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.     

Properties of Cf/SiC-ZrB2-TaxCy composite produced by reactive hot pressing and polymer impregnation pyrolysis (RHP/PIP)

C_f/SiC-ZrB₂-Ta_xC_y composite was synthesized by reactive hot pressing (RHP) of C_f cloth, polycarbosilane (PCS), ZrB₂, and Ta powders at 4 MPa and 1200 °C. PIP cycle influenced sintering process by increasing density of the composite from 2.34 to 2.82 g/cc. Residual carbon produced during the PIP cycles at 1200 °C was utilized to yield Ta_xC_y by the addition of Ta. SEM images illustrate that by increasing the number of PIP cycles, SiC derived from the PCS cover the C_f fibre, micropores, and cracks. PIP cycles and Ta_xC_y phase improved flexural strength of the composite from 20 to 114 MPa. Mass and linear ablation resistance studies at 1600–2000 °C exhibited that oxide formation at the outer surface caused a barrier; further, no oxidation underneath the composite was observed. SEM images display that at 2000 °C, SiO₂ and Ta_xO_y were molten and sealed the pores. Hence, ablation resistance was enhanced by blocking the penetration in high-temperature flame.     

Enhanced mechanical and dielectric properties of SiCf/SiC composites with silicon oxycarbide interphase

SiC_f/SiC composites with silicon oxycarbide (SiOC) interphase were successfully prepared using silicone resin as interphase precursor for dip-coating process and polycarbosilane as matrix precursor for PIP process assisted with hot mold pressing. The effects of SiOC interphase on mechanical and dielectric properties were investigated. XRD and Raman spectrum results show that SiOC interphase is composed of silicon oxycarbide and free carbon with a relatively low crystalline degree. The surface morphology of SiC fibers with SiOC interphase is smooth and homogeneous observed by SEM. The flexural strength and failure displacement of SiC_f/SiC composites with SiOC interphase vary with the thickness of interphase and the maximum value of flexural strength is 289 MPa with a failure displacement of 0.39 mm when the thickness of SiOC interphase is 0.25 µm. The complex permittivity of the composites increases from 8.8-i5.7 to 9.8-i8.3 with the interphase thicker.     

Simultaneously improving mechanical and microwave absorption properties of a novel SiCf/SiOC & mullite hybrid ceramic matrix composite

For enhanced mechanical and microwave absorption properties at the same time, the SiC_f/hybrid matrix composites were fabricated by precursor infiltration and pyrolysis (PIP) method with polysiloxane (PSO) ethanol solution, alumina sols and silica sols. As the first layer of the hybrid matrix, the SiOC ceramic was pyrolyzed from PSO solution. The remained hybrid matrix was mullite, which sintered from alumina sols and silica sols. The effects of different content of PSO solution on the morphologies, flexure strength and reflection loss values of composites were studied. Additionally, the XRD patterns, Fourier Transform Infrared (FTIR) and Raman spectrum of hybrid matrix were also investigated. With the increasingly content of PSO solution from 0% to 10 % and 20%–60% in the first infiltration-pyrolysis process, the flexure strength of composites was increased from 175.18 MPa to 301.94 MPa and decreased from 263.33 MPa to 221.30 MPa, respectively. The complex permittivity was increased with the increasing content of PSO solution from 0%–40% due to the free carbon conductive network from excessive SiOC. Moreover, the complex permittivity of SiC_f/hybrid matrix composites with 50 % and 60 % content of PSO solution was reduced due to more open porosity and broken free carbon conductive network. Additionally, the maximum reflection loss values of SiC_f/hybrid matrix composite with 50 % PSO solution were over -60 dB and the effective absorption bandwidth (EAB) of this composite reaches 3.89 GHz in the X band.     

Sandwich structure SiCf/Si3N4–SiOC–Si3N4 composites for high-temperature oxidation resistance and microwave absorption

SiC fiber reinforced ceramic matrix composites (SiC_f-CMCs) have been widely used as structural-functional materials at high temperatures. However, their mechanical and electromagnetic wave (EMW) absorbing properties will deteriorate due to high-temperature oxidation. Therefore, unique sandwich structure, consisting of inner Si₃N₄ impedance layer, middle porous SiOC loss layer and dense oxidation-resistant Si₃N₄ layer, was proposed to enhance multiple material properties in oxidation environment. Herein, SiC_f/Si₃N₄–SiOC–Si₃N₄ composites was fabricated by alternating chemical vapor infiltration (CVI) and polymer infiltration pyrolysis (PIP) methods. For these composites, SiC fiber is used as both reinforcing phase and electromagnetic (EM) absorber. CVI Si₃N₄ matrix was distributed in inner and outer layer of the SiC_f/Si₃N₄–SiOC–Si₃N₄ composites. While inner Si₃N₄ layer between BN interphase and SiOC matrix forms nano-heterogeneous interphase to consume EM energy and enhance mechanical properties of composites, outer dense and oxidation-resistant CVI Si₃N₄ coating serves to maintain properties. PIP SiOC matrix exhibits porous structure that can effectively deflect cracks and achieve multiple scattering of EMW. SiC_f/Si₃N₄–SiOC–Si₃N₄ composites with sandwich structure demonstrated excellent EMW absorbing properties and mechanical performance in high-temperature oxidation environments.     

Microstructure and damage evolution of SiCf/PyC/SiC and SiCf/BN/SiC mini-composites: A synchrotron X-ray computed microtomography study

SiC_f/PyC/SiC and SiC_f/BN/SiC mini-composites comprising single tow SiC fibre-reinforced SiC with chemical vapor deposited PyC or BN interface layers are fabricated. The microstructure evolutions of the mini-composite samples as the oxidation temperature increases (oxidation at 1000, 1200, 1400, and 1600?°C in air for 2?h) are observed by scanning electron microscopy, energy dispersive spectrometry, and X-ray diffraction characterization methods. The damage evolution for each component of the as-fabricated SiC_f/SiC composites (SiC fibre, PyC/BN interface, SiC matrix, and mesophase) is mapped as a three-dimensional (3D) image and quantified with X-ray computed tomography. The mechanical performance of the composites is investigated via tensile tests.The results reveal that tensile failure occurs after the delamination and fibre pull-out in the SiC_f/PyC/SiC composites due to the volatilization of the PyC interface at high temperatures in the air environment. Meanwhile, the gaps between the fibres and matrix lead to rapid oxidation and crack propagation from the SiC matrix to SiC fibre, resulting in the failure of the SiC_f/PyC/SiC composites as the oxidation temperature increases to 1600?°C. On the other hand, the oxidation products of B₂O₃ molten compounds (reacted from the BN interface) fill up the fracture, cracks, and voids in the SiC matrix, providing excellent strength retention at elevated oxidation temperatures. Moreover, under the protection of B₂O₃, the SiC_f/BN/SiC mini-composites show a nearly intact microstructure of the SiC fibre, a low void growth rate from the matrix to fibre, and inhibition of new void formation and the SiO₂ grain growth from room to high temperatures. This work provides guidance for predicting the service life of SiC_f/PyC/SiC and SiC_f/BN/SiC composite materials, and is fundamental for establishing multiscale damage models on a local scale.     

Effect of oxidation treatment on KD–II SiC fiber–reinforced SiC composites

Continuous silicon carbide fiber–reinforced silicon carbide matrix (SiC_f/SiC) composites have developed into a promising candidate for structural materials for high–temperature applications in aerospace engine systems. This is due to their advantageous properties, such as low density, high hardness and strength, and excellent high temperature and oxidation resistance. In this study, SiC_f/SiC composites were fabricated via polymer infiltration and pyrolysis (PIP) with the lower–oxygen–content KD–II SiC fiber as the reinforcement; a mixture of 2,4,6,8–tetravinyl–2,4,6,8–tetramethylcyclotetrasiloxane (V4) and liquid polycarbosilane (LPCS), known as LPVCS, was used as the precursor; while pyrolytic carbon (PyC) was used as the interface. The effects of oxidation treatment at different temperatures on morphology, structure, composition, and mechanical properties of the KD–II SiC fibers, SiC matrix from LPVCS precursor conversion, and SiC_f/SiC composites were comprehensively investigated. The results revealed that the oxidation treatment greatly impacted the mechanical properties of the SiC fiber, thereby significantly influencing the mechanical properties of the SiC_f/SiC composite. After oxidation at 1300 °C for 1 h, the strength retention rates of the fiber and composite were 41% and 49%, respectively. In terms of the phase structure, oxidation treatment had little effect on the SiC fiber, while greatly influencing the SiC matrix. A weak peak corresponding to silica (SiO₂) appeared after high–temperature treatment of the fiber; however, oxidation treatment of the matrix led to the appearance of a very strong diffraction peak that corresponds to SiO₂. The analysis of the morphology and composition indicated cracking of the fiber surface after oxidation treatment, which was increasingly obvious with the increase in the oxidation treatment temperature. The elemental composition of the fiber surface changed significantly, with drastically decreased carbon element content and sharply increased oxygen element content.     

Fabrication of carbon fiber reinforced ceramic matrix composites with improved oxidation resistance using boron as active filler

Boron was introduced into C_f/SiC composites as active filler to shorten the processing time of PIP process and improve the oxidation resistance of composites. When heat-treated at 1800 °C in N₂ for 1 h, the density of composites with boron (C_f/SiC-BN) increased from 1.71 to 1.78 g/cm³, while that of composites without boron (C_f/SiC) decreased from 1.92 to 1.77 g/cm³. So when boron was used, two cycles of polymer impregnation and pyrolysis (PIP) could be reduced. Meanwhile, the oxidation resistance of composites was greatly improved with the incorporation of boron-bearing species. Most carbon fiber reinforcements in C_f/SiC composite were burnt off when they were oxidized at 800 °C for 10 h. By contrast, only a small amount of carbon fibers in C_f/SiC-BN composite were burnt off. Weight losses for C_f/SiC composite and C_f/SiC-BN composite were about 36 and 16 wt%, respectively.     

Microstructure and mechanical performance of SiCf/BN/SiC mini-composites oxidized at elevated temperature from ambient temperature to 1500 °C in air

SiC_f/BN/SiC mini-composites comprising single tow SiC fibre-reinforced SiC with chemical vapour deposited (CVD) BN interface layers were fabricated. The mechanical performance and binding strength of the composites and the fibre/interface for the oxidized SiC_f/BN/SiC mini-composite samples (oxidation at 1000, 1200, 1300, 1400 and 1500 °C in air for two hours) were investigated by tensile tests and fibre push-out tests, respectively. The value of oxidation mass change was also measured. Some unusual phenomena for the SiC_f/BN/SiC mini-composites oxidized at 1000 °C were discovered in this work. The tensile strength reached a maximum value, and the mass gain rate showed as a singular negative value, while the shear strength between the fibre and the matrix was moderate. Scanning electron microscopy, energy dispersive spectrometry, infrared spectroscopy and X-ray diffraction characterization methods were used to reveal the microstructural evolution and investigate the unusual phenomenon during oxidation procedures. This work will provide guidance for predicting the service life of SiC_f/BN/SiC composite materials and may enable these materials to become a backbone for thermal structure systems in aerospace applications.     

Processing and mechanical performance of 3D Cf/SiCN composites prepared by polymer impregnation and pyrolysis

The processing of 3D carbon fiber reinforced SiCN ceramic matrix composites prepared by polymer impregnation and pyrolysis (PIP) route was improved, and factors that determined the mechanical performance of the resulting composites were discussed. 3D C_f/SiCN composites with a relative density of ∼81% and uniform microstructure were obtained after 6 PIP cycles. The optimum bending strength, Young's modulus and fracture toughness of the composites were 75.2 MPa, 66.3 GPa and 1.65 MPa m^1/2, respectively. The residual strength retention rate of the as-pyrolyzed composites was 93.3% after thermal shock test at ΔT = 780 °C. It further degraded to 14.6% when the thermal shock temperature difference reached to 1180 °C. The bending strength of the composites was 35.6 MPa after annealing at 1000 °C in static air. The deterioration of the bending strength should be attributed to the strength degradation of carbon fibers and decomposition of interfacial structure.     

Preparation of UHTCMCs by hybrid processes coupling Polymer Infiltration and Pyrolysis with Hot Pressing and vice versa

Carbon fibre reinforced ultra-high temperature ceramic (UHTC) matrix composites were fabricated coupling water-based powder slurry infiltration, Polymer Infiltration and Pyrolysis (PIP) and Hot Pressing (HP) techniques. This study aims to identify the best sequence of consolidation techniques to better integrate the carbon fibre cloths into an ultra-refractory sintered ceramic matrix of ZrB₂-SiC. Infiltrated preforms with UHTC powder slurry were densified via: a) a pre-sintering step by HP followed by two PIP cycles with polycarbosilane, and vice versa, b) two PIP cycles followed by a cycle of HP. Flexural strengths at room temperature and at 1500 °C (167 MPa and 592 MPa, respectively) were found to be significantly higher for composites obtained by the second route, suggesting that sintering of polymer-derived SiC during HP improves the structural properties of C_f/ZrB₂-SiC composites. This work presents an effective method for UHTCMC manufacturing in a shorter time than traditional PIP process.     

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.     

Oxidation behavior of 3D SiCf/SiBCN composites at 800–1200 °C

3D SiC_f/BN–SiC/SiBCN composites were fabricated via precursor impregnation and polymer infiltration pyrolysis (PIP). Oxidation behavior of the composites heated in air at 800 °C, 1000 °C and 1200 °C for 50 h was investigated. Following the oxidation treatment, it was found that the bending strength of the composites at different oxidation temperatures was degraded. The weight loss of the composites decreased gradually over the range of oxidation times of 1–50 h. In order to clarify the oxidation mechanism of the composites, reconstructed images, microstructures, phase compositions, the oxide layer formed on the composites and main chemical reactions were all analyzed. It was revealed that the degradation in the fracture strength of the composites was closely related to the oxidation of SiBCN matrix and BN-SiC interphase, whereas there was no signs of oxidation products about SiC fiber, which indicated that SiC fiber could be protected from oxygen by SiBCN matrix at 800?1200 °C in air.     

Fine study of hierarchical interphase constructed by boron nitride and carbon nanotubes in SiCf/SiC composites

A fine study of the interfacial part in the silicon carbide fiber (SiC_f) reinforced silicon carbide (SiC) composites was conducted by transmission electron microscopy. The boron nitride (BN) and carbon nanotubes (CNTs) were progressively coated on the SiC_f by chemical vapor deposition method to form a hierarchical structure. Three composites with different interfaces, SiC_f–CNTs/SiC, SiC_f@BN/SiC, and SiC_f@BN–CNTs/SiC, were fabricated by polymer infiltration and pyrolysis method. The interfaces and microstructures of the three composites were carefully characterized to investigate the improvement mechanism of strength and toughness. The results showed that BN could protect the surface of SiC_f from corrosion and oxidation so that improved the possibility of debonding and pullout. CNTs could avoid the propagation of cracks in the composites so that improved the damage resistance of the matrix. The synergistic reinforcement brought by BN and CNTs interfaces made the SiC_f@BN–CNTs/SiC composites with a tensile fracture strength as high as 359 MPa, with an improvement of 23% compared to that of SiC_f@BN/SiC.     

The effects of preparation temperature on the SiCf/SiC 3D4d woven composite

Continuous silicon carbide fiber reinforced silicon carbide matrix (SiC_f/SiC) composites have promising applications in aero-engine due to their unique advantages, such as low density, high modulus and strength, outstanding high temperature resistance and oxidation resistance. As SiC fibers are main reinforcements in SiC_f/SiC composites, the crystallization rate and initial damage degree of SiC fibers are seriously influenced by preparation temperatures of SiC_f/SiC composites, namely mechanical properties of SiC fibers and SiC_f/SiC composites are influenced by preparation temperatures. In this paper, KD-II SiC fibers were woven into 3D4d preforms and SiC matrix was fabricated by PIP process at 1100 °C, 1200 °C, 1400 °C and 1600 °C. Digital image correlation (DIC) method was adopted to measure the uniaxial tensile properties of these SiC_f/SiC composites. In addition, finite element method (FEM) based on representative volume element (RVE) was adopted to predict the mechanical properties of SiC_f/SiC composites. The good agreements between numerical results and experimental results of uniaxial tensile tests verified the validity of the RVE. In last, the transverse tensile, transverse shear, uniaxial shear properties were predicted by this method. The predicted results illustrated that axial tensile, transverse tensile and axial shear properties were greatly influenced by the preparation temperatures of SiC_f/SiC composites while transverse shear properties were not significantly various. And the mechanical properties of SiC_f/SiC composites peaked at 1200 °C among these four temperatures while their values reached their lowest points at 1600 °C because of thermal damage and brittle failure of SiC_f/SiC composites.     

Effect of intermediate heat treatment on mechanical properties of SiCf/SiC composites with BN interphase prepared by ICVI

SiC_f/SiC composites with BN interface were prepared through isothermal-isobaric chemical vapour infiltration process. Room temperature mechanical properties such as tensile, flexural, inter-laminar shear strength and fracture toughness (K_IC) were studied for the composites. The tensile strength of the SiC_f/SiC composites with stabilised BN interface was almost 3.5 times higher than that of SiC_f/SiC composites with un-stabilised BN interphase. The fracture toughness is similarly enhanced to 23 MPa m^1/2 by stabilisation treatment. Fibre push-through test results showed that the interfacial bond strength between fibre and matrix for the composite with un-stabilised BN interface was too strong (>48 MPa) and it has been modified to a weaker bond (10 MPa) due to intermediate heat treatment. In the case of composite in which BN interface was subjected to thermal treatment soon after the interface coating, the interfacial bond strength between fibre and matrix was relatively stronger (29 MPa) and facilitated limited fibre pull-out.     

Dynamic oxidation resistance and residual mechanical strength of ZrB2-CrSi2-SiC-Si/SiC coated C/C composites

To improve oxidation resistance of carbon/carbon (C/C) composites, a multiphase double-layer ZrB₂-CrSi₂-SiC-Si/SiC coating was prepared on the surface of C/C composites by pack cementation. Thermogravimetry analysis showed that the as-prepared coating could provide effective oxidative protection for C/C composites from room temperature to 1490 °C. After thermal cycling between 1500 °C and room temperature, the fracture behaviors of the as-prepared specimens changed and their residual flexural strengths decreased as thermal cycles increased. The specimen after 20 thermal cycles presented pseudo-plastic fracture characteristics and relatively high residual flexural strength (83.1%), while the specimen after 30 thermal cycles failed catastrophically without fiber pullout due to the severe oxidation damage of C/C substrate especially the brittleness of the reinforcement fibers.     

Microstructure,thermophysical properties and oxidation resistance of SiCf/SiC–YSi2–Si composite fabricated through reactive melt infiltration

As an ideal component material for advanced aeroengines, SiC composite faces severe challenges of high temperatures and oxidation. Here, a high-densification SiC_f/SiC–YSi₂–Si composite was prepared through combining PIP with RMI of Si–13 at% Y alloy to achieve enhanced performance at high temperatures. Based on the analysis of the microstructure and thermophysical properties, it found that the introduction of the highly crystalline Si–Y alloy can improve the high-temperature thermal conductivity of the composite through phonon and electron conduction. In addition, Y migrates to the surface and forms yttrium silicate with increasing oxidation temperature, which facilitates the excellent long-term oxidation resistance of the composite at 1200–1300 °C. Thus, the composite retained its high strength (89.15% and 86.84%) after oxidation at 1200 °C and 1300 °C for 100 h. The experimental results clearly demonstrate that the introduction of the Si–Y alloy is an effective way of preparing high-performance SiC composites.     

Oxidation resistance,ablation resistance and in situ ceramization mechanism of Al-coated carbon fiber/boron phenolic resin ceramizable composites modified with Ti3SiC2

Inherent defect of easy oxidation limited further application of carbon fiber/phenolic resin composites in hostile environments. Herein, a combined strategy of matrix modification and fiber coating was proposed to fabricate a novel ceramizable composite containing Al-coated carbon fibers and Ti₃SiC₂ toward thermal protection materials (TPM), which offered a promising solution to challenge facing long-term thermal protection and load-bearing subject to severe oxidation corrosion and ablation in hypersonic vehicle applications. Oxidation resistance, mechanical strength evolution, phase evolution, microstructure evolution and mechanical strength failure mechanism at elevated temperatures were studied based on thermogravimetric analysis, static ablation test, mechanical test, X-ray diffraction analysis, and scanning electron microscopy coupled with energy dispersive X-ray analysis. The resulting composites exhibited outstanding oxidation resistance, with residue yield at 1600 °C and flexural strength at 1400 °C as high as 87.7% and 31.7 MPa, respectively. It was found that dense multiphase ceramics formed by reactions between Ti₃SiC₂, O₂, pyrolytic carbon (PyC) and N₂, acted as oxygen barriers and self-healing agents during static ablation. Besides, the resulting composites exhibited satisfactory ablation resistance and the linear ablation rate was as low as 0.00853 mm/s. Furthermore, ablation mechanisms were revealed based on phase identification, microstructure characterization and thermodynamic calculation analysis. It was revealed that multiphase ceramics composed of PyC, Al coatings, Ti₃SiC₂, TiC, Al₂OC and AlB₂ contributed great to the ablation resistance during oxyacetylene ablation.     

Internal protection of C/C composites by boron-based compounds

Boron-based protections were used on carbon fibre preforms in order to protect interfacial zones in C/C composites from oxidation. Wet treatments (H₃BO₃ in aqueous solution) and B–P CVD-coatings are not stable under low pressures at 1000 °C (the matrix deposition conditions in conventional CVI). Hence, they could not be used as C/C composite internal protections. Boron-ion implantation in carbon fibres improves their tensile strength by healing superficial carbon fibre defects but is not efficient as an internal protection in C/C composites, the boron-ions being implanted too far from the carbon fibre surface. B–C CVD-deposits are also not very efficient as internal protections. They oxidize faster than the carbon and lead to an important volume decrease. Holes are then formed at the interfacial zones at the beginning of the oxidation of the C/B–C/C composite passing from the surface to the core of the material.