Fabrication and properties of Cf/ZrC‐SiC‐based composites by an improved reactive melt infiltration

C_f/ZrC‐SiC composites with a density of 2.52 g/cm³ and a porosity of 1.68% were fabricated via reactive melt infiltration (RMI) of Si into nano‐porous C_f/ZrC‐C preforms. The nano‐porous C_f/ZrC‐C preforms were prepared through a colloid process, with a ZrC “protective coating” formed surrounding the carbon fibers. Consequently, highly dense C_f/ZrC‐SiC composites without evident fiber/interphase degradation were obtained. Moreover, abundant needle‐shaped ZrSi₂ grains were formed in the composites. Benefiting from this unique microstructure, flexural strength, and elastic modulus of the composites are as high as 380 MPa and 61 GPa, respectively, which are much higher than C_f/ZrC‐SiC composites prepared by conventional RMI.     

Ablative and mechanical properties of C/C-SiC-ZrC composites modified with PyC/SiC and PyC/BN interface layers

Two kinds of novel modified C/C-SiC-ZrC composites were prepared via precursor infiltration and pyrolysis, as pyrocarbon (PyC)/silicon carbide (SiC) and PyC/boron nitride (BN) dual-layer interphases were separately structured on the fibers by means of chemical vapor infiltration. Data analysis and conclusions are served for investigating the effects of these two interface layers on mechanical and anti-ablative properties. On the mechanical property hand, both PyC/BN and PyC/SiC interphase layers play positive roles, resting with the reduction of fiber damage during the fabrication process. Compared with BN, SiC shows better enhancement as the flexural strength of PyC/BN and PyC/SiC interphase-modified composites are 214.9 and 229.2 MPa, respectively. On the ablative property hand, after oxyacetylene flame ablation for 60 s, the mass and linear ablation rates of the composites modified by PyC/SiC interface were 2.2 mg/s and 9.7 μm/s, which is much lower than that modified by PyC/BN. The inferior ablation properties of PyC/BN-CSZ were attributed to the vaporization of the B₂O₃ gas that destroys the integrity of the oxide film and oxygen erosion on the substrate through the damaged BN interface.     

Fabrication and optimization of 3D-Cf/HfC-SiC-based composites via sol-gel processing and reactive melt infiltration

In this work, 3D-C_f/HfC-SiC-based composites were fabricated and optimized via reactive melt infiltration (RMI) of Si into porous C_f/HfC-C preforms prepared by a sol-gel processing. The physical and chemical processes involved during the fabrication were identified and analyzed in details. It is revealed that fibers and interphase of the composites can be eroded during carbothermal reduction process, which can be further aggravated during RMI, with the formation of Hf-containing substance on the fibers surface. The fibers and interphase degradation is mainly induced by the reactions between HfO₂ and C/SiC interphase layers at elevated temperatures. Accordingly, a two-step carbothermal reduction treatment was proposed for the optimization of the fabrication procedure. As a result, less fiber/interphase erosion and improved mechanical properties are achieved in the composites, with the bending strength increased by ～49 % (from 214.1 ± 15.7 MPa to 319.0 ± 26.0 MPa).     

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.     

Reactive alloy melt infiltration for SiC composite matrices: Mechanistic insights

A comparative study of reactive melt infiltration using Si and Si‐Y alloys is presented to provide insight into the governing processes that control the effectiveness of the melt interaction with a carbonaceous preform and the temperature capability of the SiC matrix for ceramic matrix composites. Through experiments on two substantially different scales of capillaries in porous graphite tubes using Si and Si‐Y alloys, the current study has characterized the phenomena that play a role in the infiltration of the melt and its reaction with the preform. It is shown that (i) the interface reaction controls wetting in both large and small capillaries and the climb rate is enhanced by the presence of Y; (ii) reaction choking occurs at critical throats within the pore network, usually behind the infiltration front; and (iii) different residual silicides can form during reaction and upon cooling. A potential mechanism for SiC growth is described, and the implications for the interplay between SiC growth and infiltration are discussed.     

Microstructure and mechanical properties of carbon/carbon composites with PyC/SiC/TiC multilayer interphases

Carbon/carbon composites with PyC/SiC/TiC multilayer interphases (CCs-PST) have been successfully prepared by a joint process of chemical vapor deposition and carbothermal reduction. Effect of the Ti(OC₄H₉)₄/C₆H₄(OH)₂ molar ratio on the morphology of TiC particles was investigated and the ratio was optimized as 8:1. When the Ti(OC₄H₉)₄/C₆H₄(OH)₂ molar ratio was 8:1, many homogeneously distributed TiC nanoparticles with the sizes of 100–500 nm on the fibers were observed. The structural evolution of CCs-PST was discussed and the mechanical properties of as-prepared materials were investigated by flexural and interlaminar shear tests. The resulted composites demonstrated a PyC and SiC mixed inner interphase with the thickness of 0.5–1 $\mathrm{\mu }\mathrm{m}$ and a TiC outer interphase with a thickness about 0.5 µm. Flexural strength of 201.45 ± 5.27 MPa and modulus of 21.21 ± 1.58 GPa showed a 41.7% and 7.83% improvement respectively as compared with that of the neat CCs. The interlaminar shear strength of CCs-PST was 66.71 ± 4.87 MPa, which was 51.20% higher than that of the CCs. The improved mechanical properties were attributed to the enhanced interface bond between fibers and matrix induced by the PST.     

Addressing high processing temperatures in reactive melt infiltration for multiphase ceramic composites

Approaches for addressing the high processing temperatures required in reactive melt infiltration (RMI) processing of state-of-the-art multiphase ceramic matrix composites (CMCs) are reviewed. Ultra-high temperature ceramic composites can be realised by reactive melt infiltration of silicon, transition metals and/or alloys designed as immiscible phases, miscible phases, silicide phases and/or silicide eutectics to lower the temperature required for RMI. Whether carbides, borides or nitrides are envisaged in the resultant ceramic matrix composite, RMI presents an optimization challenge of balancing the composition of the phases incorporated and the processing temperature to be used. Current efforts aim at preparing complex and homogeneous microstructure preforms prior to RMI, minimising damage to reinforcing phases, applying rapid heating techniques, and developing in situ real-time monitoring systems during RMI. Future opportunities include integration of additive manufacturing and RMI, the increased use of process modelling and the application of in situ alongside in operando characterization techniques.     

C/SiC–ZrB2–ZrC composites fabricated by reactive melt infiltration with ZrSi2 alloy

C/SiC–ZrB₂–ZrC composites were prepared by reactive melt infiltration (RMI) combined with vacuum pressure impregnation (VPI) method. B₄C–C was first introduced into C/SiC composites with a porosity of about 30% by impregnating the mixture of B₄C and phenol formaldehyde resin, followed by pyrolysis at 900 °C. The molten ZrSi₂ alloy was then infiltrated into the porous C/SiC–B₄C–C to obtain C/SiC–ZrB₂–ZrC composites. The flexural strength was tested. The ablation behavior was investigated under an oxyacetylene torch flame. It has been found that the C/SiC–ZrB₂–ZrC showed a high flexural strength and an excellent ablation resistance. The reactions between ZrSi₂ alloy and B₄C–C were studied, and a model based on these reactions was built up to describe the formation mechanism of the matrix.     

The ablation behavior and mechanical property of C/C-SiC-ZrB2 composites fabricated by reactive melt infiltration

In order to improve the ablation resistance of carbon/carbon (C/C) composites, SiC-ZrB₂ di-phase ceramic were introduced by reactive melt infiltration. The ablation properties of these composites were evaluated by oxyacetylene torch with a heat flux of 2.38 MW/m² for 60 s. Compared with the pure C/C composites, the C/C-SiC-ZrB₂ composites show a significant improvement in the ablation resistance, and the linear and mass ablation rates decreased from 10.28×10⁻³ mm/s to 6.72×10⁻³ mm/s and from 3.08×10⁻³ g/s to 0.61×10⁻³ g/s, respectively. After ablation test, the flexural strength retentions of the C/C and C/C-SiC-ZrB₂ composites near the ablated center region are 39.7% and 81.6%, respectively. The higher strength retention rate of C/C-SiC-ZrB₂ composites was attributed to the introduction of SiC-ZrB₂ ceramic phases, which have excellent ablation resistant property. During ablation test, an ‘embedding structure’ of Zr-O-Si glass layer was formed, which could act as an effective barrier for oxygen and heat. The oxide ceramic coating could protect the C/C-SiC-ZrB₂ composites from further ablation, and thus contribute to retaining the mechanical property of C/C-SiC-ZrB₂ composites after ablation.     

Mechanical properties of SiCf/SiC composites with alternating PyC/BN multilayer interfaces

Alternating pyrolytic carbon/boron nitride (PyC/BN)_n multilayer coatings were applied to the KD–II silicon carbide (SiC) fibres by chemical vapour deposition technique to fabricate continuous SiC fibre-reinforced SiC matrix (SiC_f/SiC) composites with improved flexural strength and fracture toughness. Three-dimensional SiC_f/SiC composites with different interfaces were fabricated by polymer infiltration and pyrolysis process. The microstructure of the coating was characterised by scanning electron microscopy, X–photoelectron spectroscopy and transmission electron microscopy. The interfacial shear strength was determined by the single-fibre push-out test. Single-edge notched beam (SENB) test and three-point bending test were used to evaluate the influence of multilayer interfaces on the mechanical properties of SiC_f/SiC composites. The results indicated that the (PyC/BN)_n multilayer interface led to optimum flexural strength and fracture toughness of 566.0?MPa and 21.5?MPa?m^1/2, respectively, thus the fracture toughness of the composites was significantly improved.     

Microstructure and flexural strength of C/HfC-ZrC-SiC composites prepared by reactive melt infiltration method

C/HfC-ZrC-SiC composites were fabricated via reactive melt infiltration (RMI) of the mixed HfSi₂ and ZrSi₂ alloys. The microstructure, infiltration behavior of the hybrid silicide alloys infiltrating C/C composites, and flexural strength of C/HfC-ZrC-SiC composites was studied. Inside composites, there were more Hf-rich (Hf, Zr)C phases distributed in the exterior region, while more SiC and Zr-rich (Zr, Hf)Si₂ in the interior region. There was compositional segregation in (Hf, Zr)C, with the HfC content decreasing from the exterior region to interior region. The RMI process was performed at different temperatures to investigate the structural evolution, and a model for the reactive melt infiltration of the mixed HfSi₂ and ZrSi₂ alloys into C/C composites was established. Compared with C/HfC-SiC and C/ZrC-SiC prepared by same process, C/HfC-ZrC-SiC had the highest flexural strength of 247Mpa and 213Mpa after oxidation at 1200 ℃ for 15 min. Both the unoxidized and oxidized samples presented a pseudo-plastic fracture behavior.     

Influence of graphitization treatment on microstructure and flexural strength of C/C-ZrC-SiC composites fabricated via reactive melt infiltration

C/C-ZrC-SiC composites were prepared by chemical vapor infiltration (CVI) and molten salt assisted reactive melt infiltration (RMI). The microstructure of low density and high density C/C composites without graphitization (LC/HC) and graphitization at 2000 °C (LCG/HCG) were compared. Moreover, the effects of graphitization of LC and HC on the microstructure and flexural strength of C/C-ZrC-SiC composites were investigated in detail. The composites prepared by infiltration of LC and LCG had lower flexural strength, 220.01 ± 21.18 MPa and 197.94 ± 19.05 MPa, respectively. However, the composites prepared by HC and HCG presented higher flexural strength, 308.76 ± 12.35 MPa and 289.62 ± 8.70 MPa, respectively. This was due to the phenomenon of fiber erosion in both LC and LCG during the RMI process. After graphitization, the flexural strength of C/C-ZrC-SiC composites prepared by RMI decreased, but the fracture behavior of the composites tends to be more mild. The decreased strength of the composites were caused by the increased matrix cracks, fiber damage in high temperature and the weak interfacial bonding. The improve of failure behavior of the composites was due to interface debonding between the fiber and matrix, and composites can consume the fracture energy through fiber pull-out.     

Reaction kinetics and ablation properties of C/C-ZrC composites fabricated by reactive melt infiltration

Carbon/carbon-zirconium carbide (C/C-ZrC) composites were prepared by reactive melt infiltration. Carbon fiber felt was firstly densified by carbon using chemical vapor infiltration to obtain a porous carbon/carbon (C/C) skeleton. The zirconium melt was then infiltrated into the porous C/C at temperatures higher than the melting point of zirconium to obtain C/C-ZrC composites. The infiltration depth as a function of annealing temperature and dwelling time was studied. A model based on these results was built up to describe the kinetic process. The ablation properties of the C/C-ZrC were tested under an oxyacetylene torch and a laser beam. The results indicate that the linear and mass ablation rates of the C/C-ZrC composites are greatly reduced compared with C/SiC-ZrB₂, C/SiC, and C/C composites. The formation of a dense layer of ZrC and ZrO₂ mixture at high temperatures is the reason for high ablation resistance.     

Properties regulation of SiC ceramics prepared via stereolithography combined with reactive melt infiltration techniques

Stereolithography(SLA) combined with reactive melt infiltration (RMI) is an effective way to fabricate silicon carbide(SiC) ceramic components with complex shapes and high precision. The purpose of this paper is to increase the content of SiC in the sintered body and improve the properties of SiC ceramics prepared by SLA/RMI technologies by the impregnation of the precursor of carbon source after debinding. The effects of the concentration of phenolic resin solution on the strength of sintered body were studied. The results show that this method can reduce the coefficient of thermal expansion and improve the thermal conductivity of the final body. At the same time, when the concentration of phenolic resin solution is 40 wt%, the final body obtained the best comprehensive properties. The value of bulk density, flexural strength and elastic modulus were 2.89 g/cm³, 244.17 ± 5.13 MPa and 402.39 GPa, respectively. This strategy provides a promising prospect for the preparation of space optical mirrors with complex shapes and high strength by the SLA/RMI method.     

Ablation behavior of Cf/ZrC-SiC-based composites fabricated by an improved reactive melt infiltration

In this work, a highly dense C_f/ZrC-SiC-based composite is fabricated by an improved reactive melt infiltration (RMI). The ablation resistance of the composite is studied by air plasma test. The RMI-C_f/ZrC-SiC possesses a low porosity (3.49%) and high thermal conductivity. The dense microstructure can effectively retard oxygen from diffusing into the interior composite. Meanwhile, the high thermal conductivity makes the composite transfer heat timely during ablation, which reduces the heat accumulation on the ablation surface and weakens the thermal damage to the composite. Consequently, the as-fabricated composite exhibits an excellent ablation resistance. Compared to conventional PIP-C_f/ZrC-SiC composite, the linear and mass recession rates of the RMI-C_f/ZrC-SiC decline by 98.07% and 39.02% at a heat flux of 4.02 MW/m². Also, a continuous SiO₂-ZrO₂ layer forms on the sample surface, which isolates the sample surface from the plasma flame and protect the composites from further oxidation and ablation.     

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.     

Microstructure and mechanical properties of Cf/ZrC composites fabricated by reactive melt infiltration at relatively low temperature

Carbon fiber-reinforced zirconium carbide matrix composites (C_f/ZrC) were prepared by vacuum infiltrating porous carbon/carbon preforms with molten Zr₂Cu alloy at 1200 °C. X-ray diffraction, scanning electron microcopy and transmission electron microscopy analysis were used to characterize the composition and microstructure of the final composites. It was found that the matrix of the composites were composed of the Cu–Zr–C amorphous phase dispersed with either single- or polycrystalline ZrC. Based on the microstructural analysis, the formation mechanism of the matrix was proposed to be a solution-precipitation and grain coalescence process. The influence of the heat treatment at 1800 °C was also investigated. Results indicated that at very high temperature the volatilization of residual metal somewhat deteriorated the flexural strength and the elastic modulus, but the fracture toughness of the composites was improved due to the sintering of ZrC grains.     

Effect of the pyrolytic carbon (PyC) content on the dielectric and electromagnetic interference shielding properties of layered SiC/PyC porous ceramics

A novel layered SiC/pyrolytic carbon (PyC) porous ceramic was synthesized from a nickel foam substrate via low-pressure chemical vapor infiltration (LPCVI) with SiCl₃CH₃-NH₃-BCl₃-H₂-Ar. The microstructure and phase composition of the PyC deposited via Ni catalysis were investigated. In addition, the effect of the PyC content on the microstructure, conductivity, and electromagnetic shielding effectiveness of a two-layered SiC/PyC porous ceramic were discussed. Both the electrical conductivity (from 0.090 to 0.319?S/cm) and the total shielding effectiveness (from 19.2 to 29.0?dB) of the two-layer SiC/PyC porous ceramic (pore size: 200–400?µm) increased with the PyC content. The high-temperature shielding effectiveness of the sample showed an outstanding stability with temperature and remained nearly unchanged (only 2?dB variation) over the 25–600?°C temperature range.     

The improvement of mechanical properties of SiC/SiC composites by in situ introducing vertically aligned carbon nanotubes on the PyC interface

In order to improve the mechanical properties, vertically aligned carbon nanotubes (VACNTs) were in situ introduced on the pyrocarbon (PyC) interfaces of the multilayer preform via chemical vapor deposition (CVD) process under tailored parameters. Chemical vapor infiltration (CVI) process was then employed to densify the multilayer preform to acquire SiC/SiC composites. The results show that the growth of VACNTs on PyC interface is highly dependent to the deposition temperature, time and constituent of gas during CVD process. The preferred orientation and high graphitization of VACNTs were obtained when temperature is 800?℃ and C₂H₄/H₂ ratio is 1:3. The bending strength and fracture toughness of SiC/SiC composites with PyC and PyC-VACNTs interfaces were compared. Compared to the SiC/SiC composite with PyC interface, the bending strength and fracture toughness increase 1.298 and 1.359 times, respectively after the introduction of PyC-VACNTs interface to the SiC/SiC composites. It is also demonstrated that the modification of PyC interface with VACNTs enhances the mechanical properties of SiC/SiC composites due to the occurrence of more fiber pull-outs, interfacial debonding, crack branching and deflection     

Graphite-Si-SiC ceramics produced by microwave assisted reactive melt infiltration

A novel microstructure of graphite-Si-SiC ceramics was successfully prepared by liquid silicon infiltration of graphite-based preforms; instead of using conventional methods, the reactive infiltration process was assisted by microwaves. The effects of microwave power variation on the microstructure and the mechanical properties of infiltrated materials were studied. X-ray diffraction and Raman investigations showed the presence of both unreacted graphite and Si in addition to SiC formed at their interface. The graphitic and silicon phases were separated by a SiC network, which results more homogeneous as microwave power was increased. The amount of SiC was found to be higher in function of the growing power level; a higher conversion of graphite into SiC yielded a more dense material. The bending strength measurements confirm this, showing higher values for the samples processed using a power level of 75% of the full power compared to those obtained with 30% and 60%.