Processing and characterization of particles reinforced SiOC composites via pyrolysis of polysiloxane with SiC or/and Al fillers

Polysiloxane loaded with SiC as inert filler, and Al as active filler, was pyrolyzed in nitrogen to fabricate SiOC composites, and the processing and properties of the filled SiOC composites were investigated. Adding SiC fillers could reduce the linear shrinkage of filler-free cured polysiloxane in order to obtain monolithic SiC/SiOC composites. The flexural strength of SiC/SiOC composites reached 201.3 MPa at a SiC filler content of 27.6 vol.%. However, SiC/SiOC composites exhibited poor oxidation resistance, thermal shock resistance and high temperature resistance. Al fillers could react with hydrocarbon generated during polysiloxane pyrolysis at 600 °C and N₂ at 800 °C to form Al₄C₃ and AlN, respectively. The volume expansions resulting from these two reactions were in favor of the reduction in linear shrinkage and the improvement in flexural strength of SiC/SiOC composites. The flexural strength of Al-containing SiC/SiOC composites was 1.36 times that of SiC/SiOC composites without Al at an Al filler content of 20 vol.%. The addition of Al fillers remarkably improved the high temperature resistance and oxidation resistance of SiC/SiOC composites, but not thermal shock resistance.     

Mechanical properties of SiCp/Al2O3 ceramic matrix composites prepared by directed oxidation of an aluminum alloy

Silicon carbide particulate reinforced alumina matrix composites were fabricated using DIrected Metal OXidation (DIMOX) process. Continuous oxidation of an Al-Si-Mg-Zn alloy with appropriate dopants along with a preform of silicon carbide has led to the formation of alumina matrix surrounding silicon carbide particulates. SiC_p/Al₂O₃ ceramic matrix composites fabricated by the DIMOX process, possess enhanced mechanical properties such as flexural strength, fracture toughness and wear resistance, all at an affordable cost of fabrication. SiC_p/Al₂O₃ matrix composites were investigated for mechanical properties such as flexural strength, fracture toughness and hardness; the composite specimens were evaluated using standard procedures recommended by the ASTM. The SiC_p/Al₂O₃ ceramic matrix composites with SiC volume fractions from 0.35 to 0.43 were found to possess average bend strength in range 158-230 MPa and fracture toughness was found to be in range of 5.61-4.01 MPa√m. The specimen fractured under three-point loading as observed under scanning electron microscope was found to fail in brittle manner being the dominant mode. Further the composites were found to possess lower levels of porosity, among those prepared by DIMOX process.     

Microstructure and mechanical properties of C/C composites modified by single-source precursor derived ceramics

To improve the mechanical properties of C/C composites, the SiC(N)/TiC ceramic derived from single-source precursors (SSPs) were introduced into the C/C by precursor infiltration and pyrolysis (PIP) at 1100 °C. The shear strength of all modified composites were improved by nearly 2 times compared with the pristine C/C composites (37.4 MPa) due to the increased interfaces by multiphases incorporation. After further annealing at 1500 °C, the SiC(N)/TiC ceramic in C/C composite transferred into the nanocomposites, SiC(N)/TiC-NCs, in which nano-scale TiC particles distributed into the SiC(N) matrix. The modified samples still exhibited about 39% improvement on shear strength. Large numbers of uniform micro-cracks occurred in both above SSPs derived ceramic cases, reducing stress concentration during the shear testing. Moreover, some ring-shaped cracks were observed in the fracture region which can consume large amounts of energy in crack propagation process and then benefit to improve the shear strength.     

Comparative ablation behaviors of C/SiC-HfC composites prepared by reactive melt infiltration and precursor infiltration and pyrolysis routes

Carbon fiber reinforced silicon carbide-hafnium carbide (C/SiC-HfC) composites were prepared by reactive melt infiltration (RMI) and precursor infiltration and pyrolysis (PIP) routes. The ablation behaviors of the two composites were investigated and compared under an oxyacetylene torch flame. The C/SiC-HfC composites prepared by PIP showed a better ablation resistance than those synthetized by RMI. Microstructural observations revealed an island distribution of HfC for the sample prepared by RMI, which resulted in SiC being directly oxidized during the ablation process. In contrast, the PIP-prepared sample showed a uniform distribution of HfC, which resulted in SiC being oxidized via the Knudsen diffusion mechanism under ablation. The Knudsen diffusion of oxidants retarded the oxidation process, thereby increasing the ablation resistance of the C/SiC-HfC composites prepared by PIP.     

Simultaneous enhancement of mechanical and ablation properties of C/C composites modified by (Hf-Ta-Zr)C solid solution ceramics

In order to improve the mechanical and ablative resistance of C/C composites, (Hf-Ta-Zr)C single-phase solid solution ceramics were introduced into C/C composites by polymer infiltration and pyrolysis (PIP) to fabricate (Hf-Ta-Zr)C modified C/C composites (HTZ). Their mechanical property and ablation resistance were studied. The results showed that HTZ achieved simultaneous enhancement of mechanical property and ablative resistance. Their flexural strength and modulus could reach 219.34 MPa and 24.82 GPa, respectively. In addition, the mass and linear ablation rate of HTZ were 0.379 mg/s and 0.667 µm/s, respectively after the 90 s oxyacetylene ablation. A dense Hf-Ta-Zr-O multiphase oxide layer was formed on the surface of the HTZ during ablation process, which protected the interior modified C/C composites from ablation. Our work expands a rational design of modified C/C composites and broaden the application of solid solution ceramic in the field of ultra-high temperature ablation resistance for carbon or ceramic-based composites.     

Fabricating thick-section carbon fiber/silicon carbide composites by machining-aided chemical vapor infiltration

Chemical vapor infiltration (CVI) is a prominent process for fabricating carbon fiber/silicon carbide (C/SiC) composites. However, the preparation of enclosed-structure or thick-section C/SiC composites/components with CVI remains a challenge, since the difficulty of densification increases. Here, machining-aided CVI (MACVI) is designed, in which infiltration-assisting holes are utilized (machined) to increase matrix deposition. To validate the approach, thick-section (10 mm thick) C/SiC composites were fabricated by MACVI. Porosity analysis and microstructure characterization were performed on the fabricated MACVI C/SiC composites and their CVI counterparts, showing a density increase up to 12.7% and a porosity decrease up to 32.1%. The mechanical behavior of the fabricated MACVI C/SiC composites was characterized, showing an increase of flexural strength by a factor of 1.72 at most. Besides, the toughness also largely increases. Both the porosity decrease and the strength and toughness increase brought by MACVI demonstrate its effectiveness for fabricating stronger and tougher enclosed-structure or thick-section ceramic matrix composites/components.     

Microstructure and anti-oxidation properties of multi-composition ceramic coatings for carbon/carbon composites

To protect carbon/carbon (C/C) composites from oxidation at elevated temperature, an effective WSi₂-CrSi₂-Si ceramic coating was deposited on the surface of SiC coated C/C composites by a simple and low-cost slurry method. The microstructures of the double-layer coatings were characterized by X-ray diffraction, scanning electron microscopy and energy dispersive spectroscopy analyses. The coating exhibited excellent oxidation resistance and thermal shock resistance. It could protect C/C composites from oxidation in air at 1773 K for 300 h with only 0.1 wt.% mass gain and endure the thermal shock for 30 cycles between 1773 K and room temperature. The excellent anti-oxidation ability of the double-layer WSi₂-CrSi₂-Si/SiC coating is mainly attributed to the dense structure of the coating and the formation of stable vitreous composition including SiO₂ and Cr₂O₃ produced during oxidation.     

Fabrication and properties of lightweight SiOC modified carbon-bonded carbon fiber composites

SiOC modified carbon-bonded carbon fiber composites (CBCFs) with densities of 0.38, 0.61, 0.94 g cm⁻³ were prepared by precursor infiltration and pyrolysis method using dimethoxydimethylsilane and methyltrimethoxysilane as precursors. The densification behavior was investigated by analyzing the microstructure of CBCF-SiOC (CS) composites with different densities. The mechanical properties and oxidation resistance of the CS composites were studied. Results indicate that the CS composites with the density of 0.94 g cm⁻³ exhibit better mechanical and anti-oxidation properties.     

Electromagnetic wave absorption and mechanical properties of silicon carbide fibers reinforced silicon nitride matrix composites

It is difficult for ceramic matrix composites to combine good electromagnetic wave (EMW) absorption properties (reflection coefficient, RC less than -7 dB in X band) and good mechanical properties (flexural strength more than 300 MPa and fracture toughness more than 10 M P·m^1/2). To solve this problem, two kinds of wave-absorbing SiC fibers reinforced Si₃N₄ matrix composites (SiC_f/Si₃N₄) were designed and fabricated via chemical vapor infiltration technique. Effects of conductivity on EM wave absorbing properties and fiber/matrix bonding strength on mechanical properties were studied. The SiC_f/Si₃N₄ composite, having a relatively low conductivity (its conduction loss is about 33% of the total dielectric loss) has good EMW absorption properties, i.e. a relative complex permittivity of about 9.2-j6.4 at 10 GHz and an RC lower than ?7.2 dB in the whole X band. Its low relative complex permittivity matches impedances between composites and air better, and its strong polarization relaxation loss ability help it to absorb more EM wave energy. Moreover, with a suitably strong fiber/matrix bonding strength, the composite can transfer load more effectively from matrix to fibers, resulting in a higher flexural strength (380 MPa) and fracture toughness (12.9 MPa?m^1/2).     

Mechanical properties of graphene oxide reinforced alumina matrix composites

Graphene oxide (GO) reinforced alumina matrix composites have been fabricated by using graphene oxide synthesized by a modified Hummer's method. Samples were prepared by powder metallurgy and consolidated by Spark Plasma Sintering (SPS). The influence of GO addition on the microstructure and mechanical properties of the composites was investigated. Results show a significant increase (almost 35%) of the fracture toughness for composites containing 0.5 wt% graphene oxide compared to sintered pure alumina. In order to find reasons for this improvement Scanning/Transmission Electron Microscopy (SEM/TEM) observations were carried out. They reveal a good interface between the reinforcement and the matrix as well as such mechanisms like branching, deflection and bridging of crack propagation.     

Preparation and properties of SiOC ceramic modified carbon fiber needled felt preform composites

SiOC ceramic modified carbon fiber needled felt preform composites (C_f/SiOC) with densities of 0.4 and 0.7 g/cm³ were prepared by precursor infiltration and pyrolysis (PIP) method using methyltrimethoxysilane (MTMS) and dimethyldimethoxysilane (DMDMS) as precursors. The densification behavior was investigated through scanning electron microscopy (SEM) analysis of microstructure of C_f/SiOC composites undergoing different PIP times. The results indicate that with increase of PIP times, a great amount of SiOC ceramic was introduced into the preform, completely covering on the carbon fibers and occupying the open pores. The thermal performance, mechanical properties, and oxidation resistance of the composites were studied via various tests. The results illustrate that after two-time PIP procedure, thermal conductivities of the composites are 0.41–2.54 and 1.28–4.04 W/(m·K) in z direction and x/y plane, respectively, at RT-1500 °C. The compressive strengths of the composite arrive at 2.1 MPa in z direction and 7.8 MPa in x/y plane, which are almost 3.5 times and 6.5 times, respectively, counterparts of the raw preform. The incorporation of SiOC ceramic can remarkably improve anti-oxidation ability of the composites at 600 °C. The oxidation weight loss is merely 2.1 wt% after 60-min oxidation at 600 °C.     

Processing and properties of tape-cast alumina/zirconia laminates composites

In the present work, laminar ceramic structures formed by layers of alumina and partially stabilized zirconia were fabricated by water-based tape casting. Rheological, physical and mechanical properties of slurries and laminates were evaluated. The laminates consisted of stacked alumina and zirconia green tapes produced by thermopressing. Pyrolysis was carried out at 450 °C and sintering at 1500 °C. The alumina/zirconia laminates were studied for a better understanding of the formation behavior and crack propagation at the laminate interface. The flexural strength values of laminates depend on the stress state on their surface. The laminates with the highest amount of zirconia layers presented low strength values (6.7 MPa), while the laminates with more alumina layers had a higher strength level (57.7 MPa). This is because these laminates have alumina layers on the surface which are in a state of residual compressive stress.     

Fabrication of C/SiC composites by siliconizing carbon fiber reinforced nanoporous carbon matrix preforms and their properties

Reactive melt infiltration (RMI) has been proved to be one of the most promising technologies for fabrication of C/SiC composites because of its low cost and short processing cycle. However, the poor mechanical and anti-ablation properties of the RMI-C/SiC composites severely limit their practical use due to an imperfect siliconization of carbon matrixes with thick walls and micron-sized pores. Here, we report a high-performance RMI-C/SiC composite fabricated using a carbon fiber reinforced nanoporous carbon (NC) matrix preform composed of overlapping nanoparticles and abundant nanopores. For comparison, the C/C performs with conventional pyrocarbon (PyC) or resin carbon (ReC) matrixes were also used to explore the effect of carbon matrix on the composition and property of the obtained C/SiC composites. The C/SiC derived from C/NC with a high density of 2.50 g cm^?3 has dense and pure SiC matrix and intact carbon fibers due to the complete ceramization of original carbon matrix and the almost full consumption of inspersed silicon. In contrast, the counterparts based on C/PyC or C/ReC with a low density have a little SiC, much residual silicon and carbon, and many corroded fibers. As a result, the C/SiC from C/NC shows the highest flexural strength of 218.1 MPa and the lowest ablation rate of 0.168 µm s^?1 in an oxyacetylene flame of ～ 2200 °C with a duration time of 500 s. This work opens up a new way for the development of high-performance ceramic matrix composites by siliconizing the C/C preforms with nanoporous carbon matrix.     

Effect of in situ grown SiC nanowires on microstructure and mechanical properties of C/SiC composites

Hexagonal-shaped SiC nanowires were in situ formed in C/SiC composites with ferrocene as catalyst in the densification process of polymer impregnation and pyrolysis. The effect of SiC nanowires on microstructure and properties of the composites were studied. The results show that the in situ formed SiC nanowires were hexagonal, mostly with diamer of about 250 nm, and grew by the vapor–liquid–solid (VLS) mechanism. The C/SiC composite with nanowires shows higher bulk density and flexural strength than the one with no SiC nanowires, and the high temperature flexural strength behavior of C/SiC composites with SiC nanowires was evaluated.     

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.     

Preparation,ablation behavior and mechanism of C/C-ZrC-SiC and C/C-SiC composites

ZrC precursor was synthesized by a solution approach using ZrOCl₂·8H₂O, acetylacetonate, glycerol and boron-modified phenolic resin. A ZrC yield of ~ 40.56 wt% was obtained at 1500 °C in the C/Zr molar ratio of 1:1. C/C-ZrC-SiC composites were fabricated by a combined processes of chemical vapor infiltration (CVI) and precursor infiltration and pyrolysis (PIP) using the synthesized ZrC precursor. For comparison, C/C-SiC composites were prepared by CVI. Thermogravimetric analysis showed that C/C-ZrC-SiC composites exhibited better oxidation resistance than C/C-SiC composites. After oxyacetylene torch ablation, the mass ablation rate of C/C-ZrC-SiC composites was 9.23% lower than that of C/C-SiC composites. The porous ZrO₂ skeleton in the ablation center was prone to be peeled off by the flame flow, resulting in the higher linear ablation rate of C/C-ZrC-SiC composites. The oxide layers of ZrO₂ and SiO₂ were formed on the transition and brim region of C/C-ZrC-SiC composites and acted as effective heat and oxygen barriers. For C/C-SiC composites, the C-SiC matrix was severely depleted in the ablation center and the formed SiO₂ layer in the brim region could protect the matrix against further ablation.     

Effects of heat treatment on mechanical properties of 3D Si3N4f/BN/Si3N4 composites by PIP

The fabrication of three-dimensional silicon nitride (Si₃N₄) fiber-reinforced silicon nitride matrix (3D Si₃N_4f/BN/Si₃N₄) composites with a boron nitride (BN) interphase through precursor infiltration and pyrolysis (PIP) process was reported. Heat treatment at 1000–1200 °C was used to analyze the thermal stability of the Si₃N_4f/BN/Si₃N₄ composites. It was found after heat treatment the flexural strength and fracture toughness change with a pattern that decrease first and then increase, which are 191 ± 13 MPa and 5.8 ± 0.5 MPa·m^1/2 respectively for as-fabricated composites, and reach the minimum values of 138 ± 6 MPa and 3.9 ± 0.4 MPa·m^1/2 respectively for composites annealed at 1100 °C. The influence mechanisms of the heat treatment on the Si₃N_4f/BN/Si₃N₄ composites include: (Ⅰ) matrix shrinkage by further ceramization that causes defects such as pores and cracks in composites, and (Ⅱ) prestress relaxation, thermal residual stress (TRS) redistribution and a better wetting at the fiber/matrix (F/M) surface that increase the interfacial bonding strength (IBS). Thus, heat treatment affects the mechanical properties of composites by changing the properties of the matrix and IBS, where the load transfer efficiency onto the fibers is fluctuating by the microstructural evolution of matrix and gradually increasing IBS.     

High-temperature properties and interface evolution of C/SiBCN composites prepared by precursor infiltration and pyrolysis

C/SiBCN composites with a density of 1.64 g/cm³ were prepared via precursor infiltration and pyrolysis and the bending strength and modulus at room temperature was 305 MPa and 53.5 GPa. The precursor derived SiBCN ceramics showed good thermal stability at 1600 °C and the SiC and Si₃N₄ crystals appeared above 1700 °C. The bending strength of the composites was 180 MPa after heat treatment at 1500 °C, and maintained at 40 MPa-50 MPa after heat treatment for 2 h at 1600 °C–1900 °C. In C/SiBCN composites, SiBCN matrix could retain amorphous up to 1500 °C and SiC grains appeared at 1600 °C but without Si₃N₄. The reason for no detection of Si₃N₄ was that the carbon fiber reacted with Si₃N₄ to form an interface layer (composed of SiC and unreacted C) and a polycrystalline transition layer (composed of B and C elements), leading to the degradation of the mechanical properties.     

Low temperature mullite forming pre-ceramic resins of high ceramic yield for oxide matrix composites

Monophasic mullite precursors, namely aluminosiloxanes were synthesized by a novel synthetic route, in which co-hydrolysis and condensation of aluminium tri secbutoxide and tetraethoxy silane was achieved in presence of con. HCl in a non-polar medium. Aluminosiloxanes were characterized by FT-IR, NMR, and elemental analyses. Spectral analysis confirms the presence of Si-O-Al bonds in all the samples and also validates the incorporation of more aluminium via Si-O-Al bonds with increasing Al/Si mole ratio in the precursor. These FT-IR and NMR data also attest the precursor level homogeneity in all the samples. The aluminosiloxanes are obtained as low viscous resins and are capable of giving high ceramic residue qualifying them as ceramic matrix precursors for CMCs. The effect of Al/Si ratio on the ceramic conversion was studied. All the precursors showed the formation of mullite at 1000 °C. This low temperature mullite formation is a key factor in developing oxide CMCs without fiber damage. The results obtained from the study show that the composition of the ceramic can be controlled between a silica rich mullite phase and near-stoichiometric mullite phase by suitably selecting the Al/Si monomer feed ratio of the precursors. This aspect provides a greater scope for designing application-specific ceramic matrices for space applications.