A novel refractory multicomponent boron-carbide coating of 300 nm thickness, HfMoTaTi-BC, was deposited on carbon-carbon composites (CCC). The coating showed a face-centred cubic (FCC) structure of lattice parameter of 0.4429 nm with an average crystallite size of 5 nm. The FCC coating transformed from single-phase solid solution into multiple ceramic carbides and boride phases at 900°C during long-term thermal stability test. The exposure of HEC coated CCC to the flame (2000°C) of liquefied petroleum gas (LPG) torch for 5 minutes revealed that the film had excellent resistance to oxidation and protected the CCC material under extreme aerothermal heating.

Ultra-high temperature ceramic composites have been widely investigated due to their improved sinterability and superior mechanical properties compared to monolithic ceramics. In this work, high-entropy boron-carbide ceramic/SiC composites with different SiC content were synthesized from multicomponent carbides HfC, Mo₂C, TaC, TiC, B₄C, and SiC in spark plasma sintering (SPS) from 1600 °C to 2000 °C. It was found that the SiC addition tailors the phase formation and mechanical properties of the high-entropy ceramic (HEC) composites. The microhardness and fracture toughness of the HEC composites sintered at 2000 °C were improved from 20.3 GPa and 3.14 MPa·m^1/2 to 26.9 GPa and 5.95 MPa·m^1/2, with increasing SiC content from HEC-(SiC)0 (0 vol. %) to HEC-(SiC)3.0 (37 vol. %). The addition of SiC (37 vol. %) to the carbide precursors resulted in the formation of two high-entropy ceramic phases with two different crystal structures, face-centered cubic (FCC) structure, and hexagonal structure. The volume fraction ratio between the hexagonal and FCC high-entropy phases increased from 0.36 to 0.76 when SiC volume fraction was increased in the composites from HEC-(SiC)0 to HEC-(SiC)3.0, suggesting the stabilization of the hexagonal high-entropy phase over the FCC phase with SiC addition.

High-entropy alloy (HEA) is a multicomponent alloy material that contains five or more principal elements in equi- or near equi-atomic ratios. The entropy stabilisation leads to the formation of a crystalline solid solution accommodating the principal elements. The HEA solid solution has characteristic features such as lattice distortion, sluggish diffusion and cocktail effect that contribute to the superior properties of HEA including high strength, high hardness, excellent thermal and chemical stability, etc. The concept of HEA has been extended to ceramic materials to process high-entropy ceramic (HEC) that consists of multiple ceramic compounds such as metallic oxides, nitrides or carbides. The HECs have shown entropy stabilisation and formed single-phase ceramic solid solutions. However, the formation mechanism of high-entropic phase in HECs remains unclear and unpredictable. Generally, in order to maximise the probability of forming a high-entropy solid solution in a ceramic system, ceramic compounds with least difference in the crystal structure, preferably with only one anionic constituent element, are favoured when designing HECs, which limits the potential of discovering and developing new HECs. In this project, a multicomponent ceramic system containing six ultra-high temperature ceramics (UHTCs), B4C, HfC, Mo2C, TaC, TiC and SiC, was used to investigate the formation of high-entropy ceramics, UHTC composites, as well as the microstructure evolution, properties and high temperature applications. A ceramic composite composed of SiC and a high-entropy boron-carbide with hexagonal crystal structure was successfully processed from the carbide system in spite of the difference in the crystal structures of precursors (face-centred cubic, hexagonal and rhombohedral). The hexagonal HEC solid solution exhibited a unique AlB2 structure with alternating layers of metal and non-metal C/B atoms according to the experimental and simulation investigations. The HEC/SiC composite showed superior mechanical properties such as ultra-high hardness, excellent wear and oxidation resistance. The addition of B4C was discovered to be the key factor in the formation of the hexagonal high-entropy boron-carbide solid solution, while the final phase composition was tailored by utilising precursors of different particle size. Additionally, SiC as the reinforcement component in the HEC/SiC composite was used to tailor the microstructure, phase evolution and mechanical properties of the high-entropy boron-carbide composite. Higher content of SiC resulted in enhanced mechanical properties such as hardness and fracture toughness, as well as promoted the formation of the hexagonal high-entropy boron-carbide solid solution. To extend the investigation on the high-entropy boron-carbide composite to application, B4C, HfC, Mo2C, TaC and TiC were consolidated into a target for magnetron sputtering. The target was used to deposit oxidation-resistant high-entropy coatings using magnetron sputtering on carbon-carbon composites. The coatings showed superior mechanical performance and high temperature oxidation resistance at 2000 °C on carbon-carbon composite, suggesting potential applications of high-entropy boron-carbide ceramics as a protective coating material against oxidation at elevated temperature. This work pointed out the possibilities of synthesising high-performance HECs with superior properties from components with vast elemental and structure diversity, and thereby advanced the design criteria of HECs and provided more potential research directions for the new high-performance ceramic materials.

High-entropy ceramics is an emerging class of high-entropy materials with properties superior to conventional ceramics. Recent research has been focused on the development of new high-entropy ceramic compositions. High-entropy oxides, carbides, borides, silicides, and boron carbides had been reported with superior mechanical, oxidation, corrosion, and wear properties. The research work on the processing and characterization of bulk high-entropy ceramics and coating systems has been summarized in this chapter. The composition design, structure, chemistry, composite processing of bulk high-entropy ceramics, and evolution of microstructure and properties are reported. The literature on the deposition of high-entropy ceramic coating and the influence of coating parameters have been discussed to produce high-entropy ceramic coatings with superior mechanical, oxidation, and wear properties. 

A multicomponent composite of refractory carbides, B₄C, HfC, Mo₂C, TaC, TiC and SiC, of rhombohedral, face-centered cubic (FCC) and hexagonal crystal structures is reported to form a single phase B₄(HfMo₂TaTi)C ceramic with SiC. The independent diffusion of the metal and nonmetal atoms led to a unique hexagonal lattice structure of the B₄(HfMo₂TaTi)C ceramic with alternating layers of metal atoms and C/B atoms. In addition, the classical differences in the crystal structures and lattice parameters among the utilized carbides were overcome. Electron microscopy, X-ray diffraction and calculations using density functional theory (DFT) confirmed the formation of a single phase B₄(HfMo₂TaTi)C ceramic with a hexagonal close-packed (HCP) crystal structure. The DFT based crystal structure prediction suggests that the metal atoms of Hf, Mo, Ta and Ti are distributed on the (0001) plane in the HCP lattice, while the carbon/boron atoms form hexagonal 2D grids on the (0002) plane in the HCP unit cell. The nanoindentation of the high-entropy phase showed hardness values of 35 GPa compared to the theoretical hardness value estimated based on the rule of mixtures (23 GPa). The higher hardness was contributed by the solid solution strengthening effect in the multicomponent hexagonal structure. The addition of SiC as the secondary phase in the sintered material tailored the microstructure of the composite and offered oxidation resistance to the high-entropy ceramic composite at high temperatures.

Porous FeAl-based intermetallics with different nominal compositions ranging from Fe–40 at% Al to Fe–60 at% Al are prepared by a novel process of thermal explosion (TE) mode. The results show that the Al content significantly affects the combustion behavior of the specimens, the ignition temperature of the Fe–Al intermetallics varies from 641 to 633 °C and the combustion temperature from 978 to 1179 °C. The porous materials exhibit uniform pore structures with porosities and average pore sizes of 52–61% and 20–25 µm, respectively. The TE reaction is the dominant pore formation mechanism regardless of the alloy composition. However, differences in the porosity and average pore size are observed depending on the Al content. The compressive strength of porous Fe–Al intermetallics is in the range of 23–34 MPa, duly applied as filters. Additionally, a surface alumina layer is formed at the early stage and both of the oxidation process and the sulfidation process follows the familiar parabolic rate law in the given atmosphere, exhibiting excellent resistance to oxidation and sulfidation. These results suggest that the porous Fe–Al intermetallics are promising materials for applications in harsh environments with a high-temperature sulfide-bearing atmosphere, such as in the coal chemical industry.

Refractory carbides HfC, Mo2C, TiC, TaC, B4C, and SiC were mixed with a molar ratio of 2:1:2:2:1:2 to fabricate multicomponent ceramic composite by pulsed current processing (PCP). From the starting materials that consist of face-centered cubic (FCC), hexagonal and rhombohedral crystal structures, the investigated carbide system is reported to form a single phase B2(HfMoTaTi)C high-entropy ceramic (HEC) with SiC. The HEC phase contains uniform distribution of constitutional elements Hf, Mo, Ta, Ti, B and C, according to Energy dispersive X-ray spectroscopy (EDS) and wavelength dispersive X-ray spectroscopy (WDS) results.

The fabricated HEC phase displays a hexagonal close-packed (HCP) crystal structure, with a high average lattice distortion of 8.26% (see Figure). The HCP structure was observed by X-ray diffraction and selected area diffraction in transmission electron microscopy (TEM). Density-functional theory (DFT) optimization suggested that the hexagonal close-packed (HCP) crystal structure has alternating layers of metal atoms and carbon/boron atoms, i.e. metal atoms of Hf, Mo, Ta and Ti were distributed on the (0001) plane in the HCP lattice, while the carbon/boron atoms formed hexagonal 2D grids on the (0002) plane in the HCP unit cell. Despite of the vast differences in the crystal structures and lattice parameters among the utilized carbides, the formation of the unique hexagonal lattice structure of B2(HfMoTaTi)C can be a result of independent diffusion of the metal and nonmetal atoms. The sintered HEC ceramic composite exhibits excellent oxidation resistance at mediate temperature, 900 ºC for 50h, and elevated temperature, 2000 ºC for 20 s. Nanoindentation test shows that the HEC phase has a high hardness of 35 GPa. The remarkable improvement compared to the theoretical hardness value estimated based on the rule of mixtures (23 GPa) was contributed by the severe lattice distortion in the HCP structure. 

Quaternary high-entropy ceramic (HEC) composite was synthesized from HfC, Mo₂C, TaC, and TiC in pulsed current processing. A high-entropy solid solution that contained all principal elements along with a minor amount of a Ta-rich phase was observed in the microstructure. The high entropy phase and Ta-rich phase displayed a face-centered cubic (FCC) crystal structure with similar lattice parameters, suggesting that TaC acted as a solvent carbide during phase evolution. The addition of B₄C to the quaternary carbide system induced the formation of two high-entropy solid solutions with different elemental compositions. With the increase in the number of principal elements, on the addition of B₄C, the crystal structure of the HEC phase transformed from FCC to a hexagonal structure. The study on the effect of starting particle sizes on the phase composition and properties of the HEC composites showed that reducing the size of solute carbide components HfC, Mo₂C, and TiC could effectively promote the interdiffusion process, resulting in a higher fraction of a hexagonal structured HEC phase in the material. On the other hand, tuning the particle size of solvent carbide, TaC, showed a negligible effect on the composition of the final product. However, reducing the TaC size from −325 mesh down to <1 µm resulted in an improvement of the nanohardness of the HEC composite from 21 GPa to 23 GPa. These findings suggested the possibility of forming a high-entropy ceramic phase despite the vast difference in the precursor crystal structures, provided a clearer understanding of the phase transformation process which could be applied for the designing of HEC materials.

MoSi₂ZrB₂SiC ceramics were synthesized using Mo, Zr, Si and B₄C powders by self-propagating high-temperature synthesis and densifying by spark plasma sintering. The effects of MoSi₂ content on the combustion synthesis process, microstructure, and mechanical properties of the ceramics were investigated. The results showed that combustion synthesis is an unstable mode, spiral combustion. The Gibbs calculations and combustion temperature curves indicate there are two reactions occurring at the same time. The volume fraction of the four different phases and their relative densities were also measured and calculated. Compared to pure MoSi₂, the 1.0MoSi₂0.2ZrB₂0.1SiC (M10) ceramic exhibits excellent mechanical properties with its maximum Vickers hardness and fracture toughness being 14.0 GPa and of 5.5 MPa m¹/², respectively. The hardness is in agreement with the rule of mixture. The morphology of indentation cracks reveals that the fracture toughness improves as a result of toughening mechanisms such as crack bridge, crack deflection, and microcracks.