Microstructures and enhanced flexural properties of single-crystalline HfC nanowires in-situ modified carbon/carbon composites by electrophoresis-thermal evaporation using CNTs as the template

To improve the mechanical properties of carbon/carbon (C/C) composites, in-situ synthetized single-crystalline hafnium carbide nanowires (HfCnws) were introduced into the carbon fiber preforms by electrophoresis-thermal evaporation method. The Multi-walled carbon nanotubes (MWCNTs) were utilized as the carbon source and templates for forming HfCnws. The microstructure, chemical composition and mechanical properties of the HfCnws modified carbon/carbon (HfCnws-C/C) composites were characterized. Results reveal that HfC is produced preferentially in the inner nodular parts and end parts of MWCNTs. The raising heat-treatment temperature would influence the diffusion rate of Hf atoms and then the number of nucleation sites, which further changed the aspect ratio and morphology of HfCnws. The HfCnws have refined the grain size of pyrolytic carbon (PyC), and significantly improve the flexural strength of C/C composites by 79.3%.     

Effect of HfC nanowires grown on carbon fibers on the microstructure and thermophysical properties of C/C composites

One-dimensional (1D) hafnium carbide nanowires (HfCnws) were grown in situ on carbon fibers (CFs) via a Ni-assisted pyrolysis method of organometallic polymer precursor. Scanning electron microscopy (SEM), transmission electron microscope (TEM), polarized-light optical microscopy (PLM), and Raman were used to analyze the effect of HfCnws on the microstructure of pyrolytic carbon (PyC). The specific heat capacity (HC), thermal diffusivity (TD), thermal conductivity (TC), and coefficient of thermal expansion (CTE) of HfCnws-C/C composites were also investigated. Results show that HfCnws wrapped by carbon nanosheet were successfully synthesized. The diameter of HfCnws is about 30 nm and the thickness of carbon nanosheet is about 10 nm, which could induce the formation of isotropic (ISO) PyC. After introducing HfCnws, the TD and CTE of HfCnws-C/C composites were increased. Ni2HfCnws-C/C composites show a higher TC and TD, and the CTE increased with the increasing content of HfCnws.     

Integrative improvement on thermophysical properties and ablation resistance of laminated carbon/carbon composites modified by in situ grown HfC nanowires onto carbon fiber cloths

HfC nanowires modified carbon fiber cloth laminated carbon/carbon (HfC_nw-C/C) composites were fabricated by in situ growth of HfC nanowires on carbon cloths via catalytic CVD, followed with lamination of the cloths and densification by pyrolytic carbon (PyC). Morphologies, thermal conductivity, coefficient of thermal expansion (CTE), and ablation resistance of the composites were investigated. Due to the loading of HfC nanowires, the matrix PyC with low texture was obtained; the thermal conductivity of the composites in the Z direction was enhanced from 100℃ to 2500℃; CTE along the X–Y direction also decreased in the range of 2060 ℃ – 2500 ℃, which reaches the maximum of 24 % at 2500℃. Moreover, the 20s-ablation-resistance of HfC_nw-C/C composites exhibits mass and linear ablation rates of 5.3 mg/s and 21.0 μm/s, which are 40 % and 37 % lower than those of pure C/C composites, respectively. Our work shows laminated HfC_nw-C/C composites are a promising candidate for high-temperature applications.     

Ultra-high temperature ceramic coating for carbon/carbon composites against ablation above 2000 K

To improve the ablation resistance of carbon/carbon composites at the temperature above 2000 K, a ZrB₂-SiC-ZrC ultra-high temperature ceramic coating was prepared by combination of supersonic atmosphere plasma spray (SAPS) and reaction melt infiltration. The micro-holes in ZrB₂-Si-ZrC coating prepared by SAPS were effectively filled and the compactness and interface compatibility between the coating and C/C composites was improved through the reaction melt infiltration process. The ultra-high temperature ceramic coating exhibited good ablation resistance under oxyacetylene torch ablation above 2000 K. After ablation for 120 s, the mass and linear ablation rates of the ZrB₂-SiC-ZrC coated C/C samples were only ?0.016 × 10^?3 g/s and 1.30 µm/s, respectively. Good ablation resistance of the ultra-high temperature ceramic coating is mainly attributed to the dense coating structure and the improvement of interface compatibility between the coating and C/C composites.     

Ablation behavior of HfC coating with different thickness for carbon/carbon composites at ultra-high temperature

The thickness of the different HfC coatings from 20 μm to 50 μm were prepared on the surface of carbon/carbon (C/C) composites by low pressure chemical vapor deposition (LPCVD). The microstructure and thermal stress of the coatings after ablation were investigated, as well as the effect of thickness and thermal stress on the ablation resistance of the HfC coating was analyzed. After being ablated at a heat flux of 2.4 MW/m² for 60 s, the thermal stress gradually increased at first and then rapidly increased with the increasing thickness of coating. The results indicated that the moderate coating thickness can effectively release the thermal stress generated during the ablation process. The 40 μm-thick HfC coating showed the best ablation resistance with the mass ablation rate and line ablation rate were only 0.13 mg/s and 0.09 μm/s, respectively.     

Advances in oxidation and ablation resistance of high and ultra-high temperature ceramics modified or coated carbon/carbon composites

Carbon/carbon (C/C) composites are considered as one of the most promising materials in structural applications owing to their excellent mechanical properties at high temperature. However, C/C composites are susceptible to high-temperature oxidation. Matrix modification and coating technology with ultra-high temperature ceramics (UHTCs) have proved to be highly effective to improve the oxidation and ablation resistance of C/C composites. In this paper, recent advances in oxidation and ablation resistance of C/C composites were firstly reviewed, with attention to oxidation and ablation properties of C/C composites coated or modified with UHTCs. Then, several new methods in improving oxidation and ablation resistance were discussed, such as by using nanostructures to toughen UHTCs coatings or carbon matrix and the combination of matrix modification and coating technology. In addition, relevant ablation tests with scaled models were also briefly introduced. Finally, some open problems and future challenges were highlighted in the development and application of these materials.     

Ablation-resistant Ta0.78Hf0.22C solid solution ceramic modified C/C composites for oxidizing environments over 2200 °C

Ta_0.78Hf_0.22C solid solution ceramic was synthesized and introduced into carbon/carbon (C/C) composites by polymer infiltration and pyrolysis (PIP). Effect of the introduction of Ta_0.78Hf_0.22C on the microstructure, ablation resistance, and flexural performance of C/C composites were investigated. Results showed that the flexural strength and modulus of the composites were increased by 108 % and 117 %, respectively, after adding Ta_0.78Hf_0.22C solid solution into C/C composites. In addition, the introduction of Ta_0.78Hf_0.22C improved the ablation resistance of C/C composites under oxyacetylene ablation environment, over 2200 °C. The linear and mass ablation rates were decreased 73 % and 70 %, respectively. The oxide with low melting point, Ta₂O₅, exhibited good sealing and oxygen-barrier capacity, and the formation of new solid solution oxide particles, Hf₆Ta₂O₁₇, could pin cracks during ablation, both of them were contributed to better ablation resistance of modified C/C composites.     

Effects of surface structure unit of 2D needled carbon fiber preform on the microstructure and ablation properties of C/C-ZrC-SiC composites

To investigate the effects of different structure units on the ablation properties of C/C-ZrC-SiC composites produced from 2D needled carbon fiber preforms as reinforcements, non-woven layer, short-cut fiber web and the surface of laminated layers of the composites were ablated by oxyacetylene flame respectively. Results showed that the formation ability of surface protective layer and the fiber orientation were the key factors, determining ablation properties of different structure units. Short-cut fiber web presented the best ablation resistance due to the forming of compactly integrated ZrO₂ self-protection coating because of its sufficient ceramic content. However, only scattered oxide particles formed on the ablated surface of non-woven layer, which resulted in serious erosion of carbon fibers and carbon matrices, leading to the poor ablation resistance. Compared with the non-woven layer perpendicular to the flame, the anti-ablation property was even worse when it paralleled to the flame.     

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.     

Long-time ablation protection of carbon/carbon composites with different-La2O3-content modified ZrC coating

Long time oxidation protection at ultra-high temperatures or ablation protection has been a choke point for C/C composites. In this study, long time ablation protection of different-La₂O₃-content (5–30 vol.%) modified ZrC coating for SiC-coated carbon/carbon (C/C) composites was investigated. Results showed that ZrC coating with 15 vol.% La₂O₃ had good ablation resistance and could protect C/C composites for at least 700?s at 2160 °C. A high-thermal-stability and low-oxygen-diffusivity oxide scale containing m-ZrO₂ particles and molten phases with La_0.1Zr_0.9O_1.95 and La₂Zr₂O₇ was formed during ablation, offering the ablation protection. La could erode grain boundaries of ZrO₂ to refine ZrO₂ by short-circuit diffusion and m-ZrO₂ particles were retained due to less bulk diffusion than grain-boundary diffusion of La into ZrO₂. The erosion resulted in the formation of molten phases containing fine nano-ZrO₂, which served as viscous binder among m-ZrO₂ particles and crack sealer for the oxide scale.     

Study of the ablation of a carbon/carbon composite at ∼25 MW/m2 with a nitrogen plasma torch

Ablation of carbon/carbon (C/C) composites was investigated in a nitrogen plasma torch with a heat flux of ∼25 MW/m². The reaction products of carbon in C/C composites and nitrogen plasma jet were calculated based on the principle of free energy minimum. The calculated results show that the thermal chemical ablation and sublimation of carbon occur and C_n(g) (n = 1–3), CN(g), C₂N(g) and C₂N₂(g) may be the major reaction products consuming carbon. Ablation is apt to begin at the interfaces, especially the fibre-matrix interface and interfaces inside the matrix. Ablation of C/C composites is mainly controlled by the thermal chemical ablation, sublimation of carbon, and mechanical breakage. The formation of needle-shaped fibres and shell-shaped matrices is attributed to both the thermal chemical ablation and sublimation of carbon, while carbon fragments and fractured fibres or matrices result from the mechanical breakage.     

Rapid and low-cost carbon/carbon composites by using graphite slurry impregnated prepregs

A rapid and low-cost carbon/carbon (C/C) composites preparation method is proposed: graphite prepreg-coated carbon fiber fabric (CFF) is formed by hot pressing, followed by hot isostatic pressing and high temperature graphitization, to prepare C/C composite with low porosity and high crystallinity. In this method, the carbon fiber (CF) mass fraction can be precisely regulated in the range of 40–95% by the impregnation process conditions of CFF in graphite prepreg. The graphite particles in the preform were graphitized and bonded with CFF by high temperature graphitization. Finally, a ZrO₂ anti-ablative layer was applied using sol-gel method. The results show that when the CF mass fraction is 50%, the C/C composite with a crystallinity of 92.21 and a porosity of 3.47% can be obtained, with mass ablation rate of 0.23 mg/s and density of 1.62 g/m³. The method can prepare C/C composites with uniform density and high ablation resistance.     

Morphology and anti-ablation properties of PIP Cf/C–SiC composites with different CVI carbon content under 4.2 MW/m2 heat flux oxy-acetylene test

In this work, the needled carbon fiber preforms were used to make seven groups of carbon/carbon composite billets with different matrix carbon contents by controlling the processing time of chemical vapor infiltration (CVI). C_f/C–SiC composites were prepared by infiltration of SiC into these C/C composites billets using polycarbosilane (PCS) through precursor infiltration and pyrolysis (PIP). After oxy-acetylene torch testing (heat flux of 4.2 MW/m²) for 200s, 300s and 400s, respectively, it revealed that the anti-ablation properties of the C_f/C–SiC composite samples were enhanced by a higher content of SiC matrix. Additionally, specimens bearing longer duration tests showed a trend of lower average ablation rates. The lowest linear ablation rate is 0.008 mm/s and the mass ablation rate is 0.0019 g/s for those high SiC content samples tested for 400s. The SEM images of the tested samples showed the mechanism and the non-linear process of ablation resistance progression.     

Microstructure and ablation performances of dual-matrix carbon/carbon composites

The ablation performances of dual-matrix carbon/carbon composites were tested on a DJ-21 arc heater, and the morphologies of specimens were investigated by scanning electron microscopy (SEM). It is found that the composites have typical rough laminar pyrocarbon structure and ablation always tends to start at interfaces, defects and pores. In addition, the work indicates that ablation performances of parallel ablation are better than vertical ablation and parallel ablation is mainly controlled by block denudation while vertical ablation is more likely to be controlled by particle denudation.     

Simultaneous enhancement of mechanical and ablation properties of C/C composites modified by (Hf-Ta-Zr)C solid solution ceramics

In order to improve the mechanical and ablative resistance of C/C composites, (Hf-Ta-Zr)C single-phase solid solution ceramics were introduced into C/C composites by polymer infiltration and pyrolysis (PIP) to fabricate (Hf-Ta-Zr)C modified C/C composites (HTZ). Their mechanical property and ablation resistance were studied. The results showed that HTZ achieved simultaneous enhancement of mechanical property and ablative resistance. Their flexural strength and modulus could reach 219.34 MPa and 24.82 GPa, respectively. In addition, the mass and linear ablation rate of HTZ were 0.379 mg/s and 0.667 µm/s, respectively after the 90 s oxyacetylene ablation. A dense Hf-Ta-Zr-O multiphase oxide layer was formed on the surface of the HTZ during ablation process, which protected the interior modified C/C composites from ablation. Our work expands a rational design of modified C/C composites and broaden the application of solid solution ceramic in the field of ultra-high temperature ablation resistance for carbon or ceramic-based composites.     

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.     

Preparation of carbon/carbon‐ultra high temperature ceramics composites with ultra high temperature ceramics coating

In order to increase the oxidation resistance of carbon/carbon (C/C) composites at long‐term high temperature, C/C‐Ultra High Temperature Ceramics composites (UHTCs) with a dual‐layer UHTCs oxidation coating was successfully designed and fabricated. The microstructure and ablation resistance were investigated and discussed. After ablation in arc‐heated wind tunnel with temperature being 2200°C for 1000s, the mass ablation rate and linear ablation rate were ?1.9 × 10^?2 mg/cm²s and 2.9 × 10^?5 mm/s, respectively. The formation of thermodynamically compatible oxide scale including ZrO₂ skeleton and SiO₂ or Zr–Si–O glass on the surface were mainly contributed to the excellent ablation resistance of the composite.     

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.     

SiC-Si coating with micro-pores to protect carbon/carbon composites against oxidation

To improve the oxidation resistance of carbon/carbon (C/C) composites at high temperatures, a SiC-Si coating with micro-pores was prepared by slurry and heat-treatment on the surface of C/C composites with SiC-Si inner coating acquired by pack cementation (PC). The microstructure, phase composition, element distribution, and anti-oxidation properties of the dual-layer SiC-Si coating were investigated. The results show that a SiO₂-SiC inlay structure was formed during the oxidation process, due to a large amount of SiO₂ rapidly generated by the oxidation of SiC particles in the porous coating. The coating with this structure could inhibit the cracking of SiO₂ glass and had a good resistance to oxygen diffusion. Moreover, the crack propagation was blocked by the remaining micro-pores of the coating. The coating could protect C/C composites against oxidation for 846 h only with the mass loss of 0.16 % at 1773 K in air.     

Ablation resistance of HfC-TaC/HfC-SiC alternate coating for SiC-coated carbon/carbon composites under cyclic ablation

HfC-TaC/HfC-SiC alternate coatings with different sublayer thicknesses were fabricated on SiC-coated carbon/carbon composites by supersonic atmosphere plasma spraying. Their ablation resistance was studied under oxyacetylene torch and compared with monolayered HfC-TaC coating. The alternate coating with 6 spray cycles of HfC-TaC and 3 spray cycles of HfC-SiC sublayers exhibited the best ablation performance as confirmed by the integral coating morphology and the lowest ablation rates. A dense oxide layer acting as an oxygen insulator and the release of thermal stress induced by the formation of dendritic cracks are thought to be responsible for its great ablation resistance. For the alternate coating with 4 spray cycles of HfC-TaC and 2 spray cycles of HfC-SiC sublayers, exfoliation occurred at the interface of two adjacent sublayers, leading to violent evaporation of exposed HfC-SiC sublayer.