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

{"title":"Compound database for gaseous metal hydroxides and oxyhydroxides","authors":"Charles W. Bauschlicher Jr ,&nbsp;Nathan S. Jacobson ,&nbsp;Cameron J. Bodenschatz","doi":"10.1016/j.calphad.2024.102707","DOIUrl":"10.1016/j.calphad.2024.102707","url":null,"abstract":"<div><p>In this study computational methods are used to derive thermochemical data for Sc, Fe, Co, Ni, and Hf hydroxides and oxyhydroxides. As done previously, molecular geometries and vibrational modes were derived with DFT methods; for the enthalpies of formation more computationally intensive coupled cluster methods were necessary. For each species Δ_fH^o(298), S^o(298), and C_p in the form A + BT + CT² + D/T + E/T² with A, B, C, D, and E fitted constants are presented. These are combined with previously reported calculations for Al, Cr, Si, Ta, Al, Zr, Y, Yb, Gd, and Mn to build a compound database for metal hydroxides and oxyhydroxides. Sample calculations for applications where high temperature water vapor is encountered are shown. The majority of the database was generated from <em>ab initio</em> calculations; however, experiments were critical benchmarks for many of the species.</p></div>","PeriodicalId":9436,"journal":{"name":"Calphad-computer Coupling of Phase Diagrams and Thermochemistry","volume":"85 ","pages":"Article 102707"},"PeriodicalIF":2.4,"publicationDate":"2024-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S036459162400049X/pdfft?md5=c822b40ee24c24b010eeb802cf7a8066&pid=1-s2.0-S036459162400049X-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141194538","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":"Corrigendum to “Experimental study and thermochemical assessment of the reciprocal system Li+, K+//Cl-, CO32-” [Calphad 83 (2023) 102603]","authors":"Jia Qi,&nbsp;Elena Yazhenskikh,&nbsp;Mirko Ziegner,&nbsp;Xin Zhao,&nbsp;Guixuan Wu,&nbsp;Michael Müller,&nbsp;Dmitry Sergeev","doi":"10.1016/j.calphad.2024.102696","DOIUrl":"10.1016/j.calphad.2024.102696","url":null,"abstract":"","PeriodicalId":9436,"journal":{"name":"Calphad-computer Coupling of Phase Diagrams and Thermochemistry","volume":"85 ","pages":"Article 102696"},"PeriodicalIF":2.4,"publicationDate":"2024-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S0364591624000385/pdfft?md5=dff4b6437edc347a05e4d3b9b22e3160&pid=1-s2.0-S0364591624000385-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141039770","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":"CALPHAD-based modeling of pressure-dependent Al, Cu and Li unary systems","authors":"Elizabeth Mathew ,&nbsp;Rupesh Chafle ,&nbsp;Benjamin Klusemann","doi":"10.1016/j.calphad.2024.102692","DOIUrl":"https://doi.org/10.1016/j.calphad.2024.102692","url":null,"abstract":"<div><p>The study presents a pressure-dependent CALPHAD-based model for assessment of the Al, Cu and Li unary systems, focusing on phase changes under varying pressures. By incorporating the Murnaghan equation of state and ab initio phonon calculations, the thermal properties for stable and metastable phases are accurately predicted. To ensure a comprehensive representation of the system's response to pressure changes; compressibility, volumetric thermal expansion coefficient as a function of temperature, the derivative of bulk modulus with pressure, and molar volume for the condensed phases are integrated in the framework. The model provides essential insights into pressure-induced transformation, aiding in the understanding of solid-state processing, such as high-pressure torsion and extrusion. The results from this work are in excellent agreement with the experimental literature and can be utilized to enhance phase predictions under non-equilibrium conditions.</p></div>","PeriodicalId":9436,"journal":{"name":"Calphad-computer Coupling of Phase Diagrams and Thermochemistry","volume":"85 ","pages":"Article 102692"},"PeriodicalIF":2.4,"publicationDate":"2024-05-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S0364591624000348/pdfft?md5=7f132cdca8847af29c337fd83f108a65&pid=1-s2.0-S0364591624000348-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141083994","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 determination and thermodynamic calculation of phase equilibria in the Sm-Fe-B ternary system","authors":"W.F. Cheng ,&nbsp;X.Y. Liu ,&nbsp;C. Tan ,&nbsp;Q.R. Yao ,&nbsp;J. Wang ,&nbsp;G.H. Rao ,&nbsp;H.Y. Zhou","doi":"10.1016/j.calphad.2024.102706","DOIUrl":"https://doi.org/10.1016/j.calphad.2024.102706","url":null,"abstract":"<div><p>The phase equilibria of the Sm-Fe-B ternary system at 873 K and 1073 K were experimentally investigated by equilibrated alloy method using scanning electron microscopy with energy dispersive spectroscopy (SEM-EDS) and X-ray diffraction (XRD). Four ternary intermetallic compounds, Sm₂Fe₁₄B with a Nd₂Fe₁₄B-type structure and space group P4₂/mnm, Sm₁₇(Fe₄B₄)₁₅ with a RE_l.1Fe₄B₄-type structure and space group P4₂/n, SmFeB₄ with a YCrB₄-type structure and space group Pbam and Sm₅Fe₂B₆ with a Pr₅Co₂B₆-type structure and space group <span><math><mi>R</mi><mover><mn>3</mn><mo>‾</mo></mover><mi>m</mi></math></span> , were confirmed by the SEM-EDS results and the XRD Rietveld refinements. The isothermal sections of this ternary system at 873 K and 1073 K were established. Furthermore, in the combination with the previous assessments of the Sm-Fe, Sm-B and Fe-B binary systems and the measured and reported experimental results, thermodynamic calculation of the Sm-Fe-B ternary system was performed using the CALPHAD method. The calculated isothermal sections at 873 K and 1073 K are in good agreement with the determined experimental results. Thermodynamic parameters of the Sm-Fe-B ternary system were obtained finally, which would provide a good basis for the development of a thermodynamic database of RE-Fe-B-based magnetic alloys.</p></div>","PeriodicalId":9436,"journal":{"name":"Calphad-computer Coupling of Phase Diagrams and Thermochemistry","volume":"85 ","pages":"Article 102706"},"PeriodicalIF":2.4,"publicationDate":"2024-05-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141072640","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 CeH and CeNi5 H system","authors":"Peter Hannappel ,&nbsp;Ebert Alvares ,&nbsp;Felix Heubner ,&nbsp;Claudio Pistidda ,&nbsp;Paul Jerabek ,&nbsp;Thomas Weißgärber","doi":"10.1016/j.calphad.2024.102701","DOIUrl":"https://doi.org/10.1016/j.calphad.2024.102701","url":null,"abstract":"<div><p>Interstitial metal hydrides (MHs) have attracted considerable attention in the field of hydrogen technology, particularly in the context of storage and compression applications. Because of their minor hysteresis effects, good cyclability, activation simplicity, and high volumetric storage density, <span><math><msub><mrow><mi>LaNi</mi></mrow><mrow><mn>5</mn></mrow></msub></math></span>-based alloys are recognized as prominent candidates for hydrogen storage application. Additionally, the system’s thermodynamic and electrochemical properties can be modified to suit the requirements of a particular application by alloying specific substituents. To ascertain the thermodynamic effects of Ce addition within <span><math><msub><mrow><mi>LaNi</mi></mrow><mrow><mn>5</mn></mrow></msub></math></span>, in this work the Ce<img>H and <span><math><msub><mrow><mi>CeNi</mi></mrow><mrow><mn>5</mn></mrow></msub></math></span> <img><span><math><mi>H</mi></math></span> systems have been modeled with the CALPHAD method. For this reason, in this work, two different thermodynamic models have been developed and assessed using the same pressure-composition isotherms (PCIs) datasets obtained from literature and theoretical formation energies newly calculated employing periodic density functional theory (DFT). Direct comparison of the models against each other in terms of accuracy and physical plausibility revealed that extrapolation of thermodynamic properties to data-scarce regions is more reasonable with fewer model parameters and in agreement with other similar systems within the rare-earth (<span><math><mi>RE</mi></math></span>) metal-hydride class. In addition, the <span><math><msub><mrow><mi>CeNi</mi></mrow><mrow><mn>5</mn></mrow></msub></math></span> <img><span><math><mi>H</mi></math></span> system was investigated by assessing the <span><math><mrow><msub><mrow><mi>(Ce)(Ni)</mi></mrow><mrow><mn>5</mn></mrow></msub><msub><mrow><mrow><mo>(</mo><mi>V a,H</mi><mo>)</mo></mrow></mrow><mrow><mn>7</mn></mrow></msub></mrow></math></span> phase model, which could accurately predict hydrogen storage properties while being compatible with previously developed <span><math><msub><mrow><mi>LaNi</mi></mrow><mrow><mn>5</mn></mrow></msub></math></span> <img><span><math><mi>H</mi></math></span> models. Ultimately, the models developed in this study may be employed and extended to describe multi-component <span><math><mi>RE</mi></math></span> <img><span><math><mi>H</mi></math></span> systems and allow for thermodynamic computations that are highly desirable for accurate predictions of hydrogen absorption/desorption properties and degradation characteristics within the <span><math><msub><mrow><mi>(La,Ce)Ni</mi></mrow><mrow><mn>5</mn></mrow></msub></math></span> <img><span><math><mi>H</mi></math></span> metal hydride family.</p></div>","PeriodicalId":9436,"journal":{"name":"Calphad-computer Coupling of Phase Diagrams and Thermochemistry","volume":"85 ","pages":"Article 102701"},"PeriodicalIF":2.4,"publicationDate":"2024-05-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S0364591624000439/pdfft?md5=ce2267f6c98eba933631c6dd4c599517&pid=1-s2.0-S0364591624000439-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141067126","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 modeling of pressure-dependent phase diagram in alkali metals Li, Na and K","authors":"Ying Yang,&nbsp;He Peng,&nbsp;Zhipeng Pi,&nbsp;Fan Zhang","doi":"10.1016/j.calphad.2024.102704","DOIUrl":"https://doi.org/10.1016/j.calphad.2024.102704","url":null,"abstract":"<div><p>The high-pressure behavior of the alkali metals has attracted much attention in both experimental and theoretical aspects. This study is focused on the thermodynamic optimization of the temperature and pressure dependence of the molar volumes, the compressibility and phase diagrams of Li, Na and K according to the CALPHAD method. The pressure-temperature phase diagrams of lithium, sodium and potassium up to 50–100 GPa were calculated using the obtained thermodynamic parameters. The available experimental data, such as extremely low melting temperatures at high pressure, pressure-induced structural transitions between simple bcc and fcc crystals and the molar volume changes with the increasing pressure, were well reproduced in our calculations. The good agreements between our calculations and the experiments assessed in the literature indicated that our thermodynamic parameters are reasonable. Our thermodynamic calculations would assist to understand the phase transitions and structural properties of alkali metals at high pressure.</p></div>","PeriodicalId":9436,"journal":{"name":"Calphad-computer Coupling of Phase Diagrams and Thermochemistry","volume":"85 ","pages":"Article 102704"},"PeriodicalIF":2.4,"publicationDate":"2024-05-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141068095","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":"Combined experimental and CALPHAD investigation of equimolar AlCoCrFeNiX (X=Mo,Ta,W) High-Entropy Alloys","authors":"S. Gambaro ,&nbsp;L. Fenocchio ,&nbsp;F. Valenza ,&nbsp;P. Riani ,&nbsp;G. Cacciamani","doi":"10.1016/j.calphad.2024.102702","DOIUrl":"https://doi.org/10.1016/j.calphad.2024.102702","url":null,"abstract":"<div><p>Aiming to evaluate the effect of refractory metal additions to a quinary AlCoCrFeNi High-Entropy Alloy (HEA), three novel equimolar AlCoCrFeNi-X (X = Mo, Ta, W) HEAs were designed, arc-melted, annealed, and characterized by SEM-EDS, XRD and microhardness measurements. CALPHAD thermodynamic calculations were exploited to design compositions and thermal treatments of the selected HEAs as well as to predict constitution and interpret microstructure of the samples. On the other hand, the experimental results contributed to the validation of the in-house built GHEA thermodynamic database (including the Al, Co, Cr, Fe, Ni, Mo, Ta, W elements) used for the calculations. No TCP intermetallic was found to form in the quinary AlCoCrFeNi alloy. However, the formation of σ, Laves-C14 and μ phases was observed in the samples containing Mo, Ta, and W, respectively, in agreement with the most accepted VEC-based phases stabilization criteria. The addition of the refractory metals led to a microhardness increase for all the investigated alloys. Overall, good agreement was observed between experiments and calculations, especially for compositional trends and phase amounts, allowing the database validation and supporting its applicability to phase equilibria simulation in the six-component HEAs belonging to the Al–Co–Cr–Fe–Ni-X (X = Mo, Ta, W) systems.</p></div>","PeriodicalId":9436,"journal":{"name":"Calphad-computer Coupling of Phase Diagrams and Thermochemistry","volume":"85 ","pages":"Article 102702"},"PeriodicalIF":2.4,"publicationDate":"2024-05-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S0364591624000440/pdfft?md5=7e1873fba7c4a1e5f1e508f9f4a9ff86&pid=1-s2.0-S0364591624000440-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140906230","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":"Revisiting thermodynamics in (LiF, NaF, KF, CrF2)–CrF3 by first-principles calculations and CALPHAD modeling","authors":"Rushi Gong,&nbsp;Shun-Li Shang,&nbsp;Yi Wang,&nbsp;Jorge Paz Soldan Palma,&nbsp;Hojong Kim,&nbsp;Zi-Kui Liu","doi":"10.1016/j.calphad.2024.102703","DOIUrl":"https://doi.org/10.1016/j.calphad.2024.102703","url":null,"abstract":"<div><p>The thermodynamic description of the (LiF, NaF, KF, CrF₂)–CrF₃ systems has been revisited, aiming for a better understanding of the effects of Cr on the FLiNaK molten salt. First-principles calculations based on density functional theory (DFT) were performed to determine the electronic and structural properties of each compound, including the formation enthalpy, volume, and bulk modulus. DFT-based phonon calculations were carried out to determine the thermodynamic properties of compounds, for example, enthalpy, entropy, and heat capacity as functions of temperature. Phonon-based thermodynamic properties show a good agreement with experimental data of binary compounds LiF, NaF, KF, CrF₃, and CrF₂, establishing a solid foundation to determine thermodynamic properties of ternary compounds as well as to verify results estimated by the Neumann-Kopp rule. Additionally, DFT-based ab initio molecular dynamics (AIMD) simulations were employed to predict the mixing enthalpies of liquid salts. Using DFT-based results and experimental data in the literature, the (LiF, NaF, KF, CrF₂)–CrF₃ system has been remodeled in terms of the CALculation of PHAse Diagrams (CALPHAD) approach using the modified quasichemical model with quadruplet approximation (MQMQA) for liquid. Calculated phase stability in the present work shows an excellent agreement with experiments, indicating the effectiveness of combining DFT-based total energy, phonon, and AIMD calculations, and CALPHAD modeling to provide the thermodynamic description in complex molten salt systems.</p></div>","PeriodicalId":9436,"journal":{"name":"Calphad-computer Coupling of Phase Diagrams and Thermochemistry","volume":"85 ","pages":"Article 102703"},"PeriodicalIF":2.4,"publicationDate":"2024-05-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140901294","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 and thermodynamic assessment of the Cu–In system","authors":"Fu-Ling Chang,&nbsp;Yu-Hsin Lin,&nbsp;Han-Tang Hung,&nbsp;C.R. Kao","doi":"10.1016/j.calphad.2024.102700","DOIUrl":"https://doi.org/10.1016/j.calphad.2024.102700","url":null,"abstract":"<div><p>Owing to the low melting temperature and excellent mechanical properties, In is considered a potential low-temperature solder. However, the interfacial reaction between In and Cu substrates is still unclear, specifically regarding the stability of CuIn₂. Although CuIn₂ was often observed at the Cu–In thin film after long-term aging below 100 °C, it is considered as a metastable phase and has not been added into the Cu–In phase diagram yet. In this study, the stability of CuIn₂ and the peritectoid reaction Cu₁₁In₉ + In → CuIn₂ were established using the Cu/In diffusion couple, Cu–In alloy phase equilibria, and decomposition investigation of CuIn₂. The peritectoid temperature was determined to be in the range of 110–105 °C. Finally, thermodynamic assessment was conducted based on the experimental data and the revised Cu–In phase diagram.</p></div>","PeriodicalId":9436,"journal":{"name":"Calphad-computer Coupling of Phase Diagrams and Thermochemistry","volume":"85 ","pages":"Article 102700"},"PeriodicalIF":2.4,"publicationDate":"2024-05-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140824203","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":"Diffusion coefficients and atomic mobilities in the BCC phase of the Al–Nb–V system","authors":"Karoline Elerbrock Borowski ,&nbsp;Vitória de Melo Silveira ,&nbsp;Nabil Chaia ,&nbsp;Chuangye Wang ,&nbsp;Ji-Cheng Zhao ,&nbsp;Carlos Angelo Nunes ,&nbsp;Gilberto Carvalho Coelho","doi":"10.1016/j.calphad.2024.102699","DOIUrl":"https://doi.org/10.1016/j.calphad.2024.102699","url":null,"abstract":"<div><p>Diffusion coefficients in the BCC phase of the Al–Nb–V ternary system are studied for the first time, including an assessment of the atomic mobilities. Ternary interdiffusion coefficients are obtained from the intersecting diffusion paths of several sets of diffusion couples that are annealed at both 1100 °C and 1200 °C. Existing experimental data from the pertinent binary systems are also employed for the assessments of atomic mobilities using the 1-parameter Z-Z-Z binary diffusion coefficient model developed by Zhong et al [1]. Interdiffusion coefficients in the BCC region of the Al–V system are also extracted through a forward-simulation analysis and incorporated into the mobility modeling. A complete description of diffusion in the BCC phase of the Al–Nb–V system is presented following the Binary and Cross-Binary Parameters Only (BCBPO) model developed by Zhong and Zhao [2]. Our data will be valuable input to diffusion-related simulation of refractory high entropy alloys containing aluminum.</p></div>","PeriodicalId":9436,"journal":{"name":"Calphad-computer Coupling of Phase Diagrams and Thermochemistry","volume":"85 ","pages":"Article 102699"},"PeriodicalIF":2.4,"publicationDate":"2024-04-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140815508","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}