Oxidation behavior of oxidation protective coatings for PIP-C/SiC composites at 1500 °C

Three-dimensional carbon fiber reinforced silicon carbide (C/SiC) composites were fabricated by precursor infiltration and pyrolysis (PIP) with polycarbosilane as the matrix precursor, SiC coating prepared by chemical vapor deposition (CVD) and ZrB₂-SiC/SiC coating prepared by CVD with slurry painting were applied on C/SiC composites, respectively. The oxidation of three samples at 1500 °C was compared and their microstructures and mechanical properties were investigated. The results show that the C/SiC without coating is distorted quickly. The mass loss of SiC coating coated sample is 4.6% after 2 h oxidation and the sample with ZrB₂-SiC/SiC multilayer coating only has 0.4% mass loss even after oxidation. ZrB₂-SiC/SiC multilayer coating can provide longtime protection for C/SiC composites. The mode of the fracture behavior of C/SiC composites was also changed. When with coating, the fracture mode of C/SiC composites became brittle. When after oxidation, the fracture mode of C/SiC composites without and with coating also became brittle.     

Oxidation resistance of a gradient self-healing coating for carbon/carbon composites

A gradient self-healing coating consisting of three layers, SiC-B₄C/SiC/SiO₂, was examined as a multilayer protection for carbon/carbon composites. The inner layer was made of B₄C and β-SiC, the middle layer was a SiC based layer, and the outer layer was SiO₂ as an airproof layer. Both inner and middle layers were produced to be diphase structure by a pack cementation technique, and the outer airproof layer was prepared by hydrolyzing tetraethylorthosilicate. SEM and EDS investigations showed that the coating had a compositional gradient between B₄C and SiC. The coating showed great self-healing properties from 500 °C to 1500 °C. The weight loss rate of the coated composites was less than 1.3% after 50 h at 1500 °C, and coating represented excellent thermal shock resistance at 1500 °C. The oxidation kinetics of coated carbon/carbon composites showed that the Arrhenius curve consisted of three parts with two broken points at about 700 °C and 1100 °C, and the three parts corresponded to three different self-healing mechanisms in different temperature regions.     

Preparation and properties of C/SiC/ZrO2 porous composites by hot isostatic pressing the pyrolyzed preforms

Three phase mixture of C/SiC/ZrO₂ porous composites were prepared from commercially available phenolic resin, Si and ZrO₂ powders. In the first step, mixed powders were pyrolyzed at 850 °C in vacuum to obtain a carbonized microporous material and then hot isostatically pressed at 1200, 1300 and 1350 °C for 10 min in an argon pressure of 50 MPa to prepare C/SiC/ZrO₂ porous composites, in second step. The hot isostatic pressing led to the increase in density from 3.28 to 3.48 g/cm³ and reduction in porosity (from 32 to 20%) of the composites. X-ray diffraction analyses revealed the existence of β-SiC and carbon might be amorphous in the composites. According to the results of scanning electron microscopy, the crystal growth of β-SiC with facets was observed at 1350 °C. In addition, the energy dispersive spectroscopy showed that carbon/silicon atomic ratio was 1:1 in the crystals. X-ray photoelectron spectroscopy of the composites suggested that evolved gaseous molecules, due to the decomposition of phenolic resin, reacted with molecules containing Si to form β-SiC. The formation and growth of β-SiC in addition to the densification of matrix by hot isostatic pressing led to the increase in hardness (max.: 13.99 GPa) at higher temperatures.     

A Si–SiC oxidation protective coating for carbon/carbon composites prepared by a two-step pack cementation

To prevent carbon/carbon (C/C) composites from oxidation, a Si–SiC coating has been prepared by a two-step pack cementation technique. X-ray diffraction (XRD) and scanning electron microscopy (SEM) analysis show that the coating obtained by the first step pack cementation is a porous β-SiC structure, and a dense structure consisting α-SiC, β-SiC and Si is obtained after heat-treatment by the second step pack cementation. By energy dispersive spectroscopy (EDS) analysis, a gradient C–SiC transition layer can be formed at the C/C-coating interface. The as-received coating has excellent oxidation protection ability and can protect C/C composites from oxidation for 166 h at 1773 K in air. The weigh loss of the coated C/C is due to the formation of bubble holes on the coating surface and through-coating cracks in the coating.     

Compressive strength degradation in ZrB2-based ultra-high temperature ceramic composites

The high temperature compressive strength behavior of zirconium diboride (ZrB₂)-silicon carbide (SiC) particulate composites containing either carbon powder or SCS-9a silicon carbide fibers was evaluated in air. Constant strain rate compression tests have been performed on these materials at room temperature, 1400, and 1550 °C. The degradation of the mechanical properties as a result of atmospheric air exposure at high temperatures has also been studied as a function of exposure time. The ZrB₂-SiC material shows excellent strength of 3.1 ± 0.2 GPa at room temperature and 0.9 ± 0.1 GPa at 1400 °C when external defects are eliminated by surface finishing. The presence of C is detrimental to the compressive strength of the ZrB₂-SiC-C material, as carbon burns out at high temperatures in air. As-fabricated SCS-9a SiC fiber reinforced ZrB₂-SiC composites contain significant matrix microcracking due to residual thermal stresses, and show poor mechanical properties and oxidation resistance. After exposure to air at high temperatures an external SiO₂ layer is formed, beneath which ZrB₂ oxidizes to ZrO₂. A significant reduction in room temperature strength occurs after 16-24 h of exposure to air at 1400 °C for the ZrB₂-SiC material, while for the ZrB₂-SiC-C composition this reduction is observed after less than 16 h. The thickness of the oxide layer was measured as a function of exposure time and temperatures and the details of oxidation process has been discussed.     

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 heat treatment on the mechanical properties of PIP–SiC/SiC composites fabricated with a consolidation process

Continuous SiC fiber reinforced SiC matrix composites (SiC/SiC) have been considered as candidates for heat resistant and nuclear materials. Three-dimensional (3D) SiC/SiC composites were fabricated by the polymer impregnation and pyrolysis (PIP) method with a consolidation process, mechanical properties of the composites were found to be significantly improved by the consolidation process. The SiC/SiC composites were then heat treated at 1400 °C, 1600 °C and 1800 °C in an inert atmosphere for 1 h, respectively. The effect of heat treatment temperature on the mechanical properties of the composites was investigated, the mechanical properties of the SiC/SiC composites were improved after heat treatment at 1400 °C, and conversely decreased with increased heat treatment temperature. Furthermore, the effect of heat treatment duration on the properties of the SiC/SiC composites was studied, the composites exhibited excellent thermal stability after heat treatment at 1400 °C within 3 h.     

Effect of SiC coating and heat treatment on the thermal radiation properties of C/SiC composites

The effects of SiC coating and heat treatment on the emissivity were investigated for 2D C/SiC composites prepared by CVI in the 6–16 μm range. SiC coating had an obvious effect on the spectral emissivity of the composites but caused just 5% difference in the total emissivity. A radiation transport model was applied to explain those changes caused by SiC coating. Heat treatment affected the thermal radiation properties of the composites through the microstructure evolution. Base on the complementary analytical techniques, the changes in the emissivity were attributed to a good graphitization degree of carbon phases, large β-SiC grain sizes and high α-SiC content resulting in high emissivity.     

Design of a C/SiC functionally graded coating for the oxidation protection of C/C composites

To reduce the residual thermal stress between the carbon fiber-reinforced carbon (C/C) composites and the SiC coating layer, functionally graded materials (FGM) consisting of a C/SiC compositionally graded layer (C/SiC interlayer) were adopted. After designing the compositional distribution of the C/SiC interlayer which can relieve the thermal stress effectively, the deposition conditions of the entire compositional range of the C/SiC composites were determined using a thermodynamic calculation. According to the design and calculation the C/SiC interlayer and the SiC outer layer were deposited on the C/C composites by a low pressure chemical vapor deposition (LPCVD) method at deposition temperatures of 1100 and 1300 °C. The stress calculation and the experimental results suggested that the SiC-rich compositional profile in the FGM layer is the most effective for relieving the thermal stress and increasing the oxidation resistance.     

Improved antioxidative and mechanical properties of SiC coated C/C composites via a SiO2-SiC reticulated layer

To improve the oxidation resistances of SiC coated C/C composites by a pack cementation (PC) method at high temperature and alleviate the siliconization erosion of molten silicon on C/C substrate during the preparation of SiC coating, a SiO₂-SiC reticulated layer with SiC nanowires was pre-prepared on C/C composites through combined slurry painting and thermal treatment before the fabrication of SiC coating. The presence of porous SiO₂-SiC layer with SiC nanowires was beneficial to fabricate a compact and homogeneous SiC coating resulting from synergistic effect of further reaction between SiO₂ and pack powders and the reinforcement of SiC nanowires. Therefore, the results of thermal shock and isothermal oxidation tests showed that the mass loss of modified SiC coating was only 0.02 % after suffering 50-time thermal cycles between room temperature and 1773 K and decreased from 5.95 % to 1.08 % after static oxidation for 49.5 h in air at 1773 K. Moreover, due to the blocking effect of SiO₂-SiC reticulated layer on siliconization erosion during PC, the flexural strength of SiC coated C/C composites with SiO₂-SiC reticulated layer increased by 64.8 % compared with the untreated specimen.     

Formation of nano SiC whiskers in bauxite-carbon composite materials and their consequences on strength and density

SiC whisker is excellent in characteristics such as specific strength and chemical stability, and is useful as a composite reinforcing material. In this paper, the effect of the formation of in situ nano SiC whiskers on strength and density of bauxite-carbon composites was studied. Samples were prepared composed of 65 wt.% bauxite, 15 wt.% SiC-containing material, 10 wt.% coke, 10 wt.% resole and different values of silicon additives. The pressed samples were cured at 200 °C (2 h) and fired at 1100 °C and 1400 °C (2 h). XRD, SEM, TEM, EDX, FTIR and STA were used to characterize the samples. These characterizations indicated that SiC nano whiskers, 50-90 nm, are single crystalline β-SiC with mechanism of the formation VLS. So, firing temperature is an important factor. As, SiC nano whisker was formed at 1400 °C and improved CCS values up to four times in sample containing 6 wt.% ferrosilicon.     

Oxidation behavior of ZrB2-MoSi2-SiC composites in air at 1500 °C

We investigated the oxidation behavior and the effect of the amount of SiC added on oxidation resistance in both hot-pressed ZrB₂-MoSi₂-SiC composites, 55ZrB₂-40MoSi₂-5SiC and 40ZrB₂-40MoSi₂-20SiC (vol.%), exposed to dry air at 1500 °C for up to 10 h. Quantitative electron microprobe analysis characterizations of the chemical compounds of post-oxidized composites were carried out. Parabolic oxidation behavior was observed for both composites. The addition of SiC improved the oxidation resistance of ZrB₂-MoSi₂-SiC composites, and the improvement enhanced with amount of SiC added. The microstructure of the post-oxidized composites consisted of two characteristic regions: oxidized reactive region and unreactive bulk material region. The oxidized reactive region divided into an outermost dense silica-rich scale layer and oxidized reactive mixture layer. The improvement of oxidation resistance with SiC addition is associated with the presence of a thicker dense outermost scale layer which inhibited inward diffusion of oxygen through it.     

Synthesis of resorcinol-formaldehyde/silica composite aerogels and their low-temperature conversion to mesoporous silicon carbide

Resorcinol-formaldehyde/silica composite (RF/SiO₂) gels were acid-catalyzed formed in one pot at 27 °C within 60 min, and then dried to aerogels with supercritical fluid CO₂. After carbonization in nitrogen atmosphere and a magnesiothermic reaction at 700 °C, RF/SiO₂ aerogels were successfully converted to monolithic mesoporous silicon carbide (SiC aerogels). The starting RF/SiO₂ aerogels had an interpenetrating organic/inorganic network and the resulting SiC products preserved monolithic mesoporous morphology similar to the original templates. The as-synthesized SiC aerogels consisted of nanocrystalline β-SiC, possessed a BET surface area of 232 m²/g and showed sufficient mesoporosity. They had a direct band gap of about 3.2 eV (less than that of bulk β-SiC) and showed photoluminescence at room temperature. The mechanisms about the formation of RF/SiO₂ gels and the conversion to SiC aerogels were discussed. Potentially, the reported method can be used to convert many metal or semimetal oxide/carbon composite aerogels to carbide aerogels at relatively low temperature for many catalytic, electronic, photonic and thermal applications.     

Preparation of SiCf/Si–O–C composites by impregnation pyrolysis of polysiloxane and its electromagnetic wave absorption properties

High-temperature structural electromagnetic wave (EMW) absorption materials are increasing in demand because they can simultaneously possess the functions of mechanical load-bearing, heatproof, and EMW absorption. Herein, SiC_f/Si–O–C composites were prepared by precursor impregnation pyrolysis using continuous SiC fibers needled felt as reinforcement and polysiloxane as a precursor, respectively. The phase composition, microstructure, complex permittivity, and EMW absorption properties of SiC_f/Si–O–C composites after annealing at various temperatures were investigated. The annealing at 1400–1500°C affects positively the EMW absorption performance of the composites, because the β-SiC microcrystals and SiC nanowires were generated by the activation of carbothermal reduction reaction in the composites, and the aspect ratio of SiC nanowires increased with the rise of temperature. The composites exhibit optimal EMW absorption performance, with the effective absorption bandwidth covering the entire X-band and the minimum reflection loss (RL_min) of −32.8 dB at 4.0 mm when the annealing temperature is raised to 1500°C. This is because that the impedance matching is improved as the rising of ε′ and decreasing of ε″ due to the conversion of free carbon in the composite into SiC nanowires.     

Sintering of Al2O3-SiC composite from sol-gel method with MgO, TiO2 and Y2O3 addition

Al₂O₃-SiC composite ceramics were prepared by pressureless sintering with and without the addition of MgO, TiO₂ and Y₂O₃ as sintering aids. The effects of these compositional variables on final density and hardness were investigated. In the present article at first α-Al₂O₃ and β-SiC nano powders have been synthesized by sol-gel method separately by using AlCl₃, TEOS and saccharose as precursors. Pressureless sintering was carried out in nitrogen atmosphere at 1600 °C and 1630 °C. The addition of 5 vol.% SiC to Al₂O₃ hindered densification. In contrast, the addition of nano MgO and nano TiO₂ to Al₂O₃-5 vol.% SiC composites improved densification but Y₂O₃ did not have positive effect on sintering. Maximum density (97%) was achieved at 1630 °C. Vickers hardness was 17.7 GPa after sintering at 1630 °C. SEM revealed that the SiC particles were well distributed throughout the composite microstructures. The precursors and the resultant powders were characterized by XRD, STA and SEM.     

Thermal shock behavior of 3-dimensional C/SiC composite

The thermal shock behavior of a three-dimensional carbon fiber reinforced SiC matrix fabricated by chemical vapor infiltration (CVI) technique was studied using the air quenched method. Damage to composites was assessed by a destructive technique of measuring mechanical properties using three-point flexure and SEM characterization. C/SiC composites displayed good resistance to thermal shock, and retained 83% of the original strength after quenching from 1300 to 300°C 100 times. The critical ΔT of C/SiC in combustion environment was 700°C. The critical number of thermal shocks for the C/SiC composite was about 50 times. When the number of thermal shocks was less than 50 times, the residual flexural strength of C/SiC composites decreased with the increase of thermal shock times. When the number of thermal shocks of C/SiC was greater than 50, the strength of C/SiC did not further decrease because the crack density was saturated.     

Efficient fabrication of carbon/silicon carbide composite for electromagnetic interference shielding applications

Ceramic matrix composites are typically prepared by a costly, time-consuming process under severe conditions. Herein, a cost-effective C/SiC composite was fabricated from a silicon gel-derived source by Joule heating. The β-SiC phase was generated via carbothermal reduction, and the carbon fabric showed a well-developed graphitic structure, promoting its thermal and anti-oxidation stabilities. Owing to the excellent dielectric loss in carbon fabric, SiC and SiO₂ as well as the micropore structure of the ceramic matrix, the absolute electromagnetic interference shielding (EMI) effectiveness (SSE/t) reached 948.18 dB?cm²?g^-1 in the X-band, exhibiting an excellent EMI SE. After oxidation at 1000 °C for 10 h in the air, the SSE/t of the composite was only reduced to 846.02 dB?cm²?g^-1. The C/SiC composite promises the efficient fabrication of high-temperature resistant materials for electromagnetic shielding applications.     

Preparation and properties of 2D C/SiC-ZrB2-TaC composites

Two-dimensional (2D) C/SiC-ZrB₂-TaC composites were fabricated by chemical vapor infiltration (CVI) combined with slurry paste (SP) method. 2D laminate was prepared by stacking carbon cloth that was pasted with a mixture of polycarbosilane-ZrB₂-TaC slurry. A small amount of carbon fiber tows were introduced into the preform in the vertical direction. After heat-treated at 1800 °C, the 2D laminate was densified with SiC by CVI to obtain 2D C/SiC-ZrB₂-TaC composites. Properties including flexural strength, interlaminar shear strength, and thermal expansion of the composites were investigated. The ablation test was carried out under an oxyacetylene torch flame. The morphologies of the ablated specimens were analyzed. The results indicate that the adding vertical fiber tows and heat-treatment at 1800 °C can greatly improve the mechanical properties of the composites. The co-addition of TaC and ZrB₂ powders into C/SiC composite effectively enhance its ablation resistance.     

Additive manufacturing of Csf/SiC composites with high fiber content by direct ink writing and liquid silicon infiltration

Direct ink writing (DIW) provides a new route to produce SiC-based composites with complex structure. In this study, we additive manufactured short carbon fiber reinforced SiC ceramic matrix composites (Csf/SiC composites) with different short carbon fiber content through direct ink writing combined with liquid silicon infiltration (LSI). The effects of short carbon fiber content on the microstructure and mechanical properties of the DIW green parts and the final Csf/SiC composites were investigated. The results showed that the Csf content played an important role in maintaining the structure of the green parts. As the Csf content increases, the dimension deviation ratio of the sample decreased at all stages. With the Csf content of 40 vol%, the final Csf/SiC composite had low free Si content and high β-SiC content. The maximum density, tensile strength and bending strength of the Csf/SiC composites were 2.88 ± 0.06 g/cm³, 53.68 MPa and 253.63 MPa respectively. It is believed that this study can give some understanding for the additive manufacturing of fiber reinforced ceramic matrix composites.     

Improved thermal shock resistance of SiCnw/PyC core-shell structure-toughened CVD-SiC coating

In-situ SiC nanowire (SiCnw)/pyrolytic carbon (PyC) core-shell structures were introduced to mainly improve the thermal shock performance of chemical vapor deposition (CVD)-SiC coating on carbon/carbon (C/C) composites. The microstructure, phase composition, and mechanical properties of the CVD-SiC coating toughened by SiCnw/PyC core-shell structures were studied as well. The results show that the introduction of SiCnw/PyC core-shell structures can effectively alleviate the mismatch of coefficient of thermal expansion (CTE) between SiC coating and C/C substrate, thus enhancing the thermal shock resistance of the coating. Furthermore, the increased numbers of interfaces in the SiC coating owing to the addition of core-shell structures are beneficial to the mechanical properties of the coating after thermal shock test.