SiC/ZrB2-SiC-B4C涂层的抗氧化和耐烧蚀性能研究

碳/碳化硅复合材料(C/SiC)在使用时经常受到高温氧化和烧蚀作用。本文采用化学气相沉积(CVD)和浆料刷涂-烧结法制备了双层SiC/ZrB2-SiC-B4C涂层,对比研究了无涂层,单层SiC涂层和双层SiC/ZrB2-SiC-B4C涂层C/SiC复合材料在1500℃下的氧化和在4.2 MW/m2热流密度下的烧蚀性能。结果表明,制备态ZrB2-SiC-B4C涂层致密、完整,表面平均粗糙度约为1 μm,孔隙率约为4.2 %。在1500℃氧化30 h后,SiC/ZrB2-SiC-B4C涂层C/SiC复合材料的质量损失率约为10%,涂层表面氧化膜致密,无明显裂纹。高温烧蚀20 s后,SiC/ZrB2-SiC-B4C涂层的线烧蚀率和质量烧蚀率分别为1.0±0.3 μm/s和1.1±0.2 mg/s,与单层SiC涂层相比分别降低了75.0 %和50.0 %,SiC/ZrB2-SiC-B4C涂层烧蚀后形成的ZrO2-SiO2氧化膜可以减缓火焰对复合材料的机械剥蚀作用。     

碳/碳复合材料SiC/W-Al-Si涂层微观结构及抗氧化性能

分别采用包埋法、料浆法在碳/碳（C/C）复合材料表面制备了碳化硅（SiC）内涂层、W-Al-Si合金外涂层,借助XRD和SEM分析了所得涂层的物相组成和微观结构,并测试了带有单一SiC涂层、SiC/W-Al-Si双涂层碳/碳复合材料试样在1500℃静态空气中的抗氧化性能。结果表明：富Si的SiC内涂层结构疏松,仅能为碳/碳基体提供数小时的防氧化保护;W-Al-Si合金外涂层主要由WSi2和W（Si,Al）2两相组成;SiC/W-Al-Si双涂层厚度约为100μm,其抗氧化性能明显优于单一SiC涂层,氧化19 h后涂层试样的质量损失未超过5%;有望进一步通过优化W-Al-Si外涂层料浆比例,避免因为与SiC内涂层热膨胀不匹配而产生透性裂纹,从而发挥出超过19 h后SiC/W-Al-Si双涂层的氧化防护潜力。     

La2O3改性ZrB2-SiC涂层C/C复合材料全温域抗氧化行为研究

采用高温反应熔渗工艺制备了ZrB2-SiC和La2O3改性ZrB2-SiC涂层C/C复合材料,对比了2种涂层试样在中温(7001100℃)、高温(12001500℃)和超高温(2000℃以上)3个温域范围内的抗氧化性能。结果表明:7001100℃范围内,随着温度的升高,La2O3改性涂层试样的抗氧化性能提升幅度在逐渐提高。1200℃1500℃范围内,涂层均表现出良好的长时抗氧化性能,La2O3改性ZrB2-SiC在1200℃下恒温氧化250 h后,仍保持微量的增重;涂层复合材料良好的高温抗氧化性能主要其在是由于氧化过程中涂层表面形成的La-Si-O复合玻璃层和钉扎相ZrSiO4的协同作用提升了氧化膜的高温稳定性。在2000℃以上的氧乙炔火焰烧蚀环境下,La2O3的添加使得ZrB2-SiC涂层的质量烧蚀率和线烧蚀率均降低了近50%,其主要归因于表层La-Si-O和ZrO2玻璃层对烧蚀缺陷的愈合作用。     

HfB_2-WB_2-Si/SiC-SiC_(NW)复合涂层的制备及其抗氧化性能

为解决C/C复合材料的高温易氧化问题,依次采用前驱体浸渍裂解、反应熔体浸渗和料浆涂刷法在C/C复合材料表面制备HfB_2-WB_2-Si/SiC-SiC_(NW)复合涂层。考察Si C涂层、HfB_2-WB_2-Si/SiC涂层和HfB_2-WB_2-Si/SiC-SiC_(NW)涂层C/C复合材料在1 500℃静态空气中的抗氧化性能。结果表明:HfB_2-WB_2-Si/SiC-SiC_(NW)涂层抗氧化效果优于HfB_2-WB_2-Si/Si C涂层和Si C涂层,前者试样氧化20 h后增重0.1%,后两者则分别失重0.9%和22.8%。HfB_2-WB_2-Si/SiC-SiC_(NW)涂层较好的抗氧化性能主要归因于涂层氧化形成的连续、具有较好流动性的HfSiO_4-SiO_2-WO_3复相玻璃以及SiC纳米线(SiCNW)对涂层的增韧作用,前者有效抑制了氧气向C/C复合材料基体内部的扩散,后者则使涂层内部裂纹的数量和尺寸明显减小。     

C／C复合材料ZrB2-SiC基陶瓷涂层制备及烧蚀性能研究

为提高C／C复合材料的抗烧蚀性能,采用两步刷涂一烧结法制备了ZrB2-SiC基陶瓷涂层。首先利用反应烧结制备ZrB2-SiC—ZrC过渡层,并在此基础上制备了ZrB2-20％SiC-5％Si3N4、ZrB2．15％SIC-20％MoSi2、ZrB2．15％SiC-20％TaC3种外涂层。利用XRD和扫描电镜研究了涂层的相组成和显微形貌,并采用氧乙炔焰烧蚀仪测试了涂层在2500℃、60S的抗烧蚀性能,探讨了涂层的高温烧蚀机理。结果表明：利用反应烧结制备的过渡层与基体结合紧密,且与外涂层无明显分层现象,起到了良好的过渡作用;由于Si,N4及MoSi2起到了烧结助剂作用,使ZrB2—20％SiC-5％Si,N4、ZrB2．15％SiC．20％MoSi2外涂层结构较为致密;ZrB2—20％SiC-5％si3N4、ZrB2—15％SiC～20％MoSi2涂层表现出了较好的抗烧蚀性能,其中ZrB2-20％SiC-5％Si3N4涂层线烧蚀率及质量烧蚀率分别为0．075mm/s、0．0081/s,ZrB2—15％SIC-20％MoSi2涂层线烧蚀率及质量烧蚀率分别为0．018mm／s、0．0064g／s,而ZrB2-15％SIC-20％TaC涂层由于结构较为松散,未能起到有效的氧化防护,导致涂层被烧穿。     

C／C复合材料防氧化涂层SiC／SiC—MoSi2的制备与抗氧化性能

采用包埋法和涂刷法在C/C复合材料表面依次制备了SiC内涂层和SiC-MoSi2外涂层,借助XRD与SEM对涂层的微观结构进行了分析,研究了涂覆后的C/C复合材料在高温静态空气中的防氧化性能.结果表明:SiC/SiC-MoSi2复合涂层有效缓解了MoSi2与C/C热膨胀不匹配问题,涂层无裂纹;复合涂层在900和1500℃静态空气环境下均可对C/C复合材料有效保护100 h以上;涂层的多层、多相结构以及在高温氧化后表面生成的SiO2薄膜是其具有优异防氧化性能的原因.     

炭/炭复合材料表面SiC/ZrSiO4-SiO2复合涂层的抗氧化性能与红外发射特性研究

为提高炭/炭(C/C)复合材料的高温抗氧化性能并降低其红外发射率,采用包埋–刷涂法在其表面制备了SiC/ZrSiO_4-SiO_2复合涂层。借助XRD、SEM等表征分析了涂层的成分与微观结构,并研究了SiC/ZrSiO_4-SiO_2复合涂层包覆C/C复合材料在1500℃动态空气条件下的抗氧化性能,以及在90和500℃下的红外发射率。结果表明:由疏松结构SiC内涂层和镶嵌结构ZrSiO_4-SiO_2外涂层组成的SiC/ZrSiO_4-SiO_2复合涂层具有优异的抗氧化性能,在1500℃流动空气(0.6 L/min)等温氧化条件下氧化50 h后试样的氧化失重率仅为0.03%。在C/C复合材料表面制备SiC/ZrSiO_4-SiO_2复合涂层后其红外发射率明显降低,并随温度升高而越低。复合涂层包覆试样在90℃时3~5μm和8~14μm波段的平均红外发射率分别为0.55和0.66;在500℃时3~5μm和8~14μm波段的平均红外发射率分别为0.48和0.62。SiC/ZrSiO_4-SiO_2复合涂层包覆C/C复合材料可作为优良的低红外发射率高温热结构材料应用于航空航天领域。     

TaSi2改性ZrB2/SiC复合粉末制备及涂层抗氧化性能研究

目的 提高ZrB2/SiC涂层的致密性及抗氧化烧蚀能力。方法 设计向ZrB2/SiC涂层中掺杂TaSi2,以提升ZrB2/SiC涂层的致密度和抗氧化性能。首先通过喷雾造粒法制备了4种不同成分配比的复合团聚粉,然后采用大气等离子喷涂(APS)在C/C基体表面制备了4种团聚粉复合涂层,最后使用氧-乙炔火焰法对所制备的涂层进行了烧蚀考核。结果 通过涂层致密度对比发现,随着TaSi2的增加,涂层共晶区会有所增加,涂层致密度得到了明显改善。通过烧蚀考核发现,TaSi2的加入能够增加SiO2的含量,并产生热稳定性好的TaZr2.75O8。此外致密TaZr2.75O8的产生还能够有效改善涂层的抗氧化烧蚀性能。结论 最终得出的ZrB2/SiC涂层硅化物掺杂改性方案为30%TaSi2/42%ZrB2/28%SiC(体积分数)大气等离子喷涂制备的抗氧化烧蚀涂层,其在1 600 ℃烧蚀5 min后的质量损失率为‒1.70×10^‒4 g/s。     

包埋添加剂对 SiC-ZrC 涂层 C / C 复合材料结构和性能的影响

目的研究不同氧化物添加剂对Si C-Zr C涂层C/C复合材料相组成、微观结构和抗氧化性能的影响。方法采用包埋法,分别以Al2O3,B2O3和Mg O作为添加剂,制备Si C-Zr C涂层C/C复合材料,分析相组成及微观结构,考察复合材料在1000~1550℃静态空气气氛中的抗氧化性能。结果以Al2O3作为包埋添加剂制得的涂层致密,而以Mg O为添加剂制得的涂层较疏松。在1000~1550℃的静态空气气氛中,随着氧化温度的升高,以Al2O3为添加剂制得的复合材料失重率逐渐减小,在1550℃氧化1 h后仅为1%;以B2O3和Mg O为添加剂制得的复合材料失重率逐渐增加,在1550℃氧化1 h后分别达到15%和36%。结论与B2O3添加剂相比,Al2O3和Mg O添加剂更能促进包埋粉料的扩散。以Al2O3作为包埋添加剂制得的Si C-Zr C涂层C/C复合材料具有较好的高温抗氧化性能。     

等离子喷涂制备C/C复合材料SiC涂层的驻点烧蚀性能

目的在C/C复合材料表面制备SiC涂层,提高C/C复合材料抗烧蚀性能。方法采用真空等离子喷涂技术在C/C复合材料表面制备纯Si涂层,在惰性气氛保护下对涂层高温热处理,纯Si涂层与C元素在高温下反应,原位生成SiC涂层。利用电弧加热器在不同烧蚀温度下,分别考核涂层的驻点烧蚀性能,并采用OM、SEM、EDS和XRD等对烧蚀前后的微观形貌和物相成分进行分析。结果在C/C复合材料表面制备了致密的SiC涂层,涂层中没有明显的裂纹存在,并在涂层下方产生较深的渗透区域,深度超过涂层厚度。制备的SiC涂层在1400℃下烧蚀50 s,涂层完整,具有良好的驻点烧蚀性能;在1600℃和1650℃下烧蚀50 s,涂层部分剥落,C/C复合材料基体产生烧蚀。结论 SiC涂层在高温下氧化成Si O2玻璃态膜,并覆盖在C/C复合材料表面,对基体具有良好的保护作用。随着烧蚀温度的提高,在超音速气流的冲刷下,由于热膨胀系数不匹配和SiC主动氧化的原因,涂层在烧蚀面边缘出现剥落,且剥落现象越来越严重,涂层失去对C/C基体的保护作用,烧蚀性能下降。     

TaSi2 Oxidation Protective Coating for SiC Coated Carbon/Carbon Composites

为提高碳/碳复合材料在高温下的氧化防护性能,利用包埋技术在碳/碳复合材料表面制备了TaSi2/SiC复合涂层。通过XRD、SEM 和 EDS分析了涂层的晶相结构和形貌特征,在1773 K的空气介质中对TaSi2/SiC涂层碳/碳复合材料进行等温氧化实验。结果表明,复合涂层厚度为200 μm,涂层中含有SiC, Si 和TaSi2相,并且涂层中没有明显裂纹出现。EDS结果显示外层TaSi2相可有效地填充内层SiC涂层的空隙,使得内外两层涂层之间没有明显的界面,等温氧化实验曲线说明TaSi2/SiC复合涂层在1773 K的空气介质中可有效保护碳/碳复合材料233 h。     

A MoSi2/SiC oxidation protective coating for carbon/carbon composites

To protect carbon/carbon (C/C) composites against oxidation, a MoSi₂ outer coating was prepared on pack-cementation SiC coated C/C composites by a hydrothermal electrophoretic deposition. The phase composition, microstructure and oxidation resistance of the prepared MoSi₂/SiC coatings were investigated. Results show that hydrothermal electrophoretic deposition is an effective route to achieve crack-free MoSi₂ outer coatings. The MoSi₂/SiC coating can protect C/C composites from oxidation at 1773 K for 346 h with a weight loss of 2.49 mg cm⁻² and at 1903 K for 88 h with a weight loss of 5.68 mg cm⁻².     

Double SiC coating on carbon/carbon composites against oxidation by a two-step method

To improve the oxidation resistance of C/C composites, a double SiC protective coating was prepared by a two-step technique. Firstly, the inner SiC layer was prepared by a pack cementation technique, and then an outer uniform and compact SiC coating was obtained by low pressure chemical vapor deposition. The microstructures and phase compositions of the coatings were characterized by SEM, EDS and XRD analyses. Oxidation behaviour of the SiC coated C/C composites was also investigated. It was found that the double SiC coating could protect C/C composites against oxidation at 1773 K in air for 178 h with a mass loss of 1.25%. The coated samples also underwent thermal shocks between 1773 K and room temperature 16 times. The mass loss of the coated C/C composites was only 2.74%. Double SiC layer structures were uniform and dense, and can suppress the generation of thermal stresses, facilitating an excellent anti-oxidation coating.     

ZrO2–SiO2 gradient multilayer oxidation protective coating for SiC coated carbon/carbon composites

In order to eliminate the mismatch of thermal expansion coefficient between the ZrO₂ outer layer and the internal bonding SiC layer, ZrO₂–SiO₂ composition-gradient transition layers were prepared by a sol–gel technique using tetraethoxysilane (TEOS) and zirconyl chloride as source materials. Energy dispersive spectroscopy (EDS) analysis displays that the gradient composition ZrO₂–SiO₂ outer coating could be obtained by immersing the SiC precoated carbon/carbon (C/C) composites into the gradient composition zirconia-silica sols (ZS sol) in turn. Oxidation test shows that, after 10 h oxidation in air at 1773 K, the weight loss of the gradient ZrO₂–SiO₂ coating coated SiC-C/C is only 1.97%.     

A ZrSiO4/SiC oxidation protective coating for carbon/carbon composites

In order to improve the oxidation resistance of carbon/carbon (C/C) composites, a ZrSiO₄ coating on SiC pre-coated C/C composites was prepared by a hydrothermal electrophoretic deposition process. Phase compositions and microstructures of the as-prepared ZrSiO₄/SiC coating were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectrometer (EDS). The anti-oxidation property and failure mechanism of the multi-layer coating were investigated. Results show that hydrothermal electrophoretic deposition is an effective route to prepare crack-free ZrSiO₄ outer coatings. The multi-layer coating obviously exhibits two-layer structure. The inner layer is composed of SiC phase and the outer layer is composed of ZrSiO₄ phase. The bonding strength between the outer layer coatings and C/C–SiC substrate are 30.38 MPa. The ZrSiO₄/SiC coating displays excellent oxidation resistance and can protect C/C composites from oxidation at 1773 K for 332 h with a mass loss rate of only 0.48 × 10^− 4 g/cm²·h. The mechanical properties of the specimens are 84.36 MPa before oxidation and 68.29 MPa after oxidation. The corresponding high temperature oxidation activation energy of the coated C/C composites at 1573–1773 K is calculated to be 119.8 kJ/mol. The oxidation process is predominantly controlled by the diffusion rate of oxygen through the ZrSiO₄/SiC multi-coating. The failure of the coating is due to the formation of penetrative holes between the SiC bonding layer and the C/C matrix at 1773 K.     

SiC/SiC–YAG–YSZ oxidation protective coatings for carbon/carbon composites

SiC/SiC–YAG–YSZ coatings were prepared by pack cementation, chemical vapor deposition and slurry painting on carbon/carbon (C/C) composites. The microstructures and oxidation behavior of coatings were investigated. The results show that the coatings displayed good oxidation and thermal shock resistance due to a dense glassy layer with silicates formed on the coating of SiC–YAG–YSZ. The weight gain rate of coated C/C composites was 1.77% after oxidation for 150 h at 1773 K. SiC in outer coating can promote the formation of oxygen diffusion barrier and lead to the optimum oxidation resistance for the coatings, compared with YSZ and YAG.     

SiC nanowire-toughened SiC-MoSi2-CrSi2 oxidation protective coating for carbon/carbon composites

To prevent carbon/carbon (C/C) composites from oxidation, a dense SiC nanowire-toughened SiC-MoSi₂-CrSi₂ multiphase coating was prepared by the two-step technique composed of chemical vapor deposition (CVD) and pack cementation. The coatings were characterized by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD). SiC nanowires could decrease the dimension of cracks and improve the oxidation and thermal shock resistance of SiC-MoSi₂-CrSi₂ multiphase coating. Oxidation test shows that, after introducing SiC nanowires, the weight loss of the coated sample can be reduced from 1.06% to 0.64% after oxidation at 1773 K for 155 h and decreased from 6.92% to 3.42% after thermal cycling between 1773 K and room temperature for 30 times.     

Oxidation and ablation resistance of ZrB2–SiC–Si/B-modified SiC coating for carbon/carbon composites

ZrB₂–SiC–Si/B-modified SiC coating was prepared on the surface of carbon/carbon (C/C) composites by two-step pack cementation. The coating could efficiently provide protection for C/C composites from oxidation and ablation. The improvement of oxidation resistance was attributed to the self-sealing property of the multilayer coating. A dense glassy oxide layer could afford the high temperature up to 2573 K and efficiently protect C/C composites from ablation.     

A modified dual-layer SiC oxidation protective coating for carbon/carbon composites prepared by one-step pack cementation

To improve the oxidation resistance of SiC coating produced by pack cementation for carbon/carbon composites, a modified SiC coating has been produced by one-step pack cementation by adding ferrocene in pack compositions. The as-received coating exhibited a dual-layer dense structure, and oxidation protective ability of SiC coating could be improved by introducing ferrocene. The modified coating could protect C/C composites from oxidation for more than 100 h at 1673 K in air. The weight loss of the coated C/C composites was considered to arise from deflection of penetrating cracks formed in outer layer from inner layer to C/C matrix.     

A MoSi2-SiC-Si oxidation protective coating for carbon/carbon composites

To protect carbon/carbon (C/C) composites from oxidation, a dense coating has been produced by a two-step pack cementation technique. XRD and SEM analysis shows that the as-obtained coating was composed of MoSi₂, SiC and Si with a thickness of 80-100 μm. The MoSi₂-SiC-Si coating has excellent anti-oxidation property, which can protect C/C composites from oxidation at 1773 K in air for 200 h and the corresponding weight loss is only 1.04%. The weight loss of the coated C/C composites is primarily due to the reaction of C/C substrate and oxygen diffusing through the penetration cracks in the coating.