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.     

Hardness and toughness improvement of SiC-based ceramics with the addition of (Hf0.2Mo0.2Ta0.2Nb0.2Ti0.2)B2

The influences of different contents ranging 0–15 wt% of high-entropy boride (HEB) (Hf_0.2Mo_0.2Ta_0.2Nb_0.2Ti_0.2)B₂ on the mechanical properties of SiC-based ceramics using Al₂O₃-Y₂O₃ sintering additives sintered by spark plasma sintering process were investigated in this study. The results showed that the introduction of 5 and 10 wt% (Hf_0.2Mo_0.2Ta_0.2Nb_0.2Ti_0.2)B₂ could facilitate the densification and the grain growth of SiC-based ceramics via the mechanism of liquid phase sintering. However, the grain growth of SiC-based ceramics was inhibited by the grain boundary pinning effect with the addition of 15 wt% (Hf_0.2Mo_0.2Ta_0.2Nb_0.2Ti_0.2)B₂. The SiC-based ceramics with 15 wt% (Hf_0.2Mo_0.2Ta_0.2Nb_0.2Ti_0.2)B₂ showed the enhanced hardness (21.9±0.7 GPa) and high toughness (4.88±0.88 MPa·m^1/2) as compared with high-entropy phase-free SiC-based ceramics, which exhibited a hardness of 16.6 GPa and toughness of 3.10 MPa·m^1/2. The enhancement in mechanical properties was attributed to the addition of higher hardness of HEB phase, crack deflection toughening mechanism, and presence of residual stress due to the mismatch of coefficient of thermal expansion.     

High-entropy (Ho0.2Y0.2Dy0.2Gd0.2Eu0.2)2Ti2O7/TiO2 composites with excellent mechanical and thermal properties

High-performance ceramics with low thermal conductivity, high mechanical properties, and idea thermal expansion coefficients have important applications in fields such as turbine blades and automotive engines. Currently, the thermal conductivity of ceramics has been significantly reduced by local doping/substitution or further high-entropy reconfiguration of the composition, but the mechanical properties, especially the fracture toughness, are insufficient and still need to be improved. In this work, based on the high-entropy titanate pyrochlore, TiO₂ was introduced for composite toughening and the high-entropy (Ho_0.2Y_0.2Dy_0.2Gd_0.2Eu_0.2)₂Ti₂O₇-xTiO₂ (x = 0, 0.2, 0.4, 1.0 and 2.0) composites with high hardness (16.17 GPa), Young's modulus (289.3 GPa) and fracture toughness (3.612 MPa·m^0.5), low thermal conductivity (1.22 W·m⁻¹·K⁻¹), and thermal expansion coefficients close to the substrate material (9.5 ×10⁻⁶/K) were successfully prepared by the solidification method. The fracture toughness of the composite toughened sample is 2.25 times higher than that before toughening, which exceeds most of the current low-thermal conductivity ceramics.     

Processing and mechanical properties of B4C-SiCw ceramics densified by spark plasma sintering

Homogenous distribution of whiskers in the ceramic matrix is difficult to be achieved. To solve this problem, B₄C-SiC_w powder mixtures were freeze dried from a slurry dispersed by cellulose nanofibrils (CellNF) in this work. Dense B₄C ceramics reinforced with various amounts of SiC_w up to 12 wt% were consolidated by spark plasma sintering (SPS) at 1800 °C for 10 min under 50 MPa. During this process, CellNF was converted into carbon nanostructures. As iron impurities exist in the starting B₄C and SiC_w powders, both thermodynamic calculations and microstructure observations suggest the dissolution and precipitation of SiC_w in the liquids composed of Fe-Si-B-C occurred during sintering. Although not all the SiC_w grains were kept in the final ceramics, B₄C-9 wt% SiC_w ceramics sintered at 1800 °C still exhibit excellent Vickers hardness (35.5 ± 0.8 GPa), flexural strength (560 ± 9 MPa) and fracture toughness (5.1 ± 0.2 MPa·m^1/2), possibly contributed by the high-density stacking faults and twins in their SiC grains, no matter in whisker or particulate forms.     

Preparation,mechanical properties,and toughening mechanisms of SiCw/SiCp-reinforced zirconia-toughened alumina ceramics

Zirconia-toughened alumina (ZTA) ceramics with high mechanical properties were sintered by hot-pressing method using SiC particles (SiCp) and SiC whiskers (SiCw) as the reinforcing agents simultaneously. The influences of sintering temperature, SiCp, and SiCw contents on the microstructure and mechanical properties of ZTA ceramics were investigated. It was found that both SiCp and SiCw could contribute to grain refinement significantly and promote the mechanical properties of the ceramics. However, the excess addition of SiCp or SiCw led to the formation of pores with large sizes and degraded the mechanical properties instead. When 13 wt% SiCp was introduced, the maximum flexural strength of 1180.0 MPa and fracture toughness of 15.9 MPa·m^1/2 were obtained, whereas the maximum flexural strength of 1314.0 MPa and fracture toughness of 14.7 MPa·m^1/2 were achieved at 20 wt% SiCw. Interestingly, the simultaneous addition of SiCp and SiCw could further improve the mechanical properties, and the highest flexural strength of 1334.0 MPa and fracture toughness of 16.0 MPa·m^1/2 were achieved at a SiCw/SiCp ratio of 16/4. The reinforcement mechanisms in the ceramics mainly included the phase transformation toughening of ZrO₂, the crack deflection and bridging of SiCp and SiCw, and the pull-out of SiCw.     

Novel single phase (Ti0.2W0.2Ta0.2Mo0.2V0.2)C0.8 high entropy carbide using ball milling followed by reactive spark plasma sintering

Single phase novel (Ti_0.2W_0.2Ta_0.2Mo_0.2V_0.2)C_0.8 high entropy carbide (HEC) compacts were successfully synthesized by reactive spark plasma sintering of ball milled metal-carbon elemental mixture at temperatures of 1400−1800 °C. X-ray diffraction and element distribution maps indicated single phase carbide formation with lattice parameter ranging from 4.307 Å to 4.312 Å with small amount of TiO₂. X-ray energy dispersive spectroscopy (EDS) mapping showed uniform distribution of the transition metals in the carbide phase. The microhardness, elastic modulus, fracture toughness, electrical resistivity and thermal expansion coefficient (25 °C–600 °C) of the compact sintered at 1800 °C were found to be 25.8 ± 2.8 GPa, 461 ± 36 GPa, 3.7 ± 0.4 MPa.m^1/2, 7 × 10⁻⁴ Ω/m² and 7 × 10^-6 K⁻¹ respectively.     

Pressureless Sintering of Hafnium Carbide–Silicon Carbide Ceramics

HfC‐30 vol%SiC ceramics with a relative density of 99.7% was obtained by pressureless sintering at 2300°C for 0.5 h. The resultant ceramics showed fine microstructure with HfC grain size around 1 μm. The hardness (20.5 ± 0.2 GPa), bending strength (396 ± 56 MPa), and fracture toughness (2.81 ± 0.18 MPa·m^1/2) of HfC‐30 vol%SiC ceramics were at least 20% higher than those of monolithic HfC ceramics. The influences of SiC particle size, volume fraction, and the oxide impurity on the microstructure evolution of HfC‐based ceramics were examined. The results indicate that SiC addition and the oxygen impurity introduced by ball milling play opposite roles in the HfC grain growth during sintering. The oxide impurity introduced by ball milling caused the HfC grain coarsening, whereas SiC particles inhibited the grain growth of HfC significantly.     

Densification,microstructure, and mechanical properties of ZrC–SiC ceramics

ZrC–SiC ceramics were fabricated by high-energy ball milling and reactive hot pressing of ZrH₂, carbon black, and varying amounts of SiC. The ceramics were composed of nominally pure ZrC containing 0 to 30 vol% SiC particles. The relative density increased as SiC content increased, from 96.8% for nominally pure ZrC to 99.3% for ZrC-30 vol% SiC. As SiC content increased from 0 to 30 vol%, Young's modulus increased from 404 ± 11 to 420 ± 9 GPa and Vickers hardness increased from 18.5 ± 0.7 to 23.0 ± 0.5 GPa due to a combination of the higher relative density of ceramics with higher SiC content and the higher Young's modulus and hardness of SiC compared to ZrC. Flexure strength was 308 ± 11 MPa for pure ZrC, but increased to 576 ± 49 MPa for a SiC content of 30 vol%. Fracture toughness was 2.3 ± 0.2 MPa·m^1/2 for pure ZrC and increased to about 3.0 ± 0.1 MPa·m^1/2 for compositions containing SiC additions. The combination of high-energy ball milling and reactive hot pressing was able to produce ZrC–SiC ceramics with sub-micron grain sizes and high relative densities with higher strengths than previously reported for similar materials.     

Reactive consolidation and high-temperature strength of HfB2–SiB6

During the spark plasma sintering at 1900 °C, SiB₆ decomposes into cubic silicon carbide and boron carbide, owing to the reducing environment of the furnace. For the HfB₂-SiB₆ ceramic improvement in hardness (24.5 ± 0.7 GPa) was attributed to the formation of the B₁₂(C,Si,B)₃. Fracture toughness by indentation (6.8 ± 2.4 MPa·m^1/2), single-edge notched bend specimens (4.6 ± 0.4 MPa·m^1/2) and room-temperature strength (513 ± 21 MPa) of the HfB₂–SiB₆ composite produced by spark plasma sintering was higher or on the same level as the HfB₂–SiC ceramics. The high-temperature flexural strength tests suggested that the strength would decrease monotonically with an increase in temperature. At or below 1600 °C, only a linear stress-strain response was observed, and resulted into a mean strength of ~320 MPa. During the tests at 1800 °C, we observed a nonlinear deformation indicating ongoing plastic deformation which led to a strength decrease down to 230 ± 30 MPa.     

The new complex high-entropy metal boron carbonitride: Microstructure and mechanical properties

In this contribution, the ternary BCN anion systems of high-entropy ceramics (HEC) are consolidated by hot-pressing sintering and the impacts of sintering temperature and the content of amorphous BCN addition on microstructural evolution and mechanical performance were evaluated. Results confirmed that high-entropy, oxide, and BN(C) phases were precipitated for (Ta_0.2Nb_0.2Zr_0.2Hf_0.2Ti_0.2)(B, C, N) ceramics after sintering at 1900°C. With the decrease of BCN addition, a new phase of MiB₂ (Mi representing the metal atoms) occurred. The Vickers hardness, bending strength, elastic modulus, and fracture toughness of the optimized bulk HECs were investigated, obtained at 24.5 ± 2.3 GPa, 522.0 ± 2.6 MPa, 478.9 ± 11.1 GPa, and 5.36 ± 0.56 MPa m^1/2, respectively.     

Reduced-graphene-oxide-reinforced boron carbide ceramics fabricated by spark plasma sintering from powder mixtures obtained by heterogeneous co-precipitation

Reduced graphene oxide (rGO) sheets were uniformly dispersed in boron carbide ceramics by a heterogeneous co-precipitation method. This approach was used to improve the fracture toughness of boron carbide ceramics and to address the problem of agglomeration of graphene in the boron carbide matrix. Cetyltrimethyl ammonium bromide was used as a heterogeneous co-precipitation reaction initiator to prepare a homogeneously dispersed graphene oxide/boron carbide (GO/B₄C) mixture. Reduced graphene oxide/boron carbide (rGO/B₄C) powder mixtures with good dispersion were obtained by high temperature heat treatment. Dense rGO/B₄C composite ceramics were fabricated by spark plasma sintering at 1800 °C and 50 MPa. The fracture toughness and flexural strength of the rGO/B₄C with an rGO content of 2 vol% composite increased by 42% (from 3.43 to 4.88 MPa·m^1/2) and 28% (from 372 to 476 MPa) compared with those of pure B₄C, respectively. The markedly improved fracture toughness and flexural strength of the boron carbide ceramics were attributed to the effect of crack bridging and crack deflection by graphene sheets, graphene interface sliding, and pulling out of graphene.     

Microstructure and mechanical properties of TaC ceramics with 1–7.5 mol% Si as sintering aid

Metallic Si as sintering aid was effective in densifying tantalum carbide ceramic (TaC) by spark plasma sintering (SPS) at 1700°C. Full density was reached at 5.0 mol% Si addition (equivalent to 1.088% Si in weight) and above. Enhanced densification of TaC ceramic with Si was associated with decrease in oxygen content from ~0.24 wt% in TaC powder to ~0.03 wt% in consolidated specimen. Rest of the oxygen species was collected at multigrain conjunctions to form SiO₂‐based liquid at high temperatures. Upon cooling, Ta, Si, O, and C dissolving in the liquid precipitated minor phases of TaSi_x and SiC of low concentrations. Microstructure of TaC ceramics was refined by the Si addition, with average grain size decreasing from 11±8 μm at 1.0 mol% Si to 3±2 μm at 7.5 mol% Si addition. Ta solute in SiC and Si solute in TaC were evidenced. TaC ceramic containing 7.5 mol% Si had a relatively good flexural strength and fracture toughness of 646±51 MPa and 5.0 MPa·m^1/2, respectively.     

Mechanical properties of silicon carbide—in situ zirconium carbonitride composites

SiC–Zr₂CN composites were fabricated by conventional hot pressing from β-SiC and ZrN powders with 2 vol% equimolar Y₂O₃–Sc₂O₃ as a sintering additive. The effects of the ZrN addition on the room-temperature (RT) mechanical properties and high-temperature flexural strength of the SiC–Zr₂CN composites were investigated. The fracture toughness gradually increased from 4.2 ± 0.3 MPa·m^1/2 for monolithic SiC to 6.3 ± 0.2 MPa·m^1/2 for a SiC–20 vol% ZrN composite, whereas the RT flexural strength (546 ± 32 MPa for the monolithic SiC) reached its maximum of 644 ± 87 MPa for the SiC–10 vol% ZrN composite. The monolithic SiC had improved strength at 1200°C, whereas the SiC–Zr₂CN composites could not retain their RT strengths at 1200°C. The typical flexural strength values of the SiC–0, 10, and 20 vol% ZrN composites at 1200°C were 650 ± 53, 448 ± 31, and 386 ± 19 MPa, whereas their RT strength values were 546 ± 32, 644 ± 87, and 528 ± 117 MPa, respectively.     

Single-phase rare-earth high-entropy zirconates with superior thermal and mechanical properties

Emerging of high-entropy ceramics has brought new opportunities for designing and optimizing materials with desired properties. In the present work, high-entropy rare-earth zirconates (La_0.2Nd_0.2Sm_0.2Eu_0.2Gd_0.2)₂Zr₂O₇ and (Yb_0.2Nd_0.2Sm_0.2Eu_0.2Gd_0.2)₂Zr₂O₇ are designed and synthesized. Both high-entropy ceramics exhibit a single pyrochlore structure with excellent phase stability at 1600 °C. In addition, the Yb-containing system possesses a high coefficient of thermal expansion (10.52 × 10^?6 K^-1, RT～1500 °C) and low thermal conductivity (1.003 W·m^-1 K^-1, 1500 °C), as well as excellent sintering resistance. Particularly, the Yb-containing system has significantly improved fracture toughness (1.80 MPa·mm^1/2) when compared to that of lanthanum zirconate (1.38 MPa·mm^1/2), making it a promising material for thermal barrier coatings (TBCs) applications. The present work indicates that the high-entropy design can be applied for further optimization of the comprehensive properties of the TBCs materials.     

In situ toughened two-phase B12(C,Si, B)3–SiC ceramics fabricated via liquid silicon infiltration

In situ toughened B₁₂(C, Si, B)₃–SiC ceramics were successfully fabricated via the liquid silicon infiltration process. Two types of B₁₂(C, Si, B)₃ phases, with high and low Si contents, respectively, and plate-like SiC particles were formed by the reaction between B₄C and Si. The in situ toughening mechanism involved two effects: the multiple crack deflections caused by the increased grain boundaries, and the pullout and rupture of a significant amount of plate-like SiC particles. Block ceramics with a high fracture toughness of 6.5 ± 0.5 MPa·m^1/2 were fabricated via the in situ toughening mechanism. A strong interface bond was present between the high- and low-B₄C-content layers in the laminated ceramics, which led to residual compressive stress inside the materials. As a result, the laminated structural design enhanced the fracture toughness to 7.5 ± 0.5 MPa·m^1/2.     

Mechanical and thermal properties of silicon carbide ceramics with yttria–scandia–magnesia

Two different SiC ceramics with a new additive composition (1.87 wt% Y₂O₃–Sc₂O₃–MgO) were developed as matrix materials for fully ceramic microencapsulated fuels. The mechanical and thermal properties of the newly developed SiC ceramics with the new additive system were investigated. Powder mixtures prepared from the additives were sintered at 1850 °C under an applied pressure of 30 MPa for 2 h in an argon or nitrogen atmosphere. We observed that both samples could be sintered to ≥99.9% of the theoretical density. The SiC ceramic sintered in argon exhibited higher toughness and thermal conductivity and lower flexural strength than the sample sintered in nitrogen. The flexural strength, fracture toughness, Vickers hardness, and thermal conductivity values of the SiC ceramics sintered in nitrogen were 1077 ± 46 MPa, 4.3 ± 0.3 MPa·m^1/2, 25.4 ± 1.2 GPa, and 99 Wm⁻¹ K⁻¹ at room temperature, respectively.     

Ultra-fast high-temperature synthesis and densification of high-entropy diborides and diboride-carbide ceramics

The strong covalent bonds and low self-diffusion coefficients of high-entropy diboride (HEBs) and diboride-carbide (HEB-HEC) ceramics render their densification difficult, which limits their applications. Here, we used an ultra-fast high-temperature sintering technique to synthesize and densify several HEBs and HEB-HEC (containing 5–8 cations) ceramics within an isothermal duration of 1 min and a total sintering period of 6 min. All ceramics formed a single-phase or dual-phase high-entropy solid solution, and showed high density, high hardness and good fracture toughness. The rapid densification mechanisms were determined, and the preferential occupancy of metal cations in HEB and HEC phases was explained using a simplified ideal solution model. A good fracture toughness in the range of 3.6–5.4 MPa·m^1/2 resulted from crack deflection or blunting and bridging of the rod-like diboride or boron-rich phase. This paper presents a simple, economical, and efficient method for the synthesis and densification of high-entropy ceramics and other advanced materials.     

Ablation behavior of (TiZrHfNbTa)C high-entropy ceramics with the addition of SiC secondary under an oxyacetylene flame

The ablation behavior of high-entropy ceramics (HECs) was investigated in this study using an oxyacetylene flame at 2000 °C. Spark plasma sintering was used to construct a dense HEC (TiZrHfNbTa)C with a 20 vol% of SiC addition (HEC-20SiC). The densification of HEC-20SiC can be improved to a certain extent by adding SiC particles, increasing the hardness of HEC-20SiC to up to 24.6 GPa, and the crack deflection observed through the addition of SiC particles were considered to be the strengthening and toughening mechanisms. After ablation, Hf₆Ta₂O₁₇, Ti_5.1Ta_4.9O₂₀, Nb₂Zr₆O₁₇, TaZr_2.75O₈, and SiO₂ can be detected on an ablated surface and HEC-20SiC possesses the minimum mass ablation rate (?1.9 mg s^?1) and line ablation rate (2.1 μm s^?1) among the comparative ceramics. On the one hand, the SiC phase forms gaseous CO, CO₂, and SiO as well as viscous SiO₂ during ablation and some part of the heat can be dissipated by the evaporation of gaseous CO, CO₂, and SiO; further, pore defects can be healed by viscous SiO₂, thus inhibiting the diffusion of reactive oxygen species. On the other hand, the HEC phase with a lattice-distortion caused by single-phase solid-solution can effectively inhibit the invasion of reactive oxygen species and the outward migration of metal atoms. The invasion rate of reactive oxygen is considered to be the main step during HEC-20SiC ablation, and it is believed that higher principal component HECs can improve ablation performance even further.     

Strength of single-phase high-entropy carbide ceramics up to 2300°C

The mechanical properties of single-phase (Hf,Zr,Ti,Ta,Nb)C high-entropy carbide (HEC) ceramics were investigated. Ceramics with relative density >99% and an average grain size of 0.9 ± 0.3 µm were produced by a two-step process that involved carbothermal reduction at 1600°C and hot pressing at 1900°C. At room temperature, Vickers hardness was 25.0 ± 1.0 GPa at a load of 4.9 N, Young's modulus was 450 GPa, chevron notch fracture toughness was 3.5 ± 0.3 MPa·m^1/2, and four-point flexural strength was 421 ± 27 MPa. With increasing temperature, flexural strength stayed above ~400 MPa up to 1800°C, then decreased nearly linearly to 318 ± 21 MPa at 2000°C and to 93 ± 10 MPa at 2300°C. No significant changes in relative density or average grain size were noted after testing at elevated temperatures. The degradation of flexural strength above 1800°C was attributed to a decrease in dislocation density that was accompanied by an increase in dislocation motion. These are the first reported flexural strengths of HEC ceramics at elevated temperatures.     

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.