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

{"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}

{"title":"The Al2O3-SiO2-“V2O3” phase diagram at 1873 K","authors":"A. Vickerfält ,&nbsp;J. Huss ,&nbsp;J. Martinsson ,&nbsp;D. Sichen","doi":"10.1016/j.calphad.2024.102771","DOIUrl":"10.1016/j.calphad.2024.102771","url":null,"abstract":"<div><div>The pseudo-ternary Al₂O₃-SiO₂-“V₂O₃” phase diagram was studied at 1873 K and oxygen partial pressures of 3.4 × 10⁻¹¹, 3.3 × 10⁻¹⁰ and 3.4 × 10⁻⁹ atm. The samples were kept in a CO-CO₂ mixture to control the oxygen potential and quenched in oil after equilibration. The phase compositions of the quenched samples were analyzed using wavelength-dispersive spectroscopy. The analyses were used to construct the phase diagrams. A change in oxygen potential did not profoundly affect the Al₂O₃-corundum + V₂O₃-corundum + mullite and V₂O₃-corundum + liquid + cristobalite equilibria, in contrast to the V₂O₃-corundum + mullite + liquid equilibrium where an effect was evident. For the latter equilibrium, decreased oxygen potential resulted in higher contents of Al₂O₃ and slightly higher contents of V₂O₃ in the liquid phase, as well as slightly higher contents of Al₂O₃ in V₂O₃-corundum and mullite.</div></div>","PeriodicalId":9436,"journal":{"name":"Calphad-computer Coupling of Phase Diagrams and Thermochemistry","volume":"87 ","pages":"Article 102771"},"PeriodicalIF":1.9,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142705585","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":"Interdiffusivity matrices and atomic mobilities in fcc Ni–Fe–Mo alloys: Experiment and modeling","authors":"Taibai Fu ,&nbsp;Yuling Liu ,&nbsp;Huixin Liu ,&nbsp;Changfa Du ,&nbsp;Shiyi Wen ,&nbsp;Yong Du","doi":"10.1016/j.calphad.2024.102773","DOIUrl":"10.1016/j.calphad.2024.102773","url":null,"abstract":"<div><div>Accurate diffusivities in fcc Ni–Fe–Mo alloys are of significant importance in designing high-quality magnetic alloys. In this work, totally twelve fcc single-phase diffusion couples are assembled to determine the diffusivities of fcc Ni–Fe–Mo alloys at 1373, 1423 and 1437 K. The diffusivity matrices at the intersection compositions of diffusion paths are determined by the Matano-Kirkaldy method. In addition, the diffusivity matrices along the whole composition profiles of individual diffusion couple and the atomic mobilities of fcc Ni–Fe–Mo alloys are evaluated by the numerical inverse approach incorporated in CALTPP program. The reliability of the obtained atomic mobilities is verified by comparing the predicted diffusion behaviors with the experimental ones. Furthermore, applying the presently obtained atomic mobilities in combination with thermodynamic descriptions, the three-dimensional maps of interdiffusivites, activation energy and frequency-factor planes of fcc Ni–Fe–Mo alloys are constructed to display the composition- and temperature-dependent diffusion properties. The presently obtained diffusivities and atomic mobilities of the Ni–Fe–Mo fcc phase are expected to contribute to high-efficiency Ni–Fe–Mo magnetic alloy design.</div></div>","PeriodicalId":9436,"journal":{"name":"Calphad-computer Coupling of Phase Diagrams and Thermochemistry","volume":"87 ","pages":"Article 102773"},"PeriodicalIF":1.9,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142705582","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 Al-Cr-Pd ternary system","authors":"Siqi Wang ,&nbsp;Wei Yu ,&nbsp;Ying Ran ,&nbsp;Jingxian Hu ,&nbsp;Xinming Wang ,&nbsp;Zhi Li ,&nbsp;Fucheng Yin ,&nbsp;Ya Liu","doi":"10.1016/j.calphad.2024.102766","DOIUrl":"10.1016/j.calphad.2024.102766","url":null,"abstract":"<div><div>The phase relations of the Al-Cr-Pd ternary system above 1100 °C and the thermodynamic description were lacking to guide the compositional design of the Cr and Pd co-modified aluminide coating. Herein, the isothermal section of the Al-Cr-Pd ternary system at 1150 °C was experimentally determined through scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy and X-ray diffraction. In addition, a thermodynamic description of the ternary system was established by the application of CALPHAD (CALculation of PHAse Diagrams) technique based on the experimental results of the isothermal section at 930, 970, 990, 1020 and 1150 °C. The solidification paths of typical alloys determined in the previous literature were also fitted. A set of self–consistent thermodynamic parameters for the Al-Cr-Pd ternary system was obtained with a reasonable agreement between the experimental and calculated results. The results provide a basis for the compositional design of aluminide coatings and enrich the Al-based database.</div></div>","PeriodicalId":9436,"journal":{"name":"Calphad-computer Coupling of Phase Diagrams and Thermochemistry","volume":"87 ","pages":"Article 102766"},"PeriodicalIF":1.9,"publicationDate":"2024-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142705581","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 temperature phase relations and structure determination of solid solutions in the ternary Nd-Dy-Cu system","authors":"Srečo D. Škapin ,&nbsp;Amalija Golobič ,&nbsp;Edith De Leon ,&nbsp;Catalina O. Tudor ,&nbsp;Matjaž Spreitzer ,&nbsp;Danilo Suvorov ,&nbsp;Miha Zakotnik","doi":"10.1016/j.calphad.2024.102770","DOIUrl":"10.1016/j.calphad.2024.102770","url":null,"abstract":"<div><div>The sub-solidus phase relations in the ternary Nd-Dy-Cu system were determined for an isothermal section at 550 °C. The samples were prepared by arc-melting and subsequent annealing in a protective atmosphere for 120 h. The phases in the prepared samples were characterized by X-ray powder diffraction and scanning electron microscopy, and their composition was determined by energy-dispersive spectroscopy. The intermetallic compounds based on the Dy-Cu system are compatible with compounds based on Nd-Cu-based and exhibit a high degree of solid-state solubility. The crystal structures of the solid solutions and their transformations were determined in detail. In the Cu-rich part of the system, the compound DyCu₇, which is stable above 700 °C according to literature data, was confirmed under the applied experimental conditions and is connected to NdCu₆ by a tie line.</div></div>","PeriodicalId":9436,"journal":{"name":"Calphad-computer Coupling of Phase Diagrams and Thermochemistry","volume":"87 ","pages":"Article 102770"},"PeriodicalIF":1.9,"publicationDate":"2024-11-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142651978","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":"Phase equilibria relationship in the FetO-TiO2-CaO-SiO2 system with CaO/SiO2 weight ratio of 1.2 at 1673K","authors":"Youyu Li,&nbsp;Baijun Yan","doi":"10.1016/j.calphad.2024.102768","DOIUrl":"10.1016/j.calphad.2024.102768","url":null,"abstract":"<div><div>Phase equilibria relationship in the Fe_tO-TiO₂-CaO-SiO₂ system with CaO/SiO₂ weight ratio of 1.2 under argon atmosphere were identified experimentally at 1673K by employing high-temperature equilibration method followed by electron probe X-ray microanalysis (EPMA) and X-Ray Diffraction (XRD) measurements. It was found that there exist 7 crystal phases and 1 liquid phase in the system, and 19 different kinds of phase equilibria relationship exist among these 8 phases. The 7 crystal phases are as follows: kilchoanite (Ca₃Si₂O₇), ulvöspinel (Fe_3-xTi_xO₄), pseudobrookite (FeO·2TiO₂), ilmenite (FeTiO₃), perovskite (CaTiO₃), rutile (TiO₂) and wüstite (Fe_tO). By using L as the symbol for liquid phase, K for kilchoanite, U for ulvöspinel, B for pseudobrookite, I for ilmenite, P for perovskite, R for rutile and W for wüstite, the 19 phase equilibria relationships formed by these phases can be summarized as follows: 1) single L, 2) L + U, 3) L + R, 4) L + W, 5) L + K, 6) L + I, 7) L + B, 8) L + P, 9) L + R + P, 10) L + I + P, 11) L + B + I, 12) L + R + B, 13) L + U + W, 14) L + U + I, 15) L + U + P, 16) L + P + B, 17) L + U + I + P, 18) L + R + B + P, and 19) L + B + I + P. Finally, based on the above-determined phase equilibria relationship, a section phase diagram of the system at 1673K was constructed. From the constructed phase diagram, the evolution of phases caused by composition change can be seen graphically.</div></div>","PeriodicalId":9436,"journal":{"name":"Calphad-computer Coupling of Phase Diagrams and Thermochemistry","volume":"87 ","pages":"Article 102768"},"PeriodicalIF":1.9,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142651977","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 relationship in Gd2O3-Nd2O3-ZrO2 system at 1673 K and 1873 K","authors":"Kai Xu,&nbsp;Taowen Zheng,&nbsp;Xuezhen Che,&nbsp;Liumei Su,&nbsp;Dandan Huang","doi":"10.1016/j.calphad.2024.102767","DOIUrl":"10.1016/j.calphad.2024.102767","url":null,"abstract":"<div><div>The phase relationship in the Gd₂O₃-Nd₂O₃-ZrO₂ system at 1673 K and 1873 K was investigated by X-ray diffraction, scanning electron microscopy and electron probe microanalysis. Samples with different compositions were annealed in air at temperatures of 1673 K and 1873 K after preparation. The isothermal section of the Gd₂O₃-Nd₂O₃-ZrO₂ ternary system has been developed. No ternary compound was found at 1673 K and 1873 K. There exist fields of solid solution based on cubic (C) and monoclinic (B) modifications of Gd₂O₃, tetragonal (T) and cubic modifications of ZrO₂, A-Nd₂O₃, and pyrochlore-type Nd₂Zr₂O₇ phase.</div></div>","PeriodicalId":9436,"journal":{"name":"Calphad-computer Coupling of Phase Diagrams and Thermochemistry","volume":"87 ","pages":"Article 102767"},"PeriodicalIF":1.9,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142651976","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":"Liquidus projection and miscibility gap of the Ag-Cu-Te ternary system","authors":"Sinn-wen Chen ,&nbsp;Pin-shuo Huang ,&nbsp;Yung-Chun Tsai ,&nbsp;Yohanes Hutabalian","doi":"10.1016/j.calphad.2024.102765","DOIUrl":"10.1016/j.calphad.2024.102765","url":null,"abstract":"<div><div>Ag-Cu-Te is a significant material system, and experimental measurements have been conducted to determine its liquidus projection. Aside from the terminal solid solution phases and binary compounds, there exists a ternary compound known as AgCuTe. The ten primary solidification phases include (Ag), Ag₂Te, Ag_1.9Te, Ag₅Te₃, (Te), CuTe, Cu₃Te₂, Cu₂Te, (Cu), and AgCuTe. A liquid miscibility gap with a very wide compositional range is observed. When the alloys are at temperatures higher than those of the binodal curves, they are entirely molten. Interesting spherical-shaped microstructures are observed when the alloys solidify passing through the liquid miscibility gap. Furthermore, it has been determined that there are nine invariant reactions, consisting of three Class I reactions (L ↔ α + β + γ) three Class II reactions (L + α ↔ β + γ), and three Class III reactions (L + α + β ↔ γ). The highest and lowest invariant reaction temperatures are determined to be 849.0 °C and 308.0 °C, respectively.</div></div>","PeriodicalId":9436,"journal":{"name":"Calphad-computer Coupling of Phase Diagrams and Thermochemistry","volume":"87 ","pages":"Article 102765"},"PeriodicalIF":1.9,"publicationDate":"2024-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142651975","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":"Catastrophe theory and thermodynamic instability to predict congruent melting temperature of crystals","authors":"Marcello Merli ,&nbsp;Costanza Bonadiman ,&nbsp;Alessandro Pavese","doi":"10.1016/j.calphad.2024.102761","DOIUrl":"10.1016/j.calphad.2024.102761","url":null,"abstract":"<div><div>Melting temperature (<em>T</em>_m) is a crucial physical property of solids and plays an important role in the characterization of materials. Therefore, the capacity to predict <em>T</em>_m is a relevant issue for solid state sciences. This investigation aims i) to provide a theoretical basis for the link between catastrophe theory and thermodynamic instability; ii) to estimate <em>T</em>_m through the notion of “degenerate critical temperature” (<em>T</em>_d), related to (<em>P</em>_d,<em>V</em>_d,<em>T</em>_d), where <em>K</em>_<em>T</em> → 0 and the Gibbs function shows a <em>non</em>-Morse behaviour; iii) to compare predictions of (<em>P</em>_m,<em>T</em>_m) with observations for three crystalline pure substances that undergo congruent melting and exhibit different bonding and stability ranges: NaCl (halite), SiO_2,st (stishovite), and MgSiO₃ (perovskite). The <em>P</em>-<em>T locus</em> of <em>K</em>_<em>T</em> = 0 associated with melting is identified using the maximum values of <em>T</em>_d and Δ<em>H</em>/Δ<em>V</em> at a given pressure. We observed an average absolute discrepancy ranging between 0.2 % (halite) and 5.8 % (stishovite), and an agreement between theoretical and experimental <em>T</em>(<em>P</em>)_melting-points from better than 1 to approximately 14 %.</div></div>","PeriodicalId":9436,"journal":{"name":"Calphad-computer Coupling of Phase Diagrams and Thermochemistry","volume":"87 ","pages":"Article 102761"},"PeriodicalIF":1.9,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142577460","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}