Preparation,modification, and coating for carbon-bonded carbon fiber composites: A review

Carbon-bonded carbon fiber (CBCF) composites are considered as one of the most promising candidates in thermal insulation applications owing to their lightweight, low thermal conductivity, and high temperature resistance. Nevertheless, it is frustrating that CBCF composites exhibit inferior mechanical properties and oxidation resistance, which remains a significant challenge for their application. Matrix modification and coating technology have been proven to be effective methods to address these problems. In this paper, the preparation methods and performance of CBCF are firstly reviewed. Then, the preparation and performance of modified and coated CBCF composites are introduced in detail. Finally, the contents of this article are concluded and the outlooks for future research directions are proposed.     

Super-elastic carbon-bonded carbon fibre composites impregnated with carbon aerogel for high-temperature thermal insulation

A novel super-elastic carbon fibre composite was prepared by impregnating carbon aerogel into carbon-bonded carbon fibre (CBCF) through vacuum impregnation. The compressive strength of CBCF-CA was increased to 1.24?MPa in the z-direction, which was 6-fold more than that of neat CBCF. The CBCF-CA spontaneously recovered its size and shape without significant deformation when the pressure was released. The thermal conductivity of CBCF-CA was 0.246?W?(m·K)^?1 at 1400°C in the z-direction, which is lower than that of CBCF (0.341?W?(m·K)^?1). The average electromagnetic interference shielding e?ectiveness of CBCF-CA composites in the range of 12.4–18?GHz was higher than 40?dB, suggesting an absorption-dominant shielding feature. The CBCF-CA composite will be a new multifunctional material due to its low density, low thermal conductivity, high specific strength, excellent processability, super-elastic property and high electromagnetic shielding, which can be used for thermal insulation and protection of aerospace.     

Preparation and mechanical behaviors of SiOC-modified carbon-bonded carbon fiber composite with in-situ growth of three-dimensional SiC nanowires

Carbon-bonded carbon fiber (CBCF) composites are novel and important high-temperature insulation materials owing to their light weight, low thermal conductivity and high fracture tolerance. To further improve the mechanical property of CBCF composite, we propose a three-dimensional (3D) SiC nanowires structure, which is in situ grown on a CBCF matrix via directly annealing silicon oxycarbide (SiOC) ceramic precursor. The synthesized multiscale reinforcements including microscale SiOC ceramics and nanoscale SiC nanowires are mainly attributed to the initial phase separation of SiOC phase and subsequent solid-phase reaction of SiO and C phases. Compared to SiOC/CBCF composite, the resulting 3D SiC nanowires/SiOC/CBCF hybrid structure exhibited high flexural/tensile strength and fractured strain due to the pull-out and bridging behavior of SiC nanowires. This one-step process supplied a feasible way to synthesize 3D SiC nanowires to reinforce and toughen SiOC-modified CBCF composite.     

Microstructural and compositional characterisation of the pyrocarbon interlayer in SiC coated low density carbon/carbon composites

SiC coated carbon bonded carbon fibre (CBCF) composites, a special class of carbon/carbon composites for thermal insulation, were investigated. Successful deposition of SiC requires the CBCF material to be first given a pyrocarbon coating. SiC coating on pyrocarbon coated CBCF was assessed using several analytical techniques. X-ray diffraction identified the coating as β SiC. The fibre orientation in two perpendicular planes was determined using X-ray microtomography, and it was found to be random in one plane whereas there was a preferred orientation in the other plane. A comparison was made between the uncoated and pyrocarbon coated substrates in terms of surface roughness, purity and crystallinity, using white light interferometry, neutron activation analysis/secondary ion mass spectrometry and transmission electron microscopy, respectively. The higher roughness, greater purity and increased levels of crystallinity of pyrocarbon coated CBCF are considered to be responsible for the successful deposition of a SiC coating on this material.     

Light‐weight thermal insulating fly ash cenosphere ceramics

Light weight fly ash cenosphere (FAC) ceramic composites were developed by simple slip casting method. Thermal properties, Bulk density, Microstructure, flexural strength, and phase analysis of the FAC ceramic composites were measured. The results proved that the FAC have ability to lower bulk density and thermal conductivity effectively. The lowest thermal conductivity achieved for FAC ceramic composites (0.27 W/m.K) was further reduced 0.21 W/m.K by adding combustible additives ie activated charcoal and corn starch. The flexural strength, bulk density and thermal conductivity of FAC ceramic composites reduced consistently with an increase in FAC content. The maximum flexural strength of 13.45 MPa was achieved with 50% FAC and the minimum flexural strength of 4.07 MPa was obtained with 80% FAC. The open porosity increased from 35.51% to 43.76% and 38.19% with an addition of 15% activated charcoal and corn starch, respectively, when compared to no additives. The bulk density of 699, 619, and 675 kg/m³ was achieved with 80% FAC, 80% FAC with the addition of 15% activated charcoal and corn starch, respectively. The 80% FAC ceramic composite shows low thermal expansion coefficient 6.54 × 10^?6/°C at the temperature of 50°C then it varies between 3.7 and 5 × 10^?6/°C in the temperature range above 100°C. These results prove that the developed light weight FAC ceramic are excellent low‐cost thermal insulating materials.     

Continuous carbon fiber reinforced ZrB2-SiC composites fabricated by direct ink writing combined with low-temperature hot-pressing

As one of additive manufacturing techniques, direct ink writing has significant advantages in the manufacture of ceramic matrix composites, nevertheless, the poor impregnability of ceramic slurry makes it difficult to fill the interior of fiber bundles, causing poor mechanical properties. Here, ultrasound-assisted fiber separation technique was introduced to impregnate ceramic slurry with a continuous carbon fiber bundle during direct ink writing of continuous carbon fiber/ceramic green body and subsequent low temperature hot-pressing was combined to improve its robustness. Suitable thickness of carbon coating could bring to high fracture resistance, whereas excessively thick carbon coating will adversely affect the mechanical properties. A carbon interface with thickness around 110 nm was incorporated, the flexural strength, fracture toughness and work of fracture of C_f/ZrB₂-SiC composite reached 388.3 MPa, 10.04 MPa·m^1/2 and 2380 J/m², respectively. Therefore, direct ink writing combined with low temperature hot-pressing, was effective to fabricate high-performance ceramic matrix composites.     

Protective coatings for carbon bonded carbon fibre composites

Carbon bonded carbon fibre composites (CBCF) were modified by direct reaction with molten silicon in order to obtain a silicon carbide layer on the composite surface. Subsequently, the Si-infiltrated CBCF material was coated with a silica-based glass containing yttria and alumina by means of a slurry-dipping technique. On heat treatment the glass yielded a glass-ceramic layer thus giving a multi-layered oxidation and erosion protection system. The microstructural characterisation of the coating was conducted by standard microscopy techniques and by X-ray diffraction. The controlled crystallization of the glass-produced cristobalite, yttrium silicate (Y₂Si₂O₇, keiviite, β-form) and mullite as main crystalline phases. These are excellent ceramic materials for oxidation and erosion protection of SiC-coated carbon-based composites since their coefficients of thermal expansion (CTE) closely match that of SiC. The possibility of healing (closure) of micro cracks by a thermal treatment at 1375 °C, thus exploiting the viscous flow of the residual glass in the glass-ceramic, was explored in order to extend the service life of the protection system.     

Additive manufacturing of Csf/SiC composites with high fiber content by direct ink writing and liquid silicon infiltration

Direct ink writing (DIW) provides a new route to produce SiC-based composites with complex structure. In this study, we additive manufactured short carbon fiber reinforced SiC ceramic matrix composites (Csf/SiC composites) with different short carbon fiber content through direct ink writing combined with liquid silicon infiltration (LSI). The effects of short carbon fiber content on the microstructure and mechanical properties of the DIW green parts and the final Csf/SiC composites were investigated. The results showed that the Csf content played an important role in maintaining the structure of the green parts. As the Csf content increases, the dimension deviation ratio of the sample decreased at all stages. With the Csf content of 40 vol%, the final Csf/SiC composite had low free Si content and high β-SiC content. The maximum density, tensile strength and bending strength of the Csf/SiC composites were 2.88 ± 0.06 g/cm³, 53.68 MPa and 253.63 MPa respectively. It is believed that this study can give some understanding for the additive manufacturing of fiber reinforced ceramic matrix composites.     

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.     

Biomimetic cellular-structured MCMB@WC composites with excellent mechanical properties

Inspired by the unique structures of plant cells, tungsten carbide (WC, cytoderm) coated mesocarbon microbeads (MCMB, cytoplasm) powders were prepared by molten salt synthesis, which were then densified by spark-plasma sintering to obtain the biomimetic cellular-structured MCMB@WC composites. The in-situ formed WC cytoderm significantly contributed to the densification of the composites. Additionally, the formation of periodically arranged hard-soft architecture and perfect MCMB/WC interface bonding enhanced the mechanical properties significantly. The composite with WC concentration of 53 vol% exhibited the maximal bending strength and fracture toughness of 446 MPa and 4.48 MPa m^1/2, respectively. The developed biomimetic ceramic/graphite composites with excellent mechanical properties are expected to be applied in aerospace and other industries.     

A low-temperature prepared composite coating to protect SiC-coated C/C composites against oxidation in a wide temperature range for long-life service

To improve the oxidation resistance of carbon/carbon (C/C) composites in a wide temperature range (1173–1773 K), a composite coating containing rich B₂O₃ glass was prepared on SiC-coated C/C composites by slurry dipping-densifying at low temperature. Borosilicate and SiO₂ glasses acted as oxygen barriers at low and medium-high temperatures, respectively. Besides, Hf-oxides (HfO₂, HfSiO₄) ceramic particles improved the thermal stability of the glass and enhanced the crack resistance of glass layer. Therefore, the composite coating can effectively protect C/C composites against oxidation for 403 h at 1173 K, 723 h at 1473 K and 403 h at 1773 K with the mass gain of 3.77 g·m⁻², 21.41 g·m⁻² and 0.42 g·m⁻², respectively. After 50 times thermal cycles between room temperature and 1773 K, the mass gain of the coated sample was 3.95 g·m⁻² and the mass retention rate was up to 98.19 % during the thermos-gravimetric test from room temperature to 1773 K.     

Three-dimensional micro-pipelines high thermal conductive C/SiC composites

Carbon/silicon carbide (C/SiC) composites are usually regarded as thermal protective system materials and widely applied in hypersonic vehicles or ramjet. However, poor thermal conductivity of C/SiC composites, leading to severe heat concentration and thermal stress during the high-speed operation of hypersonic vehicle, limits their broad-range of practical applications. Modification with high thermal conductive fillers is an optional method; however, controllable dispersion and orientation of the fillers to construct continuous and ordered heat conductive channel has been proven to be a challenging task. Herein, based on high thermal conductivity fibers, a three-dimensional micro-pipeline preform was developed for the preparation of structure–function integrated C/SiC composites. The technical feasibility of the method, the characteristics of microstructures, and the thermal conductivity and bending strength of the as-obtained composites were systematically studied. Results revealed that the thermal conductivities of as-obtained composites reached 150.2 and 46.7 W m⁻¹ K⁻¹ for in-plane and out-of-plane direction, respectively. The bending strength obtained herein is 264.4 MPa, which is lower than that of polyacrylonitrile C/SiC composites. However, the fine control over the component and microstructure or densification could provide a higher value in the future research. In sum, the proposed method provides a convenient and feasible approach to prepare high thermal conductive C/SiC composites.     

Fiber Reinforced Polyimide Aerogel Composites with High Mechanical Strength for High Temperature Insulation

Glass fiber/polyimide aerogel composites are prepared by adding glass fiber mat to a polyimide sol derived from diamine, 4,4′‐oxydianiline, p‐phenylene diamine, and dianhydride, 3,3′,4,4′‐biphenyltetracarboxylic dianhydride. The fiber felt acts as a skeleton for support and shaping, reduces aerogel shrinkage during the preparation process, and improves the mechanical strength and thermal stability of the composite materials. These composites possess a mesoporous structure with densities as low as 0.143–0.177 g cm^?3, with the glass fiber functioning to improve the overall mechanical properties of the polyimide aerogel, which results in its Young's modulus increasing from 42.7 to 113.5 MPa. These composites are found to retain their structure after heating at 500 °C, in contrast to pure aerogels which decompose into shrunken ball‐like structures. These composites maintain their thermal stability in air and N₂ atmospheres, exhibiting a low thermal conductivity range of 0.023 to 0.029 W m^?1 K^?1 at room temperature and 0.057to 0.082 W m^?1 K^?1 at 500 °C. The high mechanical strengths, excellent thermal stabilities, and low thermal conductivities of these aerogel composites should ensure that they are potentially useful materials for insulation applications at high temperature.     

Preparation of low residual silicon content Si-SiC ceramics by binder jetting additive manufacturing and liquid silicon infiltration

Complex silicon carbide (SiC) ceramic components are difficult to fabricate due to their strong covalent bonds. Binder jetting (BJ) additive manufacturing has the outstanding advantages of high forming efficiency and no thermal deformation, especially suitable for printing complex structure SiC components. This study tried to obtain low silicon content silicon carbide ceramics by binder jetting followed by phenolic resin impregnation and pyrolysis (PRIP) and liquid silicon infiltration (LSI). BJ was used for the SiC green parts fabrication, and the highest compressive strength (7.7 ± 0.3 MPa) and lowest dimensional deviations (1.2–1.6 mm) were obtained with the printing layer thickness of 0.15 mm. Subsequently, PRIP treatments were introduced to increase the carbon content for the following LSI process. As the number of PRIP cycles increased, the carbon density of SiC/C preform increased and the porosity decreased. After the LSI treatment, the final Si-SiC composites processed with 2 PIRP cycles reached the highest flexural strength (257 ± 14.26 MPa) and the best wear resistance. This was attributed to the low residual silicon content (10.2 vol%) and almost no residual carbon. Furthermore, several complex structural components were fabricated using these methods. The preparation of complex components verifies the feasibility of BJ and LSI for manufacturing high-strength and high-precision SiC ceramics. Besides, this work hopes to provide technical guidance for the preparation of complex SiC composites in the future.     

Additive manufacturing of continuous carbon fiber–reinforced silicon carbide ceramic composites

A material extrusion (MEX) technology has been developed for the additive manufacturing of continuous carbon fiber–reinforced silicon carbide ceramic (C_f/SiC) composites. By comparing and analyzing the rheological properties of the slurries with different compositions, a slurry with a high solid loading of 48.1 vol% and high viscosity was proposed. Furthermore, several complex structures of C_f/SiC ceramic composites were printed by this MEX additive manufacturing technique. Phenolic resin impregnation–carbonization process reduces the apparent porosity of the green body and protects the C_f. Finally, the reactive melting infiltration (RMI) process was used to prepare samples with different C_f contents from 0 to 2 K (a bundle of carbon fibers consisting of 1000 fibers). Samples with C_f content of 1 K show the highest bending strength (161.6 ± 10.5 MPa) and fracture toughness (3.72 ± 0.11 MPa·m^1/2) while the thermal conductivity of the samples with the C_f content of 1 K reached 11.0 W/(m·K). This study provides a strategy to prepare C_f/SiC composites via MEX additive manufacturing and RMI.     

Preparation of an environment-friendly LTCC material by using waste soda-lime glass and natural volcanic ash

Glass/ceramic composites applied in the field of low-temperature co-fired ceramics (LTCC) were successfully prepared at 670–710 °C by using waste soda-lime glass (WG) as a binder and natural volcanic ash as a ceramic raw material. Based on the theories of suppression and supplementary network effects, alkaline-earth metal ions (R²⁺, R = Mg, Ca, Sr, and Ba) and B₂O₃ were applied to improve the dielectric properties of WG and composites, respectively. The influence of R²⁺ on the crystal phase evolution, microstructure, mechanical, dielectric, and thermal properties of WG-volcanic ash-based composites were systematically investigated. By doping 2.5 wt% Ba²⁺ to the environment-friendly LTCC composites, physical properties i.e., ε_r of 4.86 at 1 MHz, tan δ of 6.32 × 10^?3, coefficient of thermal expansion of 8.72 × 10^?6/°C, and thermal conductivity of 1.04 W/(m·K) are obtained. It is worth mentioning that the environment-friendly LTCC composite uses WG with a low glass transition temperature to reduce the sintering temperature and a tiny amount of a modifier to adjust the dielectric performance instead of synthesizing specific crystals by adding lots of chemical reagents. These, in turn, do not only have the potential to be used in the LTCC packaging technology but also have significance for sustainable development. Additionally, because of good chemical compatibility between aluminum and the composites, the environment-friendly LTCC composites with ultra-low sintering temperature have the potential ability to lower the cost of LTCC packaging materials.     

Additive manufacturing of continuous carbon fiber reinforced high entropy ceramic matrix composites via paper laminating,direct slurry writing,and precursor infiltration and pyrolysis

In this study, continuous carbon reinforced C_f/(Ti_0.2Zr_0.2Hf_0.2Nb_0.2Ta_0.2)C–SiC high entropy ceramic matrix composites were additively manufactured through paper laminating (PL), direct slurry writing (DSW), and precursor infiltration and pyrolysis (PIP). (Ti_0.2Zr_0.2Hf_0.2Nb_0.2Ta_0.2)C high entropy ceramic (HEC) powders were synthesized by pressureless sintering and ball milling. A certain proportion of HEC powder, SiC powder, water, binder, and dispersant were mixed to prepare the HEC-SiC slurry. Meanwhile, BN coating was prepared on the 2D fiber cloth surface by the boric acid-urea method and then the cloth was cut into required shape. Additive manufacturing were conducted subsequently. Firstly, one piece of the as-treated carbon fiber cloth was auto-placed on the workbench by paper laminating (PL). Then, the HEC-SiC slurry was extruded onto the surface of the cloth by direct slurry writing (DSW). PL and DSW process were repeated, and a C_f/HEC-SiC preform was obtained after 3 cycles. At last, the preform was densified by precursor infiltration and pyrolysis (PIP) and the final C_f/HEC-SiC composite was prepared. The open porosity of the C_f/HEC-SiC composites, with the HEC volume fractions of 15, 30 and 45%, were 7.7, 10.6, and 11.3%, respectively. And the density of the C_f/HEC-SiC composites, with the HEC volume fractions of 15, 30 and 45%, were 2.9, 2.7 and 2.3 g/cm³, respectively. The mechanical properties of the C_f/HEC-SiC composites increased firstly and then decreased with the HEC content increase, reaching the maximum value when the HEC volume fraction was 30%. The mechanical properties of the C_f/HEC-SiC composites containing 45, 30 and 15% HEC were as follows: flexural strength (180.4 ± 14 MPa, 183.7 ± 4 MPa, and 173.9 ± 4 MPa), fracture toughness (11.9 ± 0.17 MPa m^1/2, 14.6 ± 2.89 MPa m^1/2, and 11.3 ± 1.88 MPa m^1/2), and tensile strength (71.5 ± 4.9 MPa, 98.4 ± 12.2 MPa, and 73.4 ± 8.5 MPa). From this study, the additive manufacturing of continuous carbon fiber reinforced high entropy ceramic matrix composites was achieved, opening a new insight into the manufacturing of ceramic matrix composites.     

Tribological behavior of carbon fiber reinforced ZrB2 based ultra high temperature ceramics

The tribological behavior of ultra-high temperature ceramic matrix composites (UHTCMCs) was investigated to understand these materials in friction applications. Samples consisting of pitch-based randomly orientated chopped carbon fiber (CF) reinforced ZrB₂-10 vol% SiC were prepared (ZS). The tribological behavior was tested on a self-designed dynamometer, coupling the UHTCMC pads with either carbon fiber reinforced carbon−silicon carbide (C/C-SiC) or steel disks, with two applied contact pressures (1 and 3 MPa) and the surface microstructures were analyzed to unravel the wear mechanisms. Even at high mechanical stresses, tests against the C/C-SiC disk showed stable braking performance and wear. The abraded material from a steel disk formed a stable friction film by fusing together harder pad particles with abraded steel, which reduced wear and stabilized the braking performance. The high values of coefficient of friction obtained (0.5–0.7), their stability during the braking and the acceptable wear rate make these materials appealing for automotive brake applications.     

Low dielectric loss LNT/PEEK composites with high mechanical strength and dielectric thermal stability

(3-Aminopropyl)triethoxysilane treated La_(2−x)/3Na_0.06TiO₃ (x = 0.06) (LNT) microparticles filled polyetheretherketone (PEEK) composites were prepared using hot pressing process. The effects of variation of LNT ceramic filling fraction on dielectric properties, water absorption, thermal stability and mechanical strength were investigated. All composites demonstrate low water absorption (less than 0.4%) when the ceramic filling fraction is lower than 0.6V_f. The obtained composites exhibited dielectric permittivities varying from ~4 to ~22 as the ceramic fillers increased from 0.1 to 0.8V_f and low losses (~10⁻⁴ @1 MHz, 3~5 × 10⁻³ at the frequencies of microwave (10 GHz) and millimeter wave (29-50 GHz), respectively). The mechanical strength, dimensional and dielectric thermal stability of the composite are remarkably improved by the addition of LNT ceramic fillers. A composite with near zero temperature coefficients of dielectric permittivity or resonant frequency and flexural strength of ~140 MPa could be obtained. The out-of-plane coefficient of thermal expansion (CTE) could be reduced to ~20 ppm/°C as the ceramic filler loading reached 0.7V_f.     

Mechanical properties of hybrid composites prepared by ice-templating of alumina

Ceramic-polymer hybrid composites are often designed for its high strength and low density. Ice-templating (freeze casting) is a promising method for preparation of such composites. However, the most of the reported mechanical properties were gained from a small volume of material. In this work 70 cm³ of the lamellar composite with lamella length, up to 70 mm was prepared by ice-templating followed by polymer infiltration. The volume of ceramic (alumina) in starting suspensions was varied from 25 to 45 vol.% and the same manufacturing process was applied. The fracture toughness and flexural strength were determined on prepared beams from plates by loading in bending. The fractographic analysis conducted on the fracture surfaces and obtained mechanical properties demonstrated that an optimal strength/density ratio lies between 51 and 55% of alumina volume fraction. The density ranking from 2.6 to 2.8 cm⁻³ of these composites results in values of Weibull strength above 110 MPa.