Liquid-Phase Reaction-Bonding of Silicon Carbide Using Alloyed Silicon-Molybdenum Melts

We have investigated reaction-forming of silicon carbide by the infiltration of carbonaceous preforms using alloyed silicon melts, in order to synthesize composite materials free of the residual silicon phase that has previously limited mechanical properties and upper use temperatures. In this approach, rejection of the alloying component(s) from the primary silicon carbide phase into the remaining melt results in the formation of a secondary refractory phase, such as a silicide, in place of residual free silicon. Experiments conducted in the Si-Mo melt system show that relatively dense (>90%) silicon carbide-molybdenum silicide materials free of residual silicon and residual carbon can be obtained. A model for reactive infiltration based on time-dependent permeabilities is proposed. Processing variables important for control of the reaction rate relative to the infiltration rate, and associated processing flaws, are discussed.     

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.     

Microstructures and properties of Si-Zr alloy based CMCs reinforced by various porous C/C performs

C/C-SiC composites were fabricated via Si-Zr reactive alloyed melt infiltration using various C/C preforms with different porosities as reinforcements. The influence of preform porosities on the microstructure, mechanical strength and ablation resistance of the as-prepared composites were investigated. The results indicated that microstructure and properties of the C/C-SiC composites seriously depended on C/C preform porosities. The composites were mainly composed of carbon, SiC and ZrSi₂ phases, while some residual silicon still existed in the composites prepared with very large porosity preforms. Flexural strength of the composites firstly increased with increasing C/C preform porosities, then reached the highest value, 307?MPa, and finally turned to decrease with the further increasing of preform porosities. Densities of the composites increased with increasing preform porosities, while open porosities were generally small below 7%. Linear ablation rates of the composites firstly sharply decreased with increasing preform porosities and then slightly decreased to reach a balance value. In a word, C/C preform porosity was of great significance for reactive melt infiltration of C/C-SiC composites. Densities, microstructure, mechanical strength and ablation resistance of the resulting composites should be comprehensively taken into consideration to choose an optimal preform porosity for fabrication of C/C-SiC composites.     

Capillary Infiltration Rates into Porous Media with Applications to Silcomp Processing

The rate of capillary rise of a liquid into a porous medium made up of consolidated particulates is analyzed. The infiltration distance is parabolic in time and can be modeled using the Washburn analysis. The effective pore radius is measured to be one to two orders of magnitude smaller than the particle size, particle spacing, and the median pore size as measured by mercury porosimetry. This result is interpreted using a modification of the Washburn model which models the porous medium as a single pore with varying diameter. Using a two-sized single pore model, the predicted infiltration rate is consistent with the measured values. In applying the two-sized single pore model to the reactive capillary infiltration of silicon into a carbonaceous preform in the Silcomp process, the effect of pore closure by the conversion of carbon to SiC is predicted. Using pore closure dimensions measured in a partial infiltration experiment, a decrease in the infiltration rate constant is predicted and is consistent with the measured infiltration rate.     

Effect of porosity of cordierite preforms on microstructure and mechanical strength of co-continuous ceramic composites

With the aim of reducing the overall cost of the process, co-continuous metal–ceramic composites were obtained by reactive metal penetration, starting from very low cost cordierite preforms. It was investigated how the preform porosity influences both the residual porosity left in the composites after infiltration and the mechanical properties. It was demonstrated that, despite a significant fraction of the initial porosity remains in the final composite, by a suitable choice of the preform composition and preparation method the mechanical properties are not much inferior than in the case of composites obtained from the much more expensive silica glass.     

三维打印制备MAX基复相陶瓷研究进展

本文综述了三维打印(Three-Dimensional Printing,3DP)结合反应熔体渗透(Reactive Melt Infiltration,RMI)技术制备MAX基复相陶瓷的研究进展。在致密MAX基复相陶瓷的制备过程中,3DP技术的作用主要体现在两方面:一方面是实现预制体的成型,另一方面是通过孔隙结构和成分的设计控制所制备材料的微结构。3DP所制备的预制体呈现为典型的双孔径分布模式,有利于RMI的进行。通过3DP同RMI结合能够实现致密MAX基复相陶瓷的近尺寸成型,同时通过对初始原料、渗透熔体以及渗透温度等参数的优化能够实现微结构、力学性能以及电磁屏蔽性能的调控。     

Microwave heating controlled reactive melt infiltration for graphite-Si-SiC ceramics manufacturing

In this work, we investigated a procedure which exploits microwave ovens to produce SiC- based components by reactive melt infiltration of silicon into graphite preforms. The employed oven is designed to grant optical access to the sample surface, which allows to measure its temperature evolution though a noncontact pyrometer. This signal was used as a feedback to control the power provided to the preform and as an experimental output whose analysis provides insight into the reaction mechanism. Specifically, it is found that complete infiltration is achieved much before the end of the reaction. The latter is not fully self-sustained as the global reaction rate continuously decreases with time until it is no more able to keep the temperature above the silicon solidification value. At that point, the reaction stops. The analysis of the processed samples proved that this procedure allows producing fully infiltrated samples without material failure by adjusting the heat provided during the infiltration stage rather than by tuning the preform structure and composition, which is the usual approach. The proposed method is less time and energy consuming than the standard one.     

Aluminum Infiltration into Molybdenum Silicide Preforms

The presence of Mo₅Si₃ in MoSi₂ preforms hinders the reactive infiltration of aluminum. To understand the role of Mo₅Si₃, the kinetics of aluminum infiltration into pure Mo₅Si₃ is studied. Irrespective of the initial composition (MoSi₂ or Mo₅Si₃) of the preform, the final product always contains Mo(Al,Si)₂. However, the aluminum content in the two cases is different: when the preform is MoSi₂, the aluminum content is 14–18 at.%, and, when the preform is Mo₅Si₃, the aluminum content is 25–27 at.%. The activation energy for the reactive infiltration of aluminum into the Mo₅Si₃ preform is ∼26 kJ/mol.     

Liquid metal infiltration of silicon based alloys into porous carbonaceous materials. Part II: Experimental verification of modelling approaches by infiltration of Si-Zr alloy into idealized microchannels

In this work, the mechanisms leading to the pore closure in reactive melt infiltration (RMI) of carbon by pure silicon and a near eutectic Si-8 at-pct Zr alloy at 1500 and 1700 °C under vacuum were studied. Various geometrical configurations of microchannels were fabricated via laser ablation of glassy carbon plates. The micron size capillary channels allowed simplifying the complicated porosity distribution in the infiltration of powder or fibres based porous preform while keeping the physical dimensions in the range of where the physical phenomenon of pore closure takes place. The extent of infiltration was analysed by means of X-ray radiography. For RMI of pure Si, the widely accepted decrease in capillary radius by the formation of a solid state SiC layer by the reaction of liquid Si and C was observed, but did not lead to closure and it is hence not the infiltration limiting step in channels as small as 10 μm. However, in the case of the Si-Zr alloy infiltration, another mechanism of pore closure was observed, namely the precipitation of zirconium silicides at the infiltration front, due to Zr enrichment in the alloy by the continuous consumption of Si for the formation of SiC.     

Analytical and numerical study of the densification of carbon/carbon composites by a film-boiling chemical vapor infiltration process

The film-boiling chemical vapor infiltration (CVI) process is a fast process developed for composite material fabrication, and especially carbon/carbon composites. In order to help define optimal conditions, a local 1D model has been developed to study the densification front which establishes itself during the processing of a carbon/carbon fibrous preform. The model features heat conduction, precursor gas diffusion, densification reactions and structural evolution of the porous medium. The effects of total mass flux, Thiele modulus, porous medium geometry on front behavior parameters such as width, velocity and residual porosity are presented as semi-analytical correlations. An existence criterion is produced, which involves a minimal heat flux. Comparison between process-scale experiments and simulation is then possible by inserting the semi-analytical results achieved in the local study of the front into a light numerical model involving the entire preform. The model has been validated with respect to previous experimental and numerical data.     

Formation mechanism of Si-Y-C ceramic matrix by reactive melt infiltration using Si-Y alloy and properties of C/Si-Y-C composites

Herein, Si-Y eutectic alloy were introduced into porous C/C preform by reactive melt infiltration (RMI) to prepare C/Si-Y-C composite. Phase compositions and their distributions in the as-prepared composites were investigated. Result indicated that four main regions were found in the typical zone in Si-Y-C matrix, i.e., amorphous carbon, polycrystalline SiC doped with YSi2, amorphous SiC and single crystal YSi2. Based on the reaction between Si-Y alloy and C/C preform and microstructural observations, a model regarding to microstructure formation mechanism was proposed to reveal reaction process. Moreover, improved flexural strength, fracture toughness, thermal diffusivity and thermal conductivity of C/Si-Y-C composite were achieved compared to C/C-SiC.     

Gel reactive melt infiltration: A new method for large-sized complex-shaped C/C components ceramic modification

To widen the applications of conventional reactive melt infiltration (RMI) in large-sized complex-shaped C/C components, an ingenious process of gel-RMI (GRMI) was proposed in this study. The arching C/CSiC composite was prepared successfully using GRMI method with polycarbosilane (PCS)Si90Zr10 (Si: 90 at.%; Zr:10 at.%) sol. The porosity rate of the C/C preform decreased from 18.5% to 2.9%, while the density was raised from 1.40 g·cm⁻³ to 2.05 g·cm⁻³ after GRMI. The reason why C/C preform has been significantly densified is as follow: the PCS in PCS-Si90Zr10 sol formed SiC aerogel skeleton after pyrolysis, and then the Si90Zr10 powders were melted and released from the SiC aerogel into the C/C preform body when the temperature reached the melting point of Si90Zr10 alloy. The obtained C/CSiC composite showed a pseudo-ductile rupture characteristic distinguished from that of the C/C preform, and its bending strength was significantly improved from 104.2 MPa of the C/C preform to 258.8 MPa. The C/CSiC composite had a far lower mass ablation rate of 0.75 mg·s⁻¹ than that of C/C preform, 23.30 mg·s⁻¹. Moreover, the GRMI was preliminarily applied in ceramic modifying nozzle-like C/C preform, and the result showed that the nozzle-like C/C preform was successfully densified from 1.3 g cm⁻³ to 1.96 g cm⁻³. The GRMI process has great potential in ceramic modifying large-sized complex-shaped C/C components.     

Effects of preform pore structure on infiltration kinetics and microstructure evolution of RMI-derived Cf/ZrC-ZrB2-SiC composite

Reactive melt infiltration (RMI) is often used to fabricate highly dense ceramic matrix composite by infiltration of alloy melt into porous preform. Here, C_f/B₄C-C preforms with various pore structures were prepared, and the effects of pore structure on the ZrSi₂ melt infiltration and the as-received C_f/ZrC-ZrB₂-SiC composites were investigated. Compared with the preform prepared by slurry impregnation (SI), the preform prepared by sol impregnation shows more uniform pore size distribution, which leads to more homogeneous melt infiltration, as well as more uniform formation of ZrC-ZrB₂-SiC and better mechanical properties in the composites. The calculation results of infiltration kinetics indicate that the pore radius decreases quickly during the melt infiltration. As the time needed for pore closure in sol-preform is longer than that in SI-preform, it makes the infiltration kinetics more favorable in the former preform. This study can provide guidance for the pore structure regulation in the fabrication of RMI-composites.     

HfC-based coating prepared by reactive melt infiltration on C/C composite substrate

Reactive melt infiltration based on alloy design is proposed in the present work for preparing HfC-based coating on C/C composite substrate. A 50Hf10Zr40Si alloy ingot was prepared and infiltrated into a C/C preform at temperatures much lower than the melting point of the alloy to obtain the HfC-based coating. An obvious layered microstructure of the coating was formed. The carbonization reactions occurring between Hf and carbon of the surface layer of the C/C composite is the primary reason for the reactive melt infiltration process to proceed at relative low temperatures. Acetylene flame test showed that the HfC-based coating protected the C/C composite from serious oxidation.     

Microstructure Evolution and Reaction Mechanism of Biomorphous SiSiC Ceramics

Liquid Si infiltration (LSI) of beech wood-derived biocarbon (C_B) templates at 1550°C yields biomorphous SiSiC ceramics with the morphology of the initial biological preform. The biomorphous SiSiC ceramic consists of solidified Si in the cell lumina, polycrystalline β-SiC and residual carbon islands located at the position of former wood cell walls. The evolution of the microstructure during reactive Si melt infiltration was assessed by infiltration experiments at various times and investigated by X-ray diffraction as well as light scanning electron and transmission electron microscopy in combination with elemental analysis by energy-dispersive X-ray spectrometry. Four different stages of the reactive infiltration process could be distinguished, starting with a heterogeneous nucleation of nano-grained SiC on the pore surfaces of the C_B template by a Si vapor phase reaction below the Si melting temperature. After spontaneous Si melt infiltration, a stepwise reaction results in the simultaneous formation of a nano-grained SiC layer and a coarse-grained SiC phase on the inner pore surfaces. Further reaction proceeds slowly by diffusion of the reactants through the formed SiC layer and the microstructure evolution is dominated by dissolution and re-crystallization processes.     

Reactive infiltration processing of SiC/Fe–Si composites using preforms made of coked rice husks and SiC powder

A reactive infiltration processing of SiC/Fe–Si composites using preforms made of coked rice husks (RHs) and SiC powder in different ratios is reported, in which FeSi₂ alloy was used as infiltrant. The preforms were heat-treated at 1550 °C for 6 h prior to the infiltration. The coked RHs, which are composed of SiO₂ and C, were converted to SiC and poorly crystallized C by carbothermal reduction during the heat treatment. The study of the microstructure and mechanical properties of the composites shows that molten Fe–Si alloy had good wetting of the heat-treated preforms and adequate infiltration properties. Free carbon in the preform reacted with Si in the molten FeSi₂ during infiltration forming new SiC, the composition of the intermetallic liquid being moved towards that of FeSi. As a result, the infiltrated composites are composed of SiC, FeSi₂ and FeSi phases. Vickers hardness, elastic modulus, three-point flexural strength and indentation fracture toughness of the composites are found to increase with SiC additions up to 30% w/w in the preforms, reaching the values of 18.2 GPa, 290 GPa, 213 MPa and 4.9 MPa m^1/2, respectively. With the SiC addition further raised to 45% w/w, the elastic modulus, flexural strength and fracture toughness of the composite turned down probably due to high residual stress and hence the more intense induction of microcracks in the composite. De-bonding of SiC particles pulled out of the Fe–Si matrix, transgranular fracture of part of the SiC particles and in the Fe–Si matrix, and crack bridging all exist in the fracture process of the composites.     

Characterization of α-Al2O3–(Al–Si)3Ti composites

The reactions that take place during the formation of ceramic matrix composites that are based on α-Al₂O₃–(Al–Si)₃Ti interpenetrating networks were analysed. A reactive preform was pressure infiltrated with an Al–Si alloy. After pressure infiltration, the composite did not react in a full manner and further thermal annealing was required. The reduction of TiO₂ by the liquid Al–Si alloy results in the formation of (Al-Si)₃Ti (Al₆₀Si₁₂Ti₂₈). The formation of (Al–Si)₃Ti is governed by the consumption of TiO that is formed as an intermediate phase during the reduction of TiO₂.     

Microstructural and infiltration properties of woven preforms during chemical vapor infiltration

Interface-resolved direct numerical simulations (DNSs) of chemical vapor infiltration (CVI) have been performed over a range of furnace-operating conditions (Thiele moduli) and for practical woven preform geometries. A level-set method is used to resolve the geometry of the initial preform at tow scale. The interface between the vapor and solid phase is then evolved in time through the entire CVI densification cycle, fully resolving the time-varying topology between the two phases. In contrast to previous level-set methods for CVI simulation, the physical reaction and diffusion processes govern the level-set movement in the current approach. The surface deposition kinetics is described by the usual one-step model. In this paper, the DNS data are used to study the evolving porosity, surface-to-volume ratio, and flow infiltration properties (permeability and effective diffusivities). Comparisons are made to popularly-assumed structure functions and the standard, Kozeny–Carmen porous media model commonly employed in modeled CFD simulations of CVI. The virtual DNS experiments reveal a Thiele modulus and preform geometry (fabric layup) dependence which the existing microstructural and infiltration models are not able to describe throughout the entire densification process. The DNS-based, woven geometry-specific correlations can be applied directly to mean-field, furnace-scale CFD simulations.     

Reactive melt infiltration fabrication of C/C-SiC composite: Wetting and infiltration

Reactive melt infiltration is a fast and economical fabrication process for high performance C/C-SiC composite. In order to help understanding reactive melt infiltration production of C/C-SiC composite by liquid silicon, wetting and infiltration of the porous C/C composite preform by liquid silicon were investigated using a sessile drop technique. The contact angle decreased with the increase of time while the drop base diameter increased. According to the variation of drop base diameter and contact angle as a function of time, four different stages corresponding to the interfacial reaction and infiltration of liquid silicon were identified during wetting of the porous C/C composite preform by the liquid silicon. The infiltration height based on wetting curve linearly increased with time, much smaller than that calculated according to Washburn equation, which strongly indicated the reaction control of silicon infiltration.     

Technique for Monitoring Densification during Chemical Vapor Infiltration

A new technique for studying the progression of densification during the fabrication of composites by chemical vapor nfiltration is presented. The preparation of a carbon-matrix composite was investigated by momentarily inter-rupting, at various times, the carbon infiltration process to permit deposition of very thin layers of SiC. Microscopic examination of these layers on a polished cross section per-mitted determination of the extent of infiltration at various locations within the preform as a function of infiltration time. The technique also distinguishes open from closed pores and provides information on the existence of temperature gradients within the preform.