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.     

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.     

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.     

Synthesis of Ultrafine Hafnium Diboride Powders Using Solution‐Based Processing and Spark Plasma Sintering

Ultrafine hafnium diboride (HfB₂) powders were synthesized by the boro/carborthermal reduction process. Fine‐scale mixing of the reactants was achieved by solution‐based processing using hafnium oxychloride (HfOCl₂·8H₂O) and phenolic resin as the precursor of HfO₂ and carbon respectively. The heat treatment was completed at a temperature range 1300–1500°C for 1h using spark plasma sintering (SPS) apparatus. The crystallite sizes of the synthesized powders were small (<500 nm) and the oxygen content was low (0.85 wt%). The grain growth of HfB₂ could be effectively suppressed using SPS due to the fast heating rate. The effects of temperature and holding time on the synthesis of ultrafine HfB₂ powders were discussed.     

The effects of subsonic and supersonic dissociated air flow on the surface of ultra-high-temperature HfB2-30 vol% SiC ceramics obtained using the sol-gel method

By hot pressing (1900 °C, 30 MPa, holding time 15 min) of HfB₂-(SiO₂-C) composite powder, an ultra-high-temperature ceramic material of HfB₂-30 vol% SiC composition with nanocrystalline silicon carbide has been obtained. The effects of subsonic and supersonic dissociated air flow on the surface of produced materials have been studied on a high-frequency induction plasmatron in the geometry of a cylindrical sample with a flat face, fixed in a copper water-cooled holder with a 1 mm protrusion. It has been shown that a sudden rise in the average surface temperature of the samples to ∼2600 °C is characteristic for both modes, which is associated with the occurrence of local sites with a temperature >2000 °C and a subsequent increase in their area. It is a matter of evaporation of the borosilicate glass layer from the surface of the oxidized sample and formation of the ceramic layer of a highly catalytic and low thermal conductive porous HfO₂ layer, which is confirmed by the emission spectroscopy data, XRD and elemental analysis of the material surface after the experiments. The features of heating the oxidized surface of the samples under the impact of subsonic and supersonic dissociated air flow have been noted: there are differences in the location of overheated sites, initiating a sharp temperature rise and the rate of growth of their area.     

Development and Characterization of Continuous SiC Fiber‐Reinforced HfB2‐Based UHTC Matrix Composites Using Polymer Impregnation and Slurry Infiltration Techniques

This paper discusses the development of continuous SiC fiber‐reinforced HfB₂‐SiC composite laminates. A range of techniques, based on resin‐based precursors and slurries, for infiltrating porous SiC preforms with HfB₂ powder were developed. While resin‐based precursors proved to be ineffective due to low HfB₂ yield and poor adhesion, the slurry infiltration techniques were effective to varying degrees. The greatest pore filling and composite densities were achieved using pressure and vibration‐assisted pressure infiltration techniques. SiC_f/HfB₂‐SiC laminates were subsequently developed via lamination, cure and pyrolysis of fabrics using a HfB₂‐loaded polymeric SiC precursor, followed by HfB₂ slurry infiltration and preceramic polymer infiltration and pyrolysis (PIP). Repeated PIP processing, for 6–10 cycles, resulted in density increases, from the 3.03–3.22 g/cm³ range after HfB₂ slurry infiltration, to 3.97–4.03 g/cm³ after PIP processing. Correspondingly, there was a decrease in open porosity from approximately 52% to less than 11%. The matrix consisted of discreet, lightly sintered HfB₂ particles dispersed in SiC. The PIP SiC matrix was primarily nanocrystalline after 1300°C pyrolysis, but experienced grain growth with further heat treatment at 1600°C.     

Effect of in situ SiC and MoSi2 phases on the oxidation behavior of HfB2-based composites

Monolithic HfB₂ and HfB₂-15vol%SiC-15vol%MoSi₂ composite samples were oxidized by a conventional electric furnace at 1700 °C for 5 h. Microstructural and phase analysis of the oxidized samples were performed by X-ray diffraction (XRD) analysis and field emission scanning electron microscope (FESEM) equipped with energy-dispersive spectroscopy (EDS). Besides, for analyzing the oxidation mechanism of the samples, thermodynamic calculations were also accomplished by HSC software. The changes in weight and thickness of the oxide scale were measured and the oxide growth rate of the oxidized samples was subsequently calculated. The results showed that HfB₂-15vol%SiC-15vol%MoSi₂ composite was much more resisted than that monolithic HfB₂ due to the formation of a thin Si-rich glass layer on the surface of the composite sample. By acting to fill the porosities between HfO₂ grains, Si-based glass phase enhanced the oxidation resistance of HfB₂-15vol%SiC-15vol%MoSi₂ composite. Conversely, the oxidized monolithic HfB₂ had only a thick porous oxide layer (HfO₂) which led to considerably lower oxidation resistance. On the other side, three layers containing HfO₂ and Si-based glass phases were formed on the oxidized HfB₂-15vol%SiC-15vol%MoSi₂ composite. Moreover, no porosities and no porous layers were also detected on the oxidized composite sample. Consequently, HfB₂-15vol%SiC-15vol%MoSi₂ composite had a parabolic behavior owing to its diffusion-controlled oxidation under the isothermal oxidation process.     

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.     

Self‐Generating High‐Temperature Oxidation‐Resistant Glass‐Ceramic Coatings for C–C Composites Using UHTCs

Carbon–carbon (C–C) composites are ideal for use as aerospace vehicle structural materials; however, they lack high‐temperature oxidation resistance requiring environmental barrier coatings for application. Ultra high‐temperature ceramics (UHTCs) form oxides that inhibit oxygen diffusion at high temperature are candidate thermal protection system materials at temperatures >1600°C. Oxidation protection for C–C composites can be achieved by duplicating the self‐generating oxide chemistry of bulk UHTCs formed by a “composite effect” upon oxidation of ZrB₂–SiC composite fillers. Dynamic Nonequilibrium Thermogravimetric Analysis (DNE‐TGA) is used to evaluate oxidation in situ mass changes, isothermally at 1600°C. Pure SiC‐based fillers are ineffective at protecting C–C from oxidation, whereas ZrB₂–SiC filled C–C composites retain up to 90% initial mass. B₂O₃ in SiO₂ scale reduces initial viscosity of self‐generating coating, allowing oxide layer to spread across C–C surface, forming a protective oxide layer. Formation of a ZrO₂–SiO₂ glass‐ceramic coating on C–C composite is believed to be responsible for enhanced oxidation protection. The glass‐ceramic coating compares to bulk monolithic ZrB₂–SiC ceramic oxide scale formed during DNE‐TGA where a comparable glass‐ceramic chemistry and surface layer forms, limiting oxygen diffusion.     

Oxidation of HfB2–SiC ceramics under static and dynamic conditions

The kinetics and the mechanism of oxidation of ceramics based on HfB₂ and SiC, manufactured by elemental self-propagating high-temperature synthesis followed by hot pressing were investigated. The synthesis product contained HfC_(x) and HfO₂ as impurity phases. Depending on the ratio between the main components, the samples were characterized by high structural and chemical homogeneity, porosity of 3–6 vol%, hardness up to 29 GPa, bending strength of 500–600 MPa, fracture toughness of 5.6–8.9 MPa × m^1/2, and thermal conductivity of 86.0–89.7 W/(m × K). The oxidation was performed under static conditions at 1650 °C and upon exposure to a high-enthalpy gas flow. A dense layer consisting of HfO₂/HfSiO₄ grains formed on the surface of the ceramics during both oxidation conditions; the space between the grains was filled with amorphous SiO₂–B₂O₃. The best heat resistance was observed for the ceramics with 16 wt% SiC for static conditions and 8 wt% SiC for gas-dynamic conditions.     

Ablation resistance of HfB2-SiC coating prepared by in-situ reaction method for SiC coated C/C composites

To improve the ablation resistance of SiC coating, HfB₂-SiC coating was prepared on SiC-coated carbon/carbon (C/C) composites by in-situ reaction method. Owing to the penetration of coating powders, there is no clear boundary between SiC coating and HfB₂-SiC coating. After oxyacetylene ablation for 60 s at heat flux of 2400 kW/m², the mass ablation rate and linear ablation rate of the coated C/C composites were only 0.147 mg/s and 0.267 µm/s, reduced by 21.8% and 60.0%, respectively, compared with SiC coated C/C composites. The good ablation resistance was attributed to the formation of multiple Hf-Si-O glassy layer including SiO₂, HfO₂ and HfSiO₄.     

Effect of chromium additive on sintering and oxidation behavior of HfB2-SiC ceramics

The effect of chromium admixture on the processes in the HfB₂-SiC ceramic powder system during its pressureless sintering at 1600?°C was studied. It was shown that an increase in chromium content from 0% to 15.5% in the HfB₂-SiC ceramic powder mixture leads to a continuous increase in its relative density up to 90%. A transient liquid phase Cr-Si-C-B is formed at 1600?°C, and it promotes intense sintering of HfB₂ and SiC powders. The oxidation resistance of HfB₂-SiC-Cr ceramics was studied in static air at 1000–1500?°C. It was shown that the oxidation resistance is greatly improved due to a decrease in the porosity of the sintered ceramic system because of chromium additive. The presence of chromium oxide in the formed surface glassy layer can also lead to the increase in the oxidation resistance. These results suggest that chromium can be considered as a promising sintering additive for HfB₂-SiC and similar systems.     

Mechanical,Thermal, and Oxidation Properties of Refractory Hafnium and zirconium Compounds

The thermal conductivity, thermal expansion, Youngs Modulus, flexural strength, and brittle–plastic deformation transition temperature were determined for HfB₂, HfC_0·98, HfC_0·67, and HfN_0·92 ceramics. The oxidation resistance of ceramics in the ZrB₂–ZrC–SiC system was characterized as a function of composition and processing technique. The thermal conductivity of HfB₂ exceeded that of the other materials by a factor of 5 at room temperature and by a factor of 2·5 at 820°C. The transition temperature of HfC exhibited a strong stoichiometry dependence, decreasing from 2200°C for HfC_0·98 to 1100°C for HfC_0·67 ceramics. The transition temperature of HfB₂ was 1100°C. The ZrB₂/ZrC/SiC ceramics were prepared from mixtures of Zr (or ZrC), SiB₄, and C using displacement reactions. The ceramics with ZrB₂ as a predominant phase had high oxidation resistance up to 1500°C compared to pure ZrB₂ and ZrC ceramics. The ceramics with ZrB₂/SiC molar ratio of 2 (25 vol% SiC), containing little or no ZrC, were the most oxidation resistant.     

Hot Pressed HfB2 and HfB2–20 vol%SiC Ceramics Based on HfB2 Powder Synthesized by Borothermal Reduction of HfO2*

Phase pure hafnium diboride (HfB₂) powder was synthesized by borothermal reduction of hafnium dioxide using amorphous boron at relatively low temperature (1600°C) in vacuum. The synthesized HfB₂ powder had an average particle size of 1.37 μm with an equiaxed shape, and a low oxygen content of 0.79 wt%. Using the as-synthesized HfB₂ powder and a commercial SiC, HfB₂ monolithic, and HfB₂–20 vol%SiC composite were hot pressed at 2000°C to relative densities of 95.7% and 99.2%, respectively. With the addition of SiC, the grain size decreased and the fracture behavior changed from intergranular to a mixed mode, which resulted in a high flexural strength of 993±90 MPa for the composite. Fracture toughness of the composite was 6.29±0.65 MPa m^1/2, which was significantly higher than that of the HfB₂ monolithic and the reported values in literature.     

Oxidation of graphene-modified HfB2-SiC ceramics by supersonic dissociated air flow

The oxidation resistance of ultra-high-temperature ceramic material (HfB₂-30 vol%SiC)-2 vol%rGO (rGO: reduced graphene oxide) under long-term exposure (2000s) to a supersonic air flow has been studied. The ceramics were obtained by reactive hot pressing of HfB₂-(SiO₂-C)-rGO composite powder at a temperature of 1800°C (pressure 30 MPa, holding time 15 min, Ar). The surface temperature of graphene-modified ceramics under the influence of heating by high-enthalpy air flow (heat flow q reached 779 W·cm^–2) did not exceed 1700°C, which is 650–700°C less than for the HfB₂-30 vol%SiC baseline ceramics. This may be related to an increase in the efficiency of heat transfer from the sample to the water-cooled module, due to the higher thermal conductivity of the rGO-containing material. Thereby, a decrease in the material degradation degree has been noted, i.e. decrease in the recession rate and decrease in the total thickness of the oxidised ceramic layer by tenth. The peculiarities of the oxidised surface and near-surface region microstructure upon aerodynamic heating of the graphene-modified ceramic material, have been shown.     

Magnesiothermic synthesis of HfB2–HfC-SiC nanocomposite by spark plasma technique

The HfB₂-HfC-SiC nanocomposite was produced using H₃BO₃, HfO₂, Si, C, and Mg as starting materials by spark plasma for the first time. The reactions during synthesis indicate that the synthesis process progressed in self-propagating mode. The reaction mechanisms were investigated by the displacement-temperature-time (DTT) diagram, which was obtained during spark plasma cycles. The synthesis process of the composite was completed at the temperature of 400 °C in less than 30 min. The tendency to form the composite was investigated by thermodynamic calculations, and the formation of HfB₂, HfC, and SiC phases was observed by X-ray diffraction. Finally, using the Rietveld method, the mean crystallites sizes of about 54, 26, and 43 nm were calculated for HfB₂, SiC, and HfC phases, respectively.     

Oxidation behavior of hot pressed ZrB2–SiC and HfB2–SiC composites

Non-isothermal, isothermal and cyclic oxidation behavior of hot pressed ZrB₂–20 (vol.%) SiC (ZS) and HfB₂–20 SiC (HS) composites have been compared. Studies involving heating in thermogravimetric analyzer have shown sharp mass increases at 740 and 1180 °C for ZS, and mass gain till 1100 °C followed by loss for HS. Isothermal oxidation tests for 1, 24 and 100 h durations at 1200 or 1300 °C have shown formation of partially and completely stable oxide scales after ～24 h exposure for ZS and HS, respectively. X-ray diffraction, scanning electron microscopy and energy or wavelength dispersive spectroscopy has confirmed presence of ZrO₂ or HfO₂ in oxide scales of ZS or HS, respectively, besides B₂O₃–SiO₂. Degradation appears more severe in isothermally oxidized ZS due to phase transformations in ZrO₂; and is worse in HS on cyclic oxidation at 1300 °C with air cooling, because of higher thermal residual stresses in its oxide scale.     

Oxidation behaviors of ZrB2–SiC binary composites above 2000 °C

Rapid oxidation testing for monolithic ZrB₂ and ZrB₂–SiC binary composites with different SiC contents (0–30 vol%) was performed using an electric heating system above 2000 °C. The system used in this study achieved the high heating rate of 250 °C/s. The experimental results showed that the morphologies of the oxidized specimens depended strongly on the SiC content. The formation mechanism of SiC-depleted layers beneath the surface scale above 2000 °C differed completely from that below 2000 °C. Although the holding time was below 10 s, SiC-depleted layers were formed because the oxygen partial pressure of the air atmosphere was not enough to form SiO₂ by the oxidation of SiC. It was determined that ZrB₂–20 vol% SiC showed the best oxidation resistance above 2000 °C at high heating rates.     

Electrical and thermophysical properties of ZrB2 and HfB2 based composites

Electrical resistivities, thermal conductivities and thermal expansion coefficients of hot-pressed ZrB₂–SiC, ZrB₂–SiC–Si₃N₄, ZrB₂–ZrC–SiC–Si₃N₄ and HfB₂–SiC composites have been evaluated. Effects of Si₃N₄ and ZrC additions on electrical and thermophysical properties of ZrB₂–SiC composite have been investigated. Further, properties of ZrB₂–SiC and HfB₂–SiC composites have been compared. Electrical resistivities (at 25 °C), thermal conductivities (between 25 and 1300 °C) and thermal expansion coefficients (over 25–1000 °C) have been determined by four-probe method, laser flash method and thermo-mechanical analyzer, respectively. Experimental results have shown reasonable agreement with theoretical predictions. Electrical resistivities of ZrB₂-based composites are lower than that of HfB₂–SiC composite. Thermal conductivity of ZrB₂ increases with addition of SiC, while it decreases on ZrC addition, which is explained considering relative contributions of electrons and phonons to thermal transport. As expected, thermal expansion coefficient of each composite is reduced by SiC additions in 25–200 °C range, while it exceeds theoretical values at higher temperatures.     

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.