Mechanism and kinetics of high-temperature oxidation of medium- and high-entropy carbides in air

Abstract

Medium- and high-entropy carbides (MECs and HECs) have a wide range of advanced applications and, in many cases, outperform monocarbides. However, the behavior, oxidation mechanisms, and factors defining oxidation resistance of some popular HECs at high temperatures have not been studied in detail yet. In this study, the oxidation behavior of MEC and HECs including (Ta,Ti,Nb,Zr)C, (Ta,Ti,Nb,Zr,Mo)C, (Ta,Ti,Nb,Zr,Hf)C, and (Ta,Ti,Nb,Zr,W)C was investigated under both non-isothermal and isothermal conditions at temperatures up to 1200 °C, and a possible oxidation path was described. It was found that under non-isothermal heating conditions, the oxidation of HECs occurred in three stages, each governed by first-order chemical reactions, and was limited by the formation of ZrO2, Me2Me6O17, and MeMe2O7 oxides, respectively. In the case of isothermal heating, the oxidation of (Ta,Ti,Nb,Zr)C, (Ta,Ti,Nb,Zr,Mo)C, and (Ta,Ti,Nb,Zr,Hf)C follows a logarithmic law and was limited by the formation of a protective Me2Me6O17 layer. In contrast, isothermal oxidation of (Ta,Ti,Nb,Zr,W)C followed a linear law due to the formation of volatile WO3. The results of the study have a high potential for practical application for the production of HEC ceramics for various high-temperature purposes and could be used for further understanding of functional characteristics and development of the new ceramic compositions.