Oxidation Behavior from Room Temperature to 1500°C of 3D-C/SiC Composites with Different Coatings

A carbon-fiber-reinforced silicon carbide composite (3D-C/SiC) was prepared by chemical vapor infiltration. A SiC and SiC/Si-Zr coating were deposited on the composite to investigate the effect of different coatings on the oxidation behavior of 3D-C/SiC composites. The 3D-C/SiC(SiC/Si-Zr) composite decreased in weight below 1000°C and increased in weight above 1000°C. With an increasing oxidation time, the weight loss increased greatly and the weight gain increased little. The 3D-C/SiC(SiC) composite always decreased in weight over the full temperature range. With an increasing oxidation time, the weight loss increased rapidly below 1000°C and reached its minimum value at 1400°C. The 3D-C/SiC(SiC/Si-Zr) composite had a higher oxidation resistance above 1000°C, and the 3D-C/SiC(SiC) composite had a higher oxidation resistance below 1000°C. The wider the coating cracks, the larger the maximum weight loss and the lower the temperature corresponding to the maximum weight loss. With an increasing oxidation time, the activation energy of the 3D-C/SiC(SiC/Si-Zr) composite increased from 96 to 138 kJ/mol, and the 3D-C/SiC(SiC) composite increased from 130 to 180 kJ/mol.     

Ultra‐High‐Temperature Ceramic HfB2‐SiC Coating for Oxidation Protection of SiC‐Coated Carbon/Carbon Composites

To protect the carbon/carbon (C/C) composites from oxidation, an outer ultra‐high‐temperature ceramics (UHTCs) HfB₂‐SiC coating was prepared on SiC‐coated C/C composites by in situ reaction method. The outer HfB₂‐SiC coating consists of HfB₂ and SiC, which are synchronously obtained. During the heat treatment process, the formed fluid silicon melt is responsible for the preparation of the outer HfB₂‐SiC coating. The HfB₂‐SiC/SiC coating could protect the C/C from oxidation for 265 h with only 0.41 × 10^?2 g/cm² weight loss at 1773 K in air. During the oxidation process, SiO₂ glass and HfO₂ are generated. SiO₂ glass has a self‐sealing ability, which can cover the defects in the coating, thus blocking the penetration of oxygen and providing an effective protection for the C/C substrate. In addition, SiO₂ glass can react with the formed HfO₂, thus forming the HfSiO₄ phase. Owing to the “pinning effect” of HfSiO₄ phase, crack deflecting and crack termination are occurred, which will prevent the spread of cracks and effectively improve the oxidation resistance of the coating.     

Erosion Behavior of C/SiC Composites in Atomic Oxygen

A T300 carbon fiber and a SiC‐coated C/SiC composite made from the same fiber were studied in atomic oxygen environment. The carbon fiber shows significant degradation while the erosion rate of SiC‐coating of C/SiC is about 50 times lower. Evidence shows that Si is preferentially etched from the SiC surface. And XPS information showed that amorphous carbon and diamond‐like carbonare periodically generated on the tested composite surface. Statistical analysis shows that the C/SiC specimens have no significant change in flexural properties after 1‐year fluence AO treatment.     

Oxidation Behavior of Hot Pressed ZrB2‐ZrC‐SiC Ceramic Composites

Dense ZrB₂‐SiC ceramics containing 40 vol% ZrC particles are fabricated via hot pressing method. Then the sintered ceramics are oxidized in air up to 1500°C, and the oxidation kinetics of the ceramic composites is deduced in combination with the reacted fraction curves. As indicated by the experimental results, the oxidation kinetics changes from reaction‐controlled process to diffusion‐controlled one with increasing of oxidation temperature. In addition, the oxidation kinetics parameters are obtained, which indicates that the oxidation resistance decays at elevated temperatures. Furthermore, the evolution of surface morphology and oxide scale during oxidation process is clarified.     

TEM Study of the High‐Temperature Oxidation Behavior of Hot‐Pressed ZrB2–SiC Composites

The oxidation behaviors of ZrB₂‐ 30 vol% SiC composites were investigated at 1500°C in air and under reducing conditions with oxygen partial pressures of 10⁴ and 10 ^{? 8} Pa, respectively. The oxidation of ZrB₂ and SiC were analyzed using transmission electron microscopy (TEM). Due to kinetic difference of oxidation behavior, the three layers (surface silica‐rich layer, oxide layer, and unreacted layer) were observed over a wide area of specimen in air, while the two layers (oxide layer, and unreacted layer) were observed over a narrow area in specimen under reducing condition. In oxide layer, the ZrB₂ was oxidized to ZrO₂ accompanied by division into small grains and the shape was also changed from faceted to round. This layer also consisted of amorphous SiO₂ with residual SiC and found dispersed in TEM. Based on TEM analysis of ZrB₂ – SiC composites tested under air and low oxygen partial pressure, the ZrB₂ begins to oxidize preferentially and the SiC remained without any changes at the interface between oxidized layer and unreacted layer.     

Oxidation Behavior of MuIlite-Coated SiC and SiC/SiC Composites under Thermal Cycling between Room Temperature and 1200°-1400°C

Refractory oxide barrier coatings are a promising approach for improving the environmental durability of silicon-based ceramics in severe environments. The oxidation durability of a newly developed fully crystalline mullite coating on SiC and SiC/SiC composites was investigated under thermal cycling between room temperature and 1200°-1400°C with a higher frequency (1- or 2-h) and a lower frequency (20-h) cycling for times up to 1200 h. The new mullite coating exhibited significantly improved adherence and resistance to cracking when compared to conventional mullite coatings. Current issues include oxidation of SiC-based substrates, void formation at the coating/substrate interface, and cracking in the coating through the thickness.     

Effect of AlN Substitutions on the Oxidation Behavior of ZrB2–SiC Composites at 1600°C

The oxidation behavior of ZrB₂–SiC composites, with varying amounts of AlN substituting for ZrB₂, was studied isothermally under static ambient air at 1600°C for up to 5 h. Small amounts of AlN substitutions (≤10 vol%) were found to result in marginal improvement in the oxidation resistance, whereas larger amounts resulted in a significant deterioration. The size of ZrO₂ clusters formed on the oxidized surface was found to be a function of the AlN content. This effect was more pronounced after longer oxidation times (~1 h) as opposed to shorter durations (~5 min). It was postulated that presence of AlN results in the formation of Al₂O₃ during the oxidation process, subsequently resulting in a lowering of viscosity of the glassy silica scale, which facilitates the coarsening of ZrO₂ clusters. This also increases oxygen permeation through the scale which adversely affects the oxidation resistance of the high AlN content composites.     

Oxidation Behavior of ZrB2–SiC Composites at Low Pressures

ZrB₂‐60 mol%SiC composite with a eutectic microstructure was oxidized at 1573 to 1873 K with reduced total pressures (P_tot) and low oxygen partial pressures (). The mass change was continuously measured by a thermobalance, and then fit with a multiple paralinear model. Oxidation scale of SiO₂/ZrO₂+SiO₂/ZrO₂/ZrB₂ was formed at  > 0.13 kPa, whereas only porous ZrO₂ remained at  < 0.13 kPa, P_tot < 1.33 kPa and higher than 1773 K. With increasing , the parabolic oxidation constant decreased, whereas the linear oxidation constant increased.     

ZrB2-SiC/C层状复合陶瓷的高温氧化行为

利用流延法成膜和热压烧结工艺制备出了ZrB2-SiC层和石墨层交替排列、层厚均匀、界面清晰的ZrB2-SiC/C层状复合陶瓷.采用循环氧化法对ZrB2-SiC和ZrB2-SiC/C层状复合陶瓷在1000℃及1300℃空气中的氧化动力学曲线进行了研究.结果表明:在1000℃氧化增重时,ZrB2-SiC/C层状复合陶瓷在氧化反应初期表现为氧化增重,随着时间的增加,表现为氧化减重.在1300℃时,ZrB2-SiC/C层状复合陶瓷由于基体层ZrB2-SiC和弱夹层石墨相的氧化规律的相互叠加,使得其氧化增重曲线表现为抛物线规律.由XRD分析及扫描电镜观察发现,1300℃氧化15 h后,试样中不存在弱夹层石墨相,由于石墨相的挥发,材料残留孔隙.     

Ti3SiC2/SiC复合材料的抗高温氧化性研究

采用反应热压烧结法制备Ti3 SiC2/SiC复合材料,针对不同SiC含量的Ti3 SiC2/SiC复合材料在1100 ～ 1500℃下恒温氧化20h的氧化行为进行了研究.结果表明:(1)适量SiC的引入能有效的提高Ti3 SiC2/SiC复合材料的抗高温氧化性能;(2)复合材料的氧化膜分内外两层,外层成分为TiO2,逐渐向内层过渡为TiO2和SiO2的混合物.     

Effect of Si3N4 Addition on Compressive Creep Behavior of Hot‐Pressed ZrB2–SiC Composites

Compressive creep studies have been carried out on hot‐pressed ZrB₂–SiC (ZS) and ZrB₂–SiC–Si₃N₄ (ZSS) composites in air under stress and temperature ranges of 93–140 MPa and 1300°C–1425°C, respectively for time durations of ≈20–40 h. The results of these studies have shown the creep resistance of ZS composite to be greater than that of ZSS. As the temperature is increased from 1300°C to 1425°C, the stress exponent of ZS decreases from 1.7 to 1.1, whereas that of ZSS drops from 1.6 to 0.6. The activation energies for these composites have been found as ≈95 ± 32 kJ/mol at temperatures ≤1350°C, and as ≈470 ± 20 kJ/mol in the range of 1350°C–1425°C. Studies of the postcreep microstructures using scanning and transmission electron microscopy have shown the presence of glassy film with cracks at both ZrB₂ grain boundaries and ZrB₂–SiC interfaces. These results along with calculated values of activation volumes suggest grain‐boundary sliding as the major damage mechanism, which is controlled by O^2? diffusion through SiO₂ at ≤1350°C, and by viscoplastic flow of the glassy interfacial film at temperatures ≥1350°C. Studies by transmission electron microscopy have shown formation of crystalline precipitates of Si₂N₂O near ZrB₂–SiC interfaces in ZSS tested at ≥1400°C, which along with stress exponent values <1 suggests that grain‐boundary sliding involving solution‐precipitation‐type mechanism is operative at these temperatures.     

Polymer‐Derived SiC/B4C/C Nanocomposites: Structural Evolution and Crystallization Behavior

Structural evolution and crystallization behavior between 600°C and 1450°C during the preparation of bulk SiC/B₄C/C nanocomposites by the pyrolysis of CB‐PSA preceramic were investigated. The CB‐PSA preceramic converts into carbon‐rich Si–B–C ceramics up to 800°C. Structural evolution and crystallization of Si–B–C materials could be controlled by adjusting the pyrolytic temperature. The Si–B–C ceramics are amorphous between 800°C and 1000°C. Phase separation and crystallization begin at 1100°C. The crystallization of β‐SiC takes place at 1100°C and B₄C nanocrystallites generate at 1300°C. The sizes of β‐SiC and B₄C nanocrystals increase with the pyrolytic temperature rising. In addition, the boron‐doping effect on structural evolution was studied by comparing the crystallization and graphitization behavior of Si–B–C ceramics and the corresponding Si–C materials. Boron is helpful for the growth of β‐SiC nanocrystals and the graphitization, but harmful for the nucleation of β‐SiC crystallites.     

Braking Behavior of C/SiC Composites Prepared by Chemical Vapor Infiltration

Carbon fiber-reinforced silicon carbide matrix composites have the potential to overcome the shortcoming of the currently used carbon/carbon friction materials in aircraft brakes. In this article, the carbon/silicon carbide (C/SiC) composites were prepared by chemical vapor infiltration method, and the brake disks with different densities and component content were finally obtained. The friction coefficient and friction stability can be significantly improved by increasing both material density and carbon content. When the density of C/SiC composite is 2.3 g/cm³, the coefficient of friction measured is 0.23, the coefficient of friction stability remains about 0.43, the liner wear rate is less than 9.3 μm/cycle, and the weight wear rate is less than 9.1 μm/cycle. The rapid increase of friction coefficient approaching the end of braking is mainly related to the increasing of surface temperature in a short time and the enhanced adhesion and abrasion of contact conjunctions and asperities. The C/SiC composites exhibited a good stability of braking against fading versus the braking number and surface temperature. The surfaces of C/SiC brake disks were covered with wear debris including the fragment of carbon fibers after the braking tests. The wear on the surfaces is significantly determined by cyclic mechanical and thermal stresses, which result in the micro-cracks in the SiC matrix, the thin flakes of the surface materials as well as the grooves.     

Hot Corrosion Behavior of Barium Aluminosilicate-Coated C/SiC Composites at 900°C

Barium aluminosilicates (BAS) were coated on the carbon fiber-reinforced silicon carbide composites (C/SiC) as environmental barriers. The hot corrosion behavior of the coated composites was studied at 900°C in dry air and water vapor, respectively. The molten Na₂SO₄ was used as the corrosion reactant. The results indicate that the BAS coatings can effectively block the attack of molten Na₂SO₄ to C/SiC composites in dry air. However, the coated composites degrade rapidly when exposed to molten Na₂SO₄ coupled with water vapor. It is found that the BAS is corroded by Na₂SO₄ melt with the formation of BaSO₄, resulting in the destruction of BAS structure, which makes the coating lose its protection to the C/SiC composites in water vapor.     

Low‐Temperature Sintering of HfC/SiC Nanocomposites Using HfSi2‐C Additives

HfC/SiC nanocomposites were fabricated via the reactive spark plasma sintering (R‐SPS) of a nano‐HfC powder and HfSi₂‐C sintering additives. The densification temperature decreased to 1750°C as the additive content increased. XRD analysis indicated the formation of pure HfC–(19.3–33.8 vol%) SiC within the sintered composites without residual silicide or oxide phases or secondary nonoxide phases. Ultrafine and homogeneously distributed HfC (470 nm) and SiC (300 nm) grains were obtained in the dense composites using nano‐HfC powder through the high‐energy ball‐milling of the raw powders and R‐SPS. Grain growth was further suppressed by the low‐temperature sintering using R‐SPS. No amorphous phase was identified at the grain boundary. The maximum Vickers hardness, Young's modulus, and fracture toughness values of the HfC/SiC nanocomposites were 22 GPa, 292 GPa, and 2.44 MPa·m^1/2, respectively.     

Comparative Analysis of Low‐Cycle Fatigue Behavior of 2D‐Cf‐PyC/SiC Composites in Different Environments

A carbon fiber‐reinforced silicon carbide matrix composite with pyrolytic carbon interface (C_f‐PyC/SiC) and a protective coating was prepared by isothermal low pressure chemical vapor infiltration. Low‐cycle fatigue behavior of this material system was investigated at high temperatures up to 1800°C in a combustion environment and at room temperature in air, respectively. The combustion environment includes thermal mechanical loading, high temperatures, and oxidizing atmosphere. Low‐cycle fatigue tests were conducted at a maximum stress level of 180 MPa but at various temperatures and fatigue cycles. The residual strength variation of fatigue‐survived samples was due to different damage mechanisms in different environments.     

Preparation of C/C‐SiC Composites from All‐Cellulose Precursors

All‐cellulose composites (ACCs) are manufactured from high‐performance cellulose fibers and a cellulose‐containing ionic liquid (IL) as matrix‐forming dope via wet‐winding processes, using different concentrations of cellulose in the IL. ACCs are carbonized at 1650 °C and then infiltrated with liquid silicon. Application of a carbonization aid (ammonium dihydrogenphosphate, ADHP) substantially improves the carbon yield after carbonization but also results in the depletion of the mechanical properties of the final carbon/carbon silicon carbide (C/C‐SiC) material. The microstructure of the porous carbon/carbon preforms strongly depends on both the concentration of cellulose in the IL and the concentration of ADHP. A C/C‐SiC composite manufactured from 6 wt% cellulose in the matrix‐forming dope, in the absence of ADHP, has a maximum flexural strength of 60 MPa. New C/C‐SiC composites with different shapes including Z‐profiles and tubes are successfully manufactured from pre‐shaped ACC precursors. These composites keep their shape during carbonization and the final siliconization process step.     

Oxidation resistance of SiC nanowires reinforced SiC coating prepared by a CVD process on SiC‐coated C/C composites

Oxidation protective SiC nanowires‐reinforced SiC (SiCNWs‐SiC) coating was prepared on pack cementation (PC) SiC‐coated carbon/carbon (C/C) composites by a simple chemical vapor deposition (CVD) process. This double‐layer SiCNWs‐SiC/PC SiC‐coating system on C/C composites not only has the advantages of SiC buffer layer but also has the toughening effects of SiCNWs. The microstructure and phase composition of the nanowires and the coatings were examined by SEM, TEM, and XRD. The single‐crystalline β‐SiC nanowires with twins and stacking faults were deposited uniformly and oriented randomly with diameter of 50‐200 nm and length ranging from several to tens micrometers. The dense SiCNWs‐SiC coating with some closed pores was obtained by SiC nanocrystals stacked tightly with each other on the surface of SiCNWs. After introducing SiCNWs in the coating system, the oxidation resistance is effectively improved. The oxidation test results showed that the weight loss of the SiCNWs‐SiC/PC SiC‐coated samples was 4.91% and 1.61% after oxidation at 1073 K for 8 hours and at 1473 K for 276 hours, respectively. No matter oxidation at which temperature, the SiCNWs‐SiC/PC SiC‐coating system has better anti‐oxidation property than the single‐layer PC SiC coating or the double‐layer CVD SiC/PC SiC coating without SiCNWs.     

Microstructure and High‐temperature Oxidation Behavior of Ti3AlC2/W Composites

Using spark plasma sintering, Ti₃AlC₂/W composites were prepared at 1300°C. They contained “core‐shell” microstructures in which a Ti_xW_1?x “shell” surrounded a W “core”, in a Ti₃AlC₂ matrix. The composite hardness increased with W addition, and the hardening effect is likely achieved by the Ti_xW_1?x interfacial layer providing strong bonding between Ti₃AlC₂ and W, and by the presence of hard W. Microstructural development during high‐temperature oxidation of Ti₃AlC₂/W composites involves α‐Al₂O₃ and rutile (TiO₂) formation ≥1000°C and Al₂TiO₅ formation at ~1400°C while tungsten oxides appear to have volatilized above 800°C. Likely due to exaggerated, secondary grain growth of TiO₂‐doped alumina and the effect of W addition, fine (<1 μm) Al₂O₃ grains formed dense, anisomorphic laths on Ti₃AlC₂/5 wt%W surfaces ≥1200°C and coarsened to large (>5 μm), dense, TiO₂‐doped Al₂O₃ clusters on Ti₃AlC₂/10 wt%W surfaces ≥1400°C. W potentially affects the oxidation behavior of Ti₃AlC₂/W composites beneficially by causing formation of Ti_xW_1?x thus altering the defect structure of Ti₃AlC₂, resulting in Al having a higher activity and by changing the scale morphology by forming dense Al₂O₃ laths in a thinner oxide coating, and detrimentally through release of volatile tungsten oxides generating cavities in the oxide scale. For Ti₃AlC₂/5 wt%W oxidation, the former beneficial effects appear to dominate over the latter detrimental effect.     

Oxidation Behavior of SiC Whiskers at 600–1400°C in Air

The oxidation behavior of SiC whiskers (SiC_W) with a diameter size of 50–200 nm has been investigated at 600°C–1400°C in air. Experimental results reveal that SiC_W exhibit a low oxidation rate below 1100°C while a significant larger oxidation rate after that. This can be attributed to the small diameter size of SiC_W, which determines that it is hard to form a protective SiO₂ layer thick enough to hamper the diffusion of oxygen effectively. Both nonisothermal and isothermal oxidation kinetics were studied and the apparent oxidation energy was calculated to further understand the oxidation behavior of the SiC_W.