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.     

High‐Temperature Oxidation of ZrB2–SiC–AlN Composites at 1600°C

The effect of AlN substitution on oxidation of ZrB₂–SiC was evaluated at 1600°C up to 5 h. Replacement of ZrB₂ by AlN, with 30 vol% SiC resulted in improved oxidation resistance with a thinner scale and reduced oxygen affected area. On the other hand, substitution of AlN for SiC resulted in a deterioration of the oxidation resistance with an abnormal scale and significant recession. The effect of SiC content was also studied, and was found to be consistent with the literature for the composites without AlN additions. A similar effect was observed when AlN was added, with the higher SiC content materials showing improved oxidation resistance. X‐ray photoelectron spectroscopy showed the presence of Al₂O₃ and SiO₂ on the surface, which could possibly lead to a modification in the viscosity of the glassy oxide scale. Possibly, the oxidation behavior of ZrB₂–SiC composites can be improved with controlled AlN additions by adjusting the Al:Si ratios.     

Oxidation Behavior of Hot Pressed ZrB2‐ZrC‐SiC Ceramic Composites

Dense ZrB₂‐SiC ceramics containing 40 vol% ZrC particles are fabricated via hot pressing method. Then the sintered ceramics are oxidized in air up to 1500°C, and the oxidation kinetics of the ceramic composites is deduced in combination with the reacted fraction curves. As indicated by the experimental results, the oxidation kinetics changes from reaction‐controlled process to diffusion‐controlled one with increasing of oxidation temperature. In addition, the oxidation kinetics parameters are obtained, which indicates that the oxidation resistance decays at elevated temperatures. Furthermore, the evolution of surface morphology and oxide scale during oxidation process is clarified.     

TEM Study of the High‐Temperature Oxidation Behavior of Hot‐Pressed ZrB2–SiC Composites

The oxidation behaviors of ZrB₂‐ 30 vol% SiC composites were investigated at 1500°C in air and under reducing conditions with oxygen partial pressures of 10⁴ and 10 ^{? 8} Pa, respectively. The oxidation of ZrB₂ and SiC were analyzed using transmission electron microscopy (TEM). Due to kinetic difference of oxidation behavior, the three layers (surface silica‐rich layer, oxide layer, and unreacted layer) were observed over a wide area of specimen in air, while the two layers (oxide layer, and unreacted layer) were observed over a narrow area in specimen under reducing condition. In oxide layer, the ZrB₂ was oxidized to ZrO₂ accompanied by division into small grains and the shape was also changed from faceted to round. This layer also consisted of amorphous SiO₂ with residual SiC and found dispersed in TEM. Based on TEM analysis of ZrB₂ – SiC composites tested under air and low oxygen partial pressure, the ZrB₂ begins to oxidize preferentially and the SiC remained without any changes at the interface between oxidized layer and unreacted layer.     

Carbon Interlayer Between CVD SiC and SiO2 in High‐Temperature Passive Oxidation

The oxidation behavior of high‐purity silicon carbide (SiC) prepared by chemical vapor deposition was investigated by thermogravimetry, transmission electron microscopy, and Raman spectroscopy in the temperature range 1534–1902 K in pure O₂. The carbon layer formed at the SiC/SiO₂ interface upon oxidation above 1784 K. Raman peaks corresponding to D‐ and G‐bands could be identified from the carbon layer. Bubbles were observed in the SiO₂ scale after the oxidation at 1873 K. This could be attributed to the accumulation of CO gas at the SiC/SiO₂ interface, resulting in the formation of the carbon layer and bubbles. These suggest that the oxidation rate of SiC is limited by the outward diffusion of CO in the SiO₂ scale in this temperature range.     

Ultra-High-Temperature Ceramic Coatings for Oxidation Protection of Carbon–Carbon Composites

Carbon–carbon (C–C) composites are attractive materials for hypersonic flight vehicles but they oxidize in air at temperatures >500°C and need thermal protection systems to survive aerothermal heating. We investigated using multilayers of high-temperature ceramics such as ZrB₂ and SiC to protect C–C against oxidation. Our approach combines pretreatment and processing steps to create continuous and adherent high-temperature ceramic coatings from infiltrated preceramic polymers. We tested our protective coatings at temperatures above 2600°C at the National Solar Thermal Testing Facility using controlled cold-wall heat flux profiles reaching a maximum of 680 W/cm².     

Fine‐Scaled Piezoelectric Ceramic/Polymer 2‐2 Composites for High‐Frequency Transducer

A novel technique was utilized to fabricate fine‐scaled piezoelectric ceramic/polymer 2‐2 composites for high‐frequency ultrasonic transducers. Lead zirconate titanate (PZT) was used as raw material. Tape‐casted acetylene black tapes were used to define kerfs after sintering. A one‐directional supporter was utilized to avoid distortion of PZT elements. PZT elements with 20 ± 2 μm width exhibited good consistency in longitudinal direction. A resonant method was utilized to evaluate the piezoelectric and dielectric properties of the composites. A 72‐μm‐thick composite with an aspect ratio of ~3.6 exhibited a k_t of 0.61 with satisfied piezoelectric and dielectric properties. A prototype high‐frequency ultrasonic transducer was fabricated and evaluated by an underwater pulse‐echo test. The center frequency was found to be 23.75 MHz, with ?6 dB bandwidth of 5.5 MHz.     

High‐Temperature Isothermal Oxidation of Ultra‐High Temperature Ceramics Using Thermal Gravimetric Analysis

Oxidation of ZrB₂ + SiC composites is investigated using isothermal measurements to study the effects of temperature, time, and gas flow on oxidation behavior and microstructural evolution. A test method called dynamic nonequilibrium thermal gravimetric analysis (DNE‐TGA), which eliminates oxidation during the heating ramp, has been developed to monitor mass change from the onset of an isothermal hold period (15 min) as a function temperature (1000°C–1600°C) and gas flow (50 and 200 mL/min). In comparing isothermal to nonisothermal TGA measurements, the scale thicknesses from isothermal tests are up to 4 times greater, indicating that oxidation kinetics are faster for isothermal testing, where the oxide scale thickness is 110 μm after 15 min at 1600°C in air. Isothermal oxidation followed parabolic kinetics with a mass gain that is temperature dependent from 1000°C–1600°C. The mass gain increased from ~5 to 45 g/m² and parabolic rate constants increased from 0.037 to 2.2 g²/m⁴·s over this temperature range. The effect of flow velocity on oxidation is not significant under the given laminar flow environment where the gas boundary layer is calculated to be 4 mm. These values are consistent with diffusion of oxygen through the glass‐ceramic surface layer as rate limiting.     

Oxidation Resistance of AlPO4 Bonded Ceramic Coating Formed on Titanium Alloy for High‐Temperature Applications

AlPO₄ based coatings were prepared on Ti‐6Al‐2Zr‐1Mo‐1V titanium alloy using aluminum phosphate as a binder and Al₂O₃/Cr₂O₃ based mixing particles as the fillers. The microstructure, phase and chemical composition of the coatings were analyzed by SEM, XRD and EDS techniques. The high temperature infrared emissivity values of coated and uncoated titanium samples were tested. The results show that the coating had a higher infrared emissivity value (>0.8) than titanium substrate (0.15–0.3) in the wide wavelength range of 5–20 mm, which is attributed to the uniform dispersion of high emissivity Al₂O₃ and Cr₂O₃ particles in the AlPO₄ binder matrix. The coated titanium samples exhibited excellent oxidation resistance performance with significantly decreased oxidation rates at 600 and 800°C. The mass gain of the coated sample kept at a low and stable constant of 0.15 mg/cm², significantly lower than that of titanium substrate (0.54 mg/cm²) when oxidized at 600°C up to 100 h.     

Effect of Temperature on Oxidation Behavior of 3‐Dimensional C/SiC Composites Coated by Different Structural SiC and a‐BCx Coatings in Static Wet Oxygen Atmosphere

The effect of temperature on oxidation behavior of 3‐dimensional C/SiC composites coated with SiC and a‐BC_x coatings was investigated. Below 1000°C, C/SiC composites with SiC coating (sample SSS) showed low residual strength, while the composites with a‐BC_x coating (sample BBB) and the composites with a‐BC_x/a‐BC_x/SiC coatings (sample BBS) showed high residual strength. Above 1000°C, samples SSS and BBS showed high residual strength, while sample BBB showed the opposite results. Sample BBS presented better oxidation resistance during 700–1200°C. The oxidation temperature made an effect on self‐sealing mode of sample BBS.     

A Si–SiC Oxidation‐resistant Coating for Carbon/Carbon Composites by Hot‐pressing Reaction Technique

A Si–SiC coating was prepared by hot‐pressing reactive sintering (HPRS) technique for protecting carbon/carbon (C/C) composites against oxidation. The Si–SiC coating has a dense and crack‐free structure with a thickness of 70–90 μm. The Si–SiC coating by HPRS has a higher SiC content and lower Si content than the coating by pressure‐less reactive sintering (PRS). It also exhibits better oxidation‐protective ability than that prepared by PRS. With hot‐pressing, the flexural strength of the Si–SiC coated C/C composites decreases from 121 MPa to 99 MPa, and the interface bonding strength increases from 6 MPa to 10 MPa.     

Ultra‐Low Temperature Sintering and Dielectric Properties of SiO2‐Filled Glass Composites

Ultra low temperature co‐fired ceramics system based on zinc borate 3ZnO–2B₂O₃ (3Z2B) glass matrix and SiO₂ filler was investigated with regard to the phase composition, the microstructure and the dielectric properties as functions of the filler content and sintering temperature. The softening temperature of 554°C and the crystallization temperature of around 650°C for the glass were confirmed by Differential Thermal Analysis result. The X‐ray diffraction results show that all SiO₂‐filled samples were made up of SiO₂, α‐Zn(BO₂)₂, Zn₃B₂O₆ phases. And there was no chemical reaction between SiO₂ and the glass during densification. And then the dielectric constant decreased with the increasing content of SiO₂. At the level of 15 wt% SiO₂ addition, the composites can be densified at a sintering temperature of 650°C for 30 min, and showed the optimal dielectric properties at 1 MHz with the dielectric constant of 6.1 and the dielectric loss of 1.3 × 10^?3, which demonstrates a good potential for use in LTCC technology.     

Heat and Mass Transfer in Ceramic Lattices During High‐Temperature Oxidation

This work reports on the heat and mass transfer evolution of ceramic lattices during their oxidation at 1400°C and 1600°C in air. Si–SiC and Si–SiC–ZrB₂ systems were employed as skeleton material because they, previously produced as monolithic bars, showed promising oxidation behavior at high temperatures. Regular arrays of tetrakaidecahedra were first designed by CAD, then 3D printed and finally converted into ceramic by replica technique followed by reactive silicon infiltration. The surface area of each sample was calculated and specific weight variations were evaluated as a function of time. During oxidation, effective thermal conductivity and pressure drop of each sample were measured. Finally, results were correlated with the phenomena occurring during high‐temperature oxidation.     

High‐temperature tensile strength and fracture behavior of ZrB2‐SiC‐graphite composite

The tensile behavior of ZrB₂‐SiC‐graphite composite was investigated from room temperature to 1800°C. Results showed that tensile strength was 134.18 MPa at room temperature, decreasing to 50.34 MPa at 1800°C. A brittle‐ductile transition temperature (1300°C) of ZrB₂‐SiC‐graphite composite was deduced from experimental results. Furthermore, the effect of temperature on the fracture behavior of ZrB₂‐SiC‐graphite composite was further discussed by microstructure observations, which showed that tensile strength was controlled by the relaxation of thermal residual stress below 1300°C, and was affected by the plastic flow during 1300°C and 1400°C. At higher temperature, the tensile strength was dominated by the changes of microstructures.     

A Si–Mo–W Coating to Protect SiC-Coated Carbon/Carbon Composites Against Oxidation

In order to protect carbon/carbon (C/C) composites against oxidation, a Si–Mo–W coating was prepared on the surface of SiC-coated C/C composites by a simple reaction method. The microstructures of the as-received coating were characterized by scanning electron microscopy, X-ray diffraction, and energy dispersive spectroscopy analyses. The results show that the SiC/Si–Mo–W coating can protect C/C composites from oxidation in air at 1673 K for 220 h with a mass loss of 0.003%, and at 1773 K for 252 h with a mass gain of 1.56%. The excellent oxidation-resistant property of the SiC/Si–Mo–W coating at 1673–1773 K is attributed to the formation of SiO₂ film on the coating surface. The mass loss of the coated C/C composites during the oxidation test at 1873 K in air primarily resulted from the reaction of C/C substrate and oxygen diffusing through the penetration cracks in the coating.     

ZrB2-SiC/C层状复合陶瓷的高温氧化行为

利用流延法成膜和热压烧结工艺制备出了ZrB2-SiC层和石墨层交替排列、层厚均匀、界面清晰的ZrB2-SiC/C层状复合陶瓷.采用循环氧化法对ZrB2-SiC和ZrB2-SiC/C层状复合陶瓷在1000℃及1300℃空气中的氧化动力学曲线进行了研究.结果表明:在1000℃氧化增重时,ZrB2-SiC/C层状复合陶瓷在氧化反应初期表现为氧化增重,随着时间的增加,表现为氧化减重.在1300℃时,ZrB2-SiC/C层状复合陶瓷由于基体层ZrB2-SiC和弱夹层石墨相的氧化规律的相互叠加,使得其氧化增重曲线表现为抛物线规律.由XRD分析及扫描电镜观察发现,1300℃氧化15 h后,试样中不存在弱夹层石墨相,由于石墨相的挥发,材料残留孔隙.     

Oxidation Behavior of ZrB2–SiC Composites at Low Pressures

ZrB₂‐60 mol%SiC composite with a eutectic microstructure was oxidized at 1573 to 1873 K with reduced total pressures (P_tot) and low oxygen partial pressures (). The mass change was continuously measured by a thermobalance, and then fit with a multiple paralinear model. Oxidation scale of SiO₂/ZrO₂+SiO₂/ZrO₂/ZrB₂ was formed at  > 0.13 kPa, whereas only porous ZrO₂ remained at  < 0.13 kPa, P_tot < 1.33 kPa and higher than 1773 K. With increasing , the parabolic oxidation constant decreased, whereas the linear oxidation constant increased.     

Ti3SiC2/SiC复合材料的抗高温氧化性研究

采用反应热压烧结法制备Ti3 SiC2/SiC复合材料,针对不同SiC含量的Ti3 SiC2/SiC复合材料在1100 ～ 1500℃下恒温氧化20h的氧化行为进行了研究.结果表明:(1)适量SiC的引入能有效的提高Ti3 SiC2/SiC复合材料的抗高温氧化性能;(2)复合材料的氧化膜分内外两层,外层成分为TiO2,逐渐向内层过渡为TiO2和SiO2的混合物.     

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.     

Microstructural Effects on the Mechanical Properties of SiC‐15 vol% TiB2 Particulate‐Reinforced Ceramic Composites

The microstructures and mechanical properties were studied for two different SiC ceramics containing 15 vol% of TiB₂ particulates. The first was prepared from commercially available spray‐dried granules and the second by blending individual SiC and TiB₂ powders. The average TiB₂ particle sizes were 2.7 μm for the ceramic prepared from blended powders, which had a uniform distribution of TiB₂, and 2.3 μm for the ceramic prepared from spray‐dried granules, which had a nonuniform distribution of TiB₂ agglomerates. Although the two ceramics had hardness values of 26 GPa, the other properties were different. For example, the fracture toughness was 4.3 MPa·m^1/2 for the ceramic prepared from blended powders compared to 3.1 MPa·m^1/2 for the ceramic prepared from spray‐dried granules. In contrast, the Weibull modulus for the ceramic prepared from spray‐dried granules was 21 compared to 12 for the other. Calculations predicted spontaneous microcracking in the ceramic prepared from spray‐dried granules, which was confirmed by analysis of the microstructure. The presence of microcracks accounted for the higher Weibull modulus, but lower flexural strength, Young's modulus and fracture toughness for the ceramic prepared from spray‐dried granules.