High-entropy materials (HEM), including alloys, ceramics, and composites, are a novel class of materials that have gained enormous attention over the past two decades. These multi-component novel materials with unique structures always have exceptionally good mechanical properties and phase stability at all temperatures. Of particular interest for high-temperature applications, e.g., in the aerospace and nuclear sectors, is the new concept of high-entropy coatings (HEC) on low-cost metallic substrates, which has just emerged during the last few years. This exciting new virgin field awaits exploration by materials scientists and surface engineers who are often equipped with high-performance computational modelling tools, high-throughput coating deposition technologies and advanced materials testing/characterisation methods, all of which have greatly shortened the development cycle of a new coating from years to months/days. This review article reflects on research progress in the development and application of HEC focusing on high-temperature applications in the context of materials/composition type, coating process selection and desired functional properties. The importance of alloying addition is highlighted, resulting in suppressing oxidation as well as improving corrosion and diffusion resistance in a variety of coating types deposited via common deposition processes. This review provides an overview of this hot topic, highlighting the research challenges, identifying gaps, and suggesting future research activity for high temperature applications.
The high-temperature oxidation behaviour and phase stability of equi-atomic high entropy AlCrCoFeNi alloy (HEA) were studied using in situ high-temperature X-ray diffraction (HTXRD) combined with ThermoCalc thermodynamic calculation. HTXRD analyses reveal the formation of B2, BCC, Sigma and FCC, phases at different temperatures, with significant phase transitions observed at intermediate temperatures from 600 °C–100 °C. ThermoCalc predicted phase diagram closely matched with in situ HTXRD findings highlighting minor differences in phase transformation temperature. ThermoCalc predictions of oxides provide insights into the formation of stable oxide phases, predominantly spinel-type oxides, at high p(O2), while a lower volume of halite was predicted, and minor increase observed with increasing temperature. The oxidation behaviour was strongly dependent on the environment, with the vacuum condition favouring the formation of a thin, Al2O3 protective layer, while in atmospheric conditions a thick, double-layered oxide scale of Al2O3 and Cr2O3 formed. The formation of oxide scale was determined by selective oxidation of Al and Cr, as further confirmed by EDX analysis. The formation of thick oxide in air environment resulted in a thick layer of Al-depleted FFC phase. This comprehensive study explains the high-temperature phase stability and time–temperature-dependent oxidation mechanisms of AlCrCoFeNi HEA. The interplay between surface phase transformation beneath oxide scale and oxides is also detailed herein, contributing to further development and optimisation of HEA for high temperature applications.
This paper utilizes in situ X-ray diffraction (XRD) to investigate the high-temperature oxidation behaviour of CrMnFeCoNi high-entropy alloy (HEA). We found that (1) Mn is the major oxide-forming element in both vacuum and air environments, leading to the formation of non-protective oxides that deplete the bulk alloy of Mn; (2) no oxides like Cr2O3, Fe2O3, or Fe3O4 were observed during the high-temperature oxidation behaviour of CrMnFeCoNi, which contradicts some previous studies on the isothermal oxidation of CrMnFeCoNi HEA. We also analysed and compared the experimental results with thermodynamic calculations by using ThermoCalc version 2022b software following the CALPHAD method. ThermoCalc predicted spinel oxide in a vacuum environment, along with halite oxides observed in experimental results; also, in an atmospheric environment, it predicted only spinel, indicating the need for further investigation into factors to validate the thermodynamic predictions. Our study shows that the in situ HTXRD technique is a powerful tool to accurately identify time–temperature-dependent phase formation/transformation for studying oxidation behaviours and understanding oxidation mechanisms in HEAs.
In this research work, real-time three-point bending coupled with the scanning electron microscopy (SEM) technique were used to study the crack formation and growth of air plasma spraying (APS) thermal barrier coatings (TBCs). The acquired micrographs were then used to study the strain fields in the vicinity of the cracking region using digital image correlation (DIC) analysis. Fractography analysis for the fractured regions of the APS coatings was also discussed. Based on real-time observation, it was found that roughness of the coatings’ free surface (e.g., valleys) can promote the initiation of cracks since it acts as stress concentration points. Pores and splats features of the coating microstructure contribute to crack branching and crack path deflection, respectively. The former phenomenon (i.e., crack branching) negatively affects the lifetime of the TBC system as it results in an increased fracture area, while the latter can improve the fracture toughness of the coatings and its durability through improving the coating’s ability to dissipate the energy required for crack propagation.
This study presents novel insights into thermal stress development and crack propagation mechanisms in single- and multilayered suspension plasma-sprayed (SPS) coatings of gadolinium zirconate (GZ) and yttria-stabilized zirconia (YSZ), thermally treated at 1150 °C. By combining image processing with finite element simulation, we pinpointed sites of high-stress concentration in the coatings, leading to specific cracking patterns. Our findings reveal a dynamic shift in the location of stress concentration from intercolumnar gaps to pores near the top coat/thermally grown oxide (TGO) interface with TGO thickening at elevated temperatures, promoting horizontal crack development across the ceramic layers. Significantly, the interface between the ceramic layer and TGO was found to be a critical area, experiencing the highest levels of both normal and shear stresses. These stresses influence failure modes: in double-layer SPS structures, relatively higher shear stresses can result in mode II failure, while in single-layer systems, the predominant normal stresses tend to cause mode I failure. Understanding stress behavior and failure mechanisms is essential for enhancing the durability of thermal barrier coatings (TBCs) in high-temperature applications. Therefore, by controlling the interfaces’ roughness along with improving interfacial toughness, the initiation and propagation of cracks can be delayed along these interfaces. Moreover, efforts to optimize the level of microstructural discontinuities, such as intercolumnar gaps and pores, within the creaming layer and close to the TGO interface should be undertaken to reduce crack formation in the TBC system.