Carbon fiber reinforced ultra-high temperature ceramic matrix composites: A review

Recent studies on carbon fiber-reinforced ultra-high temperature ceramic matrix (C/UHTC) composites fabricated by hot-pressing, chemical vapor infiltration, polymer impregnation and pyrolysis, and melt infiltration (MI) are reviewed. Various efforts have been made to improve these preparation processes and to combine two or more of these because they have both the advantages and disadvantages in terms of the processing time, operating temperature, and the porosity of the resulting C/UHTC composites. In addition, the parameters governing the fracture toughness, thermal conductivity, and recession behavior (in oxidizing environments) of these composites have been discussed. This review demonstrates that C/UHTC composites with Zr- or Hf-based UHTC matrices fabricated via MI are potential candidates for advanced heat-resistant structural materials.     

Research and application prospect of short carbon fiber reinforced ceramic composites

With the advantage of high temperature resistance, low expansion, low density and excellent thermal stability, carbon fiber reinforced ceramic composites have a very wide range of applications in aerospace, military, energy, chemical industries and transportation. Short carbon fiber reinforced ceramic composites are characterized by simple processes, low manufacturing costs, short preparation times and automated production, can be used in fields such as friction materials and thermal protection system. This paper reviews the current status and recent advances in research on homogenization techniques, mechanical properties, thermal properties and frictional properties of short carbon fiber reinforce ceramic composites. Different processing routes for short carbon fiber reinforced ceramic composites, including reactive melt infiltration (RMI), hot pressing (HP), spark plasma sintering (SPS) and pressureless sintering, the advantages and drawbacks of each method are briefly discussed. The future development direction of low-cost manufacturing short carbon fiber reinforced ceramic composites is prospected.     

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.     

Carbon fiber/reaction-bonded carbide matrix for composite materials – Manufacture and characterization

The processing of self-healing ceramic matrix composites by a short time and low cost process was studied. This process is based on the deposition of fiber dual interphases by chemical vapor infiltration and on the densification of the matrix by reactive melt infiltration of silicon. To prevent fibers (ex-PAN carbon fibers) from oxidation in service, a self-healing matrix made of reaction bonded silicon carbide and reaction bonded boron carbide was used. Boron carbide is introduced inside the fiber preform from ceramic suspension whereas silicon carbide is formed by the reaction of liquid silicon with a porous carbon xerogel in the preform. The ceramic matrix composites obtained are near net shape, have a bending stress at failure at room temperature around 300 MPa and have shown their ability to self-healing in oxidizing conditions.     

The thermal shock behaviour of ductile particle toughened alumina composites

Over recent years, it has been established that the incorporation of metallic particles into a ceramic matrix can lead to enhanced fracture properties. Relatively few attempts, however, have been made to establish whether or not the improved fracture toughness typically observed in such composite systems can offer improved performance in demanding environments. The current study is concerned with the thermal shock behaviour of a ceramic matrix composite consisting of an alumina matrix containing 20 vol% of discrete iron particles. The composite material has been produced by both hot pressing and conventional sintering techniques. The hot pressed composite shows a greater resistance to thermal shock than the monolithic matrix, both in terms of the critical temperature differential and retained strength, whereas the sintered material has been found to behave as a typical low strength refractory ceramic. The calculation of thermal shock resistance parameters for the composites and the monolith has indicated possible explanations for the differences in thermal shock behaviour.     

The fracture properties of metal-ceramic composites manufactured via stereolithography

In this work, metal-ceramic composite parts based on aluminum and alumina were manufactured in a two-stage process. First, silica was printed using a vat photopolymerization technique, followed by a curing and sintering stage, which resulted in ceramic precursors. Subsequently, these samples were subjected to a metal infiltration process to form interpenetrating metal-ceramic composites (IPCs). These composites have attracted considerable attention in the aerospace and defense sector due to the ductility associated to the metal phase and the strength offered by the ceramics. A novel application with utility includes composite tooling which requires a low coefficient of thermal expansion (CTE) for high temperatures. The investigated specimens were tested for surface quality and shrinkage, followed by a mechanical characterization. It was recorded that the samples presented a 12%–18% of shrinkage after the sintering process. The mechanical testing showed that the hardness, compression, and flexural strength of the composites were superior to the printed and sintered ceramics. A thermal analysis on the composite showed that its CTE is more than two times lower than the common composite tooling materials. It is expected that the present work can provide the foundations for further studies on these systems in the refractory, automotive, and armor-based fields.     

Physical properties of graphite/aluminium composites produced by gas pressure infiltration method

Graphite/aluminium composites have been produced by means of gas pressure infiltration method. Two porous graphite preforms with a porosity of 10 and 13 vol%, respectively, have been infiltrated using either a commercially 99.85 pure aluminium or an AlSi7Mg alloy. Thermal expansion coefficient, electrical conductivity and flexural strength have been determined as a function of graphite preforms and metal matrices. To investigate the susceptibility of this composite system to thermal damage, specimens were thermally cycled between 60 and 300 °C up to 1020 cycles. Infiltrated graphites exhibited a significantly higher electrical conductivity (0.34-0.51 m/Ω mm²) compared to porous graphite preforms depending on graphite type and metal matrix. Thermal cycling did not influence electrical conductivity. The coefficients of thermal expansion of the composites were at least three times lower than for monolithic aluminium. Thermal cycling has reduced these values even more, most likely due to stress relaxation processes. The infiltration of porous graphite preforms with AlSi7Mg alloy or Al99.85 has increased the flexural strength of the composites resulting in values up to 105 MPa. The decrease in mechanical strength due to thermal cycling was about 10%.     

Progress in Processing and Performance of Porous-Matrix Oxide/Oxide Composites

All-oxide continuous fiber-reinforced ceramic matrix composites are enabling materials for high-temperature structural applications in oxidizing environments. However, their industrial use requires further improvements in material performance as well as a significant reduction of the processing costs. This article gives some insight into a novel colloidal processing route. A porous mullite matrix was designed to obtain damage-tolerant behavior as well as high-temperature long-term stability. Laminated composites were formed with conventional techniques similar to the manufacture of polymer matrix composites. This simple and low-cost process leads to homogeneous microstructures with improved material properties compared with the state of the art in continuous fiber-reinforced oxide/oxide composites. The developed composites in the present study exhibit favorable mechanical properties both at room temperature and after thermal aging for 1000 h at temperatures up to 1300°C.     

Directionally Solidified Boride and Carbide Eutectic Ceramics

Borides and carbides generally have outstanding hardness, excellent wear resistance, and high melting points due to their covalent bonding. Directionally solidified eutectic (DSE) composites of boride and carbide constituent phases have been investigated since the 1970s as an approach to produce dense composite microstructures with added control over the microstructure. A variety of DSE ceramic composites have been developed and evaluated as potential materials for structural and functional applications due to their unique thermo‐electro‐mechanical properties. Renewed interest over the past few decades has been motivated, in part, by the needs for ultrahigh‐temperature composites for aerospace applications along with low‐density composites for armor applications. Some directionally solidified boride and carbide DSEs exhibit advantages in material properties over monolithic materials. This study reviews historical and recent research on processing methods, microstructure, crystallography, and material properties (mechanical, electrical, thermal properties, and oxidation resistance) of directionally solidified boride and carbide eutectic ceramic composites. Opportunities along with current limitations and needs for future developments are also reviewed and discussed.     

Effects of phenolic resin contents on microstructures and properties of c/sic-diamond composites

In this paper, C/SiC-diamond composites were obtained by chemical vapor infiltration (CVI) and reactive melt infiltration (RMI), and the effects of phenolic resin contents on the microstructures and properties of as-obtained C/SiC-diamond composites were studied. The results suggested a significant influence of phenolic resin contents on the pore structure of the composites before reactive melt infiltration (RMI), as well as phase composition and density of the matrix after RMI. The mechanical properties of composites were shown to correlate with the threshold effect of phenolic resin. Sample R5 prepared with high phenolic resin contents displayed significantly declined mechanical properties. On the other hand, adjustment of the phenolic resin content yielded samples with maximum room temperature thermal conductivity reaching 14.75 W/(m·K). The theoretical thermal conductivity of the composites calculated by the Hasselman-Johnson (H-J) theoretical model was estimated to 24.52 W/(m·K). Overall, the increase in phenolic resin content led to unreacted diamond-C regions and the formation of substantial porosity. These features reduced the thermal conductivity of the resulting C/SiC-diamond composites.     

Thermal stability and ablation properties study of aluminum silicate ceramic fiber and acicular wollastonite filled silicone rubber composite

The thermal stability and ablation properties of silicone rubber filled with silica (SiO₂), aluminum silicate ceramic fiber (ASF), and acicular wollastonite (AW) were studied in this article. The morphology, composition, and ablation properties of the composite were analyzed after oxyacetylene torch tests. There were three different ceramic layers found in the ablated composite. In the porous ceramic layer, the rubber was decomposed, producing trimers, tetramers, and SiO₂. ASF and part of AW still remained and formed a dense layer. The SiO₂/SiC filaments in the ceramic layer reduced the permeability of oxygen, improving the ablation properties of the composites. The resultant ceramic layer was the densest, which acted as effective oxygen and heat barriers, and the achieved line ablation rate of the silicone composite were optimum at the proportion of 20 phr/40 phr (ASF/AW). Thermogravimetric analysis (TGA) confirmed that thermal stability of the composites was enhanced by the incorporation of ASF and AW. The formation of the ceramic layer was considered to be responsible for the enhancement of thermal stability and ablation properties. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39700.     

High strength TiC matrix Fe28Al toughened composites prepared by spontaneous melt infiltration

Fe28Al bound TiC matrix composites with TiC content of 75–90% in volume (vol.%) were successfully fabricated by spontaneous melt infiltration. Amounts of Fe28Al in excess and below the pore volume of the TiC preform were used for optimization of fabrication techniques. Young's modulus, hardness, flexural strength and fracture toughness of the composites were measured. Four-point bending strength of Fe28Al/90–75 vol.% TiC ranges to 990–1260 MPa. The high strength is attributed to the good infiltration ability of molten Fe28Al in the porous TiC preform and to processing refinements. TiC preform pre-sintering and indirect infiltration all lead to fully dense and defect-free composites. The relationship between Vickers hardness and indentation fracture toughness and the dependence of mechanical properties on microstructure of the composites were also studied. Results of SEM and XRD analysis show TiC and Fe28Al as the only crystalline phases of the composite. Fe28Al ligaments have ductile behaviour and greatly toughen the composites. Crack front deviation during fracture also increased the fracture resistance of the composites.     

A study on the effect of cenosphere on thermal and ablative behavior of cenosphere loaded ceramic/phenolic composites

Composites of ceramic woven and phenolic resin filled with cenosphere were prepared and their thermal properties and ablative properties were studied by Thermogravimetric Analysis (TGA) and oxyacetylene ablation test. Classical thermal stability parameters, based on initial decomposition temperature and mass loss at various temperatures were calculated before and after subtraction of cenosphere concentration from the TGA curves. Ablation behavior of the filled composites were investigated based on the linear ablation rate, mass ablation rate and back face temperature profiles. Without cenosphere mass subtraction, the thermal stability of the filled composites seems to be improved and reduction of mass loss was achieved with addition of cenosphere. Ablation results showed that the addition of cenosphere content exhibits the favorable ablation resistance. In comparison to neat ceramic/phenolic composites, the introduction of micro sized cenosphere particles embedded in the phenolic matrix significantly improved the ablative properties in terms of mass ablation rate and linear ablation rate.     

Zirconium-diboride silicon-carbide composites: A review

Zirconium diboride (ZrB₂) and silicon carbide (SiC) composites have long been of interest since it was observed that ZrB₂ improved the thermal shock resistance of SiC. However, processing of these materials can be difficult due to high and different sintering temperatures and differences in the thermodynamic stability of each material. ZrB₂–SiC composites have been processed in a variety of ways including hot-pressing, spark-plasma sintering, reactive melt infiltration, pack cementation, chemical vapor deposition, chemical vapor infiltration, stereolithography, direct ink writing, selective laser sintering, electron beam melting, and binder jet additive manufacturing. Each manufacturing method has its own pros and cons. This review serves to summarize more than 60 years of research and provide a coherent resource for the variety of methods and advancements in development of ZrB₂–SiC composites.     

Ceramic dies selection for electrical resistance sintering of metallic materials

Processing metallic powders by electrical resistance sintering requires the use of insulating ceramics dies. Selecting the appropriate ceramic material according to the electrical, thermal and mechanical properties is a need. Dies produced with several ceramic materials have been tested during the production of cemented carbide in order to check their behaviour in the process and final product properties. Tialite/mullite, zircon/mullite, zirconium phosphate based ceramic, yttria-stabilized zirconia and sialon, in most cases with modified compositions and shaping processes in order to achieve a high density, have been tested. Dry powder processing by cold isostatic pressing and furnace sintering resulted to be the better process for dies production. The effect of die properties on the produced cemented carbide, and the behaviour and life of the die during the production have been analysed. Very smooth die surface increases the number of cycles withstood during metallic parts production, because of lower extraction stresses, as checked for sialon dies. Zirconium phosphate based dies, with low thermal conductivity, show the most densified hard metal parts surface.     

Effects of low-temperature treatment on the properties of commercial preceramic polymers

Low-temperature, pre-gelation, thermal treatment of ceramic precursors is a common preliminary step in the polymer infiltration-and-pyrolysis-based processing of ceramic matrix composites (CMCs). A variety of polymer properties can be modified using this approach, the most important being molecular weight distribution, viscoelastic state, solidification behavior, and ceramic yield. In this work, the effects of thermal treatment on the processing properties of two commercial preceramic polymers, StarPCS™ SMP-10 and KiON Ceraset® PSZ-20, have been investigated. It was determined that the volatilization, molecular chain scission, and polymerization phenomena occurring during treatment, lead to increased viscosity, higher molecular weight, lower temperature of solidification onset, and improved ceramic yield. A wide range of tailorable viscoelastic states was obtained, and allowed the formation of continuous polymer filaments. Understanding the nature and effect of these modifications on the processing state can improve the current state of CMC processing, and open novel processing routes for constituent development.     

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.     

Thermal conductivity studies on Si/SiC ceramic composites

Ceramic heat exchangers are increasingly used in many nuclear power plants. Silicon carbide has been treated as a promising material for heat exchanger application since it has good thermal conductivity and corrosion resistance. In this work, four different types of Si/SiC ceramic composites were prepared by liquid silicon infiltration technique. Thermal conductivities of these ceramic composites at different temperatures are measured by the laser flash thermal conductivity method. Results show that the presence of free carbon and voids are notably affecting the thermal conductivity of these materials.     

The effect of processing conditions on the microstructure and impact behavior of melt infiltrated Al/SiCp composites

In the current research, pressureless melt infiltration (PMI) was applied to study the effect of different processing conditions on the final properties of Al/SiC composites, fabricated through the infiltration of aluminum melt into SiC particulates porous preforms. Charpy impact test was used to explore the impact behavior of the Al/SiC composites, obtained from variable processing conditions. Conducting the process at a higher infiltration temperature (1350 °C) increased the final relative density of composites up to the value of 0.97 of theoretical density (TD). The application of a post sintering procedure in nitrogen atmosphere after the completion of infiltration resulted in a slight increase (∼1) in the final density of composites compared to the only infiltrated ones. Instead, the final density of argon sintered composites has undergone a 0.41% reduction. This can be originated from the occurrence of chemical reactions in the N₂ atmosphere resulting in the formation of consequent phases, contrary to the argon neutral gas. Results concerning with the impact resistance demonstrated a remarkable superiority for the impact energy of the composites subjected to the combined infiltration and sintering (MIS) procedure compared to the infiltrated ones. While such an observation was found to be identical through sintering in both atmospheres, the appearance of brittle phases formed through sintering procedure in nitrogen gave rise to higher impact energy for the argon sintered composites.     

Dielectric,Mechanical, and Thermal Properties of Low-Permittivity Polymer–Ceramic Composites for Microelectronic Applications

A new low-permittivity polymer–ceramic composite for packaging applications has been developed. The ceramic-reinforced polyethylene and polystyrene composites were prepared by melt mixing and hot molding techniques. Low-loss, low-permittivity Li₂MgSiO₄ (LMS) ceramics prepared by the solid-state ceramic route were used as the filler to improve the dielectric properties of the composites. The relative permittivity and dielectric loss were increased with the increase in the ceramic loading at radio and microwave frequencies. The mechanical properties and thermal conductivity of the Li₂MgSiO₄-reinforced polymer–ceramic composite were also investigated. The stability of the relative permittivity of polymer–ceramic composites with temperature and frequency was investigated. The experimentally observed relative permittivity, thermal expansion, and thermal conductivity were compared with theoretical models.