV<sub>2</sub>O<sub>4</sub> synthesized through high-temperature solid-state calcination under elevated temperature conditions. The XRD analysis indicated that CaV<sub>2</sub>O<sub>4</sub> crystallizes in an orthorhombic structure, characterized by unit cell parameters <em>a</em> = 9.21311(10) Å, <em>b</em> = 3.008421(35) Å, <em>c</em> = 10.68206(12) Å, and <em>α</em> = <em>β</em> = <em>γ</em> = 90°. The enthalpy of formation and entropy of CaV<sub>2</sub>O<sub>4</sub> at 298.15 K are −1890.56 ± 5.84 kJ/mol J·mol<sup>−1</sup> and 129.62 ± 1.09 J·mol<sup>−1</sup> K<sup>−1</sup>, respectively. The heat capacity of CaV<sub>2</sub>O<sub>4</sub> at 573–1373 K was determined using drop calorimetry, yielding the expression <em>C</em><sub><em>p</em></sub> = 165.7748 + 3.2353 × 10<sup>−2</sup><em>T</em> - 2.64268 × 10<sup>6</sup><em>T</em><sup>−2</sup> (J·mol<sup>−1</sup>·K<sup>−1</sup>). Additional thermodynamic data for CaV<sub>2</sub>O<sub>4</sub> were derived using the <em>C</em><sub><em>p,m</em></sub> expression at elevated temperatures.</div></div>","PeriodicalId":9436,"journal":{"name":"Calphad-computer Coupling of Phase Diagrams and Thermochemistry","volume":"90 ","pages":"Article 102850"},"PeriodicalIF":1.9,"publicationDate":"2025-06-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144331373","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Experimental investigation and thermodynamic description of binary Er-Si and ternary Al-Si-Er systems 二元Er-Si和三元Al-Si-Er体系的实验研究和热力学描述

IF 1.9 3区材料科学 Q4 CHEMISTRY, PHYSICAL

Calphad-computer Coupling of Phase Diagrams and Thermochemistry

Pub Date : 2025-06-09 DOI: 10.1016/j.calphad.2025.102839

Jin Tao , Rui Zhang , Yuhan Wang , Zewei Chen , Shitao Zhang , Caimin Huang , Qianxin Long , Zhao Lu , Like Tao , Qingrong Yao , Jiang Wang

In this study, thermodynamic optimization of the Er-Si binary system was performed using the CALPHAD method. The calculated phase diagram showed good consistency with existing experimental data. Furthermore, the phase equilibrium of the Al-Si-Er ternary system was investigated via electron probe microanalysis (EPMA) and X-ray diffraction (XRD), building on prior experimental data. Based on the experimental results obtained in this work and literature reports, the thermodynamic parameters of the Al-Si-Er ternary system were optimized. Both calculated isothermal cross section at 600 °C and the vertical cross section along Al₇₀Si₃₀-Al₇₀Er₃₀ (at. %) in the ternary system are in agreement with experimental data, indicating reliability of the thermodynamic description. This work provides essential foundational data for the development of high-performance rare earth Al-Si-Er alloys.

本研究采用CALPHAD方法对Er-Si二元体系进行热力学优化。计算得到的相图与已有实验数据吻合较好。在前人实验数据的基础上，利用电子探针微分析（EPMA）和x射线衍射（XRD）研究了Al-Si-Er三元体系的相平衡。根据实验结果和文献报道，对Al-Si-Er三元体系的热力学参数进行了优化。计算了600℃时的等温截面和沿Al70Si30-Al70Er30 （at）的垂直截面。%)与实验数据一致，表明热力学描述的可靠性。该工作为开发高性能稀土Al-Si-Er合金提供了必要的基础数据。

{"title":"Experimental investigation and thermodynamic description of binary Er-Si and ternary Al-Si-Er systems","authors":"Jin Tao , Rui Zhang , Yuhan Wang , Zewei Chen , Shitao Zhang , Caimin Huang , Qianxin Long , Zhao Lu , Like Tao , Qingrong Yao , Jiang Wang","doi":"10.1016/j.calphad.2025.102839","DOIUrl":"10.1016/j.calphad.2025.102839","url":null,"abstract":"<div><div>In this study, thermodynamic optimization of the Er-Si binary system was performed using the CALPHAD method. The calculated phase diagram showed good consistency with existing experimental data. Furthermore, the phase equilibrium of the Al-Si-Er ternary system was investigated via electron probe microanalysis (EPMA) and X-ray diffraction (XRD), building on prior experimental data. Based on the experimental results obtained in this work and literature reports, the thermodynamic parameters of the Al-Si-Er ternary system were optimized. Both calculated isothermal cross section at 600 °C and the vertical cross section along Al<sub>70</sub>Si<sub>30</sub>-Al<sub>70</sub>Er<sub>30</sub> (at. %) in the ternary system are in agreement with experimental data, indicating reliability of the thermodynamic description. This work provides essential foundational data for the development of high-performance rare earth Al-Si-Er alloys.</div></div>","PeriodicalId":9436,"journal":{"name":"Calphad-computer Coupling of Phase Diagrams and Thermochemistry","volume":"90 ","pages":"Article 102839"},"PeriodicalIF":1.9,"publicationDate":"2025-06-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144243397","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Experimental determination and thermodynamic optimization of Co-Al-V ternary system Co-Al-V三元体系的实验测定及热力学优化

IF 1.9 3区材料科学 Q4 CHEMISTRY, PHYSICAL

Calphad-computer Coupling of Phase Diagrams and Thermochemistry

Pub Date : 2025-06-01 DOI: 10.1016/j.calphad.2025.102837

Xinming Wang , Ying Ran , Zheng Peng , Guangjing Liao , Siqi Wang , Xuemei Ouyang , Yan Liu , Min Zhou , Fucheng Yin , Jingxian Hu

Novel Co-based superalloys, which possess superior high-temperature performance and oxidation resistance, have been extensively employed in high-temperature applications. Studying the phase relationships of Co-based alloys is crucial for their practical applications. The phase relationships in the isothermal section of the Co-Al-V ternary system at 1373 K (1100 °C) were experimentally determined by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD). Nine three-phase regions were experimentally confirmed. On the basis of the previous data and the present experimental results, thermodynamic optimization of the Co-Al-V ternary system was conducted via the CALPHAD method. The calculated results are in good agreement with the experimental results, and a set of reasonable and self-consistent thermodynamic parameters has been obtained. These results provide a basis for the design of Co-based alloys and enrich the database of Co-based alloys.

新型钴基高温合金具有优异的高温性能和抗氧化性能，在高温应用中得到了广泛的应用。研究钴基合金的相关系对其实际应用具有重要意义。采用扫描电子显微镜（SEM）、能谱仪（EDS）和x射线衍射仪（XRD）对1373 K（1100℃）温度下Co-Al-V三元体系等温截面的相关系进行了实验研究。实验证实了9个三相区。在前人数据和本实验结果的基础上，利用CALPHAD方法对Co-Al-V三元体系进行热力学优化。计算结果与实验结果吻合较好，得到了一组合理且自洽的热力学参数。这些结果为钴基合金的设计提供了依据，并丰富了钴基合金的数据库。

{"title":"Experimental determination and thermodynamic optimization of Co-Al-V ternary system","authors":"Xinming Wang , Ying Ran , Zheng Peng , Guangjing Liao , Siqi Wang , Xuemei Ouyang , Yan Liu , Min Zhou , Fucheng Yin , Jingxian Hu","doi":"10.1016/j.calphad.2025.102837","DOIUrl":"10.1016/j.calphad.2025.102837","url":null,"abstract":"<div><div>Novel Co-based superalloys, which possess superior high-temperature performance and oxidation resistance, have been extensively employed in high-temperature applications. Studying the phase relationships of Co-based alloys is crucial for their practical applications. The phase relationships in the isothermal section of the Co-Al-V ternary system at 1373 K (1100 °C) were experimentally determined by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD). Nine three-phase regions were experimentally confirmed. On the basis of the previous data and the present experimental results, thermodynamic optimization of the Co-Al-V ternary system was conducted via the CALPHAD method. The calculated results are in good agreement with the experimental results, and a set of reasonable and self-consistent thermodynamic parameters has been obtained. These results provide a basis for the design of Co-based alloys and enrich the database of Co-based alloys.</div></div>","PeriodicalId":9436,"journal":{"name":"Calphad-computer Coupling of Phase Diagrams and Thermochemistry","volume":"89 ","pages":"Article 102837"},"PeriodicalIF":1.9,"publicationDate":"2025-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144178116","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0