Solid solution synthesis of tantalum carbide‐hafnium carbide by spark plasma sintering

Solid solutions of Tantalum carbide (TaC) and Hafnium carbide (HfC) were synthesized by spark plasma sintering. Five different compositions (pure HfC, HfC‐20 vol% TaC, HfC‐ 50 vol% TaC, HfC‐ 80 vol% TaC, and pure TaC) were sintered at 1850°C, 60 MPa pressure and a holding time of 10 min without any sintering aids. Near‐full density was achieved for all samples, especially in the HfC‐contained samples. The porosity in pure TaC samples was caused by the oxygen contamination (Ta₂O₅) on the starting powder surface. The addition of HfC increased the overall densification by transferring the oxygen contamination from TaC surface and forming ultrafine HfO₂ and Hf‐O‐C grains. With the increasing HfC concentration, the overall grain size was reduced by 50% from HfC‐ 80 vol% TaC to HfC‐20 vol% TaC sample. The solid solution formation required extra energy, which restricted the grain growth. The lattice parameters for the solid solution samples were obtained using X‐ray diffraction which had an excellent match with the theoretical values computed using Vegard's Law. The mechanical properties of the solid solution samples outperformed the pure TaC and HfC carbides samples due to the increased densification and smaller grain size.     

Controlling phase separation of TaxHf1−xC solid solution nanopowders during carbothermal reduction synthesis

Synthesis of single‐phase tantalum hafnium carbide (Ta_xHf_1?xC, 0<x<1) solid solution nanopowders via carbothermal reduction (CTR) reaction is complicated due to the difference in reactivity of parent oxides with carbon and presence of a miscibility gap in TaC‐HfC phase diagram below ~887°C. These can lead to phase separation, ie, formation of two distinct carbides instead of a single‐phase solid solution. In this study, nanocrystalline Ta_xHf_1?xC powders were synthesized via CTR of finely mixed amorphous tantalum‐hafnium oxide(s) and carbon obtained from a low‐cost aqueous solution processing of tantalum pentachloride, hafnium tetrachloride, and sucrose. Particular emphasis was given to investigate the influences of starting compositions and processing conditions on phase separation during the formation of carbide phase(s). It was found that due to the immiscibility of Ta‐Hf oxides and relatively fast CTR reaction, individual nano‐HfC and TaC phases form quickly (within minutes at 1600°C), then go through interdiffusion forming carbide solid solution phase. Moreover, the presence of excess carbon in the CTR product slows down the interdiffusion of Ta and Hf dramatically and delays the solid solution formation, whereas DC electrical field (applied through the use of a spark plasma sintering system) accelerates interdiffusion significantly but leads to more grain growth.     

Effects of milling time and reductant content on the formation of HfC-HfB2 composite powders synthesized via a solid-state reaction route

In this study, a solid-state reaction route that is a combination of high-energy ball milling (HEBM) and annealing was adopted to synthesize HfC-HfB₂ composite powders. The effects of HEBM duration (0 h, 1 h, 2 h, and 4 h) and excess reductant (Mg or C) amount on the reaction mechanism of Hf–B₂O₃–C–Mg quaternary powder system were meticulously investigated. Following the HEBM of powder blends, annealing was performed at 1600 °C for 16 h under Ar atmosphere. A purification step was conducted the annealed powders by dissolving them in an acidic solution. X-ray diffractometry (XRD) technique revealed that a small amount of Hf and C powders reacted to form HfC phase after 2 h of HEBM. After annealing and purification, in addition to the HfC phase, the HfB₂ and HfO₂ phases were observed in the powders. Besides, the intensities of XRD peaks belonging to the HfO₂ phase gradually decreased, and those of HfC increased in the annealed and purified powders with increasing milling duration and reductant amounts. Both milled and milled-annealed-purified powders exhibited a decrease in the particle size with an increase in the HEBM duration. Transmission electron microscopy (TEM) micrograph belonging to 4 h milled-annealed-purified powders containing 50 wt% excess Mg and 50 wt% excess C revealed the formation of HfC-HfB₂ composite powders whose particles ranged between 50 nm and 100 nm.     

Reaction Sintering of HfC/W Cermets with High Strength and Toughness

Hafnium carbide/tungsten (HfC/W) cermets were prepared by an in situ reaction sintering process, using hafnium oxide (HfO₂) and tungsten carbide (WC) as the raw materials. The reaction path, densification behavior, microstructure development, and mechanical properties of the cermets were comprehensively investigated. It was found that WC decomposed to tungsten semicarbide (W₂C) and tungsten (W) in sequence, and meanwhile HfC was formed by carbothermal reduction between HfO₂ and as‐released carbon from the dissociation of WC. The solid solution formation between HfC and W during sintering was also studied. The obtained cermets (>98% TD) have a Vickers' hardness of 8.16 GPa, a fracture toughness of 14.45 MPa m^1/2, and a high flexural strength of 1211 MPa.     

Phase evolution and microstructure characteristics during the carbothermal reduction of Hf(C,N,O) ceramics derived from a precursor

In this study, nanosized Hf(C,N,O) ceramics were successfully prepared from a novel precursor synthesised by combining HfCl₄ with ethylenediamine and dimethylformamide. Subsequently, the carbothermal reduction of these Hf(C,N,O) ceramics into hafnium carbide was investigated. The Hf(C,N,O) ceramics comprised Hf₂ON₂ and HfO₂ nanocrystals and amorphous carbon. Upon carbothermal reduction, conversion began at 1300 °C, when HfC first appeared, and continued to completion at 1500 °C, resulting in irregularly shaped crystallites measuring 50–150 nm. Upon increasing the dwelling time, the oxides were completely converted into carbides at 1400 °C. Furthermore, nitrogen was introduced into the reaction to catalyse the conversion of oxides into carbides considering the beneficial gas–solid reaction between CO and Hf₂ON₂. We expect that the ceramics prepared in this study will be suitable for the fabrication of high-performance composite ceramics, with properties superior to those of current materials.     

Facile one‐step high‐temperature spray pyrolysis route toward metal carbide nanopowders

Fine ultrahigh‐temperature ceramic (UHTC) powders have found very important applications in many fields. In this work, a facile high‐temperature spray pyrolysis (HTSP) approach is implemented for the synthesis of HfC and TaC UHTC nanopowders starting from organic solvent (e.g., ethanol or 1‐pentanol) solutions of metal precursors (HfCl₄ or TaCl₅). It is proposed that, during HTSP, the precursor solution droplets would continuously undergo rapid drying, thermolysis (i.e., removal of low molecular weight species such as H₂, H₂O, and CO), and finally in situ carbothermal reduction (CTR) process to give rise to metal carbide nanopowders. The as‐obtained materials are shown by SEM as uniform and separated nanoparticles (~90 nm), whereas TEM reveals the carbide (e.g., HfC) nanoparticles are actually even smaller (~10‐20 nm) and embedded in amorphous carbon from excess solvent decomposition. It is found that among different processing parameters, the organic solvent used and the metal precursor concentration could largely influence the formation of metal carbide. In addition, lower HTSP temperatures (≤~1500°C for HfC) only lead to oxide‐carbon mixtures while higher temperatures (≥~1650°C) promote carbide formation. The HTSP method developed in this work is simple, low‐cost and efficient, and could potentially be optimized further for future large‐scale manufacturing of ultrafine UHTC nanopowders.     

Consolidation and characterization of highly dense single-phase Ta–Hf–C solid solution ceramics

Herein, Ta–Hf–C solid solution ceramics were consolidated from nano-scale Ta–Hf–C solid solution powders for the first time. Four different compositions (4TaC–1HfC, 1TaC–1HfC, 1TaC–3HfC, and 1TaC–4HfC) were prepared by hot-pressed sintering at 2100°C, 70 MPa pressure and a holding time of 30 minutes. The densification, formation of single-phase solid solution and mechanical properties of the samples were systemically investigated. Relative density >95% was achieved for all four compositions with some improvement when TaC content was increased. And the formation of single-phase Ta–Hf–C solid solution was strongly demonstrated by phase analysis and crystal measurement using XRD and TEM. A significant improvement of hardness up to ~30 GPa was achieved, which was much higher than that of pure TaC (18.9 GPa) and HfC (22.1 GPa), due to the high densification and solid solution strengthening mechanism.     

High-strength medium-entropy (Ti,Zr,Hf)C ceramics up to 1800°C

Medium-entropy (Ti,Zr,Hf)C ceramics were prepared by hot pressing a dual-phase medium-entropy carbide powder with low oxygen content (0.45 wt%). The results demonstrate that the medium-entropy (Ti,Zr,Hf)C ceramics sintered at 2100°C had a relative density of 99.2% and an average grain size of 1.9 ± 0.6 μm. The flexural strength of (Ti,Zr,Hf)C carbide ceramics at room temperature was 579 ± 62 MPa. With an increase in temperature to 1600°C, the flexural strength showed an increase up to 619 ± 57 MPa, and had no significant degradation even up to 1800°C. The high-temperature flexural strengths of (Ti,Zr,Hf)C were obviously higher than those of the monocarbide ceramics (TiC, ZrC, and HfC). The primary strengthening mechanism in (Ti,Zr,Hf)C could be attributed to the high lattice parameter mismatch effects between TiC and ZrC, which not only inhibited the fast grain coarsening of (Ti,Zr,Hf)C ceramics, but also increased the grain-boundary strength of the obtained ceramics.     

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.     

Low‐Temperature Sintering of HfC/SiC Nanocomposites Using HfSi2‐C Additives

HfC/SiC nanocomposites were fabricated via the reactive spark plasma sintering (R‐SPS) of a nano‐HfC powder and HfSi₂‐C sintering additives. The densification temperature decreased to 1750°C as the additive content increased. XRD analysis indicated the formation of pure HfC–(19.3–33.8 vol%) SiC within the sintered composites without residual silicide or oxide phases or secondary nonoxide phases. Ultrafine and homogeneously distributed HfC (470 nm) and SiC (300 nm) grains were obtained in the dense composites using nano‐HfC powder through the high‐energy ball‐milling of the raw powders and R‐SPS. Grain growth was further suppressed by the low‐temperature sintering using R‐SPS. No amorphous phase was identified at the grain boundary. The maximum Vickers hardness, Young's modulus, and fracture toughness values of the HfC/SiC nanocomposites were 22 GPa, 292 GPa, and 2.44 MPa·m^1/2, respectively.     

Polymer precursor‐derived HfC–SiC ultrahigh‐temperature ceramic nanocomposites

Due to poor mechanical properties and antioxidation properties, etc of single phase ultrahigh‐temperature ceramics (UHTCs), the second phase such as SiC was usually introduced for improving those properties. Herein, a novel stratagem for synthesis of binary HfC–SiC ceramics has been presented. A Hf–O–Hf polymer as a HfO₂ precursor has been synthesized for preparing soluble HfC–SiC precursors with high solid content and low viscosity solutions without additional organic solvents. The structure of PHO was characterized by FTIR and ¹H‐NMR, the crystalline behavior and morphologies of polymer‐derived ceramics were identified by XRD, SEM‐EDS, and TEM. It was shown that PHO firstly transformed into HfO₂, and then reacted with in situ carbon derived from DVB and PCS thus producing cubic HfC through carbothermal reduction. In addition, the obtained HfC–SiC nanopowders exhibited spherical morphology with a diameter less than 100 nm, while the Hf, Si, and C are homogeneously distributed.     

Processing factors influencing the free carbon contents in boron carbide powder by rapid carbothermal reduction

High quality boron carbide powder without free carbon is desired for many applications. In this study, the factors that influence free carbon content in boron carbide powders synthesized by rapid carbothermal reduction reaction were evaluated. The dominant factors affecting free carbon contents in boron carbide powder were reaction temperature, precursor homogeneity, the particle size of reactants, and excess boron reactant amount. The reaction temperature at 1850 °C was sufficient to synthesize boron carbide with low free carbon content. Depending on process conditions, precursor homogeneity was also affected by the calcination temperature and time. Smaller particle size of reactants contributed to less carbon content and more uniformity in synthesized boron carbide. Excess boric acid effectively compensated for B₂O₃ volatilization. In the optimal sample, using 80 mol% excess nano boric acid and calcined at 500 °C, the free carbon in the synthesized boron carbide was negligible (0.048 wt.%).     

Reactive hot pressing route for dense ZrB2-SiC and ZrB2-SiC-CNT ultra-high temperature ceramics

The in-situ exothermic reactions between ZrC_0.8, B₄C and Si have assisted densification and allowed to obtain fully dense ZrB₂-31 wt.%SiC ultra-high temperature ceramics within 6 min at 1750 °C. The use of zirconium carbide instead of metallic zirconium in the green body obviated the possibility of in-situ SHS process and allowed to apply the pressure at low temperatures. The latter provided a first densification stage just above 1050 °C. A slight carbon excess was created in the green body to preserve the carbon nanotubes. The developed reactive hot pressing route (1830 °C, 3 min, 30 MPa) has been successfully used to obtain ZrB₂-SiC ceramics containing 8 vol.% of multi-wall carbon nanotubes (MW-CNT). The carbon nanotubes survived the thermal cycle and could be clearly observed in the sintered ceramics. The CNT addition improved the fracture toughness of the composite from 4.3 MPa m^1/2 for ZrB₂-31 wt.%SiC to 6.8 MPa m^1/2 for ZrB₂-29 wt.%SiC-CNT.     

Effects of high-energy ball milling and reactive spark plasma sintering on the densification of HfC-SiC composites

The combined effects of high-energy ball milling (HEBM) and reactive spark plasma sintering (R-SPS) of HfSi₂ and C powder mixture on the densification and microstructure of nanostructured HfC-SiC composites were investigated. HEBM significantly promoted the densification and improved the microstructure of the HfC-SiC composites. In contrast, the reactions between HfSi₂ and C did not directly promote the densification of the HfC-SiC composites. While the reaction was mostly completed at 1300 °C, the onset temperature of significant densification was 1610 °C. Fine and homogeneously distributed HfC and SiC particles formed by HEBM and R-SPS were the key factors for promoting the densification of the HfC-SiC composites. The fine particles had high surface energy, which provided enough driving force for densification. In addition, the homogeneously distributed SiC particles effectively suppressed the growth of HfC matrix grains during densification.     

Evolution of the composition,microstructure and electromagnetic properties of HfOC ceramics with pyrolysis temperature

The evolution of phase composition, microstructure, and dielectric characteristics of HfOC ceramics pyrolyzed at various temperatures was studied in this work. When the pyrolysis temperature increased from 900 to 1500 °C, the composition of HfOC ceramics varies from HfO₂ and amorphous carbon (C_amp) at 900 °C to coexistence of HfO₂, C_amp, and HfC at 1100–1300 °C, and HfC and C_amp at 1500 °C. With the continuous consummation of C_amp, its distribution is transformed from a slice-like structure accumulating around the particles to a shell-like structure wrapping around the particles. The atomic ratios of as-obtained HfOC ceramics are HfO_2.0C_2.8, HfO_1.9C_2.7, HfO_1.0C_1.8, and HfO_0.1C_1.1, respectively, after being pyrolyzed at 900, 1100, 1300, and 1500 °C. As the pyrolysis temperature increases, the average value of the real part increases from 13.5 to 16.5, and the imaginary part rises from 12 to 14. The microwave absorption properties of HfOC ceramics need to be enhanced further in the future work.     

Synthesis and properties of (Hf1-xTax)C solid solution carbides

Thermodynamically stable (Hf_1–xTa_x)C (x?=?0.1–0.3) compositions were selected by First Principle Calculation and synthesized in nanopowders via high-energy ball milling and carbothermal reduction of commercial oxides at 1450?°C. The formation of a solid solution during powder synthesis was investigated. The solid solution carbide powders were sintered at 1900?°C by spark plasma sintering without a sintering aid. As a result, the (Hf_1–xTa_x)C solid solution carbides exhibited high densities, excellent hardness and fracture toughness (ρ: 98.7–100.0%, HVN: 19.69–19.98?GPa, K_IC: 5.09–5.15?MPa?m^1/2) compared with previously reported HfC and HfC–TaC solid solution carbides.     

Fabrication of ultra-high-temperature nonstoichiometric hafnium carbonitride via combustion synthesis and spark plasma sintering

In this study, nonstoichiometric hafnium carbonitrides (HfC_xN_y) were fabricated via short-term (5 min) high-energy ball milling of Hf and C powders, followed by combustion of mechanically induced Hf/C composite particles in a nitrogen atmosphere (0.8 MPa). The obtained HfC_0.5N_0.35 powder exhibited a rock-salt crystal structure with a lattice parameter of 0.4606 nm. The melting point of this synthesized ceramic material was experimentally shown to be higher than that of binary hafnium carbide (HfC). The nonstoichiometric hafnium carbonitride was then consolidated under a constant pressure of 50 MPa at a temperature of 2000 °C and a dwelling time of 10 min, through spark plasma sintering. The obtained bulk ceramic material had a theoretical material density of 98%, Vickers hardness of 21.3 GPa, and fracture toughness of 4.7 MPa m^1/2.     

Effect of incorporation of hafnium diboride nanofibers on thermomechanical properties of carbon fiber–phenolic composites

Carbon fiber/phenolic (C/Ph) composites were modified with different weight ratios of hafnium diboride (HfB₂) nanofibers to apperceive thermomechanical properties of C/Ph–Hf nanocomposites. Mechanical properties, thermal stability, and ablation resistance of C/Ph–Hf nanocomposites were found to be optimum when the weight percentage of HfB₂ was equal to one. Maximum flexural strength and modulus were obtained with 118 MPa and 1.9 GPa for C/Ph–1%Hf nanocomposite, respectively. Increasing the proportion of HfB₂, by delaying the temperature of thermal degradation of nanocomposites, enhanced the thermal stability and residual of C/Ph–Hf relative to C/Ph in both nitrogen and air environments. In the oxyacetylene flame test at 2500°C for 160 s, the optimum mass ablation rate of C/Ph–1%Hf nanocomposites was found to be 0.0150 g/s compared to 0.068 g/s for blank C/Ph, along with reducing the back surface temperature by 51%. The ablation mechanism of C/Ph–Hf nanocomposites after the oxyacetylene torch test was concluded from the derivations obtained from X-ray diffraction, energy dispersion spectroscopy, and microstructure analyses. These clarified that the formation of high-temperature species, such as HfO₂, HfC, and B₄C owing to oxidation of HfB₂ and subsequent reaction products with char, resulted in an increased ablation resistance of the nanocomposites.     

Densification,mechanical, and tribological properties of ZrB2-ZrCx composites produced by reactive hot pressing

ZrB₂-ZrC_x composites were produced using Zr:B₄C powder mixtures in the molar ratios of 3:1, 3.5:1, 4:1, and 5:1 by reactive hot pressing (RHP) at 4-7 MPa, 1200°C for 60 minutes. X-ray diffraction analyses confirmed the formation of nonstoichiometric zirconium carbide (ZrC_x) with different lattice parameters and enhanced carbide formation by increasing the Zr mole fraction. An increase in applied pressure from 4 to 7 MPa was responsible for the improved relative density (RD) of 4Zr:B₄C composition from 86% to 99%. Microstructural studies on Zr-rich composites showed a reduction in unreacted B₄C particles and enriched elongated ZrB₂ platelets. Reaction and densification mechanism in 4Zr:B₄C composition were studied as a function of temperature increased from 600 to 1200°C at an applied constant pressure of 7 MPa. After 1000°C, <40 vol.% of unreacted Zr was observed during the densification process. Concurrently, low energies of carbon diffusion and carbon vacancy formation were found to enhance nonstoichiometric ZrC_x formation, which was found to be responsible for the completion of the reaction. The plastic deformation of unreacted Zr was responsible for the densification of the ZrB₂-ZrC_x composite. The results clearly showed that the applied pressure is five times lower than the reported values. Moreover, a temperature of 1200°C was sufficient to produce dense ZrB₂-ZrC_x composites. The improved microhardness, flexural strength, fracture toughness, and specific wear rate were 8.2-15 GPa, 265-590 MPa, 2.82-6.33 MPa.m^1/2, and 1.43-0.376 × 10⁻² mm²/N, respectively.     

Low-temperature synthesis and oxidation resistance of random combination of Hf,Nb, and Ta carbides microcuboids

Based on the dissolution-precipitation mechanism, this article successfully synthesized binary and ternary transition metal carbide microcuboids with random combinations of Hf, Nb, and Ta by annealing monocarbides/cobalt powders. Accelerated mass transport rate through the flow of molten alloys (Co-Hf-Nb-Ta) instead of slow solid diffusion made the low-temperature pressureless sintering technique (1500°C) a reality. Furthermore, the equilibrium morphology was driven by the gradient Gibbs potential of carbides induced by the different local curvature of powders and anisotropic interfacial energy. (Hf_0.5Ta_0.5)C possessed the optimal oxidation resistance among all mentioned carbides, even competed with (Hf_1/3Nb_1/3Ta_1/3)C. During the isothermal oxidation at 800∼1200°C, the doping of Nb and Ta in carbides assisted the monoclinic-orthorhombic HfO₂ transition at ambient pressure, besides, TaC can also restrain the orthorhombic-monoclinic transition of Nb₂O₅. Moreover, oxidation kinetics parameters concluded that the addition of HfC and TaC contributed to the decreasing reaction order and the increasing activation energy, respectively.