Microwave heated chemical vapour infiltration of SiC powder impregnated SiC fibre preforms

Abstract

Abstract

A microwave heated methyl trichlorosilane based chemical vapour infiltration technique has been used to form SiC_f/SiC composites from SiC fibre preforms preimpregnated with SiC powder using two different fabrication techniques. While infiltration rates obtained from samples loaded with powder were generally higher than for preforms without powder, preferential infiltration occurred in regions where the SiC powder was most concentrated as a result of the initial non-uniform distribution of the powder across the preforms. The consequence was density gradients in the final composites. Nevertheless, average densities as high as 75% could be achieved in a 10 h process.     

Fabrication of SiC whisker-reinforced SiC ceramic matrix composites based on 3D printing and chemical vapor infiltration technology

Spray drying, binder jetting and chemical vapor infiltration (CVI) were used in combination for the first time to fabricate SiC whisker-reinforced SiC ceramic matrix composites (SiC_W/SiC). Granulated needle-shaped SiC_W was spray dried into SiC_W spherical particles to increase flowability and thereby increase printability. Then, binder jetting was employed to print a novel SiC_W preform with two-stage pores using the SiC_W spherical particles. The subsequent CVI technology produced pure, dense, and continuous SiC matrix with high modulus and strength. Consequently, SiC_W/SiC with appropriate mechanical properties was obtained. Finally, the challenges of the novel method and the ways to improve the mechanical properties of SiC_W/SiC are discussed.     

Modelling chemical vapour infiltration of pyrolytic carbon as moving boundary problem

Chemical vapour infiltration (CVI) of pyrolytic carbon is described as a moving boundary problem to determine the evolution of the pyrolytic carbon layer in space and time. Derived from real geometries, a one-dimensional single pore model is developed yielding a nonlinear coupled system of partial differential equations for the concentrations of the gas phase species and the height of the carbon layer within cylindrical pores. The evolution of the moving boundary of the gas phase domain is governed by a non-differentiable minimisation condition. Additionally, a CVI reactor model to describe the infiltration of several cylindrical pores within a porous substrate is presented on the basis of the single pore model. Both models are new in that they combine the following features: (i) derivation of the equations rigorously taking into account the temporal change of the gas phase, (ii) the explicit construction of the position of the gas-solid interface, (iii) the influence of the local curvature of the carbon layer on its growth velocity, and (iv) modelling of chemical kinetics using a reduced reaction scheme with intermediate gas phase species and several surface reactions. The models are solved numerically using a staggered strongly decoupled scheme with implicit Euler time integration. The results allow the identification of process conditions and geometries for which a complete infiltration of the pores or the whole substrate is achieved. For low pressures, the predictions of the CVI reactor model are in agreement with the available experimental data.     

Chemical vapour infiltration of pyrocarbon: I. Some kinetic considerations

Chemical vapour infiltration of pyrocarbon is analysed with respect to (i) the nature of the hydrocarbon (carbon source), (ii) the pyrolysis chemistry and kinetics of homogeneous gas phase reactions, (iii) the kinetics of heterogeneous pyrocarbon deposition reactions, (iv) pore diffusion in the Fick and Knudsen regime, (v) total pressure, (vi) initial partial pressure of the hydrocarbon, (vii) inert diluent gases and (viii) hydrogen, both as reaction product and non-inert diluent gas. The analysis shows aspects for the optimization of chemical vapour infiltration, and it clearly shows methane to be the ideal hydrocarbon for various reasons.     

Effects of CVI SiC amount and deposition rates on properties of SiCf/SiC composites fabricated by hybrid chemical vapor infiltration (CVI) and precursor infiltration and pyrolysis (PIP) routes

The SiC_f/SiC composites have been manufactured by a hybrid route combining chemical vapor infiltration (CVI) and precursor infiltration and pyrolysis (PIP) techniques. A relatively low deposition rate of CVI SiC matrix is favored ascribing to that its rapid deposition tends to cause a ‘surface sealing’ effect, which generates plenty of closed pores and severely damages the microstructural homogeneity of final composites. For a given fiber preform, there exists an optimized value of CVI SiC matrix to be introduced, at which the flexural strength of resultant composites reaches a peak value, which is almost twice of that for composites manufactured from the single PIP or CVI route. Further, this optimized CVI SiC amount is unveiled to be determined by a critical thickness t₀, which relates to the average fiber distance in fiber preforms. While the deposited SiC thickness on fibers exceeds t₀, closed pores will be generated, hence damaging the microstructural homogeneity of final composites. By applying an optimized CVI SiC deposition rate and amount, the prepared SiC_f/SiC composites exhibit increased densities, reduced porosity, superior mechanical properties, increased microstructural homogeneity and thus reduced mechanical property deviations, suggesting a hybrid CVI and PIP route is a promising technique to manufacture SiC_f/SiC composites for industrial applications.     

Degradation of boron nitride interfacial coatings fabricated by chemical vapor infiltration on SiC fibers under ambient air/room temperature conditions

Hexagonal boron nitride (h-BN) interfacial coatings were deposited on SiC fibers by chemical vapor infiltration (CVI) and their degradation behavior under ambient air/room temperature conditions was studied with time. Degradation of the interfacial coatings with time was investigated by characterizing the morphology and microstructure of these materials with scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), and transmission electron microscopy (TEM). Thermogravimetry coupled with differential thermal analysis (TG-DTA) and X-ray photoelectron spectroscopy (XPS) was used to analyze the chemical reactions and phase transitions taking place in the BN coatings. The results showed that the as-deposited BN interfacial coatings fabricated by CVI were compact and well bonded to the SiC fibers. BN coatings remained relatively stable under ambient air/room temperature conditions for 50?h, while severe degradation was observed after 500?h of exposure. The degradation of BN interfacial coatings was mainly caused by two factors, namely, reaction with atmospheric air to produce boric oxide and amorphization of the hexagonal structure. The degradation observed under ambient air/room temperature might be due to incomplete crystallinity of BN interfacial coatings. Presence of water vapor may accelerate degradation of the coatings. The results of this degradation test can be used as a reference for the storage of BN coatings fabricated by CVI.     

Fabrication of cylindrical SiCf/Si/SiC-based composite by electrophoretic deposition and liquid silicon infiltration

Cylindrical SiC-based composites composed of inner Si/SiC reticulated foam and outer Si-infiltrated SiC fiber-reinforced SiC (SiC_f/Si/SiC) skin were fabricated by the electrophoretic deposition of matrix particles into SiC fabrics followed by Si-infiltration for high temperature heat exchanger applications. An electrophoretic deposition combined with ultrasonication was used to fabricate a tubular SiC_f/SiC skin layer, which infiltrated SiC and carbon particles effectively into the voids of SiC fabrics by minimizing the surface sealing effect. After liquid silicon infiltration at 1550 °C, the composite revealed a density of 2.75 g/cm³ along with a well-joined interface between the inside Si/SiC foam and outer SiC_f/Si/SiC skin layer. The results also showed that the skin layer, which was composed of 81.4 wt% β-SiC, 17.2 wt% Si and 1.4 wt% SiO₂, exhibited a gastight dense microstructure and the flexural strength of 192.3 MPa.     

Facile preparation of morph-genetic SiC/C porous ceramic at low temperature by processed bio-template

A porous morph-genetic SiC/C ceramic material was fabricated using biomass-derived C template, Si powder, and Fe(NO₃)₃·9H₂O as the starting materials. The effects of heating temperature, and catalyst/Si mole ratio on the formation of SiC/C ceramic were investigated. In addition, the pore size distribution was obtained through pore size analysis, and the determination of oxidation resistance of SiC/C ceramics and C template was carried out by thermogravimetric analysis. The results show that copious amounts of SiC nanowires, which were distributed on the surfaces and interiors of the C template holes, were formed at 1300 °C with 4 wt% Fe as catalyst. The SiC nanowires significantly affected the oxidation resistance and microporous structures of the prepared materials. Moreover, a possible formation mechanism for the porous SiC/C ceramic was determined.     

Synthesis of biomorphic SiC fabric ceramic from pre-processed ramie fibres

Biomorphic SiC fabric ceramic was synthesised by in situ reactive molten silicon infiltration process using artificial ramie fibres’ template, phenolic resin, and silicon. The phase compositions, microstructure, and physical characteristics of the biomorphic fabric ceramic were characterised and tested. The results show that the final ceramic retains the ramie fabric structure, and presents duplex microstructure including biomorphic SiC fibres and network SiC ceramic around the biomorphic fibres. This biomorphic SiC fabric ceramic is constituted by 95.8% of SiC, has a low density of 1.02?g?cm^?3 and a high porosity of 63.7%, and shows low linear shrinkages and better electrical resistivity along the fibre axis. The uniform and fine SiC particles with the size of ～4?µm indicate that the reaction–formation mechanism is the dissolution of carbon and the precipitation of SiC, without a second precipitation.     

空间望远镜用C/SiC镜面研制综述

综述了空间望远镜的主镜用高强度、高表面精度、低热膨胀系数的低温（约4K）用镜面的制备和检测过程.日本将Φ710mm的高强度反应烧结SiC材料已用于红外望远镜镜面.在短切炭纤维增强C/C复合材料毛坯的基础上进行液相硅渗透（LSI）而制备的C/SiC复合材料在光学镜面方面具有更大的优势.通过提高C/C复合材料毛坯中沥青基炭纤维体积分数及控制硅化速度,可有效地提高LSI-C/SiC复合材料的机械性能和表面光学精度;通过不同规格的炭纤维的混杂化,可使C/SiC复合材料热膨胀系数的各向异性降低至小于4％的差异.SiC、Si-SiC浆料涂层处理可有效地提高表面精度至2 nm rms的极高要求.     

Thermal transport characteristics in diamond/SiC composites via molten Si infiltration

Heat dissipation remains a critical challenge in optical and electronic devices and diamond/SiC composite is the premiere material solution because of its outstanding thermal and mechanical properties. Si liquid infiltration is one of the most promising techniques to fabricate fully dense diamond/SiC composites with desired phase structures and exceptional properties. In this study, the thermal conductivity from room temperature to 1000 °C was investigated for the diamond/SiC composites fabricated by a liquid Si infiltration method. The experimental thermal measurement shows a good agreement with the computational solution obtained by solving the Boltzmann transport equation. The results suggest a strong correlation between the composite thermal conductivity and diamond volume percentage. A level-off of the thermal conductivity at high diamond content reflects increased thermal resistance. In addition, the annealing effect on the composite thermal conductivity as well as the thermal stability were evaluated.     

Application of SiO2-coated SiC powder in stereolithography and sintering densification of SiC ceramic composites

Stereolithography additive manufacturing of SiC ceramic composites has received much attention. However, the forming efficiency and mechanical properties of their products need to be improved. This study aimed to prepare SiC ceramic composites with complex shapes and high flexural strength using a combination of digital light processing (DLP) and reactive solution infiltration process (RMI). A low-absorbance SiO₂ cladding layer was formed on the surface of SiC powder through a non-homogeneous precipitation process. With the densification of the cladding layer at high temperatures, SiO₂-coated SiC composite powder was used to formulate a photosensitive ceramic slurry with a solid content of 44 vol%. The resulting slurry exhibited a considerable improvement in curing thickness and rate and was used to mold ceramic green body with a single-layer slicing thickness of 100 μm using DLP. The ceramic blanks were then sintered and densified using a carbon thermal reduction combined with liquid silica infiltration (LSI) process, resulting in SiC ceramic composites with a density of 2.87 g/cm³ and an average flexural strength of 267.52 ± 2.5 MPa. Therefore, the proposed approach can reduce the manufacturing cycle and cost of SiC ceramic composites.     

Ring compression properties of SiCf/SiC composites prepared by chemical vapor infiltration

SiC fiber reinforced SiC matrix (SiC_f/SiC) composites prepared by chemical vapor infiltration are one of promising materials for nuclear fuel cladding tube due to pronounced low radioactivity and excellent corrosion resistance. As a structure component, mechanical properties of the composites tubes are extremely important. In this study, three kinds of SiC_f preform with 2D fiber wound structure, 2D plain weave structure and 2.5D shallow bend-joint structure were deposited with PyC interlayer of about 150–200?nm, and then densified with SiC matrix by chemical vapor infiltration at 1050?°C or 1100?°C. The influence of preform structure and deposition temperature of SiC matrix on microstructure and ring compression properties of SiC_f/SiC composites tubes were evaluated, and the results showed that these factors have a significant influence on ring compression strength. The compressive strength of SiC_f/SiC composites with 2D plain weave structure and 2.5D shallow bend-joint structure are 377.75?MPa and 482.96?MPa respectively, which are significantly higher than that of the composites with 2D fiber wound structure (92.84?MPa). SiC_f/SiC composites deposited at 1100?°C looks like a more porous structure with SiC whiskers appeared when compared with the composites deposited at 1050?°C. Correspondingly, the ring compression strength of the composites deposited at 1100?°C (566.44?MPa) is higher than that of the composites deposited at 1050?°C (482.96?MPa), with a better fracture behavior. Finally, the fracture mechanism of SiC_f/SiC composites with O-ring shape was discussed in detail.     

Effect of temperature on the growth of boron nitride interfacial coatings on SiC fibers by chemical vapor infiltration

In order to improve bonding property between SiC fibers and matrix of SiC_f/SiC composites, boron nitride (BN) interfacial coatings were synthesized by chemical vapor infiltration. BN coatings were fabricated from BCl₃–NH₃ gaseous mixtures at four different temperatures (843 °C, 900 °C, 950 °C and 1050 °C) with different deposition times. Growth kinetics, nucleation and growth processes, microstructure and chemical composition of boron nitride coatings were investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and Raman spectrometry. Results showed that deposition rate increased as the temperature increased from 843 °C to 950 °C. However, deposition rate decreased slightly from 23.10 ± 0.85 nm/min (950 °C) to 21.39 ± 0.67 nm/min when the temperature was increased further to 1050 °C. It could be due to the nucleation occurring in the gas and the consumption of a large amount of BCl₃ and NH₃. When deposition temperature was 843 °C, BN grains deposited on top layer of the coating could not completely cross Ehrlich-Schwoebel barrier and grew in island growth mode. On the other hand, the deposition pattern followed a layer-by-layer growth mode when deposition temperature was 1050 °C. Deposition temperature significantly affected the microstructure of as-deposited BN coatings. At 843 °C, 950 °C and 1050 °C, the coatings presented amorphous, polycrystalline and hexagonal structures, respectively.     

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.     

In-situ synthesized nano-porous titanium carbide coating on silicon carbide fibres using titanium tetrachloride vapour

Nano-porous titanium carbide (TiC) coating was in-situ synthesized by titanium tetrachloride (TiCl₄) vapour based on silicon carbide (SiC) fibre substrate. The microstructure of the coating was characterized and the reaction process and growth mechanism of terraced TiC grains were analyzed. The coating consists of TiC nanograin and the nanopores are formed by the lateral stack growth. The supersaturation of gaseous reagents at the boundary layer controls the composition and the morphology of the coating. The SiC fibre covered by the optimized TiC coating preserves the original flexibility. Finally, the SiC_f/SiC mini-composite with nano-porous TiC interphase was prepared. The fracture surface exhibits fibre pull-out and interphase fracture.     

Porous SiCnw/SiC ceramics with unidirectionally aligned channels produced by freeze-drying and chemical vapor infiltration

The current study introduces a methodology for the fabrication of porous silicon carbide nanowire/silicon carbide (SiC_nw/SiC) ceramics with macroscopic unidirectionally aligned channels and reports on their microstructural and mechanical properties. The material was produced by freezing of a water-based slurry of β-SiC nanowires (SiC_nw) with control of the ice growth direction. Pores were subsequently generated by sublimation of the columnar ice during freeze-drying. Chemical vapor infiltration (CVI) of SiC into the open pore network of the SiC_nw aerogel with unidirectionally aligned channels, resulted in the formation of highly porous SiC_nw/SiC ceramics which exhibited a unique microstructure as identified by scanning electron microscopy. The pore size distribution and the mechanical properties of the as-fabricated porous ceramics were examined by mercury intrusion porosimetry and three-point bending and compression tests, respectively, while phase composition was investigated through X-ray diffraction.     

Effect of diffusion-assisting holes on the tensile properties of a thick-section two dimensional C/SiC composite fabricated by chemical vapor infiltration

The concept of diffusion-assisting holes (DAHs) has been developed to increase matrix deposition in the middle layers of the thick-section ceramic matrix composites (CMCs) that are fabricated by chemical vapor infiltration (CVI). However, the effect of DAHs on the tensile properties of CMCs has not been studied. Here, the tensile properties and the state of matrix deposition of a 10-mm-thick two dimensional (2D) C/SiC with DAHs are investigated. Results showed, with DAHs, a zone of increased deposition with a radius of ca. 1.4 mm around a hole was introduced and the net-section strength of the 10-mm-thick 2D C/SiC was increased by 48.1%. In addition, the tensile load bearing capacity was also increased by 34.1%, although the load bearing section decreased with DAHs. The increased net-section strength and tensile load bearing capacity of the C/SiC are attributed to the increased matrix deposition in the middle layers of the thick-section composite.     

Pressure‐less joining of C/SiC and SiC/SiC by a MoSi2/Si composite

A MoSi₂/Si composite obtained in situ by reaction of silicon and molybdenum at 1450°C in Ar flow is proposed as pressure‐less joining material for C/SiC and SiC/SiC composites. A new “Mo‐wrap” technique was developed to form the joining material and to control silicon infiltration in porous composites. MoSi₂/Si composite joining material infiltration inside coated and uncoated C/SiC and SiC/SiC composites, as well as its microstructure and interfacial reactions were studied. Preliminary mechanical strength of joints was tested at room temperature and after aging at service temperatures, resulting in interlaminar failure of the composites in most cases.     

Polymer-derived SiC ceramic aerogels with in-situ growth of SiC nanowires

Herein, the SiC ceramic aerogels with in-situ growth of SiC nanowires (SiC_w/SiC CAs) have been synthesized by polymer‐derived ceramics (PDCs) method. The morphology, microstructure, and phase composition of the as-prepared samples were systematically investigated through SEM, XRD, TEM, Raman spectrum, FT-IR spectrum, and XPS spectrum techniques. The results showed that the as-obtained SiC_w has a diameter of about 80 nm and a length of 1–3.5 μm. In addition, the formation mechanism and evolution process of growth SiC_w were systematically studied using a VLS growth mechanisms. The way in this work could be expanded to synthesize other Si-based porous ceramic aerogel nanostructed with nanowires.