Preparation and high‐temperature behavior of HfC–SiC nanocomposites derived from a non‐oxygen single‐source‐precursor

A single‐source precursor for the preparation of HfC‐SiC ceramics was synthesized via a Grignard reaction using bis(cyclopentadienyl)hafnium(IV) dichloride, trans‐1,4‐dibromo‐2‐butene, and (chloromethyl)trimethylsilane as raw materials. The composition, structure, pyrolysis process and high‐temperature behavior of the precursor were investigated. The results show that the precursor with a backbone comprising Hf–C, Si–C and CH=CH groups exhibits good solubility in common solvents, such as tetrahydrofuran, dimethylbenzene, and chloroform. Pyrolysis of the precursor at 1000°C yielded a microcrystalline HfC phase with a ceramic yield of 63.86 wt%. The pyrolytic products at 1600°C were HfC–SiC nanocomposite ceramics, which exhibited good thermal stability up to 2400°C. The formation of a (Hf,Si)C solid‐solution would be beneficial for densification during the sintering process. The non‐oxygen structure, high ceramic yield, homogeneous composition and excellent high‐temperature behavior of the pyrolytic products make the as‐prepared precursor a promising material for the preparation of high‐performance ultra‐high‐temperature ceramics.     

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.     

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.     

Ultra‐High‐Temperature Ceramic HfB2‐SiC Coating for Oxidation Protection of SiC‐Coated Carbon/Carbon Composites

To protect the carbon/carbon (C/C) composites from oxidation, an outer ultra‐high‐temperature ceramics (UHTCs) HfB₂‐SiC coating was prepared on SiC‐coated C/C composites by in situ reaction method. The outer HfB₂‐SiC coating consists of HfB₂ and SiC, which are synchronously obtained. During the heat treatment process, the formed fluid silicon melt is responsible for the preparation of the outer HfB₂‐SiC coating. The HfB₂‐SiC/SiC coating could protect the C/C from oxidation for 265 h with only 0.41 × 10^?2 g/cm² weight loss at 1773 K in air. During the oxidation process, SiO₂ glass and HfO₂ are generated. SiO₂ glass has a self‐sealing ability, which can cover the defects in the coating, thus blocking the penetration of oxygen and providing an effective protection for the C/C substrate. In addition, SiO₂ glass can react with the formed HfO₂, thus forming the HfSiO₄ phase. Owing to the “pinning effect” of HfSiO₄ phase, crack deflecting and crack termination are occurred, which will prevent the spread of cracks and effectively improve the oxidation resistance of the coating.     

Limits to the Stability of the Amorphous Nature of Polymer‐Derived HfSiCNO Compounds

Substituting silicon by transition metals in polymer‐derived ceramics (PDCs) holds the potential for a new class of polymer‐derived ceramics for ultrahigh‐temperature structural applications. We present experiments that show that the solid solubility of HfO₂ extends to Hf/Si ratio of <0.22. The materials are synthesized from (miscible) organic precursors. Similar to silicon‐based materials they remain amorphous after pyrolysis at 1000°C. Small‐angle X‐ray scattering and Raman spectra remain essentially unaltered. It is postulated that Hf, like Si, forms mixed‐bond tetrahedra with C, O, and N. The difference in the enthalpy of Hf‐based, and Si‐centered tetrahedra is calculated using single‐bond energies, reinforcing the feasibility of substituting Si with Hf or with Zr atoms. Such polymer‐based HfSiCNO compounds made directly from liquid organics, by a simple manufacturing process, may also be relevant to nanoscale dielectrics with low leakage electric charge in microelectronics applications.     

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.     

Microstructure refinement and mechanical properties improvement of HfB2–SiC composites with the incorporation of HfC

HfB₂ and HfB₂–10 vol% HfC fine powders were synthesized by carbo/boronthermal reduction of HfO₂, which showed high sinterability. Using the as-synthesized powders and commercially available SiC as starting powders, nearly full dense HfB₂–20 vol% SiC (HS) and HfB₂–8 vol% HfC–20 vol% SiC (HHS) ceramics were obtained by hot pressing at 2000 °C/30 MPa. With the incorporation of HfC, the grain size of HHS was much finer than HS. As well, the fracture toughness and bending strength of HHS (5.09 MPa m^1/2, 863 MPa) increased significantly compared with HS (3.95 MPa m^1/2, 654 MPa). Therefore, it could be concluded that the incorporation of HfC refined the microstructure and improved the mechanical properties of HfB₂–SiC ceramics.     

Oxidation of SiCf/SiC‐HfB2 Composites under Laser Heating

Ceramic matrix composites with Sylramic^TM and CG Nicalon^TM SiC fibers and SiC‐HfB₂ matrices derived from a combination of polymer‐derived SiC ceramic and HfB₂ particulate slurries were prepared. The composites were tested for oxidation resistance by laser heating at 2 MW/m² to achieve temperatures near 1600°C. The oxidation resistance was compared between uncoated CG Nicalon^TM and BN‐coated Sylramic^TM fiber‐based composites. Oxidation resulted in precipitated nano‐sized HfO₂ independent of the fibers and fiber coatings.     

Qualitative analysis of hafnium diboride based ultra high temperature ceramics under oxyacetylene torch testing at temperatures above 2100 °C

Oxidation tests were carried out on HfB₂–SiC, HfB₂–HfC, HfB₂–WC–SiC, and HfB₂–WSi₂ ceramics using an oxyacetylene torch. The samples were oxidized between 2100 and 2300 °C. From cross-sectional images, scale non-adherence was noted as a limiting factor in oxidation resistance. The sample with the best scale adherence was HfB₂–WSi₂. Factors involving scale non-adherence such as vapor pressure, coefficient of thermal expansion mismatch and phase transformations were considered. In comparing the scale adherence of the samples it was hypothesized that vapor pressure buildup is the principal contributing factor in the scale adherence differences observed among the tested samples. However, the coefficient of thermal expansion mismatch and HfO₂ phase transformation cannot be neglected as contributing factors to scale non-adherence in all samples.     

Dielectric Properties of Pure and Gd‐Doped HfO2 Ceramics

The pure, 2 at.%, and 20 at.% Gd‐doped HfO₂ ceramics were prepared by the standard solid‐state reaction technique. Dielectric properties of these ceramics were investigated in the temperature range 300–1050 K and frequency range 20–5 × 10⁶ Hz. Our results revealed an intrinsic dielectric constant around 20 in the temperature below 450 K for all tested ceramics. Two oxygen‐vacancy‐related relaxations R1 and R2 were observed at temperatures higher than 450 K, which were identified to be a dipolar relaxation due to grain response and a Maxwell–Wagner relaxation due to grain‐boundary response, respectively. The dielectric properties of the pure and slightly doped (2 at.%,) samples are dominated by the grain‐boundary response, which results in a colossal dielectric behavior similar to that found in CaCu₃Ti₄O₁₂. The doping level of 20 at.% leads to the structural transformation from monoclinic phase to cubic phase. The dielectric properties of the heavily doped HfO₂ are dominated by the grain response without any colossal dielectric behavior.     

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.     

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.     

Fabrication and mechanical properties of laminated HfC–SiC/BN ceramics

Laminated HfC–SiC/BN ceramics were successfully fabricated by tape casting and hot pressing. Fully dense HfC–SiC ultra-high temperature ceramics with homogeneous structure were obtained. The introduction of the weak BN layer resulted in a slight decrease of the flexural strength but significantly improved the fracture toughness compared with monolithic HfC–SiC ceramics. The fracture toughness of laminated HfC–SiC/BN ceramics in the parallel direction peaked at 8.06 ± 0.46 MPa m^1/2, which increased by 115% than that of monolithic HfC–SiC ceramics. The composites showed non-catastrophic fracture behaviors in both parallel and perpendicular directions. It indicates that laminated structure design is a promising approach to obtain full density HfC–SiC ceramics with high fracture toughness.     

Tensile creep properties and damage mechanisms of 2D-woven C/HfC–SiC composites in high temperature

2D-C/HfC–SiC composites were prepared by a combination of precursor infiltration and pyrolysis (PIP) and chemical vapor infiltration (CVI). Creep tests were performed at 1100°C in air under different stress conditions. Unlike most, C/SiC and SiC/SiC ceramic matrix composites only underwent primary and secondary creep stages, and the C/HfC–SiC composites underwent tertiary creep stage in the creep process. The reason was that the mechanical properties of C/HfC–SiC materials prepared by PIP + CVI methods were different from those prepared by traditional methods. The microscopic morphological analysis of the sample fracture showed that the oxidation products SiO₂ and Hf–Si–O glass phases of the HfC–SiC matrix played a crack filling role in the sample during creep. In turn, it provided effective protection to the internal fibers of the sample. The creep failure of C/HfC–SiC composites in a high-temperature oxidizing atmosphere was caused by the oxidation of the fibers. The total creep process was dominated by the oxidation of carbon fibers. It is noteworthy that there was the generation of Hf_xSi_yO_z nanowires in the samples after high-temperature creep. The analysis of the experimental data showed that the creep stress had a linear negative correlation with the creep life.     

Effect of residual excess carbon on the densification of ultra-fine HfC powder

The residual carbon content of ultra-fine hafnium carbide (HfC) powder was controlled by the optimization of the synthesis process, and the effect of residual carbon on the densification of HfC powder was analyzed. The amount of residual carbon in the HfC powder could be reduced by the de-agglomeration of HfO₂ powder before the carbo-thermal reduction (CTR) process. The average particle size of HfO₂ powder decreased from 230 to 130 nm after the de-agglomeration treatment. Ultra-fine (d₅₀: 110 nm) and highly pure (metal basis purity: >99.9 % except for Zr) HfC powder was obtained after the CTR at 1600 °C for 1 h using the C/Hf mixing ratio of 3.3. In contrast, the C/Hf ratio increased to 3.6 without the de-agglomeration treatment, indicating that a large amount of excess carbon was required for the complete reduction of the agglomerated HfO₂ particles. HfC ceramics with high relative density (>98 %) were obtained after spark plasma sintering at 2000 °C under 80 MPa pressure when using the HfC powder with low excess carbon content. In contrast, the densification did not complete at a higher temperature (2300 °C) and pressure (100 MPa) when the HfC powder contained a large amount of residual carbon. The results clearly indicated that residual carbon suppressed the densification of HfC powder in case the carbide powder had low oxygen content, and the residual carbon content could be controlled by the optimization of the synthesis process. The average grain size and Vickers hardness of the sintered specimen were 6.7(±0.7) μm and 19.6 GPa, respectively.     

Deposition and ablation resistance of HfC-based coatings prepared on SiC-coated C/C composites by supersonic atmospheric plasma spraying

In order to improve the ablation properties of C/C composites, HfC-based coatings with different mass ratios of SiC were deposited on the surface of SiC-coated carbon/carbon composites by supersonic atmospheric plasma spraying. The morphologies and microstructures of the HfC-based coatings were characterised. The ablation resistance test was carried out by oxyacetylene torch. The results show that the as-prepared coatings are multiphase coatings consisting of HfC, HfO₂, SiC and SiO₂. The structure of different coatings is dense. After ablation for 60?s, the ablation centre region of coating is smooth without obvious microcrack and pinhole, and no interlaminar crack can be observed at the cross-section. An Hf–Si–O compound oxide layer is generated on the surface of coating, which is beneficial for protecting the C/C composites from being ablated. Meanwhile, the further generated HfSiO₄ can play a pinning effect, which can prevent crack extension.     

Role of WC additive on reaction,solid-solution and densification in HfB2–SiC ceramics

A comparative study of phase components and compositions was performed for the pressureless sintered HfB₂–SiC–WC composites by various analytical methods. The relative decrease of HfB₂ phase leads to a new reaction of HfO₂ removal by WC to create B₂O₃. By using SiC instead of Si₃N₄ as milling medium, the WB phase was suppressed to the trace level while the W solid-solution in HfB₂ phase was favored. The W solution in both the primary HfB₂ and resultant HfC phases indicates that the WC additive was involved throughout the sintering process by dissolving into sintering liquid, which remains at the intergranular regions to form amorphous oxides as well as trace W-rich phases. This is effectively a reactive liquid-phase sintering to realize the reaction, solid-solution and densification collectively to achieve a designable HfB₂–SiC–HfC composite by pressureless sintering, which may also be extended to other sintering methods.     

Synthesis,Characterization, and Microstructure of Hafnium Boride‐Based Composite Ceramics Via Preceramic Method

The ceramic precursor for HfB₂/HfC/SiC/C was prepared via solution‐based processing of polyhafnoxanesal, linear phenolic resin, boric acid and poly[(methylsilylene)acetylene)]. The obtained precursor could be cured at 250°C and subsequently heat treated at relative lower temperature (1500°C) to form HfB₂/HfC/SiC/C ceramic powders. The ceramic powders were characterized by element analysis, thermal gravimetric analysis, X‐ray diffraction, Raman spectroscopy, and Scanning electron microscopy. The results indicated that the ceramic powders with particle size of 200~500 nm were consisted of pure phase HfB₂, HfC, and SiC along with free carbon as fourth phase with low crystallinity.     

DFT Predictions of Crystal Structure,Electronic Structure,Compressibility, and Elastic Properties of Hf–Al–C Carbides

To understand the potential for use of the Hf–Al–C ternary compounds, (HfC)_nAl₃C₂ (Hf₂Al₃C₄ and Hf₃Al₃C₅) and (HfC)_nAl₄C₃ (Hf₂Al₄C₅ and Hf₃Al₄C₆) were investigated using density functional theory, including crystal structure, electronic structure, compressibility, and elastic properties. The theoretical density of (HfC)_nAl₃C₂ (4.10–4.16 g/cm³) is higher than that of (HfC)_nAl₄C₃ (3.92–3.98 g/cm³), due to the smaller number of lighter Al–C layers. With increasing numbers of Hf–C layers, the Hf–C and Al–C bond lengths remain almost unchanged. In none of the compounds is there a gap around the Fermi energy (E_f), which implies they are metal‐like conductors. With increasing pressure, there is greater shrinkage along the c axis than the a axis. The bond stiffness increases with increasing pressure. In general, (HfC)_nAl₃C₂ has higher elastic stiffness than (HfC)_nAl₄C₃, with the moduli increasing with the number of Hf–C layers. The Hf–Al–C compounds as well as the brittle Zr–Al–C compounds all have low shear moduli/bulk moduli ratio (G/B) from 0.71 to 0.78, suggesting that the G/B ratio is not always a suitable measure of ductility.     

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.