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Five high entropy carbide ceramics, (Hf0.2,Nb0.2,Ta0.2,Ti0.2,Zr0.2)C, (Cr0.2,Hf0.2,Ta0.2,Ti0.2,Zr0.2)C, (Hf0.2,Mo0.2,Ta0.2,Ti0.2,Zr0.2)C, (Hf0.2,Ta0.2,Ti0.2,W0.2,Zr0.2)C, and (Hf0.2,Mo0.2,Ti0.2,W0.2,Zr0.2)C, were synthesized by carbothermal reduction of oxides and direct current sintering. The five high entropy carbide ceramics were determined to be nominally phase-pure with relative densities of more than 98.9% and mean grain sizes of less than 5 μm. Average Vickers hardness values ranged from 19.2 ± 0.4 GPa for (Hf0.2,Nb0.2,Ta0.2,Ti0.2,Zr0.2)C at a load of 2 kgf to 43.5 ± 0.4 GPa for (Hf0.2,Mo0.2,Ti0.2,W0.2,Zr0.2)C at a load of 0.05 kgf. Hardness generally increased with increasing the valence electron concentration and strain as measured by the Williamson–Hall analysis. However, neither correlation was conclusive enough to be a clear indicator of hardness. Instead, it was determined that a combination of effects that includes the valence electron concentration, lattice strain, and grain size all contribute to the hardness of high entropy carbide ceramics. [ABSTRACT FROM AUTHOR]

To date, the thermal and electrical properties of three‐phase ceramics containing a boride phase, silicon carbide, and boron carbide have not been studied in detail. Further, the effect of the source of the boride powder has also not been investigated. This study produced three‐phase ceramics containing titanium diboride, silicon carbide, and boron carbide using three different TiB2 sources: commercial powder, TiB2 synthesized by boro/carbothermal reduction, or (Ti,Cr)B2 synthesized by boro/carbothermal reduction to address the effect of the TiB2 source. Ceramics containing synthesized TiB2 or (Ti,Cr)B2 reached >99% relative density, while the ceramic produced from commercial powder reached ∼93% relative density. The addition of Cr reduced both the thermal and electrical conductivities, but had little effect on the Vickers hardness. The (Ti,Cr)B2–SiC–B4C ceramic had a thermal conductivity of ∼33 W/m K, an electrical conductivity of ∼105 S/m, and a hardness of ∼61 GPa at 0.49 N. The highest hardness of ∼66 GPa at a load of 0.49 N was for the TiB2–SiC–B4C ceramic made with synthesized TiB2 powder. [ABSTRACT FROM AUTHOR]

Thermal and electrical properties were investigated for five nominally phase‐pure high entropy carbide ceramics. The compositions (Hf0.2Nb0.2Ta0.2Ti0.2Zr0.2)C, (Cr0.2Hf0.2Ta0.2Ti0.2Zr0.2)C, (Hf0.2Mo0.2Ta0.2Ti0.2Zr0.2)C, (Hf0.2Ta0.2Ti0.2W0.2Zr0.2)C, and (Hf0.2Mo0.2Ti0.2W0.2Zr0.2)C were synthesized by carbothermal reduction of oxides. The thermal diffusivity and heat capacity were measured from room temperature to 1800°C. The room temperature thermal conductivity ranged from 5.1 W/mK for (Hf0.2Mo0.2Ti0.2W0.2Zr0.2)C to 9.0 W/mK for (Cr0.2Hf0.2Ta0.2Ti0.2Zr0.2)C. The thermal conductivity increased over the temperature range with maximum conductivities of 19.6 W/mK measured for (Hf0.2Mo0.2Ta0.2Ti0.2Zr0.2)C to 29.7 W/mK for (Cr0.2Hf0.2Ta0.2Ti0.2Zr0.2)C at 1800°C. The electron contribution to thermal conductivity calculated from measured electrical resistivity varied from 41% to 52% of the total thermal conductivity. The tungsten and molybdenum containing compositions had higher phonon contributions while the niobium and chromium containing compositions had nearly equal electron and phonon contributions to thermal conductivity. [ABSTRACT FROM AUTHOR]

Oxidation behavior of additively manufactured ZrB2–SiC in air and in CO2 is reported in the temperature range of 700–1000 °C. Observed scale morphologies in air and in CO2 were similar, featuring an outer borosilicate layer and an inner porous zirconia layer containing partially oxidized silicon carbide particles and remnant borosilicate products. Oxide scale thicknesses and parabolic scaling constants in air were approximately twice those observed in CO2 across all studied temperatures. Activation energies for oxidation of 140 ± 20 kJ/mol in air and 110 ± 20 kJ/mol in CO2 were determined, indicating similar diffusion processes that appear to be rate-limiting. The formation of protective scales across wide temperature ranges both in air and in CO2 makes additively manufactured ZrB2–SiC an attractive candidate for high-temperature industrial process applications featuring varied oxidants such as heat exchangers. [ABSTRACT FROM AUTHOR]

The mechanical properties of single‐phase (Hf0.2,Nb0.2,Ta0.2,Ti0.2,Zr0.2)B2 ceramics with high purity were investigated. The resulting ceramics had relative density greater than 99%, and an average grain size of 4.3 ± 1.6 μm. At room temperature (RT), the Vickers hardness was 25.2 ± 0.6 GPa at a load of 0.49 N, Young's modulus was 551 ± 7 GPa, fracture toughness was 4.5 ± 0.4 MPa m1/2, and flexural strength was 507 ± 10 MPa. Flexural strength increased by more than 50% from 507 ± 10 MPa at RT to 776 ± 26 MPa at 1400°C. Strength remained above 750 MPa up to 2000°C, but decreased to 672 ± 18 MPa at 2100°C and the bars deformed during testing. No significant changes in residual porosity, average grain size, or oxide impurity levels were observed after testing at elevated temperatures. The increase in strength at elevated temperatures was attributed to healing of microcracks due to thermal expansion at high temperatures, and dislocation formation. The retention of strength up to 2000°C is presumably due to the lack of oxide impurities in the HEBs. This is the first reported study on the flexural strength up to 2100°C of dense and pure HEB ceramics. [ABSTRACT FROM AUTHOR]

Final‐stage sintering was analyzed for nominally phase pure zirconium diboride synthesized by borothermal reduction of high‐purity ZrO2. Analysis was conducted on ZrB2 ceramics with relative densities greater than 90% using the Nabarro–Herring stress–directed vacancy diffusion model. Temperatures of 1900°C or above and an applied uniaxial pressure of 50 MPa were required to fully densify ZrB2 ceramics by direct current sintering. Ram travel data were collected and used to determine the relative density of the specimens during sintering. Specimens sintered between 1900 and 2100°C achieved relative densities greater than 97%, whereas specimens sintered below 1900°C failed to reach the final stage of sintering. The average grain size ranged from 1.0 to 14.7 μm. The activation energy was calculated from the slope of an Arrhenius plot that used the Kalish equation. The activation energy was 162 ± 34 kJ/mol, which is consistent with the activation energy for dislocation movement in ZrB2. The diffusion coefficients for dislocation motion that controls densification were 5.1 × 10−6 cm2/s at 1900°C and 5.1 × 10−5 cm2/s at 2100°C, as calculated from activation energy and average grain sizes. This study provides evidence that the dominant mechanism for final‐stage sintering of ZrB2 ceramics is dislocation motion. [ABSTRACT FROM AUTHOR]

Boron carbide powders were synthesized from elemental powders and studied using X‐ray diffraction (XRD) and UV–visible diffuse reflectance, Raman, and diffuse reflectance IR spectroscopies. Following reaction at 1400°C for 6 h, synthesized powders exhibited possible faulting as suggested by XRD patterns. B3C, B4.3C, and B5C powders contained graphitic carbon whereas the boron carbides with higher B/C ratios contained no residual carbon, suggesting that the carbon rich phase boundary is likely temperature dependent. Analysis by Raman and IR spectroscopy suggested that Raman spectra are influenced by excitation frequency due to resonance. We suggest that measurement of boron carbides with resonant Raman lifts the selection rules to allow measurement of Raman silent modes that are present in the IR spectra. Optical reflectance of the boron carbide powders revealed that the B/C ratio governed the indirect and direct optical band gaps of the faulted powders. B3C and B4.3C powders were light gray in spite of the presence of the carbon, whereas B5C, B6.5C, B10C, and B12C were gray, green, brown, and dark brown, respectively. Increasing carbon content increased the optical indirect band gap from 1.3 eV for B12C to 3.2 eV for B3C, causing the observed color changes. [ABSTRACT FROM AUTHOR]