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

{"title":"Effect of the excess entropy on the calculated activity interaction coefficient under the Miedema model and extrapolation method","authors":"Yan Wu ,&nbsp;Yang Lv ,&nbsp;Qiwen Lv ,&nbsp;Zhenlin Huang ,&nbsp;Tianhua Ju","doi":"10.1016/j.calphad.2024.102792","DOIUrl":"10.1016/j.calphad.2024.102792","url":null,"abstract":"<div><div>Using the Miedema model combined with an extrapolation model to calculate activity interaction coefficients between alloy components has proven to be a viable approach. However, the influence of the excess entropy term on the model's calculated values has received limited detailed examination. In this paper, we investigate how excess entropy affects the model's calculated values in various alloy solutions by incorporating the Tanaka excess entropy relation within the framework of the Miedema model coupled with the Unified Extrapolation Model (UEM). A comparison with experimental values reveals the following: (1) For systems containing gaseous elements: predictions align better with experimental data when excess entropy is not considered, except in cases involving oxygen and some non-metallic elements (C, B, N, O, S). (2) For systems with non-metallic elements (e.g., C, Si): including excess entropy significantly improves alignment with experimental values. (3) For metallic solute systems: the effect of excess entropy is minimal and can generally be disregarded.</div></div>","PeriodicalId":9436,"journal":{"name":"Calphad-computer Coupling of Phase Diagrams and Thermochemistry","volume":"88 ","pages":"Article 102792"},"PeriodicalIF":1.9,"publicationDate":"2024-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143181078","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 Fe–O–Zr, Cr–O–Zr and O–Sn–Zr ternary systems","authors":"Tuan-Minh Vu ,&nbsp;Paul Gokelaere ,&nbsp;Caroline Toffolon-Masclet ,&nbsp;Jean-Marc Joubert","doi":"10.1016/j.calphad.2024.102778","DOIUrl":"10.1016/j.calphad.2024.102778","url":null,"abstract":"<div><div>The Fe–O–Zr, Cr–O–Zr, and O–Sn–Zr ternary systems have been modeled using the CALPHAD (CALculation of PHAse Diagrams) method to develop comprehensive thermodynamic descriptions essential for applications in nuclear materials and corrosion science. Experimental data from the literature and Density Functional Theory (DFT) calculations were used within this work to determine accurate thermodynamic parameters for the phases involved. The binary O–Zr system, common to all three ternary systems, was reassessed using ionic models to accurately describe the non-stoichiometry of zirconium oxide phases, which is crucial for predicting phase equilibria and material properties. To validate and refine our thermodynamic models, we conducted experimental studies specifically on the Cr–O–Zr system, and the resulting data were incorporated into our assessment to enhance its reliability and accuracy.</div></div>","PeriodicalId":9436,"journal":{"name":"Calphad-computer Coupling of Phase Diagrams and Thermochemistry","volume":"88 ","pages":"Article 102778"},"PeriodicalIF":1.9,"publicationDate":"2024-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143181077","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":"The power of computational thermochemistry in high-temperature process design and optimization: Part 2 – Pyrometallurgical process modeling using FactFlow","authors":"Kyota Poëti ,&nbsp;Juan-Ricardo Castillo-Sánchez ,&nbsp;Ugo Mahue,&nbsp;Vincent Rioux-Frenette,&nbsp;Zineb Squalli-Houssaini,&nbsp;Kentaro Oishi,&nbsp;Jean-Philippe Harvey","doi":"10.1016/j.calphad.2024.102772","DOIUrl":"10.1016/j.calphad.2024.102772","url":null,"abstract":"<div><div>Computational thermochemistry is an essential tool when it comes to the design of new industrial pyrometallurgical processes. It also enables the optimization of existing processes by analyzing the effect of various operating conditions on key indicators such as the metal recovery, the product composition, the direct emissions and the process overall energy balance. The modeling of these complex processes requires the use of multiple streams and equilibrium reactors in order to perform a large series of thermodynamic calculations. It also needs to account for the kinetic limitations of key chemical reactions. Current thermochemical software restricts users to single equilibrium reactor calculations or necessitates advanced programming knowledge to build customized pyrometallurgical processes.</div><div>In this work, we introduce a new process simulation interface called FactFlow, a multi-stream/multi-unit process simulator embedded in the FactSage package. It offers an intuitive and efficient interface for handling streams, performing equilibrium calculations and allowing the use of stream recycling loops. It also uses the extensive thermodynamic databases available in FactSage to describe the energetics of oxides, sulfides, carbides, salts and metallic phases. This new process simulator interface enables the solving of mass and energy balances of a wide range of pyrometallurgical processes related to the primary production of iron and ferroalloys, copper, titanium and more. In this work, this new interface is used to describe four pyrometallurgical processes, i.e. (i) ferrosilicon alloy production using a submerged arc furnace, (ii) the primary production of copper and the impact of E-waste recycling using a Noranda-like process, (iii) the primary titanium production via the Kroll process, and (iv) the production of direct reduction iron ore pellets via the MIDREX process. Results of the simulations performed in this work are systematically compared to data available in the literature.</div></div>","PeriodicalId":9436,"journal":{"name":"Calphad-computer Coupling of Phase Diagrams and Thermochemistry","volume":"88 ","pages":"Article 102772"},"PeriodicalIF":1.9,"publicationDate":"2024-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143181093","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}

{"title":"Experimental investigation on phase equilibria of the Nd-Y and Nd-Y-Fe systems","authors":"Chengliang Qiu ,&nbsp;Shuhong Liu ,&nbsp;Wei Yang ,&nbsp;Wei Zhai ,&nbsp;Yong Du","doi":"10.1016/j.calphad.2024.102788","DOIUrl":"10.1016/j.calphad.2024.102788","url":null,"abstract":"<div><div>Phase equilibria of the Nd-Y system at 400, 600 and 800 °C and the Nd-Y-Fe system at 400 and 600 °C were investigated by X-ray diffraction (XRD) and electron probe microanalysis (EPMA). Based on the experimental results in this work and literature, phase diagram of the Nd-Y system was refined and isothermal sections of the Nd-Y-Fe system at 400 and 600 °C were constructed. In the Nd-Y system, the solid solubility range of δ(Nd₂Y) was approximately 28.66–36.85 at.% Y at 400 °C and a two-phase region (αNd)+(αY) was observed from 34.73 to 36.52 at.% Y at 800 °C. In the Nd-Y-Fe system, eight and six three-phase regions at 400 and 600 °C were determined, respectively. Two phases of Nd₂Fe₁₇ and Y₂Fe₁₇ link up with each other from the Nd-Fe side to the Y-Fe side across the isothermal sections at both 400 and 600 °C. The maximal solubilities of Nd in the Y₆Fe₂₃, YFe₃ and YFe₂ were about 13.13, 7.06 and 6.14 at.% at both 400 and 600 °C, respectively. There was also noticeable solubility of Y in Nd₅Fe₁₇ and Fe in (αNd) and δ(Nd₂Y) at 400 and 600 °C. In addition, three newly observed ternary compounds τ₁, τ₂ and τ₃ were determined with compositions of approximately 16.50 at.% Nd-16.50 at.% Y-67.00 at.% Fe, 15.00 at.% Nd-20.00 at.% Y-65.00 at.% Fe and 20.00 at.% Nd-15.00 at.% Y-65.00 at.% Fe, respectively.</div></div>","PeriodicalId":9436,"journal":{"name":"Calphad-computer Coupling of Phase Diagrams and Thermochemistry","volume":"88 ","pages":"Article 102788"},"PeriodicalIF":1.9,"publicationDate":"2024-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143181877","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 of AlN in microalloyed steel and thermodynamic analysis","authors":"Markus Führer ,&nbsp;Sabine Zamberger ,&nbsp;Erwin Povoden-Karadeniz","doi":"10.1016/j.calphad.2024.102790","DOIUrl":"10.1016/j.calphad.2024.102790","url":null,"abstract":"<div><div>Differential Scanning Calorimetry measurements are performed with a subsequent postprocessing routine specially designed for dilute systems, aiming at the evaluation of the solvus temperature of AlN in seven microalloyed steel laboratory melts. Computer-aided EDS particle analysis of the steel microstructure confirms the DSC results. With this consistent set of new data directly related to observed AlN stability, coupled with critically assessed thermodynamic data from the literature, the thermodynamic description of the AlN phase is reconsidered.</div></div>","PeriodicalId":9436,"journal":{"name":"Calphad-computer Coupling of Phase Diagrams and Thermochemistry","volume":"88 ","pages":"Article 102790"},"PeriodicalIF":1.9,"publicationDate":"2024-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143181883","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}

{"title":"Thermodynamic study of binary phase diagram iron-selenium","authors":"Ondřej Zobač ,&nbsp;David Novák ,&nbsp;Jana Pavlů ,&nbsp;Martin Friák ,&nbsp;Aleš Kroupa","doi":"10.1016/j.calphad.2024.102774","DOIUrl":"10.1016/j.calphad.2024.102774","url":null,"abstract":"<div><div>The binary phase diagram of the Fe-Se system was modeled by the thermodynamic CALPHAD approach for the first time. The thermodynamic description of this system was mainly based on the available experimental isobaric molar heat capacity of the Fe_1.042Se (β) phase in the temperature range of 25–777 °C and on the published proposed experimental phase diagrams. The formation enthalpies of Fe_1.042Se (β), Fe₇Se₈, Fe₃Se₄, FeSe (δ) and FeSe₂ phases at 25 °C were also implemented into the phase diagram modeling. Magnetic properties and formation energy of the Fe₃Se₄ (γ) phase were theoretically calculated by ab initio methods and implemented in the assessment.</div></div>","PeriodicalId":9436,"journal":{"name":"Calphad-computer Coupling of Phase Diagrams and Thermochemistry","volume":"88 ","pages":"Article 102774"},"PeriodicalIF":1.9,"publicationDate":"2024-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143181884","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":"Corrigendum to “Thermodynamic assessment of the Ni-Co-Re system and diffusion study of its fcc phase” [Calphad 85 (2024) 102688]","authors":"Zhongwen Shi ,&nbsp;Genfeng Shang ,&nbsp;Xiao-Gang Lu","doi":"10.1016/j.calphad.2024.102731","DOIUrl":"10.1016/j.calphad.2024.102731","url":null,"abstract":"","PeriodicalId":9436,"journal":{"name":"Calphad-computer Coupling of Phase Diagrams and Thermochemistry","volume":"87 ","pages":"Article 102731"},"PeriodicalIF":1.9,"publicationDate":"2024-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143101397","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":"Corrigendum to “Thermodynamic assessment of the Ce-Rh system by the combination of ab-initio calculations and the CALPHAD approach” [Calphad 87 (2024) 102747]","authors":"H. Bouchta ,&nbsp;N. Selhaoui ,&nbsp;D.O. Poletaev ,&nbsp;M.A. Boukideur ,&nbsp;A. Bendarma ,&nbsp;S. Kardellass ,&nbsp;A. Marjaoui ,&nbsp;M. Zanouni ,&nbsp;A. Khadija","doi":"10.1016/j.calphad.2024.102756","DOIUrl":"10.1016/j.calphad.2024.102756","url":null,"abstract":"","PeriodicalId":9436,"journal":{"name":"Calphad-computer Coupling of Phase Diagrams and Thermochemistry","volume":"87 ","pages":"Article 102756"},"PeriodicalIF":1.9,"publicationDate":"2024-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143101398","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 properties of calcium antimonates from experiments and first principles","authors":"Shu Li ,&nbsp;Wenjie Wei ,&nbsp;Kaiqing Zhang ,&nbsp;Minkai Tan ,&nbsp;Boya Zhang ,&nbsp;Zhanmin Cao ,&nbsp;Na Wang","doi":"10.1016/j.calphad.2024.102777","DOIUrl":"10.1016/j.calphad.2024.102777","url":null,"abstract":"<div><div>Calcium antimonates with fluorescence characteristic are potential candidates for lighting and display devices. Their thermodynamic properties were investigated using both experiments and first-principles calculations in this study. High-purity CaSb₂O₆ and Ca₂Sb₂O₇ were synthesized via solid-state sintering in air. Their structure Rietveld refinement, microstructure, and elemental valence states were conducted. Heat capacities at high temperature were precisely measured using a MHTC 96 Line calorimeter. The fitting equation are as follows: <em>C</em>_<em>p</em> (CaSb₂O₆) = 218.807 <span><math><mrow><mo>+</mo></mrow></math></span> 3.370<span><math><mrow><mo>×</mo></mrow></math></span> 10⁻³<em>T</em> <span><math><mrow><mo>−</mo></mrow></math></span> 4.770<span><math><mrow><mo>×</mo></mrow></math></span> 10⁶/<em>T</em>², <em>C</em>_<em>p</em>(Ca₂Sb₂O₇) = 265.610 <span><math><mrow><mo>+</mo></mrow></math></span> 1.024<span><math><mrow><mo>×</mo></mrow></math></span> 10⁻²<em>T</em> <span><math><mrow><mo>−</mo></mrow></math></span> 4.985<span><math><mrow><mo>×</mo></mrow></math></span> 10⁶/<em>T</em>², respectively. The enthalpies of formation (−1892.060 kJ mol⁻¹ and -2576.297 kJ mol⁻¹), entropies (163.045 J mol⁻¹ K⁻¹ and 218.973 J mol⁻¹ K⁻¹) at 298 K, and low temperature (0–298 K) heat capacities were obtained through first-principles calculations based on density functional theory (DFT) combined with phonon calculations. Furthermore, the thermal expansion coefficient of Ca₂Sb₂O₇ is significantly higher than that of CaSb₂O₆ during the heating process. Their Gibbs energy were also estimated, at 298 K, Ca₂Sb₂O₇ exhibits a negative value of −701.178 kJ mol⁻¹ relative to CaSb₂O₆.</div></div>","PeriodicalId":9436,"journal":{"name":"Calphad-computer Coupling of Phase Diagrams and Thermochemistry","volume":"87 ","pages":"Article 102777"},"PeriodicalIF":1.9,"publicationDate":"2024-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142720253","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":"Exploration of high-ductility ternary refractory complex concentrated alloys using first-principles calculations and machine learning","authors":"Hyo-Sun Jang ,&nbsp;Jin-Woong Lee ,&nbsp;Byung Do Lee ,&nbsp;Kee-Sun Sohn ,&nbsp;Jiwon Park ,&nbsp;Chang-Seok Oh","doi":"10.1016/j.calphad.2024.102769","DOIUrl":"10.1016/j.calphad.2024.102769","url":null,"abstract":"<div><div>BCC-based refractory complex concentrated alloys (RCCAs) are attracting attention as high-temperature materials because of their exceptional strength at high temperatures, but suffer from low tensile ductility. To search for alloys with improved ductility, it is necessary to investigate the properties of RCCA systems thoroughly, however, an experimental investigation of these vast constitutional spaces is impractical. This study employed data-driven approaches that combined first-principles calculations with machine learning. We first calculated the lattice parameters and elastic constants of 1693 ternary RCCAs, subsets of RCCAs alloys consisting of Ti, Zr, Hf, Nb, Mo, V, Ta, and W, using the exact muffin-tin orbitals method with coherent potential approximation (EMTO-CPA), and generated ductility-related parameters, including Pugh's ratio, Poisson's ratio, and Cauchy pressure. Machine learning models that could predict the three parameters were searched and trained using the generated data. Subsequently, an inverse design based on optimization algorithms was performed to identify optimal alloy systems with high Pugh's ratios. The ductility of the searched alloys was verified by calculating Pugh's ratio using EMTO-CPA, followed by thermodynamic calculations to investigate their structural stability.</div></div>","PeriodicalId":9436,"journal":{"name":"Calphad-computer Coupling of Phase Diagrams and Thermochemistry","volume":"87 ","pages":"Article 102769"},"PeriodicalIF":1.9,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142705586","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}