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 a C/C-ZrC-SiC composite based on high-solid-loading slurry impregnation under oxyacetylene torch

A C/C-ZrC-SiC composite was successfully prepared by high-solid-loading slurry impregnation combined with polymer infiltration and pyrolysis. The microstructure and ablation behavior of the C/C–ZrC–SiC composite were investigated. ZrC particles were uniformly distributed in the matrix, and the obtained C/C–ZrC–SiC composite had a high density of 2.74 g/cm³. After exposure to oxyacetylene flame with a heat flux of 3.86 MW/m² for 120 s, the mass and linear ablation rates of the composite were 0.72 ± 0.11 mg/s and 0.52 ± 0.09 µm/s, respectively. The excellent ablation properties of the composite were attributed to the protection of the matrix by a three-layered oxide scale consisting of ZrO₂/SiO₂-rich/ZrO₂-SiO₂.     

Preparation,mechanical and ablation properties of a C/C-TaB2-SiC composite

A C/C-TaB₂-SiC composite was successfully prepared by high-solid-loading slurry impregnation combined with polymer infiltration and pyrolysis. The composite had a density of 3.46 g/cm³ and consisted of pyrolyzed carbon, carbon fibers, TaB₂ particles, and precursor-derived SiC with their mass fractions of 7.8 %, 13.0 %, 58.6 %, and 20.6 %, respectively. The C/C-TaB₂-SiC composite possessed a flexural strength of 248.2 ± 16.8 MPa and a fracture toughness of 13.7 ± 1.6 MPa·m^1/2, and demonstrated a non-brittle fracture behavior. After exposure to oxyacetylene flame with a heat flux of 4.18 MW/m² for 120 s, the ablation temperature of the sample surface reached a maximum of 2263 °C, and the mass and line ablation rates were 2.24 mg/s and 12.92 µm/s, respectively. The ablation resistance mainly comes from the hindrance of oxygen diffusion by the oxide layer composed of tantalum oxide and a small amount of SiO₂.     

Ablative property and mechanism of SiC-CuxSiy modified C/C-ZrC composites prepared by a rapid method

A rapid method was developed to fabricate C/C-ZrC-SiC-Cu_xSi_y composites with low open porosity by precursor infiltration and pyrolysis combining with pressure assisted reactive melt infiltration. Dominant phases of ZrC and SiC with scattered Cu_xSi_y inclusions were present in continuous infiltrated matrix, in which the dimension of submicron ZrC particles displayed gradient change. At ablation test, the heat absorbing effect of Cu_xSi_y-phase and formation of protective ZrO₂-SiO₂ cover enhanced the ablative property of composites for short-time ablation, causing ablation rates of 30 s ablation reached 1.7 ± 0.1 µm/s and 1.3 ± 0.1 mg/s, respectively. As ablation time extends to 60 s, the massive consumption of Si-phase damaged the integrity of surface oxide cover, but the partial melted ZrO₂ improved the viscosity and self-healing ability of ZrO₂-SiO₂ mixture, protecting substrate from further erosion. Thus, ablation rates were increased and decreased to 3.8 ± 0.2 µm/s and 1.2 ± 0.1 mg/s, respectively.     

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.     

The ablation behavior and mechanical property of C/C-SiC-ZrB2 composites fabricated by reactive melt infiltration

In order to improve the ablation resistance of carbon/carbon (C/C) composites, SiC-ZrB₂ di-phase ceramic were introduced by reactive melt infiltration. The ablation properties of these composites were evaluated by oxyacetylene torch with a heat flux of 2.38 MW/m² for 60 s. Compared with the pure C/C composites, the C/C-SiC-ZrB₂ composites show a significant improvement in the ablation resistance, and the linear and mass ablation rates decreased from 10.28×10⁻³ mm/s to 6.72×10⁻³ mm/s and from 3.08×10⁻³ g/s to 0.61×10⁻³ g/s, respectively. After ablation test, the flexural strength retentions of the C/C and C/C-SiC-ZrB₂ composites near the ablated center region are 39.7% and 81.6%, respectively. The higher strength retention rate of C/C-SiC-ZrB₂ composites was attributed to the introduction of SiC-ZrB₂ ceramic phases, which have excellent ablation resistant property. During ablation test, an ‘embedding structure’ of Zr-O-Si glass layer was formed, which could act as an effective barrier for oxygen and heat. The oxide ceramic coating could protect the C/C-SiC-ZrB₂ composites from further ablation, and thus contribute to retaining the mechanical property of C/C-SiC-ZrB₂ composites after ablation.     

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.     

Effect of CrSi2 on the ablation resistance of a ZrSi2-Y2O3/SiC coating prepared by SAPS

To improve the ablation resistance of carbon/carbon (C/C) composites, a proportional amount of ZrSi₂-CrSi₂-Y₂O₃ mixed particles were deposited on the surface of SiC-coated C/C composites by supersonic air plasma spraying (SAPS) to form a ZrSi₂-CrSi₂-Y₂O₃/SiC coating. The microstructure and phase compositions of the coating were studied by SEM, EDS, XRD and its anti-ablation performance was tested by oxyacetylene torch. The experimental results showed that the ZrSi₂-CrSi₂-Y₂O₃ outer coating had a dense microstructure without obvious pores and microcracks, and the thickness reached approximately 150 μm. In the process of being eroded and scoured by the oxyacetylene flame, the coating exhibited excellent anti-ablation property, which was attributed to the mosaic microstructure formed by ZrO₂ and a Si-O-Cr liquid film on the coating surface. After experiencing an ablation time of 80 s, the linear ablation rate and the mass ablation rate of the coating were -1.0 ± 0.03 μm s^-1 and -0.16 ± 0.014 mg s^-1, respectively.     

High-temperature erosion resistance of ZrB2-based ceramic coating for lightweight carbon/carbon composites under simulated atmospheric re-entry conditions by high frequency plasma wind tunnel test

A double-layers ZrB₂-based ceramic coatings containing ZrB₂, MoSi₂, SiCw and borosilicate glass were prepared on lightweight and porous ZrB₂-modified carbon–bonded carbon fiber composites (CBCFs/ZrB₂) by a trace oxygen sintered technology. The high-temperature erosion resistance of the coated CBCFs/ZrB₂ was investigated under simulated atmospheric re-entry conditions by a high frequency plasma wind tunnel test with a heat fluxes of 1.3 MW/m and stagnation pressure of 1.2kPa. The results showed that the coated composites exhibited excellent ablation resistance for 800 s and the different positions of coating exhibit different response temperatures and microstructures. After ablation, the micrographs of marginal position show more compact than central position at sample surface. In addition, the side of the samples exhibits crack region, B₂O₃ precipitates region and virgin coating region.     

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 behaviour of Csf/ZrB2-SiC composites fabricated by direct ink writing and reactive melt infiltration

Pitch-based short carbon fibres reinforced C_sf/ZrB₂-SiC composites were fabricated by direct ink writing of short carbon fibres, followed by slurry impregnation and reactive melt infiltration. Ablation behaviour of the C_sf/ZrB₂-SiC composite was studied by air plasma test. It is indicated that the skeleton of the oriented short carbon fibres provides heat diffusion channels. Consequently, temperatures at the ablation surface are as low as ∼1730 ^oC and ∼2000 ^oC respectively at 4 MW/m² and 5 MW/m². The composite presents outstanding ablation-resistant performance with a linear recession rate of ∼ − 0.04 µm/s and mass recession rate of ∼ − 3.40 mg/s at 4 MW/m², ∼ − 0.17 µm/s and ∼ 3.58 mg/s at 5 MW/m². It is revealed that the fibres area and matrix area of the composite present different ablation mechanisms. The fibres area is ablated severely, while the matrix area presents excellent ablation-resistance with continuous ZrO₂-SiO₂ protective layer.     

Ablation behaviors of SiC nanowire-reinforced ZrC-SiC coating-matrix integrated C/C composites with different ratios of precursors

A novel method to prepare a coating on the C/C composite is discussed. The precursor infiltration pyrolysis method is usually applied to prepare interior ceramic matrix, thus SiC nanowires that can absorb the surficial precursor are added to prepare surficial ceramics. The method accomplishes the integration of the coating and the matrix so that no coating peels off after ablation. Moreover, the material with a ZrC/SiC precursor ratio of 5:1 (Z5S1), whose mass and linear rates are 0.47 mg/s and 0.95 µm/s, exhibits the highest overall resistance to ablation. The results demonstrate that higher ZrC content and more uniform phase distribution are beneficial to keep ZrO₂ in solid and form a denser and firmer oxide layer, which is more effective in improving the ablation resistance of the C/C composite.     

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.     

Effect of CVI SiC content on ablation and mechanism of C/C-SiC-ZrC-Cu composites

C/C-SiC-ZrC-Cu composites were fabricated by chemical vapor infiltration, precursor infiltration-pyrolysis and vacuum-pressure infiltration methods. During Cu infiltration, the Cu_6·69Si and Cu₃Si new phases are generated through reaction between SiC and molten Cu. The formed Cu_6·69Si, Cu₃Si, ZrC and SiC phases can improve the wettability and interface combination between Cu and the doped carbon matrix. The ablation tests demonstrate that the CVI SiC content significantly affects the structure of protective oxide layer, and induces inverse effects in ablation center at 2500 ^°C and 3000 ^°C. The relatively high CVI SiC content enhances the ablation resistance of composites at 2500 ^°C, but increases the linear ablation rate at 3000 ^°C due to the excessive evaporation and mechanical denudation. During ablation, the formed Si-Zr-C-O layer underneath ablation center and the Si-Cu-C-O layer on transition or marginal areas can prevent carbon matrix from serious oxidation. After ablation for 20 s, the C/C-SiC-ZrC-Cu composites with high CVI SiC content display the best anti-ablation property at 2500 ^°C, and the ablation rates are 3.5 ± 0.1 μm/s and 3.4 ± 0.1 mg/s.     

Bimodal microstructure ZrB2-MoSi2 coating prepared by atmospheric plasma spraying for carbon/carbon composites against long-term ablation

To protect carbon/carbon composites against long-term ablation, a bimodal microstructure ZrB₂-MoSi₂ coating, consisting of an outer ZrB₂-MoSi₂ layer modified by Y₂O₃ and an inner basal ZrB₂-MoSi₂ layer, was prepared by atmospheric plasma spraying. The microstructure, phase composition and ablation resistance of the proposed coating were investigated in detail. Results showed that the bimodal coating maintained integrity in structure except for phase composition. There was no visible interlayer between the inner ZrB₂-MiSi₂ layer and the outer modified one. Mass ablation rate of the bimodal microstructure ZrB₂-MoSi₂ coated C/C composites was −2.02 × 10⁻³ g/s under an oxyacetylene flame ablation at 1873 K for 600 s, which exhibited better ablation resistance than a single ZrB₂-MoSi₂ coating. The excellent ablation resistance was ascribed to the positive effect of Y₂O₃, which not only pined in the glassy phase and alleviated the volatilization of SiO₂ glass phase by reacting with SiO₂ to form high viscosity of Y₂SiO₅, but also stabilized ZrO₂ and promoted its recrystallization and growth.     

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.     

Preparation and properties of TaSi2-MoSi2-ZrO2-borosilicate glass coating on porous SiCO ceramic composites for thermal protection

A TaSi₂-MoSi₂-ZrO₂-borosilicate glass (TMZG) coating was prepared by a slurry method on a carbon fibre-reinforced porous silicon oxycarbide (SiCO) ceramic composite for thermal protection. The coating was well adhered to the substrate and showed a uniform thickness of approximately 375?µm. After thermal cycling from 1873?K to room temperature six times (total oxidation time of 180?min), the shape and dimension of the TMZG remain almost unchanged with no cracking or peeling of the coating surface. The TMZG-coated sample exhibits good oxidation resistance because of a molten SiO₂ film with ZrSiO₄ particles distributed on the outer layer of the coating. After ablation testing under an oxyacetylene flame at 1927?K for 90?s, the linear ablation rate of the TMZG coated sample are 8.33?×?10^?4 mm/s. The whole coating retains integrity, preventing substrate ablation during the test. The TMZG coating with excellent temperature resistance shows broad applicability in thermal insulation materials.     

Electrodeposited TiB2 on graphite as wettable cathode for Al production

Titanium diboride (TiB₂) is considered as a promising cathode material for Al production. However, the manufacture of TiB₂ cathodes is facing numerous challenges. In this study, electrodeposition of TiB₂ on graphite was performed in molten fluoride (FLiNaK) electrolyte at 600°C by using a periodically interrupted current technique for various electrodeposition times (from 10 to 75 minutes) and at two different current densities (−0.12 and −0.5 A/cm²). It is shown that the TiB₂ coating morphology/microstructure strongly depends on the applied current density. Denser coatings were obtained at j_on = −0.12 A/cm² with a growth rate of ca. 0.7 µm/min. The thicker films display a preferential crystallographic orientation along the [110] plan. At j_on = −0.5 A/cm², TiB₂ coatings are deposited at a growth rate of ca. 6 µm/min with no crystallographic texture. They present a porous and stratified morphology with numerous transversal macrocracks. All TiB₂ coatings show excellent wettability for molten Al as confirmed by sessile drop experiments. However, significant molten Al infiltration occurs in the TiB₂ coatings, which accumulates at the coating/graphite interface, inducing the coating delamination.     

HfB2 coating on C/C composites prepared by chemical vapor deposition: Thermodynamics and experimental investigation

A thermodynamic calculation on the HfB₂ coating prepared by chemical vapor deposition (CVD) through HfCl₄-BCl₃-H₂-Ar system was performed, together with the relevant verification experiments. The calculation results indicated that HfB₂ coating could be obtained above 900 °C with the ratios of BCl₃/HfCl₄ and H₂/HfCl₄ higher than 1 and 12, respectively. The experimental results demonstrated that the deposition temperature, H₂ and BCl₃ flow rates had significant effects on the grain size, growth rate and phase composition of HfB₂ coatings. A dense and uniform HfB₂ coating was prepared at 1150 °C with a BCl₃/HfCl₄ ratio of 3 and a H₂/HfCl₄ ratio of 20, whose mass and linear ablation rates were 15.61 mg/s and 15.58 μm/s under oxyacetylene flame.     

Preparation and ablation properties of SiC nanowire-reinforced ZrC–SiC coating-matrix integrated C/C composites

A modification of the precursor infiltration pyrolysis (PIP) method was explored to prepare the integrated doped ceramic matrix and coating by the added SiC nanowires layer and shape-stabilization process. The epitaxial layer of SiC nanowires provided surficial attachments for the precursor. And the shape-stabilization process aggregated loose ceramic particles into a coating. Then the SiC nanowire-reinforced ZrC–SiC coating-matrix integrated C/C (S/SZ-CZ/C) composite was simply prepared by the modified PIP method. The bonding strength between the coating and matrix of the S/SZ-CZ/C composite was improved. Through the ablation test, the mass and linear ablation rate of the S/SZ-CZ/C composite were 0.46 mg/s and 0.67 μm/s, which were 60.34 % and 74.91 % lower than those of the SiC nanowire-reinforced C/C–ZrC (S/CZ/C) composite, respectively. The integration of the coating and matrix enabled the formation of a continuous oxide layer of molten SiO₂ and ZrO₂ in the ablation process, which helped to block the oxygen and heat during the ablation test. Thus the ablation resistance of the materials was systematically and effectively improved.