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

{"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":"2025-09-01","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}

{"title":"Extension of the modified quasichemical model in the distinguishable-pair approximation to multicomponent solutions via an on-the-fly interpolation framework","authors":"Kun Wang ,&nbsp;Patrice Chartrand","doi":"10.1016/j.calphad.2025.102852","DOIUrl":"10.1016/j.calphad.2025.102852","url":null,"abstract":"<div><div>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.</div></div>","PeriodicalId":9436,"journal":{"name":"Calphad-computer Coupling of Phase Diagrams and Thermochemistry","volume":"90 ","pages":"Article 102852"},"PeriodicalIF":1.9,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144549246","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":"Investigation of diffusivities and mechanical properties in BCC Ti rich Ti-Zr-Ta system","authors":"Yuwei Ning ,&nbsp;Fali Liu ,&nbsp;Xiaoma Tao ,&nbsp;Guanglong Xu ,&nbsp;Hongmei Chen ,&nbsp;Yifang Ouyang ,&nbsp;Yong Du","doi":"10.1016/j.calphad.2025.102827","DOIUrl":"10.1016/j.calphad.2025.102827","url":null,"abstract":"<div><div>In this work, a combination of diffusion couple technique and nanoindentation were employed to investigate the diffusion behaviors and mechanical properties of Ti-Zr-Ta alloys annealed at 1373 K for 26 h. The experiments focused on Ti-rich body-centered cubic (BCC) Ti-Zr-Ta ternary alloys. Diffusion coefficients were determined using the Whittle-Green and generalized Hall methods, while nanoindentation was utilized to characterize Young's modulus and hardness of the alloys. The results indicate that the diffusion rate of Zr is considerably higher than that of Ta, and the diffusion rate of both elements exhibits a strong dependence on concentration. The mechanical testing results demonstrate a significant increase in the hardness and Young's modulus of the alloy as the Ta content increases. In contrast, the Zr content shows a relatively limited effect on hardness and Young's modulus. These results provide an essential reference for further optimization of the microstructure and mechanical properties of Ti-Zr-Ta alloys at elevated temperatures.</div></div>","PeriodicalId":9436,"journal":{"name":"Calphad-computer Coupling of Phase Diagrams and Thermochemistry","volume":"89 ","pages":""},"PeriodicalIF":1.9,"publicationDate":"2025-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143783489","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":"CALPHAD-guided suppression of detrimental Fe-containing phases in secondary aluminum alloys","authors":"Chuan Zhang ,&nbsp;Alan A. Luo ,&nbsp;Fan Zhang","doi":"10.1016/j.calphad.2025.102830","DOIUrl":"10.1016/j.calphad.2025.102830","url":null,"abstract":"<div><div>Recycling aluminum alloys provides significant economic and environmental advantages, yet the formation of Fe-containing intermetallic phases, particularly the brittle β-AlFeSi phase, in secondary (recycled) aluminum alloys presents challenges to their mechanical and corrosion properties. This study investigates the role of Cr and Mn additions in suppressing these detrimental phases in the Al-Si-Fe system based on CALPHAD modeling and experimental validation. The findings highlight the effectiveness of CALPHAD simulations in accurately predicting as-cast microstructures and sludge formation temperatures for the alloys examined in this study, as well as those reported in the literature. The addition of Cr and Mn promotes the stabilization of the α-Al₁₅M₃Si₂ phase and inhibits the formation of the detrimental β-AlFeSi phase. Furthermore, virtual experiments were carried out to identify optimal compositional and thermal conditions for efficient recycling. A model relating Fe content to optimal Cr and Mn additions for industrial recycling, expressed as <span><math><mrow><mi>w</mi><mrow><mo>(</mo><mrow><mi>F</mi><mi>e</mi></mrow><mo>)</mo></mrow><mo>=</mo><msqrt><mrow><mn>0.9</mn><mo>∗</mo><msup><mrow><mi>w</mi><mrow><mo>(</mo><mrow><mi>M</mi><mi>n</mi></mrow><mo>)</mo></mrow></mrow><mn>2</mn></msup><mo>+</mo><mn>0.4</mn><mo>∗</mo><msup><mrow><mi>w</mi><mrow><mo>(</mo><mrow><mi>C</mi><mi>r</mi></mrow><mo>)</mo></mrow></mrow><mn>2</mn></msup></mrow></msqrt><mo>+</mo><mn>0.4</mn></mrow></math></span> is proposed to guide compositional adjustments. This integrated approach, coupling experimental validation with thermodynamic modeling, highlights the effectiveness of CALPHAD in addressing the Fe impurity challenges and enhancing the sustainability of aluminum alloy recycling.</div></div>","PeriodicalId":9436,"journal":{"name":"Calphad-computer Coupling of Phase Diagrams and Thermochemistry","volume":"89 ","pages":"Article 102830"},"PeriodicalIF":1.9,"publicationDate":"2025-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143839096","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 determination and thermodynamic optimization of Co-Al-V ternary system","authors":"Xinming Wang ,&nbsp;Ying Ran ,&nbsp;Zheng Peng ,&nbsp;Guangjing Liao ,&nbsp;Siqi Wang ,&nbsp;Xuemei Ouyang ,&nbsp;Yan Liu ,&nbsp;Min Zhou ,&nbsp;Fucheng Yin ,&nbsp;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}

{"title":"Optimization of heat capacities of wurtzite phases as a single system and thermodynamic properties of nihonium nitride","authors":"V.P. Vassiliev ,&nbsp;C.M. Stanley","doi":"10.1016/j.calphad.2025.102824","DOIUrl":"10.1016/j.calphad.2025.102824","url":null,"abstract":"<div><div>In this work, two independent methods were used to describe the heat capacity of reference compounds with the wurtzite structure, as well as their isostructural analogs of fourth group elements in the solid state: 1) a semi-empirical method using a multiparameter function and 2) a method based on the density functional theory. In the first method, to describe a set of isostructural experimental data <em>C</em>_<em>p</em><em>(T)</em> of substances in the solid state, a description of each individual phase was carried out in the first approximation, and then, after finding a set of its fitting parameters <em>(X)</em>, a description of the entire set of data as an integral system, where the set of each individual fitting parameter was described by a polynomial equation of functions included in the multiparameter family with the best description of the set of all data. The parameters of unexplored substances were found by interpolation of the multiparameter function. The fitting parameters <em>(X)</em> are a function of the atomic number of the elements Si, Ge, Sn, Pb, and Fl or the half-sum of the atomic numbers of the binary phases A^IIIB^V: B, Al, Ga, Tl, and Nh with the element germanium having a characteristic point for the set of parameters <em>(X)</em> depending on the atomic number. For each substance, the parameters are found by minimizing the discrepancy between the theoretical dependence <em>C</em>_<em>p</em><em>(T)</em> and the corresponding experimental data. According to the fine structure constant (α = 1/137) (or Sommerfeld constant), there are no other elements in this group. Therefore, the limiting heat capacity of the wurtzite phases is at element 114 (¹¹⁴Fl) and has a value of <em>C</em>_<em>p</em> = 30.5 ± 0.3 J · mol-at⁻¹ · K⁻¹.</div><div>The second method allows us to describe the heat capacities (C_p) for these materials using a new first-principles method based on the density functional theory. This method, called the Beyond Quasi-Harmonic method, includes all anharmonic vibrations - volume changes and phonon-phonon interactions. Our calculated values for III-V compounds with wurtzite and sphalerite structures show good agreement between the two methods.</div><div>This work also presents optimized thermodynamic properties, Gibb's energy, enthalpy and entropy of formations, as well as standard entropy and melting point of III-V nitrides, including nihonium nitride.</div></div>","PeriodicalId":9436,"journal":{"name":"Calphad-computer Coupling of Phase Diagrams and Thermochemistry","volume":"89 ","pages":"Article 102824"},"PeriodicalIF":1.9,"publicationDate":"2025-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143776558","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 Mo–Os, W–Os and Mo–Os–W systems","authors":"Baogang Liu ,&nbsp;Yong Du ,&nbsp;Lei Huang ,&nbsp;Yafei Pan","doi":"10.1016/j.calphad.2025.102823","DOIUrl":"10.1016/j.calphad.2025.102823","url":null,"abstract":"<div><div>Based on critical evaluation of the literature data, the Mo–Os and W–Os binary systems have been reviewed and assessed by means of the CALPHAD technique. The substitutional solution models are adopted to describe the liquid, bcc (βMo, βW) and hcp (αOs) phases, and the compound energy models with two sublattices are to describe the σ and Mo₃Os phases. The phase equilibrium data of the Mo–Os and W–Os systems are well produced by the present modeling. Using the obtained thermodynamic parameters of the sub-binary systems, the thermodynamic description has been extended to the Mo–Os–W ternary system, covering the whole composition and temperature ranges. There is no ternary compound in this system. The σ phase forms a continuous solid solution crossing the phase diagram. A set of self-consistent thermodynamic parameters for the Mo–Os–W system is systematically optimized to describe to the bcc, σ and Mo₃Os phases. Comprehensive comparisons between the calculated and reported phase diagram information show that the reliable information is satisfactorily accounted for by the present modeling. The liquidus projection and reaction scheme of the Mo–Os–W system are also generated by using the present thermodynamic parameters.</div></div>","PeriodicalId":9436,"journal":{"name":"Calphad-computer Coupling of Phase Diagrams and Thermochemistry","volume":"89 ","pages":"Article 102823"},"PeriodicalIF":1.9,"publicationDate":"2025-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143704753","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":"High throughput determination of diffusion coefficients and hardness using diffusion couple technique of γ-phase Fe-Ni-Cu alloys at 1000 °C","authors":"Susanta Kumar Nayak,&nbsp;Kaustubh N. Kulkarni","doi":"10.1016/j.calphad.2025.102809","DOIUrl":"10.1016/j.calphad.2025.102809","url":null,"abstract":"<div><div>A high-throughput method was employed for γ-phase Fe-Ni-Cu alloy system. In this study solute and intrinsic diffusivities are determined from interdiffusion coefficients, alongside determining nano-indent hardness from diffusion couple experiments. This could be an important study to obtain various diffusivities and hardness-composition relationship with minimum experiments. Analysis of inter and intrinsic diffusion coefficients, along with thermodynamic factors, revealed significant diffusional interactions among the alloy elements. In addition, it has been shown that Cu is the slowest diffusing species, and the solute diffusivities alone cannot be used as criterion for determining the kinetics of alloying elements. The diffusion interactions in inter and intrinsic diffusion need not to be similar but interdiffusion coefficients are more convenient in practical uses. A high-throughput hardness-composition relations were developed, which illustrate the applicability of diffusion couples to enable high throughput determination of various properties as functions of compositions.</div></div>","PeriodicalId":9436,"journal":{"name":"Calphad-computer Coupling of Phase Diagrams and Thermochemistry","volume":"89 ","pages":"Article 102809"},"PeriodicalIF":1.9,"publicationDate":"2025-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143551038","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 Mg-Zn-Nd system and its application to solidification","authors":"Chengyang Ma ,&nbsp;Shao-Yang Wang ,&nbsp;Weisen Zheng ,&nbsp;Jingya Wang ,&nbsp;Huarui Cao ,&nbsp;Xiao-Gang Lu","doi":"10.1016/j.calphad.2025.102820","DOIUrl":"10.1016/j.calphad.2025.102820","url":null,"abstract":"<div><div>The excellent thermal conductivity and mechanical properties of Mg-Zn-Nd alloys are closely linked to the formation of intermetallic compounds and the solubility in the αMg matrix after their formation. However, recent experimental findings on new ternary compounds highlight gaps in the understanding of the phase equilibrium relationships, which complicates design of advanced Mg-Zn-Nd alloys. To address this, all the experimental phase equilibrium data available in the literature were critically evaluated. Thermodynamic modeling of the Mg-Zn-Nd system was performed based on the selected reliable experimental data and updated binary thermodynamic descriptions. The seven ternary compounds (τ1 to τ6 and (Mg,Zn)₁₂Nd) in the Mg-Zn-Nd system were modeled using compound energy formalism (CEF), particularly considering the consistency between their homogeneity range and crystallographic sublattices. The thermodynamic model parameters optimized in this study satisfactorily reproduced the isothermal sections, isoplethal sections, and liquidus projections. Combined with the Scheil–Gulliver model, the solidification behavior of Mg-Zn-Nd alloys was predicted. The predicted results were consistent with the experimental data, further demonstrating the reliability and practical applicability of the thermodynamic description developed in this study.</div></div>","PeriodicalId":9436,"journal":{"name":"Calphad-computer Coupling of Phase Diagrams and Thermochemistry","volume":"89 ","pages":"Article 102820"},"PeriodicalIF":1.9,"publicationDate":"2025-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143578983","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 determination and thermodynamic assessment of the Dy-Fe-B system","authors":"Wei Yang ,&nbsp;Yiwei Wang ,&nbsp;Shuhong Liu ,&nbsp;Peisheng Wang ,&nbsp;Wei Zhai","doi":"10.1016/j.calphad.2025.102826","DOIUrl":"10.1016/j.calphad.2025.102826","url":null,"abstract":"<div><div>The phase equilibria of the Fe-Dy-B system on the Fe-Dy side are crucial for the development of Nd-Dy-Fe-B permanent magnets. Alloys located on the Fe-Dy side were prepared and annealed at 1073 K and 1173 K for 60 days. The annealed samples were analyzed by electron probe microanalysis (EPMA) and X-ray diffraction (XRD). In this work, three ternary compounds τ₁, τ₃, and τ₄ were identified on the Fe-Dy side at 1073 K and 1173 K. The previously reported τ₂ phase was not observed in the present work. Nine three-phase regions were determined in the present study and the isothermal sections of the Dy-Fe-B system on the Dy-Fe side at 1073 K and 1173 K were constructed. Based on the experimental data, thermodynamic modeling of the system was performed using the CALculation of PHAse Diagrams (CALPHAD) method. The calculated results show good agreement with the experimental data.</div></div>","PeriodicalId":9436,"journal":{"name":"Calphad-computer Coupling of Phase Diagrams and Thermochemistry","volume":"89 ","pages":"Article 102826"},"PeriodicalIF":1.9,"publicationDate":"2025-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143679057","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}