Reactive Processing of a ZrB2 / ZrC / Zr–Si Ceramic Composite with a Controlled Oxygen Potential

A Zr–Si liquid reacted with B₄C in a graphite enclosure was configured to control the oxygen potential (10^?45 kPa) to form a ZrB₂ / ZrC / Zr – Si ceramic composite. The graphite enclosure was placed in a temperature gradient with the hot zone at >2133 K to react Zr – Si with B₄C and with the opposite end approximating 933–1000 K at the position of an aluminum melt. A ZrB₂ / ZrC / Zr – Si composite forms with the scanning‐electron microscope (SEM), microstructures showing rectangular ZrB₂ precipitates and hexagonally shaped ZrC precipitates embedded in a Zr – Si matrix.     

Processing and mechanical properties of hot-pressed zirconium diboride – zirconium carbide ceramics

ZrB₂ was mixed with 0.5 wt% carbon and up to 10 vol% ZrC and densified by hot-pressing at 2000 °C. All compositions were > 99.8% dense following hot-pressing. The dense ceramics contained 1–1.5 vol% less ZrC than the nominal ZrC addition and had between 0.5 and 1 vol% residual carbon. Grain sizes for the ZrB₂ phase decreased from 10.1 µm for 2.5 vol% ZrC to 4.2 µm for 10 vol% ZrC, while the ZrC cluster size increased from 1.3 µm to 2.2 µm over the same composition range. Elastic modulus was ~505 GPa and toughness was ~2.6 MPa·m^½ for all compositions. Vickers hardness increased from 14.1 to 15.3 GPa as ZrC increased from 2.5 to 10 vol%. Flexure strength increased from 395 MPa for 2.5 vol% ZrC to 615 MPa for 10 vol% ZrC. Griffith-type analysis suggests ZrB₂ grain pullout from machining as the strength limiting flaw for all compositions.     

Influence of total pressure on the microstructures and growth mechanism of ZrC coatings prepared by chemical vapor deposition from the Zr-Br2-C3H6-H2-Ar system

Zirconium carbide (ZrC) coatings were deposited on graphite substrates by chemical vapor deposition from the Zr-Br₂-C₃H₆-H₂-Ar system. The influence of total pressure on the growth of ZrC was investigated in the range of 5–60 kPa. As the total pressure increased, the deposition rate increased evidently, and the preferential orientation of ZrC coatings changed from the (200) plane to the (220) plane. The growth mechanism changed from a mass transport reaction to a surface reaction at the total pressure of 20–40 kPa. At the total pressure below 20 kPa, the deposition was dominated by crystal growth, so the coatings were composed of well-faceted pyramidal-shaped crystals growing along the <001> direction. At the total pressure above 60 kPa, the growth of ZrC coatings was controlled by the nucleation mechanism, so the coatings were cluster-like crystals rapidly growing along the <110> direction. In addition, low pressure was conducive to the formation of near-stoichiometric ZrC without free carbon. These variations of ZrC coatings can mainly be attributed to gas supersaturation and remarkably changed transport diffusion coefficients with increasing total pressure.     

Temperature-dependent elastic and thermodynamic properties of ZrC,HfC, and their solid solutions (Zr0.5Hf0.5)C

Zirconium carbide (ZrC) and hafnium carbide (HfC) have been identified as ultrahigh temperature ceramics with excellent thermal conductivity performance. The temperature profiles of ZrC and HfC have been studied; however, the temperature-dependent of solid solution of (Zr_0.5Hf_0.5)C is still lacking. Herein, we report the temperature-dependent elastic and thermodynamic properties of (Zr_0.5Hf_0.5)C using first-principles calculations. The covalent characters of ZrC, HfC, and (Zr_0.5Hf_0.5)C are weakened at high temperatures by analyzing their respective electronic structures. In addition, the equilibrium volumes at different temperatures can be determined from the energy–volume (E–V) curves under the quasi-harmonic approximation. Throughout the temperature ranges studied, the HfC material shows the highest bulk modulus and lowest thermal expansion. When T > 1000 K, (Zr_0.5Hf_0.5)C exhibits better shear and Young's modulus performance close to HfC and shows the highest anisotropy. The lattice thermal conductivity decreased as temperature increased for ZrC, HfC, and (Zr_0.5Hf_0.5)C, and (Zr_0.5Hf_0.5)C has the smallest lattice thermal conductivity. These results provide fundamental and useful information for the practical application of ZrC, HfC, and (Zr_0.5Hf_0.5)C.     

Laser ablation behaviors of vacuum plasma sprayed ZrC-based coatings

ZrC, ZrC-30 vol% SiC, and ZrC-30 vol% TiC coatings were fabricated by vacuum plasma spray and the laser ablation behaviors were evaluated by a CO₂ laser beam under two heat fluxes (15.9 and 25.5 MW/m²). The phase compositions and microstructures of the coatings after ablation were investigated and the effect of SiC and TiC additives was analyzed. The results showed that the ZrC–SiC coating displayed better ablation resistance compared with the ZrC and ZrC–TiC coatings under 15.9 MW/m² heat flux. While the ZrC–TiC coating exhibited the improved ablation resistance under 25.5 MW/m² heat flux. The continuous and integral ZrO₂–SiO₂ scale provided protective effect for the ZrC–SiC coating. A liquid ZrO₂–TiO₂ layer which owned self-healing ability was formed for the ZrC–TiC coating in both heat fluxes. However, the state of the formed liquid, like amount, viscosity, evaporation, and decomposition, was influenced by the environment and was vital for the ablation resistance. This work might give a clue for designing ultrahigh-temperature ceramics as potential laser ablation–resistant coating materials.     

Synthesis and pyrolysis behavior of a soluble polymer precursor for ultra-fine zirconium carbide powders

A soluble polymer precursor for ultra-fine zirconium carbide (ZrC) was successfully synthesized using phenol and zirconium tetrachloride as carbon and zirconium sources, respectively. The pyrolysis behavior and structural evolution of the precursor were studied by Fourier transform infrared spectra (FTIR), differential scanning calorimetry, and thermal gravimetric analysis (DSC–TG). The microstructure and composition of the pyrolysis products were characterized by X-ray diffraction (XRD), laser Raman spectroscopy, scanning electron microscope (SEM) and element analysis. The results indicate that the obtained precursor for the ultra-fine ZrC could be a Zr–O–C chain polymer with phenol and acetylacetone as ligands. The pyrolysis products of the precursor mainly consist of intimately mixed amorphous carbon and tetragonal ZrO₂ (t-ZrO₂) in the temperature range of 300–1200 °C. When the pyrolysis temperature rises up to 1300 °C, the precursor starts to transform gradually into ZrC, accompanied by the formation of monoclinic ZrO₂ (m-ZrO₂). The carbothermal reduction reaction between ZrO₂ and carbon has been substantially completed at a relatively low temperature (1500 °C). The obtained ultra-fine ZrC powders exhibit as well-distributed near-spherical grains with sizes ranging from 50 to 100 nm. The amount of oxygen in the ZrC powders could be further reduced by increasing the pyrolysis temperature from 1500 to 1600 °C but unfortunately the obvious agglomeration of the ZrC grains will be induced.     

Reactive Hot Pressing of ZrC–SiC Ceramics at Low Temperature

Composites of ZrC–SiC with relative densities in excess of 98% were prepared by reactive hot pressing of ZrC and Si at temperature as low as 1600°C. The reaction between ZrC and Si resulted in the formation of ZrC_1?x, SiC, and ZrSi. Low‐temperature densification of ZrC?SiC ceramics is attributed to the formed nonstoichiometric ZrC_1?x and Zr–Si liquid phase. Adding 5 wt% Si to ZrC, the three‐point bending strength of formed ZrC_0.8–13.4 vol%SiC ceramics reached 819 ± 102 MPa with hardness and toughness being 20.5 GPa and 3.3 MPa·m^1/2, respectively.     

Effect of ZrC particle distribution on the ablation resistance of C/C-SiC-ZrC composites fabricated using precursor infiltration pyrolysis

C/C-SiC-ZrC composites with different ZrC distributions were fabricated using precursor infiltration pyrolysis combined with different drying processes. The microstructural and ablation resistance properties of the composites with different ZrC distributions were investigated. For the C/C-SiC-ZrC composites fabricated using conventional heating-drying, where ZrC particles were largely agglomerated into islands with a dimension range of 10–20 μm, the mass and linear ablation rates under a plasma flame for 60 s were 0.558 mg/s and 16.33 μm/s, respectively. By contrast, for the composites fabricated using freeze-drying, where isolated ZrC particles with a size range of 200–300 nm were uniformly dispersed in the matrix, the mass and linear ablation rates were only 0.078 mg/s and 14.20 μm/s, respectively. This difference in the distribution of ZrC particles led to the difference in ablation resistances, as the uniformly distributed fine ZrC particles were easily oxidized and well dispersed in SiO₂ molten glass, which increased the viscosity of the molten glass layer. The high-viscosity SiO₂-ZrO₂ molten layer covering the surface of the composites effectively prevented the penetration of oxygen and resisted the scour of airflow.     

Synthesis of fine zirconium carbide powder by carbothermal reaction of carbon‐coated zirconia particles

In this study, a novel method for the synthesis of fine ZrC powder was presented. It consists of chemical vapor deposition (CVD) of C from CH₄ on ZrO₂ particles followed by carbothermal reaction. Firstly, optimal CVD conditions (1300 K and 30 minutes) yielding the stoichiometric amount of C deposit (23 wt%) were determined. Carbothermal reaction behavior of the carbon‐coated oxide particles was then investigated in Ar flow at 1700‐1800 K for 0‐120 minutes. Mass measurements, XRD and SEM techniques were used to characterize the products at various stages of the process. Lattice constants and mass losses of the samples increased to the levels of ZrC with increasing temperature and time. Almost pure ZrC powder (oxygen content: 0.59 wt%) with a mean particle size of ~170 nm was synthesized at 1800 K within 120 minutes. The present study demonstrates that ZrC powder can be synthesized at lower temperatures and shorter reaction times using C‐coated ZrO₂ powders compared with the conventional method which uses a mixture of ZrO₂ and solid C particles.     

Improving the sinterability of ZrC–SiC composite powders by Mg addition

High-density ZrC–SiC composite ceramics are typically sintered under demanding conditions, specifically, high sintering pressures and high temperatures. However, the need for such conditions can be alleviated by the use of ZrC–SiC composite nanoparticles with a high sintering activity. In the present study, core-shell-structured hybrid ZrC–SiC composite nanoparticles were synthesised with the addition of Mg by using a sol-gel process combined with in-situ carbothermal reduction reactions. The synthesis route, characterisation, and sintering mechanism were investigated in detail. It was found that the addition of MgCl₂ to the precursors of ZrC–SiC can not only strengthen the network structure of ZrC–SiC gel but also lead to the formation of an amorphous Mg–Si–O oxide coating on the nanoparticle surfaces, which enhances the sinterability of ZrC–SiC nanoparticles. As a result, a compact ZrC–SiC composite ceramic with a higher relative density (up to 91.3%) than the contrast sample was successfully prepared by pressure-free sintering at 1700 °C.     

Synthesis,Characterization, and Microstructure of ZrC/SiC Composite Ceramics via Liquid Precursor Conversion Method

The ceramic precursor for ZrC/SiC was prepared via solution‐based processing using polyzirconoxane, polycarbosilane, and divinylbenzene. The precursor could be transformed into ZrC/SiC ceramic powders at relative low temperature (1500°C). The cross‐linking process of precursor was studied by FT–IR. The conversion from precursor into ceramic was investigated by TGA, XRD. The ceramic compositions and microstructures were identified by element analysis, Raman spectra, SEM, and corresponding EDS. The results indicated that the ceramic samples remained amorphous below 1000°C and t–ZrO₂ initially generated at 1200°C. Further heating to 1400°C led to the formation of ZrC and SiC with the phase transformation of ZrO₂ and almost pure ZrC/SiC could be obtained upon heat‐treatment at 1500°C. During heat treatments, the ceramic sample changed from compact to porous due to carbothermal reduction. The ceramic powders with particle size of 100 nm~400 nm consisted of high crystalline degree ZrC and SiC phases, and Zr, Si, C were well distributed at the different sites in ceramic powders. The free carbon content was lowered to 1.60 wt% in final ZrC/SiC composite ceramics.     

Ablation mechanism of C/C–SiC and C/C–SiC–ZrC composites in hypersonic oxygen-enriched environment

In this study, C/C–SiC and C/C–SiC–ZrC composites were prepared via chemical vapor infiltration and polymer infiltration pyrolysis, and the ablation mechanism under hypersonic oxygen-rich environmental conditions was investigated. The C/C–SiC composites demonstrate an excellent ablation resistance in a hypersonic oxygen-rich environment with a relatively low temperature and speed of approximately 1800 K and 1100 m/s, respectively. It is only in the ablation center area with higher temperatures that a certain degree of thermochemical ablation was observed. The mass and linear ablation rates of C/C–SiC composites (0.027 g/s and 0.117 mm/s, respectively) showed a significant increase in a hypersonic oxygen-rich environment with a temperature and velocity of approximately 2050 K and 2000 m/s, respectively. The high-temperature ablation resistance of ZrC-modified C/C–SiC–ZrC composites improved significantly. However, the ZrC ceramic component had a considerable impact on the ablation resistance of the material. The structural integrity of C/C–20SiC–30ZrC composites was relatively high in hypersonic oxygen-rich environments with a jet temperature and velocity of 2050 K and 2000 m/s, respectively, and mass and linear ablation rates were 0.012 g/s and 0.015 mm/s, respectively. When the ZrC content increased by 40%, the ablation resistance of the composite reduced significantly, whereas the mass and linear ablation rates increased to 0.043 g/s and 0.130 mm/s, respectively.     

Microstructure and mechanical performance evolution of C/C–ZrC composites exposed to oxyacetylene flame

C/C–ZrC composites were prepared by isothermal chemical vapor infiltration (ICVI) combined with reactive melt infiltration (RMI). The ablation behavior of the C/C–ZrC was investigated using an oxyacetylene flame. The effect of ablation time on the microstructure and mechanical property evolution of the composite was studied. The results showed that as the ablation time prolonged, the linear and mass ablation rates of the composite increased firstly and then stabilized. After 15 s ablation, the flexural strength and modulus of the C/C–ZrC were interestingly increased by 141.8% and 40.9%, which reached 138.42 MPa and 6.45 GPa, respectively. During ablation, the preferential oxidation effect of ZrC could mitigate the oxidation of pyrolytic carbon (PyC) and carbon fibers, and the volume change induced by the ZrC →ZrO₂ phase transformation could weaken its bonding with PyC, which was beneficial for releasing the internal residual stresses of the C/C–ZrC and then contributed to the mechanical performance improvement.     

ZrC–C and ZrO2–C as Novel Supports of Pd Catalysts for Formic Acid Electrooxidation

The Pd/ZrC–C and Pd/ZrO₂–C catalysts with zirconium compounds ZrC or ZrO₂ and carbon hybrids as novel supports for direct formic acid fuel cell (DFAFC) have been synthesized by microwave‐assisted polyol process. The Pd/ZrC–C and Pd/ZrO₂–C catalysts have been characterized by X‐ray diffraction (XRD), X‐ray photoelectron spectroscopy (XPS), energy dispersive analysis of X‐ray (EDAX), transmission electron microscopy (TEM), and electrochemical measurements. The physical characteristics present that the zirconium compounds ZrC and ZrO₂ may promote the dispersion of Pd nanoparticles. The results of electrochemical tests show that the activity and stability of Pd/ZrC–C and Pd/ZrO₂–C catalysts show higher than that of Pd/C catalyst for formic acid electrooxidation due to anti‐corrosion property of zirconium compounds ZrC, ZrO₂, and metal–support interaction between Pd nanoparticles and ZrC, ZrO₂. The Pd/ZrC–C catalyst displays the best performance among the three catalysts. The peak current density of formic acid electrooxidation on Pd/ZrC–C electrode is nearly 1.63 times of that on Pd/C. The optimal mass ratio of ZrC to XC‐72 carbon is 1:1 in Pd/ZrC–C catalyst with narrower particle size distribution and better dispersion on surface of the mixture support, which exhibits the best activity and stability for formic acid electrooxidation among all the samples.     

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.     

Phase decomposition of (Ti,Zr)(C,N) solid solutions prepared by spark plasma sintering

(Ti, Zr)(C, N) solid solutions with 10–90 mol% of ZrC were prepared by spark plasma sintering (SPS) using TiCN and ZrC powders as starting materials. The decomposition behavior of the (Ti, Zr)(C, N) solid solutions as a function of heat treatment temperature (1273–2173 K) was investigated. (Ti, Zr)(C, N) solid solutions with 20–80 mol% of ZrC were decomposed into TiCN-rich (Ti, Zr)(C, N) and ZrCN-rich (Zr, Ti)(C, N) phases when heat-treated in the temperature ranged from 1373 to 2173 K for 3.6 ks, respectively. After heat treatment, lamellar microstructure was formed with an orientation relationship of TiCN-rich (Ti, Zr)(C, N) {100} // ZrCN-rich (Zr, Ti)(C, N) {100}. The Vickers hardness and fracture toughness simultaneously increased with increasing heat-treatment temperature and showed the maximum values of 25.0 GPa and 2.5 MPa m^1/2, respectively, for Ti_0.5Zr_0.5C_0.75N_0.25 at the heat-treatment temperature of 1873 K.     

Fabrication and microstructure of 3D Cf /ZrC-SiC composites: through RMI method with ZrO2 powders as pore-making agent

3D C_f/ZrC–SiC composites were prepared by a combination process of slurry infiltration and reactive melt infiltration. ZrO₂ powders and ZrSi₂ alloy, both of which reacted with amorphous carbon, were used as pore-making agent and infiltrator, respectively. After carbothermal reduction at 1650 °C, X-ray diffraction analysis revealed that ZrO₂ powders were completely converted into ZrC by reacting with amorphous carbon, and an in-situ formed submicron porous configuration was observed at the areas containing ZrO₂. Results showed that the matrix in composites mainly consisted of SiC, ZrC and a small quantity of residual metal. SEM and TEM images revealed the formation of ZrC or SiC intergranular particles in the matrix and the characteristic around the residual resin carbon. The composites had a bending strength of 94.89±16.7 MPa, fracture toughness of 11.0±0.98 MPa m^1/2, bulk density of 3.36±0.01 g/cm³, and open porosity of 4.64±0.40%. The formation mechanisms of ZrC–SiC dual matrix and intrabundles׳ structure were discussed in the article.     

Reactive Hot Pressing and Properties of Zr1−xTixB2–ZrC Composites

Reactive hot pressing was used to prepare Zr_1?xTi_xB₂–ZrC composites with advantageous microstructure and mechanical properties from ZrB₂–TiC powders. The reaction mechanisms and the effects of different levels of TiC on the physical and mechanical properties of the resulting composite were explored in detail and compared to conventionally hot‐pressed ZrB₂ and ZrB₂–ZrC. Incorporation of 10 to 30 vol% TiC enabled full densification and restrained grain growth, reducing the final average grain size from 5.6 μm in pure ZrB₂ to a minimum of 1.4 μm in samples with 30 vol% TiC. The flexural strengths and hardnesses of the composites sintered with TiC were consequently greater than the conventionally processed ZrB₂–ZrC materials, increasing from 440 MPa and 17.4 GPa to a maximum of 670 MPa and 24.2 GPa at 10 vol% TiC. However, despite a decrease in the total average grain size, the flexural strength at higher TiC levels was limited by an increase in ZrC grain growth, which was observed to determine the flexural strength of the reaction sintered composites similar to the case of ZrB₂–SiC.     

Microstructure and mechanical properties of Cf/ZrC composites fabricated by reactive melt infiltration at relatively low temperature

Carbon fiber-reinforced zirconium carbide matrix composites (C_f/ZrC) were prepared by vacuum infiltrating porous carbon/carbon preforms with molten Zr₂Cu alloy at 1200 °C. X-ray diffraction, scanning electron microcopy and transmission electron microscopy analysis were used to characterize the composition and microstructure of the final composites. It was found that the matrix of the composites were composed of the Cu–Zr–C amorphous phase dispersed with either single- or polycrystalline ZrC. Based on the microstructural analysis, the formation mechanism of the matrix was proposed to be a solution-precipitation and grain coalescence process. The influence of the heat treatment at 1800 °C was also investigated. Results indicated that at very high temperature the volatilization of residual metal somewhat deteriorated the flexural strength and the elastic modulus, but the fracture toughness of the composites was improved due to the sintering of ZrC grains.     

Synthesis of nanosized zirconium carbide powders by a combinational method of sol–gel and pulse current heating

Zirconium carbide nanopowders were synthesized by a novel method combining the advantages of sol–gel method and rapid synthesis using pulse current heating. The core-shelled structure of ZrO₂/C mixture was obtained during the sol–gel process, and further heat treatment in SPS led to the fast formation of ZrC. The particle size of ZrO₂ played an important role in the synthesis of nanosized ZrC powders. In addition, the coalescence and grain growth of ZrC particles could be also limited due to the fast heating rate. As a result, the reactions were thoroughly completed at a relatively low temperature and ZrC nanopowders of 60–100 nm were obtained. The corresponding powders also had low oxygen content (∼0.64 wt%) and residual carbon content (∼0.27 wt%). Additive-free ZrC powders could be sintered to ∼99% relative density with an average grain size of 0.8 μm at low temperature of 1750 °C.