Calphad-computer Coupling of Phase Diagrams and Thermochemistry最新文献

{"title":"Phase equilibria and thermodynamic assessment of the Co–Cr binary system","authors":"Kazushige Ioroi,&nbsp;Haruhi Kumeta,&nbsp;Xiao Xu,&nbsp;Ryosuke Kainuma,&nbsp;Toshihiro Omori","doi":"10.1016/j.calphad.2025.102853","DOIUrl":"10.1016/j.calphad.2025.102853","url":null,"abstract":"<div><div>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.</div></div>","PeriodicalId":9436,"journal":{"name":"Calphad-computer Coupling of Phase Diagrams and Thermochemistry","volume":"90 ","pages":"Article 102853"},"PeriodicalIF":1.9,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144570977","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}

{"title":"Experimental study and thermodynamic assessment of the MgSO4-CaSO4 system","authors":"Amedeo Morsa ,&nbsp;Elena Yazhenskikh ,&nbsp;Mirko Ziegner ,&nbsp;Egbert Wessel ,&nbsp;Rhys Dominic Jacob ,&nbsp;Michael Müller ,&nbsp;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 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.</div></div>","PeriodicalId":9436,"journal":{"name":"Calphad-computer Coupling of Phase Diagrams and Thermochemistry","volume":"90 ","pages":"Article 102855"},"PeriodicalIF":1.9,"publicationDate":"2025-09-01","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}

{"title":"XTDB, an XML based format for Calphad databases","authors":"Bo Sundman ,&nbsp;Fabio Miani ,&nbsp;Axel van de Walle ,&nbsp;Bengt Hallstedt ,&nbsp;Ursula R. Kattner ,&nbsp;Florian Tang ,&nbsp;Taichi Abe ,&nbsp;Reza Naraghi ,&nbsp;Erwin Povoden-Karadeniz ,&nbsp;Aurelie Jacob ,&nbsp;Shuanglin Chen ,&nbsp;Richard Otis ,&nbsp;Kazuhisa Shobu ,&nbsp;Malin Selleby ,&nbsp;Alexander Pisch","doi":"10.1016/j.calphad.2025.102849","DOIUrl":"10.1016/j.calphad.2025.102849","url":null,"abstract":"<div><div>The calculation of phase diagram (Calphad) method uses models that depend on assessed parameters to describe the thermodynamic properties of materials. These model parameters are assessed by researchers and students using experimental and theoretical data on binary and ternary systems that can be merged to multicomponent databases and used to calculate properties and simulate processes for a wide range of materials.</div><div>There are several different software using the Calphad method for calculations and they may use slightly different models and database formats. This paper will provide a short background on the current state of database development and proposes a new format based on the eXtensive Markup Language (XML) as a unified database format. This change is particularly important as several new models for the pure elements are currently being introduced in the Calphad databases.</div></div>","PeriodicalId":9436,"journal":{"name":"Calphad-computer Coupling of Phase Diagrams and Thermochemistry","volume":"90 ","pages":"Article 102849"},"PeriodicalIF":1.9,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144687100","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}

{"title":"Development of oxide melt solution calorimetry for transition metal diborides","authors":"Stuart C. Ness ,&nbsp;Tucker Moore ,&nbsp;Steve Kilczewski ,&nbsp;Kristopher Behler ,&nbsp;Matthew Dunstan ,&nbsp;Scott J. McCormack","doi":"10.1016/j.calphad.2025.102867","DOIUrl":"10.1016/j.calphad.2025.102867","url":null,"abstract":"<div><div>Oxide-Melt Solution Calorimetry (OMSC) has been used to investigate standard enthalpies of formation in transition metal diborides, a first for the technique. Formation enthalpies for the Group IV and Group V transition metal diborides have been measured (TiB₂: Δ_fH^⦵ = −280 ± 11 kJ/mol, ZrB₂: Δ_fH^⦵ = −328 ± 10 kJ/mol, NbB₂: Δ_fH^⦵ = −245 ± 12 kJ/mol, HfB₂: Δ_fH^⦵ = −336 ± 11 kJ/mol, TaB₂: Δ_fH^⦵ = −195 ± 25 kJ/mol) and compared with good agreement to literature values. Multiple thermochemical pathway confirmations are reported. This data is required for the development of robust diboride phase diagrams for ultra-high temperature applications.</div></div>","PeriodicalId":9436,"journal":{"name":"Calphad-computer Coupling of Phase Diagrams and Thermochemistry","volume":"90 ","pages":"Article 102867"},"PeriodicalIF":1.9,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144904505","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}

{"title":"Crystal structure and thermodynamic properties of post-spinel-type CaV2O4 at high temperatures (298.15–1373 K)","authors":"Dapeng Zhong ,&nbsp;Jie Yu ,&nbsp;Xin Jin ,&nbsp;Guishang Pei ,&nbsp;Wenhao Yu ,&nbsp;Qingyun Huang ,&nbsp;Changcai Zhou ,&nbsp;Xuewei Lv ,&nbsp;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 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 <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 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 <em>C</em>_<em>p</em> = 165.7748 + 3.2353 × 10⁻²<em>T</em> - 2.64268 × 10⁶<em>T</em>⁻² (J·mol⁻¹·K⁻¹). Additional thermodynamic data for CaV₂O₄ were derived using the <em>C</em>_<em>p,m</em> 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":"2025-09-01","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}

{"title":"Thermodynamic assessment of the quaternary Cr–Fe–H–Zr system","authors":"Tuan-Minh Vu ,&nbsp;Caroline Toffolon-Masclet ,&nbsp;Jean-Marc Joubert","doi":"10.1016/j.calphad.2025.102861","DOIUrl":"10.1016/j.calphad.2025.102861","url":null,"abstract":"<div><div>The thermodynamic assessments of the two ternary Cr–H–Zr and Fe–H–Zr systems are carried out using the CALPHAD approach. The hydrogenation properties of all the intermetallic compounds of these two systems are assessed. The formation enthalpies of the <em>E</em>1<em>a</em>-Zr₃FeH₇ and <span><math><mrow><mi>C</mi><mn>16</mn></mrow></math></span>-Zr₂FeH₅ hydrides are evaluated by DFT calculations. The Pressure-Composition-Temperature diagrams of the Zr(Cr_xFe_1-x)₂ (0.4 &lt; x &lt; 1.1) of the <em>C</em>14 Laves phase are optimized. The calculations and optimization are carried out under para-equilibrium conditions in which the complete system was treated like a pseudo-binary system.</div></div>","PeriodicalId":9436,"journal":{"name":"Calphad-computer Coupling of Phase Diagrams and Thermochemistry","volume":"90 ","pages":"Article 102861"},"PeriodicalIF":1.9,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144714307","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}

{"title":"Modified polyhedron model for predicting standard enthalpy of formation and entropy of mixed oxides","authors":"Jesus A. Arias Hernandez,&nbsp;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":"2025-09-01","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}

{"title":"Experimental investigation and thermodynamic calculation of the Si-Zr-Ag ternary system","authors":"Zhaohui Long ,&nbsp;Shan Yang ,&nbsp;Lunjun Gong ,&nbsp;Hong Bo ,&nbsp;Cong Li ,&nbsp;Haohan She ,&nbsp;Fucheng Yin","doi":"10.1016/j.calphad.2025.102858","DOIUrl":"10.1016/j.calphad.2025.102858","url":null,"abstract":"<div><div>The phase equilibria in the Si-Zr-Ag ternary system at 650 °C and 750 °C were investigated using the equilibrated alloy approach. Scanning electron microscopy equipped with energy dispersive spectroscopy (SEM-EDS) and X-ray diffraction (XRD) have been applied to characterize the phase constitution of the alloys. At 650 °C and 750 °C, Six three-phase regions have been detected. The ternary compounds τ₁ and τ₂ were found in the two isothermal sections. τ₁ was identified as a body-centered cubic structure by transmission electron microscopy (TEM) analysis, with the lattice parameters determined as a = 0.3738 nm, α = β = γ = 90°. Based on the experimental results on phase equilibrium, the CALPHAD approach was used to develop the thermodynamic description of the Si-Zr-Ag ternary system. The calculated isothermal sections show excellent agreement with the experimental ones. Then, the liquidus projection was predicted with the obtained thermodynamic parameters.</div></div>","PeriodicalId":9436,"journal":{"name":"Calphad-computer Coupling of Phase Diagrams and Thermochemistry","volume":"90 ","pages":"Article 102858"},"PeriodicalIF":1.9,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144611619","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}

{"title":"Experimental investigation and thermodynamic re-assessment of the Fe-Co-W phase diagram","authors":"C.B. Li,&nbsp;Z.Q. Wang,&nbsp;L.D. Ye,&nbsp;J.F. Wu,&nbsp;K.G. Wang,&nbsp;L.B. Liu,&nbsp;L.G. Zhang","doi":"10.1016/j.calphad.2025.102856","DOIUrl":"10.1016/j.calphad.2025.102856","url":null,"abstract":"<div><div>This work determined the isothermal sections of the Fe-Co-W system at 1273 K and 1073 K using the equilibrated alloy method. The solubility ranges of the μ-(Fe,Co)₇W₆, λ-Fe₂W, and Co₃W compounds in the Fe-Co-W ternary system were identified. No new ternary compounds were observed. Based on existing experimental data, a thermodynamic optimization of the Fe-Co-W ternary system and related binary systems was conducted. The (A)₄(A,B)₂(A,B)₁(A,B)₆ lattice model was employed to describe the μ-(Co,Fe)₇W₆ compound, and the thermodynamic database of the Co-W binary system was re-assessed. A new thermodynamic database for the Fe-Co-W system was established, demonstrating high consistency with the experimental data.</div></div>","PeriodicalId":9436,"journal":{"name":"Calphad-computer Coupling of Phase Diagrams and Thermochemistry","volume":"90 ","pages":"Article 102856"},"PeriodicalIF":1.9,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144655015","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}

{"title":"Estimation of component activities of ternary liquid alloys by partial radial distribution functions of binary liquid alloys obtained from ab initio molecular dynamics simulation","authors":"Jiulong Hang ,&nbsp;Xiumin Chen ,&nbsp;Yi Lu ,&nbsp;Tianao Zhang ,&nbsp;Dongping Tao","doi":"10.1016/j.calphad.2025.102864","DOIUrl":"10.1016/j.calphad.2025.102864","url":null,"abstract":"<div><div>The key binary parameters of solution thermodynamic models are usually determined by the measured activity data of binary solutions, and then thermodynamic properties of the relevant ternary or even multi-component solutions can be predicted. However, in the absence of experimental data, it is currently still difficult and challenging to determine these parameters reliably. In this paper, the partial radial distribution functions (PRDF) of 9 binary liquid alloys are obtained by ab initio molecular dynamics (AIMD) simulation. Based on the statistical average principle of physical quantities, a simplified expression of the average pair potential energy (APPE) of fluid molecules with PRDF is correctly derived. Then it can be correlated with the binary model parameters of the Regular Solution Model (RSM), the Wilson equation, the Non-Random Two-Liquid equation (NRTL), and the Molecular Interaction Volume Model (MIVM), and their values are determined. Based on this, the component activities of the 9 binary as well as the 4 ternary liquid alloys systems were estimated and compared with those obtained by the fitting parameter method and the Miedema model. The results show that for the 9 binary alloys systems, when the symmetric PRDF method is used, the standard deviation (SD) and the average relative deviation (ARD) of Wilson equation are 0.073 and 25 % respectively; when the asymmetric PRDF method is used, the SD and ARD of RSM are 0.067 and 15 %; when the fitting parameter method is used, the SD and ARD of Wilson equation are 0.016 and 4 %; when the Miedema model is used, its SD and ARD are 0.090 and 35 %, respectively. For the 4 ternary alloys systems, when the symmetric method is used, the SD and ARD of Wilson equation are 0.068 and 16 % respectively; when the asymmetric method is used, the SD and ARD of RSM are 0.061 and 14 %; when the fitting parameter method is used, the SD and ARD of MIVM are 0.028 and 6 %; when the combined method of the Miedema model and the Toop model is used, its SD and ARD are 0.052 and 13 %, respectively. This indicates that the simplified expression of APPE related with PRDF can be used to obtain the key binary parameters of some thermodynamic models for estimating all component activities of ternary or even multi-component liquid alloys in the absence of activity experimental data of binary liquid alloys.</div></div>","PeriodicalId":9436,"journal":{"name":"Calphad-computer Coupling of Phase Diagrams and Thermochemistry","volume":"90 ","pages":"Article 102864"},"PeriodicalIF":1.9,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144770603","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}