Strengthening/toughening of 2D C/SiC composites by coating

SiC and SiC_w/SiC coatings were prepared on two-dimensional carbon fiber reinforced silicon carbide ceramic matrix composites (2D C/SiC), and strengthening/toughening of the composite by the coatings was investigated. After coating, the density of the C/SiC composites was increased effectively and the mechanical properties were improved significantly. Compared with SiC coating, SiC_w/SiC coating showed the more significant effect on strength/toughness of the composites. Coatings had two effects: surface strengthening and matrix strengthening. The latter was the dominant effect. The surface strengthening can increase the crack initiation stress, while the matrix strengthening can enhance the crack propagation resistance. The former effect increased the strength and the latter effect increased the toughness.     

Ablation behavior and mechanism of C/C–ZrC–SiC composites under an oxyacetylene torch at 3000 °C

C/C–ZrC–SiC composites with continuous ZrC–SiC ceramic matrix were prepared by a multistep technique of precursor infiltration and pyrolysis process. Ablation properties of the composites were tested under an oxyacetylene flame at 3000 °C for 120 s. The results show that the linear ablation rate of the composites was about an order lower than that of pure C/C and C/C–SiC composites as comparisons, and the mass of the C/C–ZrC–SiC composites increased after ablation. Three concentric ring regions with different coatings appeared on the surface of the ablated C/C–ZrC–SiC composites: (i) brim ablation region covered by a coating with layered structure including SiO₂ outer layer and ZrO₂–SiO₂ inner layer; (ii) transition ablation region, and (iii) center ablation region with molten ZrO₂ coating. Presence of these coatings which acted as an effective oxygen and heat barrier is the reason for the great ablation resistance of the composites.     

Microstructure and ablation behavior of SiC coated C/C–SiC–ZrC composites prepared by a hybrid infiltration process

In this study, C/C–SiC–ZrC composites coated with SiC were prepared by precursor infiltration pyrolysis combined with reactive melt infiltration. The pyrolysis behavior of the hybrid precursor was investigated using thermal gravimetric analysis-differential scanning calorimetry, X-ray diffraction, and scanning electron microscopy techniques. The microstructure and ablation behavior of the composites were also investigated. The results indicate that the composites exhibit an interesting structure, wherein a ceramic coating composed of SiC and a small quantity of ZrC covers the exterior of the composites, and the SiC–ZrC hybrid ceramics are partially embedded in the matrix pores and distributed around the carbon fibers as well. The composites exhibit good ablation resistance with a surface temperature of over 2300 °C during ablation. After ablation for 120 s, the mass and linear ablation rates of the composites are 0.0026 g/s and 0.0037 mm/s, respectively. The great ablation resistance of the composites is attributed to the formation of a continuous phase of molten SiO₂ containing SiC and ZrO₂, which seals the pores of the composites during ablation.     

Ablation resistance of HfC–SiC coating prepared by supersonic atmospheric plasma spraying for SiC-coated C/C composites

In order to improve the ablation properties of carbon/carbon composites, HfC–SiC coating was deposited on the surface of SiC-coated C/C composites by supersonic atmospheric plasma spraying. The morphology and microstructure of HfC–SiC coating were characterized by SEM and XRD. The ablation resistance test was carried out by oxyacetylene torch. The results show that the structure of coating is dense and the as-prepared HfC–SiC coating can protect the C/C composites against ablation. After ablation for 30 s, the linear ablation rate and mass ablation rate of the coating are −0.44 μm/s and 0.18 mg/s, respectively. In the ablation center region, a Hf–Si–O compound oxide layer is generated on the surface of HfC–SiC coating, which is conducive to protecting the C/C composites from ablation. With the ablation time increasing to 60 s, the linear ablation rate and mass ablation rate are changed to −0.38 μm/s and 0.26 mg/s, respectively. Meanwhile, the thickness of the outer Hf–Si–O compound layer also increases.     

Effects of porous C/C density on the densification behavior and ablation property of C/C–ZrC–SiC composites

C/C–ZrC–SiC composites were prepared by precursor infiltration and pyrolysis process using a mixture solution of organic zirconium-containing polymer and polycarbosilane as precursors. Porous carbon/carbon (C/C) composites with density of 0.92, 1.21 and 1.40 g/cm³ were used as preforms, and the effects of porous C/C density on the densification behavior and ablation resistance of C/C–ZrC–SiC composites were investigated. The results show that the C/C preforms with a lower density have a faster weight gain, and the obtained C/C–ZrC–SiC composites own higher bulk density and open porosity. The composites fabricated from the C/C preforms with a density of 1.21 g/cm³ exhibit better ablation resistance with a surface temperature of over 2400 °C during ablation. After ablation for 120 s, the linear and mass ablation rates of the composites are as low as 1.02 × 10⁻³ mm/s and −4.01 × 10⁻⁴ g/s, respectively, and the formation of a dense and continuous coating of molten ZrO₂ solid solution is the reason for their great ablation resistance.     

Microstructure and ablation property of gradient ZrCSiC modified C/C composites prepared by chemical liquid vapor deposition

Chemical liquid vapor deposition was adopted to fabricate gradient ZrCSiC modified C/C composites, and the microstructure and ablation resistance were studied. Results displayed the content of SiC decreased from the composites edge to the center but that of ZrC increased, indicating SiC and ZrC ceramics have the gradient distribution in the composites. The gradient composites possessed a low CTE and high thermal conductivity. The low CTE restricted the formation and expansion of defects, which could slow the oxygen diffusion in the composites. The high thermal conductivity could transfer the heat quickly in ablation process, which reduced the heat accumulation on the ablation surface and weakened the thermal erosion. Therefore, the gradient composites possessed an outstanding anti-ablation property at two heat fluxes. Compared with the uniformed distribution composites, the linear and mass ablation rates of the gradient composites decreased by 60.9% and 66.7% at heat flux of 2.38 MW/m² and decreased by 55.9% and 67.2% at heat flux of 4.18 MW/m². Because of the gradient distribution, porous ZrO₂ coating, ZrO₂SiO₂ coating and SiO₂ coating with SiO₂ nanowires were generated on the ablation center, ablation transition zone and ablation edge, respectively. These coatings isolated the sample surface from the flame and inhibited the transport of oxygen into the sample inner.     

Ablation behavior of single and alternate multilayered ZrC-SiC coatings under oxyacetylene torch

Based on the investigation of ablation behavior and thermal stress of the monolayered ZrC-SiC coatings with different SiC amounts, an alternate coating consisting of 4 sublayers with 10 and 70 vol.% SiC was prepared on SiC-coated carbon/carbon (C/C) composites through plasma spraying technique. Ablation tests were carried out under oxyacetylene torch with a heat flux of 2.38 MW/m². The alternate coating could offer 90 s ablation shield for C/C composites, providing superior ablation properties than all monolayered coatings. The improved ablation resistance is mostly induced by the fact that the outmost scale with abundant ZrO₂ particles was able to better endure the mechanical denudation from the torch. Moreover, due to the indirect contact with torch, the innermost sublayers were placed into relatively mild environment, thereby most of Si-based oxides could be retained and further hinder oxygen transport inward during ablation.     

Effect of the surface microstructure of SiC inner coating on the bonding strength and ablation resistance of ZrB2-SiC coating for C/C composites

The present study has been conducted in order to investigate the effect of the surface morphology of SiC inner coating on the bonding strength and ablation resistance of the sprayed ZrB₂-SiC coating for C/C composites. The microstructure of SiC inner coatings prepared by chemical vapor deposition and pack cementation at different temperatures were analyzed by X-ray diffraction, scanning electron microscopy, and 3D Confocal Laser Scanning Microscope. Tensile bonding strength and oxyacetylene ablation testing were used to characterize the bonding strength and ablation resistance of the sprayed ZrB₂-SiC coating, respectively. Results show that SiC inner coating prepared by chemical vapor deposition has a smooth surface, which is not beneficial to improve the bonding strength and ablation resistance of the sprayed ZrB₂-SiC coating. SiC inner coating prepared by pack cementation at 2000 °C has a rugged surface with the roughness of 72.15 µm, and the sprayed ZrB₂-SiC coating with it as inner layer exhibits good bonding strength and ablation resistance.     

Ablation resistance of HfB2-SiC coating prepared by in-situ reaction method for SiC coated C/C composites

To improve the ablation resistance of SiC coating, HfB₂-SiC coating was prepared on SiC-coated carbon/carbon (C/C) composites by in-situ reaction method. Owing to the penetration of coating powders, there is no clear boundary between SiC coating and HfB₂-SiC coating. After oxyacetylene ablation for 60 s at heat flux of 2400 kW/m², the mass ablation rate and linear ablation rate of the coated C/C composites were only 0.147 mg/s and 0.267 µm/s, reduced by 21.8% and 60.0%, respectively, compared with SiC coated C/C composites. The good ablation resistance was attributed to the formation of multiple Hf-Si-O glassy layer including SiO₂, HfO₂ and HfSiO₄.     

Ablation behavior of C/SiC with YSZ and ZrB2 coatings under high-energy laser irradiation

Carbon fiber-reinforced silicon carbide (C/SiC) composites are important candidates for laser protection materials. In this study, ablation mechanism of C/SiC coated with ZrO₂/Mo and ZrB₂–SiC/ZrO₂/Mo under laser irradiation was studied. ZrB₂–SiC multiphase ceramic and ZrO₂ ceramic were successfully coated on C/SiC composite by atmospheric plasma spraying technology with Mo as transition layer. Phase evolution and morphology of composite were investigated by X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. Moreover, ablation behavior of the composite was investigated by laser confocal microscopy. Results showed that ablation mechanism of C/SiC composite was controlled by phase transformation, thermal reaction, and thermal diffusion, with solid–liquid transition of ZrB₂ and ZrO₂ being dominant factor. Endothermic reaction and good thermal diffusivity of coatings were also important factors affecting ablation performance. Reflectivity effect of ZrO₂ coating was limited under high-energy laser irradiation. Compared with ZrO₂/Mo single-phase-monolayer coating, designed ZrB₂–SiC/ZrO₂/Mo coating showed better ablation performance, and breakdown time of C/SiC increased from 10 to 40 s. The depletion of liquid phase in molten pool was identified as an important factor responsible for rapid failure of C/SiC. The coating failed when the entire liquid phase was consumed within molten pool, followed by rapid damage of C/SiC substrate. Results of this study can provide theoretical guidance and research ideas for design and application of laser protective materials.     

Ablation behaviour of a TaC coating on SiC coated C/C composites at different temperatures

To improve the ablation resistance of carbon/carbon (C/C) composites, a TaC coating was prepared by supersonic plasma spraying on SiC coated C/C composites. The microstructure and morphology of the coatings were characterised by Scanning Electron Microscopy and X-ray diffraction. The ablation properties were studied at different temperatures under oxyacetylene torch. At 2100 °C, the oxides were blown away and resulted in high ablation rates: 1.2×10^?2 mm/s and 3.9×10^?3 g/s. However, most oxides can remain in ablation centre and serve as a coating at low temperature (1900 and 1800 °C). Therefore, the TaC/SiC coated samples exhibited zero linear ablation rate and lower mass ablation rate.     

Microstructures and ablation resistance of WSi2/ZrSi2/ZrxHf1-xC/SiC coating based on a pattern strengthening one-step method

To improve the ablation performance of carbon/carbon (C/C) composite materials, a WSi₂–ZrSi₂ composite-reinforced Zr_xHf_1–xC/SiC coating was prepared on the substrate surface via patterning strengthening method. The results show that this coating can protect the substrate from failure for 300 s under an oxyacetylene flame at 2600 °C. Owing to the presence of W, an extremely dense oxide layer was formed on the surface of the coating during initial ablation, which progressively led to the expulsion of the product of oxidation (WO₃) from the inner layer, as well as to holes and cracks on healing the coating surface, thereby significantly improving the ablation performance of the C/C composites. In addition, the excellent ablative performance and mechanism of the coating were analysed using volatility diagrams.     

Oxidation and ablation behaviours of a SiCnw@SiC–Si coating fabricated for carbon-fibre-reinforced carbon-matrix composites via thermal evaporation and gaseous silicon infiltration

A SiC-nanowire-modified SiC–Si (SiC_nw@SiC–Si) coating was prepared for carbon-fibre-reinforced carbon-matrix (C/C) composites using a two-step method based on thermal evaporation and gaseous silicon infiltration, and the effects of SiC nanowires on the oxidation and ablation behaviours of the coated samples were studied. Oxidation tests conducted at 1500 °C revealed that the weight loss of the SiC–Si-coated C/C composite was 15.85% after 6 h, whereas the SiC_nw@SiC–Si-coated C/C composite experienced a significantly lower weight loss of 1.27% after 50 h. Ablation tests suggested that the mass and linear ablation rates of the SiC_nw@SiC–Si-coated C/C composite were 0.05 mg/s and 0.09 μm/s, respectively; they were reduced by 78.26 and 92.74%, respectively, compared with those of the SiC–Si-coated C/C composite. Careful characterisation suggested that the network structure of the SiC nanowires in the SiC–Si phase can suppress crack propagation and firmly attach to the coating surface to enhance the interfacial adhesion between the coating and substrate, leading to improved anti-oxidation and anti-ablation properties. The SiC_nw@SiC–Si coating could offer a technological foundation for preventing the oxidation and ablation of C/C composites in aerospace engineering.     

Cyclic ablation behavior and microstructure evolution of multi-layer coating on C/C composites under oxyacetylene torch

The cyclic ablation resistance of coated carbon/carbon (C/C) composites play crucial roles in their further engineering applications and development due to the cyclic ablation environment accompanied by rapid heating and cooling and high-speed heat flow scouring, which can reflect the performance stability of the coating. In this research, a (SiC/HfC)₄/SiC (SHS) multi-layer coating was prepared on C/C composites. Compared with single layer (SiC and HfC coating) coated sample, the mass and linear ablation rate of SHS coated sample after three ablation cycles (60 s × 3) were only 0.64 mg/s and 0.53 μm/s, respectively. This is mainly because the introduction of many interfaces inhibits the propagation of cracks, the irregular cracks region only exists in the outer layer. Besides, the oxide layer with dense structure was formed near the C/C substrate, which could prevent oxygen from penetrating into the coating and continue to play a protective role.     

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.     

Comparing ablation properties of NbC and NbC-25 mol.% ZrC coating on SiC-coated C/C composites

In this work, ablation properties of NbC and NbC-25 mol.% ZrC coating, deposited on SiC-coated C/C composites by supersonic atmospheric plasma spraying, were tested by an oxyacetylene torch. Results showed that, for NbC coating, an unexpected smooth liquid film mostly composed of niobium suboxides (such as NbO₂ and NbO), rather than pure Nb₂O₅, generated during ablation for 45 s. Mechanical erosion resulted from the molten SiO₂, and the relatively low viscosity of the outer oxide layer owing to insufficiently high melting point of niobium suboxides were the key factors for the failure mechanism of NbC coating. While NbC–ZrC coating abated for 90 s has a 97.49 and 66.53% decrease of linear and mass ablation rate relative to NbC coating ablated for 45 s, since ZrO₂ hindering the evaporation of SiO₂ droplets, and more thermal-stable Nb–O–Zr liquid film endow (NbC–ZrC)/SiC/C/C composites with an outstanding anti-ablation property.     

Ablation behavior and thermal protection performance of TaSi2 coating for SiC coated carbon/carbon composites

For extending application of TaSi₂ in complex coating system, the ablation behavior and thermal protection performance of TaSi₂ coating is studied to evaluate its potential applications for anti-ablation protection of C/C composites. TaSi₂ coating is prepared by supersonic atmospheric plasma spraying (SAPS) on the surface of SiC coated carbon/carbon (C/C) composites. Phase variation and microstructure are characterized by XRD and SEM, respectively. During the ablation process, the coating is quickly oxidized to SiO₂ and Ta₂O₅ accompanied by a lot of heat consumption. The linear and mass ablation rates are 0.9?µm?s^?1 and ??0.4?mg?s^?1 after ablation for 80?s, respectively Results show that the prepared coating possesses optimal ablation performance under the heat flux of 2.4?MW/m². Moreover, the TaSi₂ coating and SiC inner coating have good chemical and physical compatibility during the ablation process. Therefore, the excellent performance of TaSi₂ coating during the ablation process makes it a candidate for anti-ablation protection for C/C composites.     

Microstructure and ablation mechanism of C/C–SiC composites

C/C–SiC composites were prepared by molten infiltration of silicon powders, using porous C/C composites as frameworks. The porosities of the C/C–SiC composites were about 0.89–2.8 vol%, which is denser than traditional C/C composites. The ablation properties were tested using an oxyacetylene torch. Three annular regions were present on the ablation surface. With increasing pyrocarbon fraction, a white ceramic oxide layer formed from the boundary to the center of the surface. The ablation experimental results also showed that the linear and mass ablation rates of the composites decreased with increasing carbon fraction. Linear SiO₂ whiskers of diameter 800 nm and length approximately 3 μm were formed near the boundaries of the ablation surfaces of the C/C–SiC composites produced with low-porosity C/C frameworks. The ablation mechanism of the C/C–SiC composites is discussed, based on a heterogeneous ablation reaction model and a supersaturation assumption.     

Phase, microstructure, and oxidation resistance of yttrium silicates coatings prepared by a hydrothermal electrophoretic deposition process for C/C composites

Oxidation-resistant yttrium silicates coatings for SiC precoated carbon/carbon composites were prepared by a novel hydrothermal electrophoretic deposition process. Sonochemical-synthesized yttrium silicates nanocrystallites, isopropanol, and iodine were respectively used as source materials, solvent, and charging agent during the deposition. Phase compositions, surface and cross-section microstructures of the as-prepared multilayer coatings were characterized by an X-ray diffractometer (XRD) and a scanning electron microscopy (SEM). The influence of deposition temperatures on the phase, microstructure, and oxidation resistance of the multilayer coated C/C composites was particularly investigated. Results show that the as-prepared outer coatings are composed of yttrium silicates crystallites with a main phase of Y₂Si₂O₇ and Y₂SiO₅. The thickness and density of the yttrium silicates coatings are improved with the increase of deposition temperature. Compared with SiC coating prepared by pack cementation, the multilayer coatings prepared by pack cementation with a later hydrothermal electrophoretic deposition process exhibit better antioxidation properties. The as-prepared multilayer coatings can effectively protect C/C composites from oxidation at 1773 K in air for 35 h with a weight loss of 0.32 × 10⁻³ g/cm².     

Nanosized (Zr,Hf)O2 coating reinforced by AlN whiskers for the ablation protection of SiC coated C/C composites

In this work, AlN whisker-reinforced (Zr, Hf)O₂ coating was prepared on SiC coated carbon/carbon composites by sol-gel and plasma spraying methods. Its cyclic ablation resistance was evaluated using an oxyacetylene torch with a heat flux of 2.38 MW/m². After ablation, the coating showed apparently decreased crack sizes and quantity as compared with the one without AlN whisker addition, pointing out its better crack tolerance. Moreover, the coating had a thinner oxidized region based on the linear ablation rate (−0.042 µm/s), greatly lower than that of pure oxide coating (−0.922 µm/s). After detailed observation and characterization, probable protection mechanism was proposed.