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

{"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":"2025-08-27","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":"Multi-objective optimization design of Al-Si alloys based on machine learning","authors":"Yunxuan Zhou ,&nbsp;Zihao Wang ,&nbsp;Wenhui Tao ,&nbsp;Yongkang Sun ,&nbsp;Junjie Wu ,&nbsp;Gang Wang ,&nbsp;Yu Xiu ,&nbsp;Huiyu Ji ,&nbsp;Yulin Liu ,&nbsp;Anping Dong ,&nbsp;Jie Wang ,&nbsp;Jun Wang ,&nbsp;Mengmeng Wang ,&nbsp;Qi Liu","doi":"10.1016/j.calphad.2025.102870","DOIUrl":"10.1016/j.calphad.2025.102870","url":null,"abstract":"<div><div>This study proposes a systematic inverse-design methodology for aluminum alloys, integrating machine learning (ML) with multi-objective optimization. Based on an industrial dataset comprising 3790 alloy records, a database was constructed, incorporating the mass fractions of 14 elements along with 160 weighted atomic descriptors. Forward feature selection identified optimal descriptor subsets-19 features for Brinell hardness(HB) and 14 for electrical conductivity(EC). A comparative assessment of several regression algorithms identified Extreme Gradient Boosting (XGBoost) as the most accurate predictor. The optimized XGBoost models were coupled with the expected-improvement (EI) criterion to construct a multi-objective expected-improvement (MOEI) function, which was subsequently maximized using particle swarm optimization (PSO). This iterative procedure converged on an as-cast alloy composition of Al-5.86Si-1.93Cu-0.56Mn-0.65Mg-0.28Cr-1.67Ni-1.36Zn-0.10Ti-0.92Fe-0.049Sr (wt%), striking an optimal balance between HB and EC. CALPHAD-based thermodynamic calculations and microstructural validation confirmed that the alloy achieves 96.1 HB and 24.4 % IACS. Experimental measurements deviated by less than 3.5 HB and 2.2 % IACS from the predictions, demonstrating that the inverse design workflow can reproduce target properties within experimental uncertainty.</div></div>","PeriodicalId":9436,"journal":{"name":"Calphad-computer Coupling of Phase Diagrams and Thermochemistry","volume":"90 ","pages":"Article 102870"},"PeriodicalIF":1.9,"publicationDate":"2025-08-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144893462","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":"Phase equilibria, phase structure and phase transition of Y-Fe-B alloys: Experimental investigation and thermodynamic calculation","authors":"Weifeng Cheng ,&nbsp;Jiang Wang ,&nbsp;Qingrong Yao ,&nbsp;Qing Chen ,&nbsp;Guanghui Rao ,&nbsp;Huaiying Zhou","doi":"10.1016/j.calphad.2025.102866","DOIUrl":"10.1016/j.calphad.2025.102866","url":null,"abstract":"<div><div>The phase equilibria of the Y-Fe-B ternary system were investigated using scanning electron microscopy coupled with energy dispersive spectroscopy (SEM-EDS) and X-ray diffraction (XRD). Six ternary intermetallic compounds were identified through SEM-EDS analysis and XRD Rietveld refinements: Y₂Fe₁₄B (Nd₂Fe₁₄B-type structure and space group <em>P</em>4_<em>2</em><em>/mnm</em>), YFe₄B₄ (Nd_1+ϵFe₄B₄-type structure and space group <em>Pccn</em>), YFe₂B₂ (CeAl₂Ga₂-type structure and space group <em>I</em><em>4</em><em>/mmm</em>), YFeB₄ (YCrB₄-type structure and space group <em>Pbam</em>), Y₅Fe₂B₆ (Pr₅Co₂B₆-type structure and space group <em>R-3m</em>) and Y₃FeB₇ (Y₃ReB₇-type structure and space group <em>Cmcm</em>). The solidification microstructure, phase compositions and phase transitions of Y_<em>x</em>Fe_{94-<em>x</em>}B₆ and Y_11.7Fe_{88.3-<em>x</em>}B_<em>x</em> as-cast alloys were examined using SEM-EDS and differential scanning calorimetry (DSC). Furthermore, by integrating the previous calculations of the Y-Fe and Fe-B binary systems with the results determined in this study and reported in the literature, thermodynamic calculation of the Y-Fe-B ternary system was conducted by means of the CALPHAD method, based on the present optimization of the Y-B binary system. The calculated phase diagrams and thermodynamic properties of the Y-B binary system are in good agreement with the reported results, while the calculated vertical and isothermal sections of the Y-Fe-B ternary system are consistent with the experimental data. Finally, the available thermodynamic parameters for the Y-Fe-B ternary system were obtained, providing a robust foundation to develop a thermodynamic database of magnetic RE-Fe-B-based alloys.</div></div>","PeriodicalId":9436,"journal":{"name":"Calphad-computer Coupling of Phase Diagrams and Thermochemistry","volume":"90 ","pages":"Article 102866"},"PeriodicalIF":1.9,"publicationDate":"2025-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144889780","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":"Experiment investigation and thermodynamic assessment of the ternary Ti-Al-Hf system","authors":"Guangcheng Xiao,&nbsp;Kaige Wang,&nbsp;Lideng Ye,&nbsp;Yueyan Tian,&nbsp;Jifeng Yang,&nbsp;Ligang Zhang,&nbsp;Libin Liu","doi":"10.1016/j.calphad.2025.102865","DOIUrl":"10.1016/j.calphad.2025.102865","url":null,"abstract":"<div><div>Based on experimental data measured by scanning electron microscope (SEM), X-ray diffraction (XRD) and electron probe microanalysis (EPMA), isothermal sections of Ti-Al-Hf at 900 °C and 1100 °C were established. A total of four three-phase regions and eight two-phase regions were found at the two temperatures, and a ternary compound τ was also found. The maximum solubility of Ti₂Al₅ for Hf at 900 °C was obtained, and the maximum solubility of binary compounds TiAl, TiAl₂, HfAl₂, Hf₂Al for the third element and Al, Hf, Ti in the τ phase was also measured. Based on the experimental data, the thermodynamic evaluation of the Ti-Al-Hf system was carried out using the CALPHAD(CALculation of PHAse Diagrams) method for two isothermal sections. The liquid phase, Bcc phase and Hcp phase were modeled using the substitutional solution model, and the ternary phase τ was treated as a stoichiometric compound. Its thermodynamic model was defined as (Hf)₂(Al)₂(Ti)₁. The final calculation results were in good agreement with the experimental results, including phase equilibrium and alloy composition.</div></div>","PeriodicalId":9436,"journal":{"name":"Calphad-computer Coupling of Phase Diagrams and Thermochemistry","volume":"90 ","pages":"Article 102865"},"PeriodicalIF":1.9,"publicationDate":"2025-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144828272","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":"2025-08-05","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}

{"title":"Thermodynamic investigation on ion structure of LiF-PrF3-Pr6O11 melt","authors":"Shumei Chen ,&nbsp;Xukun Peng ,&nbsp;Chunfa Liao ,&nbsp;Xinyu Wu ,&nbsp;Xu Wang ,&nbsp;Liqing Li ,&nbsp;Jinwanxiang Liu ,&nbsp;Yunfen Jiao","doi":"10.1016/j.calphad.2025.102863","DOIUrl":"10.1016/j.calphad.2025.102863","url":null,"abstract":"<div><div>The ionic behavior in the LiF-PrF₃-Pr₆O₁₁ melt system is of critical importance for the praseodymium reduction process. This study investigates the effects of the LiF/PrF₃ molar ratio (CR, <em>n</em>(LiF)/<em>n</em>(PrF₃)) and temperature on the ionic species and their concentrations in melt through quantum chemical calculations and thermodynamic analysis. The results indicate that in the LiF-PrF₃ melt, the dominant anions are [PrF₄]^-, [PrF₆]^3-, [PrF₇]^4-, [Pr₂F₇]^- and F⁻. As the CR increases, the melt tends to form [PrF_x]^3−x anions with higher fluoride coordination numbers. With rising temperature, the complex ions in the melt transform into simpler ionic species. Upon dissolving of Pr₆O₁₁ in the LiF-PrF₃ melt, the predominant anionic species formed are [PrOF₆]^5-, [Pr₂OF₅]^-, [Pr₂OF₈]^4-, [Pr₂OF₉]^5- and [Pr₂OF₁₀]^6-. An increase in CR promotes the transformation of [Pr₂OF_x]^4−x anions into structures with higher fluoride coordination numbers. Simultaneously, the content of [PrOF₆]^5- anions increases progressively, and when the CR exceeds 3, [PrOF₆]^5- becomes the dominant anionic species in the melt. Increasing the melt temperature inhibits the coordination reactions of [Pr₂OF_x]^4−x anions and accelerates their dissociation into [PrOF_x]^1−x anions.</div></div>","PeriodicalId":9436,"journal":{"name":"Calphad-computer Coupling of Phase Diagrams and Thermochemistry","volume":"90 ","pages":"Article 102863"},"PeriodicalIF":1.9,"publicationDate":"2025-07-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144738206","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":"2025-07-28","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":"Phase diagram and thermodynamic modeling of the Sb-O system","authors":"Shu Li ,&nbsp;Wenjie Wei ,&nbsp;Boya Zhang ,&nbsp;Zhanmin Cao","doi":"10.1016/j.calphad.2025.102860","DOIUrl":"10.1016/j.calphad.2025.102860","url":null,"abstract":"<div><div>A comprehensive review and evaluation of the phase equilibrium and thermodynamic properties of the Sb-O system across its entire compositional range was provided. Controversial issues were addressed through additional experimental studies, including the transition temperatures between the α and β phases of Sb₂O₃, the eutectic temperature of β-Sb₂O₃ and α-Sb₂O₄ to liquid, and the decomposition products of Sb₆O₁₃. Using the CALPHAD method, the liquid phase and three stable antimony oxides (Sb₂O₃, Sb₂O₄, and Sb₆O₁₃) were modeled. The liquid phase, from metallic liquid to oxide melt, is described by a modified Quasichemical model that accounts for the strong short-range order in the oxide liquid at the Sb₂O₃ composition. The final established Sb-O phase diagram at 1 atm, which can accurately reproduce all available thermodynamic and phase equilibrium data, is presented.</div></div>","PeriodicalId":9436,"journal":{"name":"Calphad-computer Coupling of Phase Diagrams and Thermochemistry","volume":"90 ","pages":"Article 102860"},"PeriodicalIF":1.9,"publicationDate":"2025-07-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144702609","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":"2025-07-23","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":"Thermodynamic modeling of the Au-Sn-X (X=Bi, Zn, Ni) ternary systems","authors":"M. Li,&nbsp;M.H. Rong,&nbsp;Y. Wu,&nbsp;P.F. Tan,&nbsp;J. Wang","doi":"10.1016/j.calphad.2025.102859","DOIUrl":"10.1016/j.calphad.2025.102859","url":null,"abstract":"<div><div>The phase equilibria and thermodynamic properties of Au-Sn-based alloys are of great significance for designing Au-based alloys as lead-free solders to replace high-lead solders. In this work, based on the experimental data reported in the literature, thermodynamic parameters of AuSn₂ and AuSn₄ in the Au-Sn binary system were modified. The calculated phase diagram and thermodynamic properties of the Au-Sn binary system are in good agreement with the experimental results. Furthermore, by combining the updated calculations of the Au-Sn binary system in this work with the previous assessments of the Au-Bi, Au-Zn, Au-Ni, Sn-Bi, Sn-Zn and Sn-Ni binary systems, thermodynamic modeling of the Au-Sn-X (X = Bi, Zn, Ni) ternary systems was conducted using the CALPHAD method. The liquidus projections, isothermal sections and vertical sections of the Au-Sn-X (X = Bi, Zn, Ni) ternary systems were calculated, which are in good agreement with the reported experimental data. The reasonable thermodynamic parameters of the Au-Sn-X (X = Bi, Zn, Ni) ternary systems were obtained in this work, which would provide a good foundation for further establishing a compatible thermodynamic database of multi-component Au-Sn-based alloy systems to design novel lead-free solders.</div></div>","PeriodicalId":9436,"journal":{"name":"Calphad-computer Coupling of Phase Diagrams and Thermochemistry","volume":"90 ","pages":"Article 102859"},"PeriodicalIF":1.9,"publicationDate":"2025-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144680185","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}