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.     

First-principles study,fabrication, and characterization of (Hf0.2Zr0.2Ta0.2Nb0.2Ti0.2)C high-entropy ceramic

The formation possibility of (Hf_0.2Zr_0.2Ta_0.2Nb_0.2Ti_0.2)C high-entropy ceramic (HHC-1) was first analyzed by the first-principles calculations, and then, it was successfully fabricated by hot-pressing sintering technique at 2073 K under a pressure of 30 MPa. The first-principles calculation results showed that the mixing enthalpy and mixing entropy of HHC-1 were −0.869 ± 0.290 kJ/mol and 0.805R, respectively. The experimental results showed that the as-prepared HHC-1 not only had an interesting single rock-salt crystal structure of metal carbides but also possessed high compositional uniformity from nanoscale to microscale. By taking advantage of these unique features, it exhibited extremely high nanohardness of 40.6 ± 0.6 GPa and elastic modulus in the range from 514 ± 10 to 522 ± 10 GPa and relatively high electrical resistivity of 91 ± 1.3 μΩ·cm, which could be due to the presence of solid solution effects.     

Microstructures and oxidation mechanisms of (Zr0.2Hf0.2Ta0.2Nb0.2Ti0.2)B2 high-entropy ceramic

A nano dual-phase powder with great sinterability was synthesized by molten-salt assisted borothermal reductions at 1100 °C using B, ZrO₂, HfO₂, Ta₂O₅, Nb₂O₅ and TiO₂ powders as raw materials. Single-phase (Z_r0.2Hf_0.2Ta_0.2Nb_0.2Ti_0.2)B₂ high-entropy ceramic was prepared by spark plasma sintering using the as-synthesized nano dual-phase powder. Oxidation behavior of the (Zr_0.2Hf_0.2Ta_0.2Nb_0.2Ti_0.2)B₂ ceramic was investigated over the range of 30–1400 °C in air and the result indicated that the rapid oxidation of ceramic began at 1300 °C. The phenomenon could be ascribed to the rapid volatilization of B₂O₃ from oxide scale. A layered structure was formed at the cross section of (Zr_0.2Hf_0.2Ta_0.2Nb_0.2Ti_0.2)B₂ ceramic after oxidation. The relationship between partial pressures of gaseous metal oxides and oxygen partial pressures was calculated, which inferred that the formation of layered structure could be ascribed to the active oxidation of (Zr_0.2Hf_0.2Ta_0.2Nb_0.2Ti_0.2)B₂, the generation of gaseous metal oxides, their outward diffusion and further oxidation.     

(Hf0.2Zr0.2Ta0.2Nb0.2Ti0.2)C high‐entropy ceramics with low thermal conductivity

A novel high‐entropy carbide ceramic, (Hf_0.2Zr_0.2Ta_0.2Nb_0.2Ti_0.2)C, with a single‐phase rock salt structure, was synthesized by spark plasma sintering. X‐ray diffraction confirmed the formation of a single‐phase rock salt structure at 26‐1140°C in Argon atmosphere, in which the 5 metal elements may share a cation position while the C element occupies the anion position. (Hf_0.2Zr_0.2Ta_0.2Nb_0.2Ti_0.2)C exhibits a much lower thermal diffusivity and conductivity than the binary carbides HfC, ZrC, TaC, and TiC, which may result from the significant phonon scattering at its distorted anion sublattice. (Hf_0.2Zr_0.2Ta_0.2Nb_0.2Ti_0.2)C inherits the high elastic modulus and hardness of the binary carbide ceramics.     

First-principles prediction,fabrication and characterization of (Hf0.2Nb0.2Ta0.2Ti0.2Zr0.2)B2 high-entropy borides

The microstructure and mechanical properties of (Hf_0.2Nb_0.2Ta_0.2Ti_0.2Zr_0.2)B₂ high-entropy boride (HEB) were first predicted by first-principles calculations combined with virtual crystal approximation (VCA). The results verified the suitability of VCA scheme in HEB studying. Besides, single-phase (Hf_0.2Nb_0.2Ta_0.2Ti_0.2Zr_0.2)B₂ ceramics were successfully fabricated using boro/carbothermal reduction (BCTR) method and subsequent spark plasma sintering (SPS); furthermore, the effects of different amounts of B₄C on microstructure and mechanical properties were evaluated. Due to the addition of B₄C and C, all samples formed single-phase solid solutions after SPS. When the excess amount of B₄C increased to 5 wt%, the sample with fine grains exhibited superior comprehensive properties with the hardness of 18.1 ± 1.0 GPa, flexural strength of 376 ± 25 MPa, and fracture toughness of 4.70 ± 0.27 MPa m^1/2. Nonetheless, 10 wt% excess of B₄C coarsened the grains and decreased the strength of the ceramic. Moreover, the nanohardness (34.5–36.9 GPa) and Young's modulus (519–571 GPa) values with different B₄C contents just showed a slight difference and were within ranges commonly observed in high-entropy diboride ceramics.     

Low-temperature synthesis of high-entropy (Hf0.2Ti0.2Mo0.2Ta0.2Nb0.2)B2 powders combined with theoretical forecast of its elastic and thermal properties

A theoretical calculation combined with experiment was used to study high-entropy (Hf_0.2Ti_0.2Mo_0.2Ta_0.2Nb_0.2)B₂ (HEB-HfTiMoTaNb). The theoretical calculation suggested HEB-HfTiMoTaNb could be stable over a wide temperature range. Then, a novel solvothermal/molten salt-assisted borothermal reduction method was proposed to efficiently pre-disperse transitional metal atoms in a precursor and synthesize (Hf_0.2Ti_0.2Mo_0.2Ta_0.2Nb_0.2)B₂ nanoscale powders at 1573 K for 6 h, which is nearly 300 K lower than previous reports. The characterization results indicated that the as-synthesized nanoscale HEB-HfTiMoTaNb powder was hexagonal single-phase with homogeneous elements distribution and uniform size, and the oxygen content of the particles is 0.97 wt%. Simultaneously, the mechanical properties, anisotropic nature, and thermal properties of HEB-HfTiMoTaNb were investigated by density functional theory (DFT) calculations. The Cannikin's law was adopted to explain the improvement of comprehensive mechanical properties. In addition, a significant reduction of thermal conductivity was observed for HEB-HfTiMoTaNb and it only was 1/15 of the value of HfB₂. This work suggests a reliable technique for synthesis of nanosized HEB powders and discovery of high-entropy materials under the guidance of first-principle theory.     

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.     

Improvement of densification and microstructure of HfB2 ceramics by Ta/Ti substitution for Hf

Ultrafine HfB₂ powders were synthesized by the combination of borothermal reduction of HfO₂ and solid solution of 5 mol% TiB₂ or 5 mol% TaB₂, prototypically, (Hf_0.95Ti_0.05)B₂ and (Hf_0.95Ta_0.05)B₂. The influence of substitution on the particle growth, high-temperature stability, densification, microstructure, and mechanical properties of HfB₂ was investigated. Results showed that the particle sizes of HfB₂, (Hf_0.95Ti_0.05)B₂ and (Hf_0.95Ta_0.05)B₂ powders prepared by borothermal reduction at 1500°C were 1.73, 0.87, and 0.21 µm, respectively. The substitution of TaB₂ led to a greater decrease in particles size than TiB₂. After heat treatment at 1800°C, the particle sizes of HfB₂, (Hf_0.95Ti_0.05)B₂ and (Hf_0.95Ta_0.05)B₂ powders increased to 2.60, 1.59, and 0.32 µm, respectively, indicative of the good high-temperature stability of TaB₂-substituted HfB₂. The relative densities of HfB₂, (Hf_0.95Ti_0.05)B₂ and (Hf_0.95Ta_0.05)B₂ ceramics after spark plasma sintering at 2000°C were 76.1%, 85.2% and 99.8%, respectively. The fully dense (Hf_0.95Ta_0.05)B₂ ceramics with fine microstructure showed comparably high Vickers hardness of 21.1 GPa combined with flexural strength of 521.2 MPa. It was proved that the solid solution of TaB₂ could effectively inhibit the grain growth of HfB₂ powders, and improve the densification, microstructure, and mechanical properties of HfB₂ ceramics.     

Diffusion bonding of (Hf0.2Zr0.2Ti0.2Ta0.2Nb0.2)C high-entropy ceramic with metallic Ni foil

To prepare large-sized and complex-shaped components, the feasibility of direct diffusion bonding of (Hf_0.2Zr_0.2Ti_0.2Ta_0.2Nb_0.2)C high-entropy ceramic (HEC) and its diffusion bonding with a metallic Ni foil was investigated, and the interfacial microstructure and mechanical properties of HEC/HEC and HEC/Ni/HEC joints were analyzed. For the direct diffusion bonding, reliable joints with a shear strength of 146 MPa could be achieved when the bonding temperature reached 1500 °C under a pressure of 30 MPa. By introducing a metallic Ni foil as the interlayer, the HEC was successfully bonded at the diffusion temperatures from 1150 °C to 1250 °C under 10 MPa through the formation of Ti₂Ni compound phase. Meanwhile, the HEC(Ni) phase formed by the diffusion of Ni into HEC and Ni(s, s) bulks precipitated in the bonding transition zone. The maximum joint shear strength of 151 MPa was obtained by optimizing the Ni-foil thickness, bonding temperature, and holding time.     

Low-temperature sintering of single-phase,high-entropy carbide ceramics

Dense (Hf, Zr, Ti, Ta, Nb)C high-entropy ceramics were produced by hot pressing (HP) of carbide powders synthesized by carbothermal reduction (CTR). The relative density increased from 95% to 99.3% as the HP temperature increased from 1750°C to 1900°C. Nominally phase pure ceramics with the rock salt structure had grain sizes ranging from 0.6 µm to 1.2 µm. The mixed carbide powders were synthesized by high-energy ball milling (HEBM) followed by CTR at 1600°C, which resulted in an average particle size of ~100 nm and an oxygen content of 0.8 wt%. Low sintering temperature, high relative densities, and fine grain sizes were achieved through the use of synthesized powders. These are the first reported results for low-temperature densification and fine microstructure of high-entropy carbide ceramics.     

Grain coalescence in (Ti0.2Zr0.2Hf0.2Nb0.2Ta0.2)C during spark plasma sintering

High-entropy (Ti_0.2Zr_0.2Hf_0.2Nb_0.2Ta_0.2)C ceramics (HEC) are fabricated via spark plasma sintering using different die configurations, including the conductive and insulating dies. Compared to the conductive die, the grain sizes of samples sintered in the insulating die are significantly larger, which is attributed to the higher local temperature as a result of the higher current density in the sample. Furthermore, the microstructure evolution and grain growth mechanism of HEC are investigated for the first time. We find that at moderate temperatures (∼1600°C), the grain growth of HEC can occur by a grain coalescence mechanism, forming numerous irregular grains in the porous sample. Three factors are crucial to induce grain coalescence, including the formation of partial melting layers on particle surfaces, nanograin rearrangement via rotation and sliding, and the formation of low-angle grain boundaries. During the final sintering stage, the irregular grains will change into polyhedral shapes by grain boundary migration. These findings are of assistance to better understand and control the microstructure evolution of HEC and other ultrahigh-temperature carbide ceramics.     

Pressureless sintering and properties of (Hf0.2Zr0.2Ta0.2Nb0.2Ti0.2)C high-entropy ceramics: The effect of pyrolytic carbon

A novel (Hf_0.2Zr_0.2Ta_0.2Nb_0.2Ti_0.2)C high-entropy ceramic was successfully prepared by pressureless sintering at 2200 °C. With increasing content of resin-derived-carbon, the density, and mechanical and thermal properties increased up to a maximum content of 2～4 wt% resin addition, after which further addition was detrimental. All specimens showed high strength (≥347±36 MPa), with the highest value achieving 450±64 MPa, and fracture toughness significantly higher (>20 %) than those of the corresponding monocarbides and Ta_0.5Hf_0.5C, (Ta_1/3Zr_1/3Nb_1/3)C. The thermal conductivity was approximately equivalent to the lowest value of the corresponding mono-carbides, which was assumed to be due to the lattice distortion effect.     

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.     

Enhanced high-temperature strength in textured (Ti1/3Zr1/3Hf1/3)B2 medium-entropy ceramics via strong magnetic field

This study prepared textured (Ti_1/3Zr_1/3Hf_1/3)B₂ medium-entropy ceramics for the first time that maintain enhanced flexural strength up to 1800°C using single-phase (Ti_1/3Zr_1/3Hf_1/3)B₂ powders, slip casting under a strong magnetic field, and hot-pressed sintering methods. Effects of WC additive and strong magnetic field direction on the phase compositions, orientation degree, microstructure evolution, and high-temperature flexural strength of (Ti_1/3Zr_1/3Hf_1/3)B₂ were investigated. (Ti_1/3Zr_1/3Hf_1/3)B₂ grain grows along the a,b-axes, resulting in a platelet-like morphology. Pressure parallel and perpendicular to the magnetic field direction can promote the orientation degree and hinder the texture structure formation, respectively. Reaction products of W(B,C) and (Ti,Zr,Hf)C between (Ti_1/3Zr_1/3Hf_1/3)B₂ and WC additive can efficiently refine the (Ti_1/3Zr_1/3Hf_1/3)B₂ grain size and promote grain orientation. (Ti_1/3Zr_1/3Hf_1/3)B₂ ceramics doped with 5 vol.% WC yielded a Lotgering orientation factor of 0.74 through slip casting under a strong magnetic field (12 T) and hot-pressed sintering at 1900°C. Furthermore, cleaning the boundary by W(B,C) and introducing texture can enhance the grain-boundary strength and improve its high-temperature flexural strength. The four-point flexural strength of textured (Ti_1/3Zr_1/3Hf_1/3)B₂-5 vol.% WC ceramics was 770 ± 59 MPa at 1600°C and 638 ± 117 MPa at 1800°C.     

Formation and properties of Ca2+ substituted (Ce0.2Zr0.2Ti0.2Sn0.2Hf0.2)O2 high-entropy ceramics

Five equimolar multicomponent oxides were synthesized by replacing one of five cations in (Ce_0.2Zr_0.2Ti_0.2Sn_0.2Hf_0.2)O₂ with Ca²⁺. The results reveal that except for the one in which Ce⁴⁺ replaced by Ca²⁺, the other four components can form single-phase high-entropy fluorite oxides (HEFOs) at different temperatures, which indicates that Ce⁴⁺ is very important for the formation of single-phase HEFOs. The sintering behavior, lattice parameter and properties containing density, porosity, flexural strength and thermal conductivity of the four single-phase HEFOs were investigated. With the change of substituted ions, grain size, relative density, flexural strength and thermal conductivity of the materials vary greatly, which are correlated to the size disorder and mass disorder of these materials. The results of this paper provide a reference for the composition designing and performance tailoring of equimolar HEFOs.     

Selection principle of the synthetic route for fabrication of HfB2 and HfB2-SiC ceramics

Densification, microstructure, and mechanical properties of spark plasma sintered HfB₂ and HfB₂-SiC ceramics using HfB₂ powders from borothermal reduction and boro/carbothermal reduction were investigated and compared. It was found that HfB₂ceramics obtained by boro/carbothermal reduction exhibited a significantly higher sinterability compared to that by borothermal reduction. Inversely, HfB₂-SiC ceramics obtained by borothermal reduction exhibited a refined microstructure and better mechanical properties (Vickers hardness: 23.60 ± 2.43 GPa; fracture toughness: 5.89 ± 0.30 MPa.m^1/2) than that by boro/carbothermal reduction. These results indicated that optimal fabrication of HfB₂-based ceramics could be achieved by the selection of synthetic route of HfB₂ powders.     

Pressureless densification,microstructure tailoring and properties of Ta0.8Hf0.2C-based composites

Ta_0.8Hf_0.2C (TH) ceramics are desirable for applications in ultra-high temperature environments, but they are difficult to be sintered pressurelessly. TH ceramics were densified up to 98.8% from commercial powders via pressureless sintering (PLS) at 2473 K. SiC was introduced as secondary phase to tailor microstructures and improve properties of TH. The influence of SiC volume fraction on the densification, microstructure evolution and room-temperature properties of TH-based ceramics were examined. Average grain size of TH was refined from 13.6 down to 2.0 μm. 10 vol% SiC addition contributed to densification of Ta_0.8Hf_0.2C-SiC (THS) composites with a relative density of 99.6%. The mechanical properties of THS were fairly good, and thermal properties of sintered THS displayed a remarkable improvement compared with TH: the coefficient of thermal expansion (CTE) showed a reduction of 8.6% while the thermal conductivity increased from 18.6 to 41.5 W/m K.     

Processing-dependent stabilization of a dissimilar rare-earth boride in high-entropy (Ti0.2Zr0.2Hf0.2Ta0.2Er0.2)B2 with enhanced hardness and grain boundary segregation

This study demonstrates that 20% of a rare-earth (RE) diboride (ErB₂) can be stabilized in a high-entropy transition metal (TM) diboride, despite the dissimilar chemical properties of RE and TM elements and large differences in lattice parameters of ErB₂ and typical TMB₂. However, the phase formation depends on the fabrication route, which is a noteworthy observation. Specifically, single-phase (Ti_0.2Zr_0.2Hf_0.2Ta_0.2Er_0.2)B₂ is synthesized via reactive spark plasma sintering (SPS) using elemental boron and metal elements. In contract, a specimen made by borocarbothermal reduction of binary oxides and SPS possess significant amounts of two Er-rich secondary phases. Notably, the RE addition in high-entropy TM diboride leads to improved hardness. Aberration-corrected scanning transmission electron microscopy (AC STEM) and energy-dispersive X-ray spectroscopy (EDS) elemental analyses further reveal significant Er segregation at grain boundaries. This work suggests that high-entropy ceramics can have significant solubilities of dissimilar components that may enable new, tunable, and improved properties.     

Phase evolution and thermal stability of novel high-entropy (Mo0.2Nb0.2Ta0.2V0.2W0.2)Si2 ceramics

Owing to the high melting points and high-temperature stability, transition-metal disilicides are potential components for aerospace, automotive, and industrial engineering applications. However, unwanted oxidation known as PEST oxidation severely limits their application owing to the formation of volatile transition metal oxides, especially in the temperature range of 500–1000 °C. To overcome this problem, a new class of high-entropy disilicides, (Mo_0.2Nb_0.2Ta_0.2V_0.2W_0.2)Si₂, was selected by first-principles calculations and then successfully fabricated using a hot-pressing sintering technique. Furthermore, the phase evolution, thermal expansion behavior, thermal conductivity, and oxidation behavior were systematically investigated. Compared with MoSi₂, (Mo_0.2Nb_0.2Ta_0.2V_0.2W_0.2)Si₂ possessed a lower thermal conductivity (10.9–14.7 W·m^?1·K^?1) at 25–1000 °C, higher thermal expansion coefficients (8.6 ± 1.3^–6 K^–1) at 50–1200 °C, and especially an excellent thermal stability at 500–1000 °C owing to slow diffusion and selective oxidation. This work provides a strong foundation for the synthesis and application of high-entropy disilicides.