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

{"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":"2025-04-17","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":"Interdiffusion coefficients and atomic mobilities in the bcc phase of the Ti-Fe-Mo system","authors":"Hongyu Zhang ,&nbsp;Zhe Yuan ,&nbsp;Fali Liu ,&nbsp;Weimin Bai ,&nbsp;Yuan Yuan ,&nbsp;Maohua Rong ,&nbsp;Jiang Wang ,&nbsp;Ligang Zhang ,&nbsp;Libin Liu","doi":"10.1016/j.calphad.2025.102829","DOIUrl":"10.1016/j.calphad.2025.102829","url":null,"abstract":"<div><div>Establishing the atomic mobility database for the Ti-Fe-Mo system is essential for analyzing and simulating diffusion-controlled processes in novel low-cost biomedical titanium alloys. In this study, twelve sets of diffusion couples were prepared at annealing temperatures of 1273 K, 1323 K, and 1373 K, with annealing time of 24 h, 10 h, and 6 h, respectively. The compositional distance profiles at the diffusion couple interfaces were measured using an Electro Probe Micro-Analysis (EPMA). Numerical inverse methods were applied to calculate diffusion coefficients in a high-throughput method, complemented by the Matano-Kirkaldy approach to determine diffusion coefficients at diffusion couple intersections. The results from both methods demonstrated strong agreement. Based on accurate thermodynamic descriptions and diffusion coefficients, the kinetic parameters of the Ti-Fe-Mo sub-binary systems were re-evaluated. Using HitDIC software in conjunction with compositional distance profiles, the atomic mobility database for this system was ultimately established. Additionally, the frequency factor and activation energy, vary with composition, can be derived using the Arrhenius equation.</div></div>","PeriodicalId":9436,"journal":{"name":"Calphad-computer Coupling of Phase Diagrams and Thermochemistry","volume":"89 ","pages":"Article 102829"},"PeriodicalIF":1.9,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143829649","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":"2025-04-06","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":"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":"2025-04-05","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":"2025-03-26","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":"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":"2025-03-24","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}

{"title":"Phase transformation temperatures of Sn-Ag-Bi-Cu quaternary system","authors":"Sinn-wen Chen ,&nbsp;Yi-An Lee ,&nbsp;Cheng-Hsi Ho ,&nbsp;Jun Zhu ,&nbsp;Hsin-Chieh Huang ,&nbsp;Te-Wei Lin ,&nbsp;Chuan Zhang","doi":"10.1016/j.calphad.2025.102822","DOIUrl":"10.1016/j.calphad.2025.102822","url":null,"abstract":"<div><div>Sn-Ag-Bi-Cu and its constituent systems are important material systems, especially for electronic soldering. Although these alloys have attracted significant interest for industrial applications and have been the subject of various Calphad studies, it is surprising to find that there are significant deviations observed between the calculated and experimentally determined results regarding the phase transformation temperatures. To address this issue, Sn-Ag, Sn-Bi, Sn-Cu, Sn-Ag-Bi, Sn-Ag-Cu, Sn-Bi-Cu and Sn-Ag-Bi-Cu alloys on the Sn-rich side are prepared. Simultaneous thermal analysis and holding-quenching experimental measurements are conducted to determine their liquidus temperatures and invariant reaction temperatures. The experimentally determined results are then compared with the Calphad-calculated results and utilized to improve the thermodynamic parameters in the Calphad models. The calculated results with the revised databases are in good agreement with the experimental measurements.</div></div>","PeriodicalId":9436,"journal":{"name":"Calphad-computer Coupling of Phase Diagrams and Thermochemistry","volume":"89 ","pages":"Article 102822"},"PeriodicalIF":1.9,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143679059","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":"Multicomponent cluster variation method: Application to high entropy alloys","authors":"Vikas Jindal,&nbsp;Shrikant Lele","doi":"10.1016/j.calphad.2025.102825","DOIUrl":"10.1016/j.calphad.2025.102825","url":null,"abstract":"<div><div>Cluster expansion, a method commonly used in computational thermodynamics, expresses the configurational properties of alloys as a sum of products of correlation functions and cluster expansion coefficients (CECs). The CECs are defined using a basis in configurational space that is not unique and changes during the extension of the generalized Ising model from binary alloys to multicomponent alloys. In contrast to the CALPHAD formulation, this change severely restricts the development and use of CEC-based databases. To address this, a new framework is introduced where lower-order CECs remain unchanged in higher-order systems. This is achieved by choosing configurational variables (and corresponding CECs) which are not dependent on a particular choice of basis as correlation functions (CFs). Such a set is provided by cluster variables (CVs), which represent the fraction of cluster configurations of various types. A carefully selected subset of independent CVs is chosen as CFs. Completeness of the basis is demonstrated by deriving expressions for all remaining CVs in terms of these new CFs for disordered bcc, fcc, and hcp structures. A set of CECs for the bcc phase of the Nb-Ti-V-Zr system has been developed using this new formulation. Optimized CECs of all binary and ternary subsystems of the Nb-Ti-V-Zr have been used in its construction. This is a crucial step towards creating a self-consistent computational thermodynamics database. The utility of the Nb-Ti-V-Zr database was demonstrated through calculations of thermodynamic quantities, SRO parameters, and phase diagrams. Additionally, a procedure is outlined to transform existing CALPHAD databases to CEC-based databases under certain assumptions.</div></div>","PeriodicalId":9436,"journal":{"name":"Calphad-computer Coupling of Phase Diagrams and Thermochemistry","volume":"89 ","pages":"Article 102825"},"PeriodicalIF":1.9,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143679058","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 B-Co-Ti ternary system","authors":"Xuemei Ouyang ,&nbsp;Quan wang ,&nbsp;Fucheng Yin ,&nbsp;Yuling Shi ,&nbsp;Jingxian Hu","doi":"10.1016/j.calphad.2025.102819","DOIUrl":"10.1016/j.calphad.2025.102819","url":null,"abstract":"<div><div>The phase equilibrium of the B-Co-Ti ternary system is important for the preparation and development of Co-containing TiB₂-based ceramics. To obtain the liquidus projection, 54 kinds of as-cast alloys were prepared via arc melting. The microstructures and solidification paths of the 54 kinds of alloys were analyzed by scanning electron microscopy, electron probe microanalysis, X-ray diffraction and differential scanning calorimetry. The results show that the proposed liquidus projection of the B-Co-Ti ternary system contains 15 primary precipitation regions: BCC, CoTi₂, CoTi, Co₂Ti, Co₃Ti, αCo, TiB, Ti₃B₄, TiB₂, (B), CoB, Co₂B, Co₃B, τ₁ and τ₂. Six E-type and nine U-type ternary invariant reactions are suggested on the basis of experimental data. The thermodynamic calculation of the B-Co-Ti ternary system was carried out, and a set of self-consistent thermodynamic parameters was obtained. The calculated liquidus projection and 800 °C isothermal sections are in good agreement with the experimental data.</div></div>","PeriodicalId":9436,"journal":{"name":"Calphad-computer Coupling of Phase Diagrams and Thermochemistry","volume":"89 ","pages":"Article 102819"},"PeriodicalIF":1.9,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143632063","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 sulfur and the nickel-sulfur systems","authors":"Wenhao Ma ,&nbsp;Julian Gebauer ,&nbsp;Andreas Klaus Czerny ,&nbsp;Maryam Rahimi Chegeni ,&nbsp;Isabella Gallino ,&nbsp;Ralf Busch ,&nbsp;Hans Jürgen Seifert","doi":"10.1016/j.calphad.2025.102821","DOIUrl":"10.1016/j.calphad.2025.102821","url":null,"abstract":"<div><div>The sulfur and the nickel-sulfur binary systems are important in many fields. In this work, the pure sulfur is remodeled within the framework of the third-generation database approach from 0 K to above the melting point. Likewise, a new thermodynamic dataset is developed for the nickel sulfur binary system. The new thermodynamic dataset provides a reliable description of all relevant intermetallic and non-stoichiometric phases. The supercooled liquid described using the two-state liquid model is considered more realistic. An assessment on the sulfur solubility in FCC nickel is also conducted in this work. The calculated phase diagram, thermodynamic and thermophysical data show good agreement with the literature.</div></div>","PeriodicalId":9436,"journal":{"name":"Calphad-computer Coupling of Phase Diagrams and Thermochemistry","volume":"89 ","pages":"Article 102821"},"PeriodicalIF":1.9,"publicationDate":"2025-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143632031","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}