Application of polyhedron model to predict heat capacity of mixed oxides

Jesus Alejandro Arias-Hernandez; Sun Yong Kwon; Elmira Moosavi-Khoonsari

doi:10.1016/j.calphad.2025.102836

Application of polyhedron model to predict heat capacity of mixed oxides

Jesus Alejandro Arias-Hernandez
, Sun Yong Kwon
, Elmira Moosavi-Khoonsari

Multiscale Modeling & Materials by Desig

Research output: Contribution to journal › Article › peer-review

Abstract

The heat capacity of mixed oxides can be estimated using a linear summation of the heat capacities of their structural constituent polyhedra. This approach is particularly useful for hygroscopic and volatile oxides, where experimental data can be difficult to obtain. The present work aims to enhance the polyhedron model (PM) by incorporating contributions from second-order transitions, including magnetic and site order-disorders, into C_p and expanding it to include ZnO and PbO-containing systems in comparison to the previous version of the model. A regression analysis was performed over the new dataset consisting of the properties of 85 compounds in the system Li-Na-K-Ca-Mg-Mn-Fe-Pb-Zn-Al-Ti-Si-O to obtain optimized C_p for 20 constituent polyhedra. We validate the updated PM against experimental data, demonstrating an overall improvement between 7 and 9 % in the estimation of C_p compared to the previous version of the model. We also compare the updated model with well-established models in the literature, such as the Neumann-Kopp Rule, and ab-initio calculations. The PM shows higher precision than NKR and the linear summation nature of PM endows the model with simplicity which contrasts with ab-initio calculations. Additionally, the model has demonstrated an inherent self-correction capability relative to the original input values, as shown for K₂Si₄O₉. The model is also applied to predict the heat capacity of 10 compounds in the Na₂O-PbO-SiO₂ and Na₂O-ZnO-SiO₂ systems, where experimental data are lacking.

Original language	English
Article number	102836
Journal	Calphad: Computer Coupling of Phase Diagrams and Thermochemistry
Volume	89
DOIs	https://doi.org/10.1016/j.calphad.2025.102836
State	Published - Jun 2025

Funding

This manuscript has been authored by UT-Battelle, LLC under Contract No. DE-AC05-00OR22725 with the U.S. Department of Energy. The United States Government retains and the publisher, by accepting the article for publication, acknowledges that the United States Government retains a non-exclusive, paid-up, irrevocable, world-wide license to publish or reproduce the published form of this manuscript, or allow others to do so, for United States Government purposes. The Department of Energy will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan (http://energy.gov/downloads/doe-public-access-plan).The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Elmira Moosavi-Khoonsari reports financial support was provided by Natural Sciences and Engineering Research Council of Canada. Sun Yong Kwon reports a relationship with UT-Battelle LLC that includes: employment. If there are other authors, they declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.The authors would like to acknowledge the financial support of the NSERC Discovery Grant from the Government of Canada for this project. This manuscript has been authored by UT-Battelle, LLC under Contract No. DE-AC05-00OR22725 with the U.S. Department of Energy. The United States Government retains and the publisher, by accepting the article for publication, acknowledges that the United States Government retains a non-exclusive, paid-up, irrevocable, world-wide license to publish or reproduce the published form of this manuscript, or allow others to do so, for United States Government purposes. The Department of Energy will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan (http://energy.gov/downloads/doe-public-access-plan). This manuscript has been authored by UT-Battelle, LLC under Contract No. DE-AC05-00OR22725 with the U.S. Department of Energy . The United States Government retains and the publisher, by accepting the article for publication, acknowledges that the United States Government retains a non-exclusive, paid-up, irrevocable, world-wide license to publish or reproduce the published form of this manuscript, or allow others to do so, for United States Government purposes. The Department of Energy will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan ( http://energy.gov/downloads/doe-public-access-plan ). The authors would like to acknowledge the financial support of the NSERC Discovery Grant from the Government of Canada for this project. This manuscript has been authored by UT-Battelle, LLC under Contract No. DE-AC05-00OR22725 with the U.S. Department of Energy. The United States Government retains and the publisher, by accepting the article for publication, acknowledges that the United States Government retains a non-exclusive, paid-up, irrevocable, world-wide license to publish or reproduce the published form of this manuscript, or allow others to do so, for United States Government purposes. The Department of Energy will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan ( http://energy.gov/downloads/doe-public-access-plan ).

Keywords

Heat capacity
Oxides
Polyhedron Model
Second-order transitions
Thermodynamics

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10.1016/j.calphad.2025.102836

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title = "Application of polyhedron model to predict heat capacity of mixed oxides",

abstract = "The heat capacity of mixed oxides can be estimated using a linear summation of the heat capacities of their structural constituent polyhedra. This approach is particularly useful for hygroscopic and volatile oxides, where experimental data can be difficult to obtain. The present work aims to enhance the polyhedron model (PM) by incorporating contributions from second-order transitions, including magnetic and site order-disorders, into Cp and expanding it to include ZnO and PbO-containing systems in comparison to the previous version of the model. A regression analysis was performed over the new dataset consisting of the properties of 85 compounds in the system Li-Na-K-Ca-Mg-Mn-Fe-Pb-Zn-Al-Ti-Si-O to obtain optimized Cp for 20 constituent polyhedra. We validate the updated PM against experimental data, demonstrating an overall improvement between 7 and 9 \% in the estimation of Cp compared to the previous version of the model. We also compare the updated model with well-established models in the literature, such as the Neumann-Kopp Rule, and ab-initio calculations. The PM shows higher precision than NKR and the linear summation nature of PM endows the model with simplicity which contrasts with ab-initio calculations. Additionally, the model has demonstrated an inherent self-correction capability relative to the original input values, as shown for K2Si4O9. The model is also applied to predict the heat capacity of 10 compounds in the Na2O-PbO-SiO2 and Na2O-ZnO-SiO2 systems, where experimental data are lacking.",

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AU - Arias-Hernandez, Jesus Alejandro

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PY - 2025/6

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N2 - The heat capacity of mixed oxides can be estimated using a linear summation of the heat capacities of their structural constituent polyhedra. This approach is particularly useful for hygroscopic and volatile oxides, where experimental data can be difficult to obtain. The present work aims to enhance the polyhedron model (PM) by incorporating contributions from second-order transitions, including magnetic and site order-disorders, into Cp and expanding it to include ZnO and PbO-containing systems in comparison to the previous version of the model. A regression analysis was performed over the new dataset consisting of the properties of 85 compounds in the system Li-Na-K-Ca-Mg-Mn-Fe-Pb-Zn-Al-Ti-Si-O to obtain optimized Cp for 20 constituent polyhedra. We validate the updated PM against experimental data, demonstrating an overall improvement between 7 and 9 % in the estimation of Cp compared to the previous version of the model. We also compare the updated model with well-established models in the literature, such as the Neumann-Kopp Rule, and ab-initio calculations. The PM shows higher precision than NKR and the linear summation nature of PM endows the model with simplicity which contrasts with ab-initio calculations. Additionally, the model has demonstrated an inherent self-correction capability relative to the original input values, as shown for K2Si4O9. The model is also applied to predict the heat capacity of 10 compounds in the Na2O-PbO-SiO2 and Na2O-ZnO-SiO2 systems, where experimental data are lacking.

AB - The heat capacity of mixed oxides can be estimated using a linear summation of the heat capacities of their structural constituent polyhedra. This approach is particularly useful for hygroscopic and volatile oxides, where experimental data can be difficult to obtain. The present work aims to enhance the polyhedron model (PM) by incorporating contributions from second-order transitions, including magnetic and site order-disorders, into Cp and expanding it to include ZnO and PbO-containing systems in comparison to the previous version of the model. A regression analysis was performed over the new dataset consisting of the properties of 85 compounds in the system Li-Na-K-Ca-Mg-Mn-Fe-Pb-Zn-Al-Ti-Si-O to obtain optimized Cp for 20 constituent polyhedra. We validate the updated PM against experimental data, demonstrating an overall improvement between 7 and 9 % in the estimation of Cp compared to the previous version of the model. We also compare the updated model with well-established models in the literature, such as the Neumann-Kopp Rule, and ab-initio calculations. The PM shows higher precision than NKR and the linear summation nature of PM endows the model with simplicity which contrasts with ab-initio calculations. Additionally, the model has demonstrated an inherent self-correction capability relative to the original input values, as shown for K2Si4O9. The model is also applied to predict the heat capacity of 10 compounds in the Na2O-PbO-SiO2 and Na2O-ZnO-SiO2 systems, where experimental data are lacking.

KW - Heat capacity

KW - Oxides

KW - Polyhedron Model

KW - Second-order transitions

KW - Thermodynamics

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JF - Calphad: Computer Coupling of Phase Diagrams and Thermochemistry

M1 - 102836

ER -

Application of polyhedron model to predict heat capacity of mixed oxides

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