Application of the pack cementation process on SiC/SiC ceramic matrix composites

The potentials and limitations of a halide-activated pack cementation process on SiC/SiC Ceramic Matrix Composites for the development of bond coats as part of environmental barrier coating (EBCs) systems were investigated. Different pack compositions using chromium, aluminum and alloys of these elements were tested and the kinetics of coating formation were examined in addition to their microstructure. The results and their analogy to diffusion couples were discussed and it was shown that coating elements which form silicides and carbides are promising candidates for coatings deposited on SiC/SiC via pack cementation. Based on such considerations a two-step pack cementation was proposed, which used chromium, one of the suitable elements, in a first step, to finally achieve an alumina-forming coating. The oxidation resistance of the developed coating was tested via thermogravimetric analysis and compared to the uncoated material. The coating protected the fiber-matrix interface of the SiC/SiC Ceramic Matrix Composites from oxidation.     

Effect of silicon/graphite ratio and temperature on oxidation protective properties of SiC/ZrB2–SiC coatings prepared by pack cementation

To investigate the silicon/graphite ratio and temperature on preparation and properties of ZrB₂–SiC coatings, ZrB₂, silicon, and graphite powders were used as pack powders to prepare ZrB₂–SiC coatings on SiC coated graphite samples at different temperatures by pack cementation method. The composition, microstructure, thermal shock, and oxidation resistance of these coatings were characterized and assessed. High silicon/graphite ratio (in this case, 2) did not guarantee higher coating density, instead could be harmful to coating formation and led to the lump of pack powders, especially at temperatures of 2100 and 2200 °C. But residual silicon in the coating is beneficial for high density and oxidation protection ability. The SiC/ZrB₂–SiC (ZS50-2) coating prepared at 2000 °C showed excellent oxidation protective ability, owing to the residual silicon in the coating and dense coating structure. The weight loss of ZS50-2 after 15 thermal shocks between 1500 °C and room temperature, and oxidation for 19 h at 1500 °C are 6.5% and 2.9%, respectively.     

Microstructures and oxidation behaviors of Al-modified and Al2O3-modified SiC coatings on carbon/carbon composites via pack cementation

Al₂O₃-modified SiC (AOSC) and Al-modified SiC (ASC) coatings were prepared on carbon/carbon (C/C) composites by one-time pack cementation (PC). Their microstructures and anti-oxidation performances were studied. Compared with ASC coating, AOSC coating shows more conspicuous defects (micro-cracks and holes) and lower densification. ASC coating can offer better oxidation resistance and thermal shock resistance to C/C composites than AOSC coating. Al additive can more efficiently improve the sinterability of SiC, which causes the above results. Besides, Al₂O₃ oxidation product is more stable than SiO₂ (l) of oxidized SiC at 1500 °C based on the thermodynamic analysis.     

SiC nanowire-toughened MoSi2-WSi2-SiC-Si multiphase coating for improved oxidation resistance of C/C composites

To improve the oxidation resistance of carbon/carbon (C/C) composites at high temperature, a SiC nanowire-toughened MoSi₂-WSi₂-SiC-Si multiphase coating was prepared by chemical vapor deposition (CVD) and pack cementation. The microstructure, mechanical properties and oxidation resistance of the coating were investigated. After the introduction of SiC nanowires, the elastic modulus, hardness, and fracture toughness of the MoSi₂-WSi₂-SiC-Si coating were increased by 25.48%, 4.09% and 45.03%, respectively. The weight loss of the coated sample with SiC nanowires was deceased from 4.83–2.08% after thermal shock between 1773 K and room temperature for 30 cycles and the weight loss is only 3.24% after isothermal oxidation at 1773 K in air for 82 h. The good oxidation resistance of the coating is mainly attributed to that SiC nanowires can effectively inhibit the propagation of cracks in the coating by the toughening mechanisms including bridging and pull-out.     

Oxidation protection and mechanism of the HfB2-SiC-Si/SiC coatings modified by in-situ strengthening of SiC whiskers for C/C composites

To improve the oxidation resistance and alleviate the thermal stress of the HfB₂-SiC-Si/SiC coatings for C/C composites, in-situ formed SiC whiskers (SiC_w) were introduced into the HfB₂-SiC-Si/SiC coatings via chemical vapor deposition (CVD). Effects of SiC_w on isothermal oxidation and thermal shock resistance for the HfB₂-SiC-Si/SiC coatings were investigated. Results showed that the SiC_w-HfB₂-SiC-Si/SiC coatings exhibited excellent oxidation resistance for C/C composites with only 0.88% weight loss after oxidation for 468?h at 1500?°C, which was markedly superior to 4.86% weight loss for coatings without SiC_w. Meanwhile, after 50 times thermal cycling, the weight loss of the SiC_w-HfB₂-SiC-Si/SiC coated samples was 4.48%, which showed an obvious decrease compared with that of the HfB₂-SiC-Si/SiC coated samples. The SiC_w-HfB₂-SiC-Si/SiC coatings exhibited excellent adhesion to the C/C substrate and had no penetrating cracks after oxidation. The improved performance of the SiC_w-HfB₂-SiC-Si/SiC coatings could be ascribed to the SiC_w, which effectively relieved CTE mismatch and remarkably suppressed the cracks through toughening mechanisms including whiskers pull-out and bridging strengthening. The above results were confirmed by thermal analysis based on the finite element method, which demonstrated that SiC_w could effectively alleviate thermal stress generated by temperature variation. Furthermore, the SiC_w-HfB₂-SiC-Si/SiC coating can provide a promising fail-safe mechanism during the high temperature oxidation by the formation of HfSiO₄ and SiO₂, which can deflect cracks and heal imperfections.     

Oxidation behavior of oxidation protective coatings for PIP-C/SiC composites at 1500 °C

Three-dimensional carbon fiber reinforced silicon carbide (C/SiC) composites were fabricated by precursor infiltration and pyrolysis (PIP) with polycarbosilane as the matrix precursor, SiC coating prepared by chemical vapor deposition (CVD) and ZrB₂-SiC/SiC coating prepared by CVD with slurry painting were applied on C/SiC composites, respectively. The oxidation of three samples at 1500 °C was compared and their microstructures and mechanical properties were investigated. The results show that the C/SiC without coating is distorted quickly. The mass loss of SiC coating coated sample is 4.6% after 2 h oxidation and the sample with ZrB₂-SiC/SiC multilayer coating only has 0.4% mass loss even after oxidation. ZrB₂-SiC/SiC multilayer coating can provide longtime protection for C/SiC composites. The mode of the fracture behavior of C/SiC composites was also changed. When with coating, the fracture mode of C/SiC composites became brittle. When after oxidation, the fracture mode of C/SiC composites without and with coating also became brittle.     

Oxidation resistance of SIC-AlN ceramics coated by oxidation-assisted-pack cementation process

Liquid-phase-pressureless-sintered SiC-AlN-Y₂O₃ composites were coated by means of modified pack cementation process (OXPAC, OXidation-assisted-PAck Cementation) using rare-earth oxides, RE₂O₃ (RE = Sc, Er, Sm, Lu, Ho), as reactive powders. The coatings, composed by the oxidation products of SiC, AlN and rare-earth silicates, were adherent to the substrate, without porosity and with a thickness of 10 μm. The oxidation resistance of the coated SiC-AlN-Y₂O₃ ceramics was also investigated at 1500 °C for a period of 200 h. The coated samples showed specific weight gain lower than the uncoated and pre-oxidised samples. Furthermore, the specific weight gain linearly increased with the rare-earth cationic radius.     

Effect of the incorporation of SiC nanowire with double protective layers on SiC coating for C/C composites

To maintain the thermal stability of SiC nanowires during SiC coating fabrication process, carbon and SiC double protective layers were covered on the surface of nanowires. And SiC nanowires with double protective layers toughened SiC coating were prepared by pack cementation. The results showed that after introducing the SiC nanowires with double protective layers, the fracture toughness of the SiC coating was increased by 88.4 %. The coating protected C/C for 175 h with a mass loss of 3.67 %, and after 51 thermal shock cycles, the mass losses of the oxidized coating were 3.96 %. The double protective layers are beneficial to improve the thermal stability of nanowires, leading to good fracture toughness and thermal shock resistance of SiC coating. SiC nanowires consume the energy of crack propagation by fracture, pullout and bridging, leading to an increase in fracture toughness.     

Wear behavior of SiC nanowire-reinforced SiC coating for C/C composites at elevated temperatures

To improve the wear resistance of SiC coating on carbon/carbon (C/C) composites, SiC nanowires (SiCNWs) were introduced into the SiC wear resistant coating. The dense SiC nanowire-reinforced SiC coating (SiCNW-SiC coating) was prepared on C/C composites using a two-step method consisting of chemical vapor deposition and pack cementation. The incorporation of SiCNWs improved the fracture toughness of SiC coating, which is an advantage in wear resistance. Wear behavior of the as-prepared coatings was investigated at elevated temperatures. The results show that the wear resistance of SiCNW-SiC coating was improved significantly by introducing SiC nanowires. It is worth noting that the wear rate of SiCNW-SiC coating was an order of magnitude lower than that of the SiC coating without SiCNWs at 800 °C. The wear mechanisms of SiCNW-SiC coating at 800 °C were abrasive wear and delamination. Pullout and breakage of SiC grains resulted in failure of SiC coating without SiCNWs at 800 °C.     

Influence of different coating structures on the oxidation resistance of MoSi2 coatings

Two different structures of MoSi₂ coatings were prepared on Niobium based alloys by using a two step process. The as-deposited type(a) MoSi₂ coating structure consists of a MoSi₂ layer on the surface and a NbSi₂ layer underneath, while the type(b) MoSi₂ coating consists of an outer MoSi₂ layer and an inner unsiliconized Mo layer. The oxidation behaviors of the two different types MoSi₂ coatings were examined at 1200 °C for 100 h in air, and the mass gains of type(a) and type(b) MoSi₂ coated specimens were 0.64 mg/cm² and 0.59 mg/cm² respectively. The excellent oxidation resistance of both type(a) and type(b) MoSi₂ coated samples at 1200 °C was due to the formation of a dense and continuous SiO₂ scale during oxidation. As the CTE mismatch between the outer MoSi₂ coating and the inner layer, cracks distributed within both type(a) and type(b) MoSi₂ coating structures.     

Effect of co-deposited SiC nanowires and carbon nanotubes on oxidation resistance for SiC-coated C/C composites

To protect carbon/carbon composites (C/Cs) against oxidation, SiC coating toughened by SiC nanowires (SiCNWs) and carbon nanotubes (CNTs) hybrid nano-reinforcements was prepared on C/Cs by a two-step technique involving electrophoretic co-deposition and reactive melt infiltration. Co-deposited SiCNWs and CNTs with different shapes including straight-line, fusiform, curved and bamboo dispersed uniformly on the surface of C/Cs forming three-dimensional networks, which efficiently refined the SiC grains and meanwhile suppressed the cracking deflection of the coating during the fabrication process. The presence of SiCNWs and CNTs contributed to the formation of continuous glass layer during oxidation, while toughed the coating by introducing toughing methods such as bridging effect, crack deflection and nanowire pull out. Results showed that after oxidation for 45 h at 1773 K, the weight loss percentage of SiC coated specimen was 1.35%, while the weight gain percentage of the SiCNWs/CNTs reinforced SiC coating was 0.03052% due to the formation of continuous glass layer. After being exposed for 100 h, the weight loss percentage of the SiCNWs/CNTs reinforced SiC coating was 1.08%, which is relatively low.     

Microstructure and oxidation behaviors at 800°C and 1250°C of MoSi2/ReSi2/NbSi2 compound coating prepared by electrodeposition and then pack cementation

MoRe duplex film has been electrodeposited from aqueous solution innovatively and then applied to fabricate protective silicide coating for the NbTiSi based alloy successively. The XRD, SEM and EDS results indicated the formation of MoSi₂/ReSi₂/NbSi₂ compound coating after halide reactivated pack cementation (HAPC) treatment. Pesting oxidation of MoSi₂ layer was suppressed and the NbTiSi based alloy was effectively protected at 800?°C with a mass gain of 0.48?mg?cm^?2 after oxidation for 100?h. At 1250?°C, continuous mass gain was observed with a mass gain of 2.6?mg?cm^?2 after exposure of 10?h. The synergistic combination of MoSi₂ and NbSi₂ layer enabled admirable protection of the substrate, in which MoSi₂ layer worked as the major anti-oxidation coating and the NbSi₂ layer could be a reservoir for Si. The contrast experiments indicate that ReSi₂ layer could improve the integrity and adherence of MoSi₂ layer, reduce the outward diffusion of alloying elements and oxidation of NbSi₂ layer, and then improve oxidation resistance of the compound coating ultimately.     

Comparison of microstructure and oxidation behavior of La-Mo-Si coatings deposited by two approaches

To investigate the effect of preparation methods on the La-Mo-Si (LMS) coatings, we developed a new LMS coating system using pack cementation (PC) and supersonic atmospheric plasma spraying (SAPS). Microstructure analysis showed that the SAPS-LMS coating possessed a higher porosity than that of the PC-LMS coating. Higher porosity can provide more channels to the oxidative and corrosive gasses to permeate the SAPS-LMS ceramic top-coat. After static oxidation for 150 h under 1773 K, the mass loss of SAPS-LMS coating (3.12 wt%) was much higher than that of the PC-LMS coating (0.05 wt%), and the parabolic rate constants presented faster oxidation kinetic in SAPS-LMS coating with respect to the PC-LMS coating. These results revealed that the protection effectiveness of SAPS-LMS coating was inferior to PC-LMS coating. Compared with SAPS-LMS coating, microscopic pores and cracks appeared in the PC-LMS coating with a thicker oxide film, which benefits from the formed La-Si-O-Al glass oxide with an excellent ability for crack healing. The reasons for poor antioxidant performance of SAPS-LMS coating are the higher volatility of La-Si-O glass containing Mo₅Si₃ and a weak interfacial interaction between coatings and substrate.     

SiC/SiC复合材料及其应用

日本开发的Nicalon和Tyranno两种品牌的SiC纤维占有世界上绝对性的市场份额。SiC/SiC复合材料典型的界面层是500 nm厚的单层热解碳(PyC)涂层或多层(PyC-SiC)n涂层,在湿度燃烧环境及中高温条件下界面层的稳定性是应用研究的重点。SiC/SiC复合材料,包括CVI-SiC基体和日本开发的Tyranno hex和NITE-SiC基体等,具有耐高温、耐氧化性和耐辐射性的特点,在航空涡轮发动机部件、航天热结构部件及核聚变反应堆炉第一壁材料等方面正开展工程研制应用。     

Cf/SiC 复合材料的 ZrB2-SiC/SiC 超高温陶瓷涂层研究

采用两步包埋法在Cf/SiC复合材料表面制备了Zr B_2-SiC/SiC超高温陶瓷涂层。借助SEM、XRD对涂层的微观结构及物相组成进行了分析研究,并进行了高温静态氧化和热震测试。研究表明,1500°C氧化5 h后,涂层表面覆盖有平整的玻璃相氧化层,氧化失重率为6.4%;热震测试10次后涂层的氧化失重率为14%。Zr B_2-SiC/SiC涂层能有效提高Cf/SiC复合材料的高温抗氧化性能。     

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.     

Oxidation and erosion resistance of multi-layer SiC nanowires reinforced SiC coating prepared by CVD on C/C composites in static and aerodynamic oxidation environments

A multi-layer SiC nanowires reinforced SiC (SiCnws-SiC) coating was prepared in-situ on carbon/carbon (C/C) composites by three chemical vapor deposition (CVD) processes. The microstructure and phase composition of the nanowires fabricated on the first-layer SiCnws-SiC coating and the coatings were examined by SEM, TEM, and XRD. The bamboo-like SiC nanowires with a 50?nm diameter and a length of several tens of micrometers are straight, randomly orientated and distributed like a net on the first-layer SiCnws-SiC coating. The growth direction is [111], and the growth mechanism is VS. The multi-layer SiCnws-SiC coating has three layers: the thickness of the first-layer is roughly 400?µm, and the outer two layers are about 200?µm. Each layer has a sandwich structure. The isothermal oxidation and erosion resistance of the multi-layer SiCnws-SiC coating were investigated in an electrical furnace and a high temperature wind tunnel. The results indicated that the weight loss of the multi-layer SiCnws-SiC coated C/C composites was only 1.8% after oxidation in static air at 1773?K for 361?h. Further, the coated sample failed due to fracture of the coating at the clamping position (i.e. 80?mm) after erosion at 1873?K for 130?h in the wind tunnel. The weight loss of the coated C/C composites occurred due to the formation of penetrating cracks in the coating during the oxidation thermal shock. The maximum bending moment and the larger clamping force caused the coating fracture and resulted in intense oxidation of the substrate and the failure of the specimen.     

炭/炭复合材料MoSi2/SiC抗氧化涂层的研究

采用包埋法制备C／C复合材料抗氧化MoSi2／SiC梯度涂层，同时对抗氧化涂层的形成、组织结构以及抗氧化性能与渗料的关系和抗氧化机理进行了研究。结果表明：采用包埋法制备的C／C复合材料抗氧化MoSi2／SiC梯度涂层致密，但有少量裂纹，涂层有良好的抗氧化效果。当Si与SiC保持一定的比例时，渗料中MoSi2的含量为50％时，涂层具有最好的抗氧化效果；当MoSi2与SiC保持一定的比例时，渗料中Si的含量为20％时，涂层具有最好的抗氧化效果。     

SiC/Si-MoSi2抗氧化涂层的制备及性能研究

为了提高石墨材料的抗氧化性,在石墨表面制备SiC/Si-MoSi2抗氧化涂层。首先以Si粉为原料,采用液硅渗透法制备SiC内层;然后以Mo粉和Si粉为原料,配制成m(Mo)∶m(Si)分别为1∶5、1.5∶5、2∶5和2.5∶5的料浆,采用料浆烧结法制备Si-MoSi2外层。利用SEM和EDS分析SiC/Si-MoSi2涂层于1400℃氧化前后的结构及组成。结果表明,料浆的Mo粉和Si粉配比对涂层的抗氧化性能有很大影响,当m(Mo)∶m(Si)=2∶5时,涂层具有最佳的抗氧化性能,且表现出长时间的抗氧化能力。     

Effect of SiC coating and heat treatment on the thermal radiation properties of C/SiC composites

The effects of SiC coating and heat treatment on the emissivity were investigated for 2D C/SiC composites prepared by CVI in the 6–16 μm range. SiC coating had an obvious effect on the spectral emissivity of the composites but caused just 5% difference in the total emissivity. A radiation transport model was applied to explain those changes caused by SiC coating. Heat treatment affected the thermal radiation properties of the composites through the microstructure evolution. Base on the complementary analytical techniques, the changes in the emissivity were attributed to a good graphitization degree of carbon phases, large β-SiC grain sizes and high α-SiC content resulting in high emissivity.