Microstructure and ablation performance of HfC/PyC core-shell structure nanowire-reinforced Hf1-xZrxC coating

To improve the ablation performance of C/C composites, HfC/PyC core-shell structure nanowire (HfCnw/PyC)-reinforced Hf_1-xZr_xC coating was prepared via three-step chemical vapor deposition (CVD) method. Effects of HfCnw/PyC and PyC layer thickness on the microstructure, residual stress and ablation performance of Hf_1-xZr_xC coating were studied. HfCnw/PyC-reinforced coatings exhibited equiaxial crystal structure. After incorporating HfCnw/PyC, ablation property of Hf_1-xZr_xC coating was enhanced because of the skeleton role of HfO₂ nanowires. PyC possessed low coefficient of thermal expansion (CTE) and high heat conductivity, but poor ablation performance. Hence, with the increase in thickness of PyC layer, ablation property of the coating first increased and then decreased. HfCnw/PyC-reinforced Hf_1-xZr_xC coating with PyC layer thickness of about 50 nm exhibited the best ablation property.     

Mechanical and thermophysical properties of carbon/carbon composites with hafnium carbide

Carbon/carbon (C/C) composites with addition of hafnium carbide (HfC) were prepared by immersing the carbon felt in a hafnium oxychloride aqueous solution, followed by densification and graphitization. Mechanical properties, coefficients of thermal expansion (CTE), and thermal conductivity of the composites were investigated. Results show that mechanical properties of the composites decrease dramatically when the HfC content is greater than 6.5 wt%. CTE of the composites increases with the increase of HfC contents. The composites with addition of 6.5 wt% HfC show the highest thermal conductivity. The high thermal conductivity results from the thermal motion of CO in the gaps and pores, which can improve phonon–defect interaction of the C/C composites. Thermal conductivities of the composites decrease when the HfC content is greater than 6.5 wt%, which is due to formation of a large number of cracks in the composites. Cracks increase the phonon scattering and hence restrain heat transport, which results in the decrease of thermal conductivity of the composites.     

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.     

Microstructure,mechanical and anti-ablation properties of SiCnw/PyC core-shell networks reinforced C/C–ZrC–SiC composites fabricated by a multistep method of chemical liquid-vapor deposition

C/C–ZrC–SiC composites reinforced by SiC nanowire (SiCnw)/pyrocarbon (PyC) core-shell networks were prepared by a multistep method of chemical liquid-vapor deposition (CLVD). The microstructure, mechanical property and ablation resistance were researched. The investigations presented that the PyC was deposited on the SiC nanowires, and the micro-scale core-shell structures were produced. Moreover, these micro-scale structures not only connected with the fibers and matrices, but also filled the pores in the composites. In contrast with C/C–ZrC–SiC composites, the flexural modulus and strength of SiCnw/PyC-C/C–ZrC–SiC composites increased by 36.91% and 44.53%, and the fracture mode was changed from the brittle to pseudo-plastic fracture. After the oxyacetylene torch ablation at two temperatures for 90s, the composites strengthened by SiCnw/PyC core-shell possessed a better resistant ablation. At ablation temperature of 2300 °C, the mass loss rate and linear reduction rate of the composites with core-shell networks decreased by 66.18% and 57.55% in contrast with the non-reinforced composites, and declined by 56.46% and 57.48% at ablation temperature of 3000 °C. The obvious decrease of ablation rates was ascribed to the dense microstructure, the small coefficient of thermal expansion (CTE), the good thermal conductivity, and the resistant ablation roles of SiCnw/PyC core-shell systems.     

Thermophysical properties of carbon/carbon composites and physical mechanism of thermal expansion and thermal conductivity

Five different carbon/carbon composites (C/C) have been prepared and their thermophysical properties studied. These were three needled carbon felts impregnated with pyrocarbons (PyC) of different microstructures, chopped fibers/resin carbon + PyC, and carbon cloth/PyC. The results show that the X-Y direction thermal expansion coefficient (CTE) is negative in the range 0-100 °C with values ranging from −0.29 to −0.85 × 10⁻⁶/K. In the range 0-900 °C, their CTE is also very low, and the CTE vs. T curves have almost the same slope. In the same temperature range composites prepared using chopped fibers show the smallest CTE values and those using the felts show the highest. The microstructure of the PyC has no obvious effect on the CTE for composites with the same preform architecture. Their expansion is mainly caused by atomic vibration, pore shrinkage and volatilization of water. However, the PyC structure has a large effect on thermal conductivity (TC) with rough laminar PyC giving the highest value and isotropic PyC giving the lowest. All five composites have a high TC, and values in the X-Y direction (25.6-174 W/m K) are much larger than in the Z direction (3.5-50 W/m K). Heat transmission in these composites is by phonon interaction and is related to the preform and PyC structures.     

Mechanical properties and ablation resistance of HfC nanowire modified carbon/carbon composites

Hafnium carbide nanowires (HfCnws) were in-situ grown in carbon/carbon (C/C) composites, and subsquently the preforms were densified by isothermal chemical vapor infiltration to obtain HfCnws modified carbon/carbon (HfCnws-C/C) composites. Morphology and microstructure of HfCnws were examined, and the effect of HfCnws on the mechanical property and ablation resistance of C/C composites were also investigated. Results show that introducing HfCnws refined the grain size of pyrolytic carbon (PyC). The out-of-plane compression, interlaminar shear and flexual strength of HfCnws-C/C composites increased by 120.80%, 45.60% and 94.65%, respectively compared with pure C/C, and the HfCnws-C/C shows good ablation resistance under oxy-acetylene flame ablation.     

Microstructure,thermophysical properties,and ablation resistance of C/HfC-ZrC-SiC composites

Carbon/carbon composites modified by HfC-ZrC-SiC were fabricated by reactive melt infiltration with the aim of improving their ablation resistance for application in aerothermal environments. Their microstructure, thermophysical and ablation properties were investigated. Results show that the thermal diffusivity decreases with increasing temperature for all composites. The thermal conductivity of the C/HfC-ZrC-SiC composites decreasing with increasing HfC molar fraction is related to decreased grain size and increased porosity, which impede phonon interaction and increase the phonon scattering. High HfC content effectively improves the oxidation and ablation resistance of the composites. C/HfC-ZrC-SiC composites containing 8.8?mol.% HfC exhibited the best ablation resistance owing to a compact and continuous HfO₂-ZrO₂ mixed layer that formed on the ablated surface.     

Influence of HfC nanowires on the growth behavior,microstructure and ablation resistance of CVD-HfC coating

HfC nanowire-toughened HfC ablation resistant coating was prepared on carbon/carbon composites by two steps of chemical vapor deposition. Effects of HfC nanowires on the growth behavior, microstructure and ablation resistance of the HfC coating were researched. Due to the incorporation of HfC nanowires, the deposition rate of the HfC coating was improved, the HfC coating was composed of particle-stacked crystals. After incorporating HfC nanowires, the bonding strength and fracture toughness of the HfC coating increased. HfC nanowires could restrain the crack propagation of HfC coating during ablation, contributing to improving the ablation resistance of HfC coating. After ablation for 60?s, the mass ablation rate of the HfC-coated C/C sample reduced from 0.44 to 0.26?mg/s because of the incorporation of HfC nanowires.     

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.     

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 resistance of HfC coating reinforced by HfC nanowires in cyclic ablation environment

To improve the ablation resistance of carbon/carbon composites in cyclic ablation environment, SiC/HfC ceramic coating reinforced by HfC nanowires was prepared. The microstructure, bonding strength, coefficient of thermal expansion and cyclic ablation resistance of the as-prepared coating were investigated. After incorporating HfC nanowires, the bonding strength between inner SiC coating and outer HfC coating was increased. HfC nanowires could relieve the coefficient of thermal expansion mismatch between inner and outer coating and improve the toughness of the outer coating. By introducing HfC nanowires, the coated sample’s cyclic ablation resistance was improved. After cyclic ablation under oxyacetylene flame for 60 s × 3, the mass and linear ablation rates of the coated sample with HfC nanowires were only 0.444 mg/s and −0.767 μm/s, respectively.     

HfC nanowires to improve the toughness and oxidation resistance of Si-Mo-Cr/SiC coating for C/C composites

To improve the oxidation resistance of carbon/carbon (C/C) composites, a dense HfC nanowire-toughened Si-Mo-Cr/SiC multilayer coating was prepared by chemical vapor deposition (CVD) and pack cementation. The microstructure, thermal shock and isothermal oxidation resistance of the coating were investigated. HfC nanowires could improve the toughness of the coating and suppress the coating cracking. After incorporating HfC nanowires in the coating, both of the thermal shock and isothermal oxidation resistance of the coating were obviously improved. The multilayer coating with HfC nanowires could effectively protect C/C composites at 1773 K for 270 h, whose weight loss is only 0.19%. The good oxidation resistance is mainly attributed to the formation of a compound glass layer containing SiO₂ and Cr₂O₃.     

Thermophysical properties of carbon fiber reinforced multilayered (PyC–SiC)n matrix composites

Three kinds of carbon fiber reinforced multilayered (PyC–SiC)_n matrix (C/(PyC–SiC)_n) composites (n = 1, 2 and 4) were prepared by means of layer-by-layer deposition of PyC and SiC via chemical vapor infiltration. Thermal expansion behaviors in the temperature range of 800–2500 °C and thermal conductivity from room temperature to 1900 °C of C/(PyC–SiC)_n composites with various microstructures were investigated. The results show that with increasing PyC–SiC sequences number (n), the coefficients of thermal expansion of the composites decrease due to the increase of interfacial delamination, providing room for thermal expansion. The thermal diffusivity and thermal conductivity also decrease with the increase of sequences number, which are attributed to the enhancement of phonon-interface scattering resulted from the increasing number of interfaces. Modified parallel and series models considering the interfacial thermal resistance are proposed to elaborate thermal conductivity of the composites, which is in accordance with the experimental results.     

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%.     

Effects of HfC nanowire amount on the microstructure and ablation resistance of CVD-HfC coating

To improve the ablation resistance of HfC coating for carbon/carbon (C/C) composites, various fractions of HfC nanowires were incorporated into the HfC coating by chemical vapor deposition (CVD). Effects of HfC nanowire amount on the microstructure and ablation resistance of the CVD-HfC coating were investigated. Results indicated that the HfC nanowire layer became thicker and denser with the deposition time extending. HfC nanowires could inhibit the formation of cracks and interlaminar gaps in the HfC coating. With the increase of HfC nanowire amount, the HfC coating became thicker, while its porosity and roughness firstly decreased and then increased. Ablation tests indicated that the incorporation of HfC nanowires could effectively improve the ablation resistance of the HfC coating, which could be ascribed to the decreasing surface temperature of the coated samples and the effective alleviation of cracking and delamination of the coating during ablation. The HfC coating with HfC nanowires deposited for 1?h exhibited better ablation resistance owing to its compact microstructure, and its mass and linear ablation rates were only 0.41?mg/s and ??1.53?µm/s after ablation for 120?s.     

Fabrication and properties of SiCnw-reinforced SiC composites by reactive melt infiltration with BN and PyC interface

To tailor the fiber–matrix interface of SiC nanowires-reinforced SiC (SiC_nw/SiC) ceramic matrix composites (CMCs) for improved mechanical properties, SiC nanowires were coated with BN and pyrolytic carbon (PyC) compound coatings prepared by the dip-coating process in boric acid and urea solution and the pyrolysis of phenolic resin. SiC_nw/SiC CMC with PyC/BN interfaces were fabricated by reactive melt infiltration (RMI) at 1680°C for 1 h. The influences of phenolic resin content on the microstructure and mechanical properties of the CMC were investigated. The results showed that the flexural strength and fracture toughness reach the maximum values of 294 MPa and 4.74 MPa m^1/2 as the phenolic resin content was 16 and 12 wt%, respectively. The displacement–load curve of the sample exhibited a gradient drop with increasing phenolic resin content up to 12 wt%. The results demonstrated that the PyC/BN compound coatings could play the role of protecting the SiC_nw from degradation as well as improving the more moderate interfacial bonding strengths during the RMI.     

Effects of HfC/PyC core-shell structure nanowires on the microstructure and mechanical properties of Hf1-xZrxC coating

To elevate the mechanical and anti-ablation properties of Hf_1-xZr_xC coating on C/C composites, HfC/PyC core-shell structure nanowires (HfCnw/PyC) with different PyC layer thickness were synthesized by two steps of CVD. Influences of HfCnw/PyC on the microstructure and mechanical properties of Hf_1-xZr_xC coating were researched. Toughening mechanism of HfCnw/PyC was also investigated. PyC layer exhibited a lamellar structure and combined well with HfCnw. After incorporating HfCnw/PyC, Hf_1-xZr_xC coating structure converted from columnar crystal to isometric crystal. HfCnw improved H, E, K_c and bonding strength of Hf_1-xZr_xC coating, which is ascribed to the nanowire pullout, debonding, bridging and crack deflection mechanism. With the PyC layer thickness increasing, H and E of the coating reduced, K_c and bonding strength of the coating increased. Because of the moderate bonding strength between HfCnw/PyC and coating matrix, lamellar structure of PyC layer and higher K_c of PyC, toughening effectiveness of the core-shell structures gradually enhanced with the PyC layer thickness increasing.     

Effects of SiC/HfC ratios on the ablation and mechanical properties of 3D Cf/HfC-SiC composites

Effects of SiC/HfC ratios on the ablation and mechanical properties of 3D C_f/HfC–SiC composites by precursor impregnation and pyrolysis (PIP) process were investigated systematically. Both strength (flexural and compressive strength) and modulus increase as the SiC/HfC ratio are improved. The compact and stiff HfC-SiC matrix in addition to the carbon fiber and PyC interphase with less reaction damage accounts for the improved mechanical properties of C_f/HfC-SiC with higher SiC/HfC ratios. Meanwhile, both weight loss and erosion depth of C_f/HfC-SiC are improved with the increased SiC/HfC ratios. Therefore, in order to balance the ablation and mechanical properties, an appropriate SiC/HfC ratio should be considered.     

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.     

Improved thermal shock resistance of SiCnw/PyC core-shell structure-toughened CVD-SiC coating

In-situ SiC nanowire (SiCnw)/pyrolytic carbon (PyC) core-shell structures were introduced to mainly improve the thermal shock performance of chemical vapor deposition (CVD)-SiC coating on carbon/carbon (C/C) composites. The microstructure, phase composition, and mechanical properties of the CVD-SiC coating toughened by SiCnw/PyC core-shell structures were studied as well. The results show that the introduction of SiCnw/PyC core-shell structures can effectively alleviate the mismatch of coefficient of thermal expansion (CTE) between SiC coating and C/C substrate, thus enhancing the thermal shock resistance of the coating. Furthermore, the increased numbers of interfaces in the SiC coating owing to the addition of core-shell structures are beneficial to the mechanical properties of the coating after thermal shock test.