Effect of ZrB2 and Polyvinyl Butyral Content on the Oxidation Resistance of ZrB2–SiC Coatings Produced by Slurry Brushing Method

ZrB₂–SiC coatings are prepared on the surface of graphite by slurry brushing method to improve the oxidation resistance. Effects of ZrB₂ content and polyvinyl butyral (PVB)–ethanol solution concentration on microstructure and static oxidation behavior of the ZrB₂–SiC coatings are investigated at 1200 °C in air. The results indicate that increasing ZrB₂ content improves the oxidation resistance of the coatings. When ZrB₂ content increases from 30 to 45 wt%, weight loss rates of the coated samples after oxidation at 1200 °C for 120 min decrease from −0.92% to −1.67%. Increasing binder solution concentration raises component content in the coatings. As PVB–ethanol binder concentration increases from 0.025 to 0.075 g mL⁻¹, weight loss rates of the coated samples after oxidation at 1200 °C for 120 min decrease from 0.32% to −0.38%. Excellent oxidation resistance of ZrB₂–SiC coating is attributed to self-sealing ability of B₂O₃ and borosilicate glass. The composite glass can inhibit oxygen diffusion by filling defects in the coating promptly. The borosilicate glass phase can enhance the fluidity of the composite glass. ZrO₂ and ZrSiO₄ particles restrict the growth of the microcrack, which improves the oxidation resistance of ZrB₂–SiC coating.     

Multi-layer CVD-SiC/MoSi2–CrSi2–Si/B-modified SiC oxidation protective coating for carbon/carbon composites

To further improve the oxidation resistance of coating for carbon/carbon (C/C) composites, a multi-layer CVD-SiC/MoSi₂–CrSi₂–Si/B-modified SiC coating was prepared on the surface of C/C composites by pack cementation and chemical vapour deposition method, respectively. The microstructures, oxidation and thermal shock resistance of the coating were studied. The influence of B content in pack powder on the microstructure and oxidation resistance of B-modified SiC coating was also investigated. The results show that the B-modified SiC coating prepared with 10 wt.% B exhibited the best oxidation protection ability for C/C composites at 1173 K. The multi-layer coatings could protect the C/C composites at 1173 K for 30 h and 1873 K for 200 h, and endure 30 thermal cycles between 1873 K and room temperatures. The oxidation resistance and thermal shock resistance is mainly attributed to their dense structure and self-sealing property.     

The anti-oxidation behavior and infrared emissivity property of SiC/ZrSiO4–SiO2 coating

In order to improve the oxidation resistance and decrease the infrared emissivity of carbon/carbon(C/C) composites, the SiC and SiC/ZrSiO₄–SiO₂ (SZS) coating were prepared by pack cementation and slurry painting method. The phase compositions and microstructures of the as-prepared coatings were characterized by X-ray diffraction, scanning electron microscopy and energy dispersive spectrometer. The anti-oxidation property, failure and infrared emissivity of single SiC coating and SZS coating were investigated. The results show that the weight loss of single SiC coated sample reached 2.1 ± 0.025 % after 58 h isothermal oxidation at 1,500 °C. While the SZS coating exhibits superior oxidation resistance and can protect C/C matrix from oxidation for more than 198 h with a weight-gain of 3.67 ± 0.025 %. The failure mechanisms of single SiC coating are mainly resulting from unself-healing defects caused by the CO₂ gas which generated during the oxidation process of SiC. The investigation of infrared emissivity property reveals that, the infrared emissivity of SZS coating increases gradually from 0.45 to 0.72 between 3 and 14 μm. The infrared emissivity at 500 °C increases gradually from 0.2 to 0.65 between 3 and 14 μm. The coupled effect between dipole moments and lattice vibration in higher temperature becomes weaker, which in turn lead to the reducing of infrared emissivity in turn. From the anti-oxidation and infrared emissivity property point of view, the SZS coating may be one of the most promising candidates for the anti-oxidation at high temperature and low infrared emissivity of C/C composite.     

Preparation and properties of 2D C/ZrB2-SiC ultra high temperature ceramic composites

Two-dimensional C/ZrB₂-SiC composites were fabricated by chemical vapor infiltration (CVI) process combined with slurry paste (SP) method. ZrB₂ was introduced in the matrix by stacking the pasted carbon cloth with ZrB₂-polycarbosilane slurry. After heat-treated at 900 °C, the stacked carbon cloth preform was infiltrated SiC by CVI process to obtain 2D C/ZrB₂-SiC composites. Mechanical properties such as flexural strength and interlaminar shear strength were investigated. The ablation tests were carried out on an oxyacetylene torch flame. The small linear erosion rates indicate that the composites have good ablation resistance properties. These results demonstrate that CVI combined with SP method is a useful way to fabricate 2D C/ZrB₂-SiC composites.     

原位反应法制备Cf/SiC复合材料MoSi2-SiC-Si涂层

以C_f/SiC复合材料为基体, 采用原位反应法制备了MoSi₂-SiC-Si涂层, 借助XRD、扫描电镜及能谱对涂层的结构及组成进行了分析研究, 并考查了其高温抗氧化性能. 结果表明, 涂层总厚度约120μm, 主要由MoSi₂、SiC和Si组成. MoSi₂-SiC-Si涂层具有优异的高温抗氧化性能, 在1500℃静态空气中氧化96h, 涂层试样失重仅1.8%. 涂层试样失重的主要原因是由于氧气通过涂层中的贯穿性裂纹与C_f/SiC复合材料基体发生了反应.     

Effect of a weak fiber interface coating in ZrB2 reinforced with long SiC fibers

This study reports the microstructural analysis and mechanical properties of a ZrB₂ ceramic containing long BN-coated Hi-Nicalon SiC fibers. A composite was produced and thoroughly characterized by transmission electron microscopy to study the interfaces at the nanoscale level. Full densification was accomplished by hot pressing at 1450 °C. The fiber in the sintered material retained its pristine aspect, confirming that the coating was effective in preventing degradation due to interactions with the matrix. Pull-out was observed on fractured surfaces, but toughness values were about 4.5 MPa√m, which was comparable to those of ZrB₂ materials with SiC additions in the form of particles or short fibers. However, the composites exhibited a controlled fracture behavior, as confirmed by a notably higher work of fracture, 140 J/m², compared with 20–30 J/m² of unreinforced ZrB₂ or ZrB₂ containing chopped fibers.     

Oxidation behavior and mechanical properties of C/SiC composites with Si-MoSi2 oxidation protection coating

A new kind of oxidation protection coating of Si-MoSi₂ was developed for three dimensional carbon fiber reinforced silicon carbide composites which could be serviced upto 1550 °C. The overall oxidation behavior could be divided into three stages: (i) 500 °C < T < 800 °C, the oxidation mechanism was considered to be controlled by the chemical reaction between carbon and oxygen; (ii) 800 °C < T < 1100 °C, the oxidation of the composite was controlled by the diffusion of oxygen through the micro-cracks, and; (iii) T > 1100 °C, the oxidation of SiC became significant and was controlled by oxygen diffusion through the SiC layer. Microstructural analysis revealed that the oxidation protection coating had a three-layer structure: the out layer is oxidation layer of silica glass, the media layer is Si + MoSi₂ layer, and the inside layer is SiC layer. The coated C/SiC composites exhibited excellent oxidation resistance and thermal shock resistance. After the composites annealed at 1550 °C for 50 h in air and 1550 °C 100 °C thermal shock for 50 times, the flexural strength was maintained by 85% and 80% respectively. The relationship between oxidation weight change and flexural strength revealed the criteria for protection coating was that the maximum point of oxidation weight gain was the failure starting point for oxidation protection coating.     

C/C复合材料Ta2O5-TaC/SiC抗氧化抗烧蚀涂层研究

采用包埋法和低压化学气相沉积(CVD)法在碳/碳(C/C)复合材料表面依次制备了Ta2O5-TaC内涂层和SiC外涂层,用X射线衍射分析(XRD)、扫描电镜(SEM)及电子能谱(EDS)对涂层的相组成、微观形貌和元素组成进行了分析,研究了涂覆涂层后C/C复合材料在1 500℃静态空气中的防氧化性能及在氧-乙炔烧蚀中的抗烧蚀性能。结果表明:采用两步法制得的Ta2O5-TaC/SiC复合涂层结构致密,该复合涂层有效提高了C/C复合材料的抗氧化和抗烧蚀性能;Ta2O5-TaC/SiC复合涂层在1 500℃静态空气环境下可对C/C复合材料有效保护100 h以上;涂层试样在氧乙炔烧蚀环境中烧蚀60 s表明涂层可将C/C复合材料的线烧蚀率降低47.07%,质量烧蚀率降低29.20%。     

Si-Al-Ir Oxidation Resistant Coating for Carbon/Carbon Composites by Slurry Dipping

A Si-Al-Ir oxidation resistant coating was prepared for SiC coated carbon/carbon composites by slurry dipping. The phase composition, microstructure and oxidation resistance of the as-prepared Si-Al-Ir coating were studied by XRD (X-ray diffraction), SEM (scanning electron microscopy), and isothermal oxidation test at 1773 K in air, respectively. The surface of the as-prepared Si-Al-Ir coating was dense and the thickness was approximately 100 μm. Its anti-oxidation property was superior to that of the inner...     

Ablation behavior and mechanism of SiC/Zr–Si–C multilayer coating for PIP-C/SiC composites under oxyacetylene torch flame

To improve the ablation resistance of PIP-C/SiC composites, SiC/Zr–Si–C multilayer coating was prepared by chemical vapor deposition (CVD) using methyltrichlorosilane (MTS) and hydrogen as the precursors and molten salt reaction using KCl–NaCl, sponge Zr and K₂ZrF₆, then the ablation capability of the coated composites was tested under oxyacetylene torch flame. The linear and mass ablation rates were much lower than those of uncoated samples. The linear and mass ablation rates of the three coating coated samples reached 0.0452 mm/s and 0.031 g/s, decreased by 27.3% and 27.1%, respectively. Moreover, the linear and mass ablation rates of the five coating coated samples reached 0.0255 mm/s and 0.0274 g/s, decreased by 59.0% and 35.5%. The gases released during ablation could take away a lot of heat, which was also helpful to the protection of the composites.     

超音速等离子体喷涂MoSi2涂层工艺研究

涂层技术是C/C复合材料高温抗氧化与抗烧蚀的有效手段,单一的SiC涂层很难为C/C复合材料提供有效的长寿命保护。金属间化合物MoSi2高温时会形成一层致密的SiO2保护膜,具有特别优异的高温抗氧化性能,常作为C/C复合材料的高温抗氧化涂层。本文采用超音速等离子喷涂法在带SiC涂层的C/C复合材料表面制备了MoSi2涂层,主要研究了喷涂功率、主气(Ar)流量对粉料表面温度、飞行速度、沉积率以及对涂层表面微观结构和结合强度的影响。结果表明:喷涂功率在47.5~52.5 kW之间,既能使粒子有较高的速度和温度,还能保证粉末不过熔,在喷涂功率为50 kW时,粉料的沉积率最高,氧化不高,涂层表面致密性好,截面结合紧密,结合强度高;Ar流量为65 L/min时,能够保证MoSi2粉末有较高的表面温度与较快飞行速度,沉积率最高,氧化不高,涂层表面致密,几乎没有孔隙与裂纹。因此,调控超音速等离子体喷涂工艺参数能够在带SiC涂层的C/C复合材料表面得到致密且结合良好的MoSiO2涂层。     

A multilayer MoSi2-SiC-B coating to protect SiC-coated carbon/carbon composites against oxidation

To protect carbon/carbon (C/C) composites against oxidation, a multilayer MoSi₂-SiC-B coating was prepared on the SiC-coated C/C composites by a simple and low-cost slurry method. The phase, microstructure and element distribution of the as-received coating were analyzed using X-ray diffraction, scanning electron microscopy and energy dispersive X-ray spectroscopy. The as-received coating could effectively protect C/C composites against oxidation at 850 °C in air for 100 h without mass loss, which exhibits better oxidation protective ability than the multilayer MoSi₂-SiC coating prepared by the same method. At intermediate temperature (850 °C), the excellent oxidation protective ability of the coating is mainly attributed to the formation of the molten B₂O₃ for sealing the microcracks and preventing oxygen from attacking the C/C substrate.     

高温氧化及热震对SiC/ZrB2-SiC/SiC涂层炭/炭复合材料力学行为的影响

为提高炭/炭(C/C)复合材料的高温抗氧化性能,同时分析涂层制备及高温氧化对涂层材料力学行为的影响,在C/C复合材料表面采用反应熔渗、料浆涂刷结合化学气相沉积工艺制备了SiC/ZrB2-SiC/SiC三层高温抗氧化涂层。利用SEM和XRD分析复合涂层的微观结构和相组成,考察涂层复合材料1500℃高温抗氧化和1500℃-室温的抗热震性能,研究高温氧化及热震对涂层C/C复合材料力学行为的影响。结果表明,复合涂层试样1500℃静态空气环境下具有优异的抗氧化及抗热震性能:1500℃氧化20 h后试样保持增重,1500℃至室温热震50次后增重为0.69%。因涂层制备过程中粉料的渗入反应,复合材料弯曲强度增长了7.08%。在经历1500℃氧化20 h和1500℃至室温50次热震后,涂层复合材料弯曲强度有所下降,且因材料界面结合力的减弱使得纤维拔出特征明显,材料塑性断裂特征增强。     

Quantitative evaluation of the oxidation behavior of ZrB2-15 vol.%SiC at a low oxygen partial pressure

Oxidation tests of ZrB₂–SiC composite were carried out at 1373–1923 K under a low oxygen partial pressure of 57 Pa. By making composite with SiC, ZrB₂ shows good oxidation resistance. The ZrB₂-15 vol.%SiC composite shows better oxidation resistance at higher temperatures than ZrB₂-30 vol.%SiC with respect to mass decrease. The SiC depleting is the main cause of this mass decrease and is quite significant under the low oxygen partial pressure. The SiC depleting seems to start to occur at around 1673 K or higher. The mass changes of ZrB₂-15 vol.%SiC are quantitatively discussed by introducing an empirical equation. A first attempt of the evaluation of passive/active transition has been conducted using the obtained values.     

SiC-Si-ZrSiO_4 Multiphase Oxidation Protective Coating for Carbon/Carbon Composites

In order to improve the anti-oxidation property of carbon/carbon （C/C） composites, a novel SiC-Si-ZrSiO4 multiphase oxidation protective coating was produced on the surface of C/SiC coated carbon/carbon compo ites by a pack cementation technique. The phase composition and microstructure of the as-prepared coatings were characterized by XRD （X-ray diffraction）, SEM （scanning electron microscopy） and EDS （energy dispersive spectroscopy）. Oxidation behavior of the multiphase coated C/C composites was also investigated. It showed that the as-prepared coating characterized by excellent oxidation resistance and thermal shock re- sistance could effectively protect C/C composites from oxidation at 1773 K for 57 h in air and endure the thermal cycle between 1773 K and room temperature for 12 times, whereas the corresponding weight loss is only 1.47%. The excellent oxidation protective ability of the SiC-Si-ZrSiO4 coating could be attributed to the C/SiC gradient inner layer and the multiphase microstructure of the coating.     

包埋法制备SiC涂层内残留Si的高温抗氧化作用机制

采用包埋法在C/C基体上制备了SiC涂层, 借助X射线衍射仪(XRD)和扫描电镜(SEM)对涂层的相组成及微观形貌进行了观察和分析, 研究了涂层在1500℃静态空气中的氧化行为, 并进一步阐述了涂层的抗氧化机制。结果显示: 包埋法制备的涂层由α-SiC、 β-SiC及游离Si组成, 经XRD半定量分析得到不同工艺制备的涂层中游离Si含量不同; 游离Si含量越高涂层越致密; 氧化性能显示涂层中适量的游离Si有利于涂层的抗氧化, 当涂层中游离Si质量分数为1.3%和2.9%时其抗氧化性能均较好, 在1500℃静态空气中氧化7 h失重率分别为0.19%和0.16%。      

Microstructure and mechanical properties of ZrB2-SiC composites

A ZrB₂-based composite containing 20 vol.% nanosized SiC particles (ZSN) was fabricated at 1900 °C for 30 min under a uniaxed load of 30 MPa by hot-pressing. The microstructure and mechanical properties of the composite were investigated. It was shown that the grain growth of ZrB₂ matrix was effectively suppressed by submicrosized SiC particles located along the grain boundaries. In addition, the mechanical properties of ZSN composite were strongly improved by incorporating the nanosized SiC particles into a ZrB₂ matrix, especially for flexural strength (925 ± 28 MPa) and fracture toughness (6.4 ± 0.3 MPa•m^1/2), which was much higher than that of monolithic ZrB₂ and ZrB₂-based composite with microsized SiC particles, respectively. The formation of intragranular nanostructures plays an important role in the strengthening and toughening of ZrB₂ ceramic.     

Influence of the microstructure evolution of ZrO2 fiber on the fracture toughness of ZrB2–SiC nanocomposite ceramics

ZrB₂–SiC nanocomposite ceramics toughened by ZrO₂ fiber were fabricated by spark plasma sintering (SPS) at 1700 °C. The content of ZrO₂ fiber incorporated into the ZrB₂–SiC nanocomposites ranged from 5 mass% to 20 mass%. The content, microstructure, and phase transformation of ZrO₂ fiber exhibited remarkable effects on the fracture toughness of the ZrO_2(f)/ZrB₂–SiC composites. Fracture toughness of the composites greatly improved to a maximum value of 6.56 MPa m^1/2 ± 0.3 MPa m^1/2 by the addition of 15 mass% of ZrO₂ fiber. The microstructure of the ZrO₂ fiber exhibited certain alterations after the SPS process, which enhanced crack deflection and crack bridging and affected fracture toughness. Some microcracks were induced by the phase transformation from t-ZrO₂ to m-ZrO₂, which was also an important reason behind the improvement in toughness.     

Oxidation behaviour of three-dimensional woven C/SiC composites

Abstract

The oxidation behaviour of a three-dimensional woven C/SiC composite protected with an SiC seal coating and with an SiC coating combined with an SiO₂–B₂O₃ glassy coating have been respectively investigated through an experimental approach based on mass and flexural strength changes. Three main temperature domains exist for C/SiC composites protected with an SiC seal coating. At low temperatures (<700°C), the mechanisms of reaction between carbon and oxygen control the oxidation kinetics. At an intermediate temperatures (between 700 and 1100°C), the oxidation kinetics are controlled by gas phase diffusion through a network of microcracks in the SiC matrix and coating. At high temperatures (>1100°C), the oxidation kinetics are controlled by oxygen diffusion through the SiO₂ scale formed on the SiC coating. Composites of C/SiC with an SiC/(SiO₂–B₂O₃) coating exhibit better oxidation resistance. The filling of the pores and the microcracks and the flow of the glassy coating at higher temperatures result in a global decrease of mass loss in the composites. By researching the relationship between the residual flexural strength and the mass variation in different temperature ranges, it is shown that the change in the residual flexural strength is dominated by the degradation of carbon phase.     

碳/碳复合材料MoSi2/SiC涂层在动态氧化环境下的性能研究

为了考察MoSi₂/SiC防氧化涂层体系在动态氧化环境下的防护能力,对碳/碳复合材料MoSi₂/SiC涂层试样在1100~1500℃下进行了高温燃气高质流冲刷环境下的氧化试验。结果表明,在1100~1500℃的燃气动态环境下,具有稳定的氧化失重速率,氧化失重曲线近似呈直线关系,氧化失重和氧化失重速率均随着氧化温度的升高而降低,表现出该涂层抗高质流冲刷和氧化的能力随温度的升高而提高,在该温度区间内,随着温度的升高,具有更优异的抗氧化和抗高质流冲刷的能力。