Microstructures and mechanical properties of high-entropy (Ti0.2Zr0.2Hf0.2Nb0.2Ta0.2)C ceramics with the addition of SiC secondary phase

The relationships between microstructures and mechanical properties especially strength and toughness of high-entropy carbide based ceramics are reported in this article. Dense (Ti_0.2Zr_0.2Hf_0.2Nb_0.2Ta_0.2)C (HEC) and its composite containing 20 vol.% SiC (HEC-20SiC) were prepared by spark plasma sintering. The addition of SiC phase enhanced the densification process, resulting in the promotion of the formation of the single-phase high-entropy carbide during sintering. The high-entropy carbide phase demonstrated a fast grain coarsening but SiC particles remarkably inhibited this phenomena. Dense HEC and HEC-20SiC ceramics sintered at 1900 °C exhibits four-point bending strength of 332 ± 24 MPa and 554 ± 73 MPa, and fracture toughness of 4.51 ± 0.61 MPa·m^1/2 and 5.24 ± 0.41 MPa·m^1/2, respectively. The main toughening mechanism is considered to be crack deflection by the SiC particles.     

Ultra-high temperature ablation behavior of MoAlB ceramics under an oxyacetylene flame

The ultra-high temperature ablation of a polycrystalline, fully dense, predominantly single phase MoAlB ceramic discs under an oxyacetylene flame is examined. The linear ablation rate decreases from 1.3 μm/s during the first 30 s to - 0.7 μm/s after 60 s when the surface temperature reached about 2050 °C (with a flame temperature around 3000 °C). Up to 60 s, the MoAlB is ablation resistant due to the formation of a protective and viscous surface Al₂O₃ layer. As the ablation time is prolonged, the protective Al₂O₃ scale becomes porous and is almost fully destroyed at the central ablation region after 120 s. This accelerates the formation of large amounts of volatile species (mainly B and Mo oxides), resulting in a reduction in the ablation resistance.     

Ablation behavior of CVD-TaC coatings with different crystal structures for C/C composites under oxyacetylene flame

TaC coatings with four kinds of crystal structures were prepared on carbon/carbon composites by chemical vapor deposition. The surface morphologies, microstructure transformation, and ablative behaviors of TaC coated C/C specimens were investigated. Results show that the coatings with acicular crystal structure exhibit better ablation resistance with lower ablation rates, especially the needle-piled sample. The bistratal structure composed of dense glass layer and compact TaC layer is beneficial for maintaining the integrity of acicular samples after ablation. But the formation of lamella grains and porous middle layer is the main factor for the damage and even exfoliation of the columnar specimens.     

Microstructure and properties of the AlCrMoZrTi/(AlCrMoZrTi)N multilayer high-entropy nitride ceramics films deposited by reactive RF sputtering

The AlCrMoZrTi/(AlCrMoZrTi)N multilayer high-entropy nitride ceramic films (HENCFs) fabricated by reactive RF magnetron sputtering presented (200) preferentially oriented FCC crystal structures. With the increase in the modulation period, the nitrogen content and surface roughness of the multilayer films gradually increased, the template effect between the nanocrystalline and amorphous forms was weakened, and the multilayer interface structure decreased. The S4 film with a modulation period of 1500 nm had the highest hardness and modulus (16.6 and 225.7 GPa, respectively) and the highest H/E* and H³/E*² values. The results of friction experiments showed that the S1 film with the smallest modulation period had a stable friction coefficient and small wear rate on both Si and Cu substrates, and it exhibited the best friction and wear performance due to its low surface roughness, high toughness and compressive yield resistance, and dense multilayer structure. The friction mechanisms of the HECNFs on Si and Cu substrates were mainly adhesive wear, abrasive wear, and a small amount of oxidative wear.     

Ultra-high temperature ablation behavior of Ti2AlC ceramics under an oxyacetylene flame

The linear and mass ablation rates of Ti₂AlC ceramics under an oxyacetylene flame at a temperature up to 3000 °C were examined by measuring the dimensions and weight change of the ablated samples. The linear ablation rate was decreased from 0.14 μm s⁻¹ for the first 30 s of the ablation to 0.08 μm s⁻¹ after 180 s. Ti₂AlC ceramics gained small amounts of weight upon ablation, which is attributed to the formation of oxidation products on the ablated surface. The ablation surface exhibits a two-layer structure: an oxide outer layer, consisting mainly of α-Al₂O₃ and TiO₂ and some Al₂TiO₅, and a porous sub-surface layer containing Ti₂Al_1−xC and TiC_xO_y. With increasing ablation time, the content of TiO₂ and Al₂TiO₅ in the outer layer increased, and more pores developed in the sub-surface layer. The thermal oxidation of Ti₂AlC under the flame and scouring of the viscous oxidation products by high-speed flow of gas torch are the main ablation mechanisms.     

Synthesis,microstructure and mechanical properties of high-entropy (VNbTaMoW)C5 ceramics

High-entropy ceramics (HEC) with a fixed composition of (VNbTaMoW)C₅ were prepared by spark plasma sintering (SPS) from 1500 °C to 2200 °C. XRD, TEM, HRTEM, SAED and EDX were used to investigate effects of the sintering temperatures on compositional homogeneity, constituent phases and microstructure of the HECs. The results showed that single-phase HEC formed at a temperature as low as 1600 °C while ultimate elemental distribution homogeneity could be obtained at 2200 °C. Elemental distribution homogenization was accompanied by microstructural coarsening and oxide impurities aggregating at grain boundaries as temperature increased. SPS at 1900 °C for 12 min could yield uniform HECs (VNbTaMoW)C₅ with Vickers hardness, nanohardness, fracture toughness and Young’s modulus reaching 19.6 GPa, 29.7 GPa, 5.4 MPa m^1/2 and 551 GPa, respectively. The resultant HECs showed excellent wear resistance when coupled with WC at room temperature.     

Microstructural damage evolution of (WTiVNbTa)C5 high-entropy carbide ceramics induced by self-ions irradiation

High-entropy carbide ceramics (WTiVNbTa)C₅ were prepared by spark plasma sintering and irradiated with 1.0 MeV C-ions at room temperature (RT) and 650 ℃. Irradiation induced damage evolution and mechanical properties change were investigated. GIXRD and TEM results showed that the irradiation led to lattice expansion and micro-strain formation in the samples, which originated from the irradiation induced defects. The black-dot defects dominated in the damaged microstructure at fluence of 1E16 ions/cm² and transformed into dislocation loops and networks with the fluence increased at RT. Reduction of irradiation damage and formation of defect denuded zone were observed at 650 ℃. No amorphization or void formation were observed for all samples after irradiation. The irradiation hardening was most severe at fluence of 1E16 ions/cm² and recovered at higher fluence or temperature, while the elastic modulus monotonically decreased. The correlation between microstructural evolution and mechanical properties response was discussed.     

Novel high-entropy microwave dielectric ceramics Sr(La0.2Nd0.2Sm0.2Eu0.2Gd0.2)AlO4 with excellent temperature stability and mechanical properties

Novel high-entropy Sr(La_0.2Nd_0.2Sm_0.2Eu_0.2Gd_0.2)AlO₄ ceramics with a layered perovskite structure have been prepared via the standard solid-state reaction method. The design of high-entropy improves the bond valence and subsequently optimizes the large negative temperature coefficient of resonant frequency (τ_f = ?32 ppm/°C) of the simple SrLaAlO₄ ceramics. Excellent temperature stability (τ_f = ?6 ppm/°C) together with a relative permittivity (ε_r) of 18.6 and a quality factor (Qf = 14,509 GHz) are obtained in Sr(La_0.2Nd_0.2Sm_0.2Eu_0.2Gd_0.2)AlO₄ ceramics sintered at 1475 °C. It indicates that the present ceramics have great application prospects in passive microwave components such as resonators and filters. Meanwhile, significant improvements in compressive strength and strain are achieved, which are 1040 MPa and 15.7% for Sr(La_0.2Nd_0.2Sm_0.2Eu_0.2Gd_0.2)AlO₄ compared to 583 MPa and 12% in SrLaAlO₄. The enhanced mechanical properties originate from the dislocation strengthening mechanism as the intertwining of interlayer lattices is revealed from the high-resolution transmission electronic micrographs.     

Formation mechanism and high-temperature self-lubricating behavior of (HfMoNbTaTi)C system single-phase high-entropy ceramics

It is a substantial challenge to obtain single-phase ceramics with self-lubricating properties. Most conventional lubricated ceramics benefit from the addition of solid lubricants, which largely deteriorate theirs mechanical properties. Here, we report a single-phase (HfMoNbTaTi)C system high-entropy ceramic with self-lubricity inspired by the novel high-entropy design concept and regulation of high-temperature lubrication components (with different Mo contents). The formation mechanism of the single-phase structure is ascribed to the increasing of carbon vacancies with the increasing of Mo content. Meanwhile, the tribological performances are greatly enhanced at high temperature. Especially for (Hf_0.149Mo_0.404Nb_0.149Ta_0.149Ti_0.149)C_0.745 ceramic (with 20 wt% Mo) against Al₂O₃ ball at 900 °C, the average friction coefficient is as low as 0.6, and its wear rate is reduced an order of magnitude. The results show that the self-lubrication mechanisms are tribo-chemical reactions to generate lubricating tribo-films.     

Ablation behavior and mechanism of boron nitride - magnesium aluminum silicate ceramic composites in an oxyacetylene combustion flame

In the present study, ablation behavior and properties of BN-MAS (magnesium aluminum silicate) composites impinged with an oxyacetylene flame at temperatures up to 3100 °C were investigated. As ablation time ranged from 5 to 30 s, the mass and linear ablation rates increased from 0.0027 g/s and 0.001 mm/s to 0.0254 g/s and 0.087 mm/s, respectively. A SiO₂-rich protective oxide layer formed during the ablation process, which contributed to the oxidation resistance of the composites. Ablation products mainly consisted of magnesium-aluminum borosilicate glass, mullite, spinel and indialite. The thermal oxidation of h-BN during flame ablation and scouring of MAS by high-speed gas flow were the main ablation mechanisms.     

Ablation behavior of a C/C-ZrC-SiC composite based on high-solid-loading slurry impregnation under oxyacetylene torch

A C/C-ZrC-SiC composite was successfully prepared by high-solid-loading slurry impregnation combined with polymer infiltration and pyrolysis. The microstructure and ablation behavior of the C/C–ZrC–SiC composite were investigated. ZrC particles were uniformly distributed in the matrix, and the obtained C/C–ZrC–SiC composite had a high density of 2.74 g/cm³. After exposure to oxyacetylene flame with a heat flux of 3.86 MW/m² for 120 s, the mass and linear ablation rates of the composite were 0.72 ± 0.11 mg/s and 0.52 ± 0.09 µm/s, respectively. The excellent ablation properties of the composite were attributed to the protection of the matrix by a three-layered oxide scale consisting of ZrO₂/SiO₂-rich/ZrO₂-SiO₂.     

High-temperature oxidation behavior of (Hf0.2Zr0.2Ta0.2Nb0.2Ti0.2)C high-entropy ceramics in air

High-entropy metal carbides have recently been arousing considerable interest. Nevertheless, their high-temperature oxidation behavior is rarely studied. Herein the high-temperature oxidation behavior of (Hf_0.2Zr_0.2Ta_0.2Nb_0.2Ti_0.2)C high-entropy metal carbide (HEC-1) was investigated at 1573-1773 K in air for 120 minutes. The results showed that HEC-1 had good oxidation resistance and its oxidation obeyed a parabolic law at 1573-1673 K, while HEC-1 was completely oxidized after isothermal oxidation at 1773 K for 60 minutes and thereby its oxidation followed a parabolic-linear law at 1773 K. An interesting triple-layered structure was observed within the formed oxide layer at 1673 K, which was attributed to the inward diffusion of O₂ and the outward diffusion of Ti element and CO or CO₂ gaseous products.     

Effect of carbon content on the microstructure and mechanical properties of high-entropy (Ti0.2Zr0.2Nb0.2Ta0.2Mo0.2)Cx ceramics

High-entropy (Ti_0.2Zr_0.2Nb_0.2Ta_0.2Mo_0.2)C_x ceramics, with different carbon contents (x=0.55?1), were prepared by spark plasma sintering using powders synthesized via a carbothermal reduction approach. Single-phase, high-entropy (Ti_0.2Zr_0.2Nb_0.2Ta_0.2Mo_0.2)C_x ceramics could be obtained when using a carbon content of x=0.70?0.85. Combined ZrO₂ and Mo-rich carbide phases, or residual graphite, existed in the ceramics due to either a carbon deficiency or excess at x=0.55 and 1, respectively. With the carbon content increased from x=0.70 to x=0.85, the grain size decreased from 4.36 ± 1.55 μm to 2.00 ± 0.91 μm, while the hardness and toughness increased from 23.72 ± 0.26 GPa and 1.69 ± 0.21 MPa·m^1/2 to 25.45 ± 0.59 GPa and 2.37 ± 0.17 MPa·m^1/2, respectively. This study showed that the microstructure and mechanical properties of high-entropy carbide ceramics could be adjusted by the carbon content. High carbon content is conducive to improving hardness and toughness, as well as reducing grain size.     

Ablation properties and mechanisms of BN-coated Cf-reinforced SiBCNZr ceramic composites under an oxyacetylene combustion torch

The ablation properties andmechanisms of BN-coated C_f-reinforced SiBCNZr composites under an oxyacetylene combustion torch were investigated. The mass and linear ablation rates of the C_f/SiBCNZr ceramic matrix composites were lower than those of C_f/SiBCN and SiC_f/SiBCN composites, reaching 0.0022 mg/s and 0.0136 mm/s, respectively. The ablation resistance of the SiBCN ceramics was enhanced by the addition of Zr, whereas the BN-coated C_f increased the thermal shock resistance of the SiBCNZr ceramics. No macrocracks were found on the ablation surface of the C_f/SiBCNZr specimen. The ablation mechanisms based on different ablation temperatures, phase evolution during ablation, and ablation morphologies in the different ablation regions consisted of oxidation of the carbon fibre and ceramic matrix, emission of various gases, the flow of high-viscosity SiO₂, and denudation of C_f under the erosion of the ablation flame.     

Ablation behavior of three-dimensional braided C/SiC composites by oxyacetylene torch under different environments

SiC ceramic matrix composites reinforced by three-dimensional braided carbon fibers were prepared via polycarbosilane infiltration pyrolysis (PIP). The ablation behavior of the composites was characterized by an oxyacetylene torch under different environments. The morphology and microstructure of the as-ablated composites were examined by scanning electron microscopy and the composition of the new phase was confirmed by energy dispersive spectroscopy. Two conditions showed different ablation mechanisms. The erosion mechanism of the high speed oxyacetylene torch was the main ablation behavior under oxygen free environment. Thermo-chemicals ablation was the main ablation behavior under abundant oxygen environment.     

Ablation behavior of single and alternate multilayered ZrC-SiC coatings under oxyacetylene torch

Based on the investigation of ablation behavior and thermal stress of the monolayered ZrC-SiC coatings with different SiC amounts, an alternate coating consisting of 4 sublayers with 10 and 70 vol.% SiC was prepared on SiC-coated carbon/carbon (C/C) composites through plasma spraying technique. Ablation tests were carried out under oxyacetylene torch with a heat flux of 2.38 MW/m². The alternate coating could offer 90 s ablation shield for C/C composites, providing superior ablation properties than all monolayered coatings. The improved ablation resistance is mostly induced by the fact that the outmost scale with abundant ZrO₂ particles was able to better endure the mechanical denudation from the torch. Moreover, due to the indirect contact with torch, the innermost sublayers were placed into relatively mild environment, thereby most of Si-based oxides could be retained and further hinder oxygen transport inward during ablation.     

Microstructure and dielectric properties of perovskite-structured high-entropy ceramics of Pb(Zr0.25Ti0.25Sn0.25Hf0.25)O3

A dielectric high-entropy ceramic with a composition of Pb(Zr_0.25Ti_0.25Sn_0.25Hf_0.25)O₃ was designed through B-site doping, and then prepared by solid phase reaction method combined with conventional sintering in air for 3 h at 1200 ^°C, 1250 ^°C and 1300 ^°C, respectively. All the high-entropy ceramics of Pb(Zr_0.25Ti_0.25Sn_0.25Hf_0.25)O₃ possess a perovskite structure with uniform elemental distribution and their average grain size falls within the range of 3.19–5.5 μm. For the sample sintered at 1250 ^°C, the dielectric loss is less than 0.07 in the testing frequency of 1 kHz∼1 MHz in 30–350 ^°C, and the dielectric constant reaches a peak of 14356 at about 270 ^°C at 1 kHz. At room temperature, the remnant polarization P_r reaches 28.8 μC/cm². The results demonstrate that the high-entropy ceramic of Pb(Zr_0.25Ti_0.25Sn_0.25Hf_0.25)O₃ has great potentials in the dielectric and ferroelectric field.     

High-entropy carbide ceramics with refined microstructure and enhanced thermal conductivity by the addition of graphite

Aiming at the refined microstructure and enhanced thermal conductivity of high-entropy carbide (HEC) ceramics for high-temperature applications, the addition effect of graphite was comprehensively investigated in this study. HEC ceramics incorporated with different contents of graphite were solidified by spark plasma sintering (SPS) using self-synthesized high-entropy (Ti_0.2Zr_0.2Hf_0.2Nb_0.2Ta_0.2)C powder and graphite as starting materials. The results demonstrate that the incorporated graphite removed the oxygen impurity in the mixed powders, decreased the oxygen content and increased the lattice parameter of the HEC phase, and improved the densification behavior of HEC ceramics. On the other hand, the addition of graphite brings a refinement of HEC grains and improves the mechanical properties. More importantly, the thermal conductivity of the HEC ceramics was significantly increased owing to the removing effect of oxide impurity by the added graphite. It is considered that the lattice "purified" HEC grains with low oxygen content contribute to the improvement in thermal conductivity of the ceramics.     

Phase stability,mechanical and thermodynamic properties of (Hf,Zr, Ta,M)B2 (M= Nb,Ti, Cr,W) quaternary high-entropy diboride ceramics via first-principles calculations

As the high-entropy design concept applied to the diboride ceramic system, high-entropy diboride ceramics with a wide range of composition control, is expected to become a new high-performance material for extreme high-temperature environments. Herein, the effects of four transition metal elements (Nb, Ti, Cr, W) on the phase stability and properties of (Hf, Zr, Ta)B₂-based high-entropy diboride ceramics are systematically investigated via the first-principles calculations. All components were identified as thermodynamically, mechanically and dynamically stable from enthalpy of formation, elastic and phonon spectrum calculations. Among these, compared with the (Hf, Zr, Ta)B₂ ceramics, the addition of Nb and Ti on the metal sublattice is beneficial to improve the mechanical properties of ceramics, including Young's modulus, hardness and fracture toughness, while the introduction of Cr and W weakens the strength of covalently and ionic bonds inside the material, reducing its mechanical properties. The predicted thermophysical properties show that the high-entropy diboride ceramics containing Nb and Ti have better high-temperature comprehensive performance, including higher Debye temperature, thermal conductivity and lower thermal expansion characteristics, which is conducive to the application in extreme high-temperature environments. This research will provide important guidance for the design and development of new high-performance high-entropy diboride ceramics.