Oxidation protection of carbon/carbon composites with SiC/indialite coating for intermediate temperatures

In order to improve the oxidation resistance of carbon/carbon composites at intermediate temperatures, a novel double-layer SiC/indialite coating was prepared by a simple and low-cost method. The internal SiC transition layer was prepared by pack cementation and the external indialite glass–ceramic coating was produced by in situ crystallization of ternary MgO–Al₂O₃–SiO₂ glass. The microstructures and morphologies of coating were determined by scanning electron microscopy (SEM), X-ray diffraction (XRD) and energy dispersive spectroscopy (EDS). Oxidation resistance of the as-coated C/C composites was evaluated in ambient air at temperature from 800 °C to 1200 °C. Nearly neglectable mass loss was measured after 100 h isothermal oxidation test, indicating that SiC/indialite coating possesses excellent oxidation protection ability. The as-coated samples have a good thermal shock resistance and no obvious damage was found in the coating even after suffered more than 11 thermal cycles between test temperature and room temperature. The oxidation protection mechanism of this coating was also discussed.     

SiOC modified carbon-bonded carbon fiber composite with SiC nanowires enhanced interfibrous junctions

Carbon-bonded carbon fiber (CBCF) composites are promising lightweight and high efficient thermal insulators to be applied in aerospace area, but their practical applications are usually restricted by the low mechanical performance and poor oxidation resistance. To overcome these drawbacks, many efforts have been made in the fabrication of ceramic coated CBCF composites. However, the densities of these modified composites are usually very high, which would result in the reduction in their thermal insulation performance. Herein, we prepared a CBCF composite with SiC nanowires enhanced interfibrous junctions and SiOC ceramic coated carbon fibers (SiCNWs-SiOC-CBCF). Similar to CBCF, the SiCNWs-SiOC-CBCF exhibits a low density of 0.35 g/cm³ and an anisotropic and highly porous architecture. The SiCNWs-SiOC-CBCF possesses a compressive strength of 3.8 MPa and a compression modulus of 195.7 MPa in the X (or Y) direction, ~26.7% and 150% higher than those of CBCF respectively. It can also suffer from an isothermal treatment in air at 900°C for 120 minutes. The combination of these properties makes the SiCNWs-SiOC-CBCF a good candidate for thermal insulator to be applied in extreme conditions.     

Improved antioxidative and mechanical properties of SiC coated C/C composites via a SiO2-SiC reticulated layer

To improve the oxidation resistances of SiC coated C/C composites by a pack cementation (PC) method at high temperature and alleviate the siliconization erosion of molten silicon on C/C substrate during the preparation of SiC coating, a SiO₂-SiC reticulated layer with SiC nanowires was pre-prepared on C/C composites through combined slurry painting and thermal treatment before the fabrication of SiC coating. The presence of porous SiO₂-SiC layer with SiC nanowires was beneficial to fabricate a compact and homogeneous SiC coating resulting from synergistic effect of further reaction between SiO₂ and pack powders and the reinforcement of SiC nanowires. Therefore, the results of thermal shock and isothermal oxidation tests showed that the mass loss of modified SiC coating was only 0.02 % after suffering 50-time thermal cycles between room temperature and 1773 K and decreased from 5.95 % to 1.08 % after static oxidation for 49.5 h in air at 1773 K. Moreover, due to the blocking effect of SiO₂-SiC reticulated layer on siliconization erosion during PC, the flexural strength of SiC coated C/C composites with SiO₂-SiC reticulated layer increased by 64.8 % compared with the untreated specimen.     

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,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.     

Self‐Generating High‐Temperature Oxidation‐Resistant Glass‐Ceramic Coatings for C–C Composites Using UHTCs

Carbon–carbon (C–C) composites are ideal for use as aerospace vehicle structural materials; however, they lack high‐temperature oxidation resistance requiring environmental barrier coatings for application. Ultra high‐temperature ceramics (UHTCs) form oxides that inhibit oxygen diffusion at high temperature are candidate thermal protection system materials at temperatures >1600°C. Oxidation protection for C–C composites can be achieved by duplicating the self‐generating oxide chemistry of bulk UHTCs formed by a “composite effect” upon oxidation of ZrB₂–SiC composite fillers. Dynamic Nonequilibrium Thermogravimetric Analysis (DNE‐TGA) is used to evaluate oxidation in situ mass changes, isothermally at 1600°C. Pure SiC‐based fillers are ineffective at protecting C–C from oxidation, whereas ZrB₂–SiC filled C–C composites retain up to 90% initial mass. B₂O₃ in SiO₂ scale reduces initial viscosity of self‐generating coating, allowing oxide layer to spread across C–C surface, forming a protective oxide layer. Formation of a ZrO₂–SiO₂ glass‐ceramic coating on C–C composite is believed to be responsible for enhanced oxidation protection. The glass‐ceramic coating compares to bulk monolithic ZrB₂–SiC ceramic oxide scale formed during DNE‐TGA where a comparable glass‐ceramic chemistry and surface layer forms, limiting oxygen diffusion.     

Erosion protective coatings for low density, highly porous carbon/carbon composites

A simple and low cost method based on slurry coating was used to produce silicon carbide, titanium carbide and glass-ceramic coatings on low density carbon/carbon composites in order to improve their erosion resistance. Microstructural analyses were performed for substrate and coatings by optical microscopy, and scanning and transmission electron microscopy. As-received and coated composites were submitted to erosion tests using a sandblasting machine according to ASTM G76-95. The best results were obtained with a silica-alumina-yttria based glass-ceramic coating.     

Thermal expansion coefficient tailoring of LAS glass-ceramic for anodic bondable low temperature co-fired ceramic application

The Li–Al–Si glass-ceramics were prepared by conventional glass-ceramic fabrication method. The influences of Na₂O content on the sintering property, microstructure, and coefficient of thermal expansion were investigated. The results show that the coefficient of thermal expansion of LAS glass-ceramics can be tailored to match that of silicon by the addition of Na₂O content. Na₂O has a remarkable influence on the crystallinity of Li–Al–Si glass-ceramic. The coefficient of thermal expansion of Li–Al–Si glass-ceramic is thus tunable between that of glass phase and crystal phase. The Si–O bond length change in stretch vibration modes introduced by Na₂O also contributes to the variation of coefficient of thermal expansion of the Li–Al–Si glass-ceramics. The coefficient of thermal expansion of the Li–Al–Si glass-ceramic with 1.5 wt% Na₂O addition is about +3.34 ppm/°C at 350 °C and shows a good compatibility to that of silicon in a wide temperature range, which makes it a promising candidate for anodic bondable low temperature co-fired ceramic substrate applications.     

Mullite-Al2O3-SiC oxidation protective coating for carbon/carbon composites

In order to exploit the unique high temperature mechanical properties of carbon/carbon (C/C) composites, a new type of oxidation protective coating has been produced by a two-step pack cementation technique in an argon atmosphere. XRD analysis showed that the internal coating obtained from the first step was a gradient SiC layer that acts as a buffer layer, and the multi-layer coating formed in the second step was an Al₂O₃-mullite layer. It was found that the as-received coating characterized by excellent thermal shock resistance on the surface of C/C composites during exposure to an oxidizing atmosphere at 1873 K, could effectively protect the C/C composites from oxidation for 45 h. The failure of the coating is due to the formation of bubble holes on the coating surface.     

Effect of temperature gradient on the erosion behavior of SiC coating for carbon/carbon composites in a combustion environment

SiC coating with a thickness of 50–70 µm was prepared on the surface of C/C composites by in-situ reaction method. The SiC coated C/C composites were then tested in a wind tunnel where a temperature gradient from 200 to 1600 °C could be obtained to investigate their erosion behavior. The results of wind tunnel test indicated that the service life of C/C composites was prolonged from 0.5 to 44 h after applying the SiC coating. After the wind tunnel test, three typical oxidation morphologies, including glassy SiO₂ layer, porous SiO₂ layer and clusters of honeycomb-like SiO₂ grains, were found on the SiC coated C/C composites. With the decrease of oxidation temperature, the amount of glassy SiO₂ declined and the thermal stress increased, which induced the cracking followed by the degradation of the SiC coating.     

The toughening design of multi-layer antioxidation coating on C/C matrix via SiC-SiCw transition layer grown in-situ

Poor antioxidant and thermal-shock capacities of C/C composites thermal barrier coating (TBC) caused by cracking and shedding of coatings has been a major obstacle blocking the development of C/C composites. Herein, in-situ growth of whisker reinforced silicon carbide transition layer and inter-embedding mechanism of multi-gradient coatings were brought into the design of TBC to enhance the antioxidant and thermal-shock capacities. A three-layer gradient coating SiC-SiC_w/ZrB₂-SiC/ZrSiO₄-aluminosilicate glass (ZAG) from inside to outside, in which ZrB₂-SiC/ZAG serve as oxygen barrier layers with self-healing ability and SiC-SiC_w provides thermal stress buffering and bonding against cracking and shedding of coatings, is designed. The ZAG mainly forms a dense oxygen blocking frontier with self-healing ability through fluidized glass, while the ZrB₂-SiC can react actively with infiltrated oxygen in a way of self-sacrifice, preventing oxygen erosion to C/C matrix and SiC-SiC_w transition layer. As a result, the collaborative work among layers endows this coating with excellent high temperature service performance. This work provides a new insight for the design of excellent TBC.     

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.     

Strengthening of Al2O3 porous composites with a glass-ceramic binder doped with nanocopper

Glass ceramics are the result of controlled crystallisation of one or more crystalline phases embedded in the glass matrix, which usually results in better mechanical properties than conventional glasses. Crystalline phases precipitated in the vitrified bond improve mechanical strength and provide new functions that are not present in the original glass. The most widely encountered issue in standard composites is the presence of inclusions, generated during the process of thermal treatment, of finely dispersed crystalline phases, which are spread in the amorphous phase.Another way of increasing the mechanical properties of composites is via surface crystallisation of the binder. The mechanical strength can be significantly and permanently increased by inducing compressive stress at the glass surface. In the case of the binder designed here, the generated crystalline phase is willemite (Zn₂SiO₄), which is characterised by a low coefficient of thermal expansion (CTE). Zn₂SiO₄ usually crystallises at the glass surface, which results in the development of favourable compressive stresses in the glass-crystalline binder.Transition metal oxides significantly affect the crystallisation characteristics, thus influencing the thermal behaviour of glass ceramics. The majority of current publications focus on studies of the influence of copper on certain properties, and mainly the optical and photonic properties, and the influence of copper on the mechanical properties of silicate systems is still poorly recognised. This article investigates the mechanical and physical properties of porous Al₂O₃ composites with a glass-ceramic bond doped with nanocopper.     

In-field reparation of the damaged coatings for C/C composites

Protective coatings are critical to the successful application of the carbon/carbon (C/C) composites in the thermal protection systems of space vehicles. The damages of such coatings during installation and operation would threaten the safety of flight. In this contribution, an in-field technology based on a multilayer structure was developed to repair the damaged coatings of C/C composites. The multilayer structure contains a silicon buffer inner layer, a mullite heat-resistant middle layer and a borosilicate glass outer layer. The oxidation tests in air at 1300 °C and 1500 °C indicated that the weight loss of the repaired samples was greatly reduced compared with that of the damaged ones. The plasma wind tunnel tests for both repaired and damaged coatings further demonstrated that the multilayer structure could effectively protect the damaged composites from ablation in oxidation environments.     

A gradient composite coating to protect SiC-coated C/C composites against oxidation at mid and high temperature for long-life service

To improve the oxidation resistance of carbon/carbon (C/C) composites at mid and high temperature, a gradient composite coating was designed and prepared on SiC-coated C/C composites by in situ formed-SiO₂ densifying the porous SiC-ZrSi₂ pre-coating. SiO₂ gradient distribution was conducive to inhibiting the cracking of the coating. A dual-layer structure with the outer dense layer and the inner microporous layer was formed in the coating during densifying. The dense layer had excellent oxygen diffusion resistance and the microporous layer alleviated CTE mismatch between SiC inner coating and dense layer. Moreover, ZrSiO₄ particles inhibited crack propagation and stabilized SiO₂ glass. Therefore, the coating can protect the C/C composites from oxidation at 1473 K, 1573 K and 1773 K for 810 h, 815 h and 901 h, respectively. The coated samples underwent 30 thermal cycles between room temperature and 1773 K without mass loss, exhibiting good thermal shock resistance.     

Ultra‐High‐Temperature Ceramic HfB2‐SiC Coating for Oxidation Protection of SiC‐Coated Carbon/Carbon Composites

To protect the carbon/carbon (C/C) composites from oxidation, an outer ultra‐high‐temperature ceramics (UHTCs) HfB₂‐SiC coating was prepared on SiC‐coated C/C composites by in situ reaction method. The outer HfB₂‐SiC coating consists of HfB₂ and SiC, which are synchronously obtained. During the heat treatment process, the formed fluid silicon melt is responsible for the preparation of the outer HfB₂‐SiC coating. The HfB₂‐SiC/SiC coating could protect the C/C from oxidation for 265 h with only 0.41 × 10^?2 g/cm² weight loss at 1773 K in air. During the oxidation process, SiO₂ glass and HfO₂ are generated. SiO₂ glass has a self‐sealing ability, which can cover the defects in the coating, thus blocking the penetration of oxygen and providing an effective protection for the C/C substrate. In addition, SiO₂ glass can react with the formed HfO₂, thus forming the HfSiO₄ phase. Owing to the “pinning effect” of HfSiO₄ phase, crack deflecting and crack termination are occurred, which will prevent the spread of cracks and effectively improve the oxidation resistance of the coating.     

TaB2–SiC–Si multiphase oxidation protective coating for SiC-coated carbon/carbon composites

To improve the oxidation resistance of the carbon/carbon (C/C) composites, a TaB₂–SiC–Si multiphase oxidation protective ceramic coating was prepared on the surface of SiC coated C/C composites by pack cementation. Results showed that the outer multiphase coating was mainly composed of TaB₂, SiC and Si. The multilayer coating is about 200 μm in thickness, which has no penetration crack or big hole. The coating could protect C/C from oxidation for 300 h with only 0.26 × 10^?2 g²/cm² mass loss at 1773 K in air. The formed silicate glass layer containing SiO₂ and tantalum oxides can not only seal the defects in the coating, but also reduce oxygen diffusion rates, thus improving the oxidation resistance.     

Oxidation resistance of a gradient self-healing coating for carbon/carbon composites

A gradient self-healing coating consisting of three layers, SiC-B₄C/SiC/SiO₂, was examined as a multilayer protection for carbon/carbon composites. The inner layer was made of B₄C and β-SiC, the middle layer was a SiC based layer, and the outer layer was SiO₂ as an airproof layer. Both inner and middle layers were produced to be diphase structure by a pack cementation technique, and the outer airproof layer was prepared by hydrolyzing tetraethylorthosilicate. SEM and EDS investigations showed that the coating had a compositional gradient between B₄C and SiC. The coating showed great self-healing properties from 500 °C to 1500 °C. The weight loss rate of the coated composites was less than 1.3% after 50 h at 1500 °C, and coating represented excellent thermal shock resistance at 1500 °C. The oxidation kinetics of coated carbon/carbon composites showed that the Arrhenius curve consisted of three parts with two broken points at about 700 °C and 1100 °C, and the three parts corresponded to three different self-healing mechanisms in different temperature regions.     

Intelligent cooling structure design of "Z-pins like" silicon rods to enhance the ablation resistance of C/C-ZrC-SiC composites above 2500 °C

In order to improve the ablation resistance of C/C-ZrC-SiC composites by reducing the damage of the protective oxide layer, novel "Z-pins like" silicon rods, which were designed and fabricated by liquid phase sintering, were utilised as a dissipative agent. The microstructure evolution and thermal dissipation behaviour were investigated after ablating above 2500 °C for 300 s. After the "Z-pins like" silicon rods were implanted, the anti-ablative property of the C/C-ZrC-SiC composites was drastically improved by the dissipative thermal protection mechanism. The linear ablation rate of the "Z-pins like" silicon rod-reinforced C/C-ZrC-SiC composite was -0.28 μm/s, which is 112.72% lower than the unmodified composite. Additionally, the actual ablative temperature dropped approximately 357 °C, which enabled abundant SiO₂ to remain in the ablation centre. Furthermore, a dense SiO₂-rich oxide layer with a low oxygen diffusion coefficient is formed that covers the entire ablative surface.     

Mechanical and thermal performances of epoxy resin/graphitic carbon nitride composites

In this paper, a series of graphitic carbon nitride (g-C₃N₄) was synthesized under different thermal oxidation etching temperatures and epoxy/g-C₃N₄ composites were prepared via solution blending. The morphology and structure of g-C₃N₄ were investigated by transmission electron microscope, X-ray diffraction (XRD), Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. The tensile fracture morphology and structure of epoxy resin (EP) composites were demonstrated by scanning electron microscopy and XRD, respectively. Mechanical properties of EP composites were characterized by tensile testing, and the thermal performances were investigated by dynamic mechanical thermal analysis and thermal gravimetric analysis. The results revealed that the active groups on g-C₃N₄ sheets increased under thermal oxidation etching and the C to N ratio of g-C₃N₄ decreased from 0.94 to 0.76 with the increasing etching temperature. Noticeably, the tensile strength of EP composites was enhanced by 58% with the addition of C₃N₄-NS-500 and the thermal properties were also improved significantly, including T_0.5 (the decomposition temperature at the mass loss of 50%) increased by 21.5 °C and glass transition temperature improved by 8 °C. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48598.