炭材料高温抗氧化莫来石/SiC复合涂层的制备及其1150℃高温抗氧化性能(英文)

采用化学气相反应及料浆刷涂烧结复合工艺在石墨表面制备高温抗氧化莫来石/SiC复合涂层。XRD物相分析结果显示涂层外层由莫来石及微量SiO2相组成,涂层内层主要由β-SiC相组成。通过高温抗氧化试验研究涂层的高温抗氧化行为并测试涂层氧化后的洛氏硬度。结果表明:所制备的莫来石/SiC复合涂层具有良好的高温抗氧化及热震性能,经过1150℃、109h的高温氧化及12次1150℃→室温的循环热震试验后,涂层试样的质量增加率为0.085%。硬度测试结果表明:所制备的莫来石/SiC复合涂层各层之间具有良好的结合性能。     

SiC–MoSi2/ZrO2–MoSi2 coating to protect C/C composites against oxidation

To improve the oxidation resistance of carbon/carbon (C/C) composites in air at high temperatures, a SiC–MoSi₂/ZrO₂–MoSi₂ coating was prepared on the surface of C/C composites by pack cementation and slurry method. The microstructures and phase compositions of the coated C/C composites were analyzed by scanning electron microscopy and X-ray diffraction, respectively. The result shows that the SiC–MoSi₂/ZrO₂–MoSi₂ coating is dense and crack-free with a thickness of 250–300 μm. The preparation and the high temperature oxidation property of the coated composites were investigated. The as-received coating has excellent oxidation protection ability and can protect C/C composites from oxidation for 260 h at 1773 K in air. The excellent anti-oxidation performance of the coating is considered to come from the formation of ZrSiO₄, which improves the stability of the coating at high temperatures.     

微波加热制备SiC/Mullite球体的工艺和性能

以粉煤灰微珠和炭黑为原料,通过微波加热碳热还原法原位合成了SiC/Mullite球体。利用X射线衍射(XRD),场发射扫描电子显微镜(FESEM)对产物进行了物相和结构表征。研究表明：在1100 ~1300 ℃之间,微珠表面的SiO2通过固(SiO2)–固(C)反应机理而形成SiC,而内部Mullite依然维持微珠球形骨架,从而形成SiC/Mullite球体。温度高于1300 ℃时,SiC通过固–液–气机理定向生长为晶须且Mullite亦参与反应,从而使粉煤灰微珠失去其球形形貌。本试验的最佳工艺条件为n(C): n(SiO2)=4.2,温度1200 ℃下恒温1 h     

固相法合成原位碳包覆LiFePO4复合正极材料及其性能

以LiH2PO4和FeC2O4.2H2O为原料,聚乙烯醇为碳源,通过机械化学活化辅助固相法合成原位碳包覆的LiFePO4材料;考察合成温度对LiFePO4/C材料晶体结构、物理和电化学性能的影响。结果表明:700℃下处理的产物结晶良好、分布均匀、颗粒细小;在最佳的热处理条件下,热解碳在LiFePO4颗粒表面形成了良好的纳米导电层,LiFePO4/C材料在0.1C、0.5C、1C和2C倍率下放电比容量分别为155.7、150.1、140.1和130 mA.h/g,且材料在0.1～2C范围内充放电都有很平稳的平台,极化小,并具有较高的高倍率(2C)放电比容量和较好的循环性能。     

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.     

硅钽含量对C/C复合材料SiC/TaSi_2复合涂层结构和抗氧化性能的影响

采用包埋技术在C/C复合材料表面制备SiC/TaSi2抗氧化复合涂层,通过恒温氧化实验以及X射线衍射分析、扫描电镜观察,研究了包埋粉料中硅钽含量对复合涂层微观结构和高温抗氧化性能的影响.结果表明,随着硅钽比的减小,复合涂层的厚度先增大后减小;硅钽比为5:1所制备的复合涂层具有相对较大的厚度和较为致密的结构,且TaSi2含量相对较高,体现出优良的抗氧化和抗热震性能,在1500℃氧化241.8 h和经过18次1500℃←室温急冷急热后,带有该涂层的C/C试样失重仅为1.04%.穿透性裂纹的形成是长时间氧化后涂层失效的主要原因.     

Effect of SiC whiskers on the oxidation protective properties of SiC coatings for carbon/carbon composites

In order to effectively employ the unique high temperature mechanical properties of carbon/carbon composite substrates, SiC coatings reinforced by SiC whiskers were prepared by pack cementation method. The effect of SiC whiskers on the oxidation resistance properties of the single-layer coating and double-layer coating was investigated. SiC whiskers in the single-layer SiC coating have little effect on the anti-oxidation property but obviously improve the thermal shock property. The double-layer coating with inner-layer reinforced coating exhibits more perfect anti-oxidation ability than the double-layer coating with SiC inner-layer coating.     

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.     

C/C复合材料航空刹车副表面防氧化涂料的研制

以磷酸,磷酸盐,ＳｉＣ,ＳｉＯ２,Ｂ４Ｃ和含硼化合物等为原料研制了以硅、硼化合物为主的多组分陶瓷混合物涂料。采用该涂料以刷涂的方式制备的Ｃ／Ｃ复合材料复合涂层具有显著的防氧化效果。研究表明,涂覆有涂层的Ｃ／Ｃ复合材料试样在９００℃氧化１０ｈ后,其氧化损失率为１０．３７％;试样在空气中９００℃,３ｍｉｎ＝室温,２ｍｉｎ急冷急热,如此在１０ｈ内循环１００次后,氧化损失率为８．４１％,涂层与基体结合牢固     

SiC涂层对C/C复合材料高温氧乙炔焰烧蚀性能影响

采用化学气相反应法在C/C复合材料表面制备抗氧化SiC涂层,借助X射线衍射仪、扫描电镜及能谱等分析手段,研究涂层的结构;通过氧乙炔焰烧蚀试验考察SiC涂层对C/C复合材料高温耐烧蚀性能影响。结果表明:SiC涂层可明显提高C/C复合材料的高温短时耐烧蚀性能,经过20 s的高温氧乙炔焰烧蚀后,C/C复合材料试样的线烧蚀率和质量烧蚀率分别为13μm/s和6.6 mg/s,SiC涂层试样的线烧蚀率和质量烧蚀率分别为22μm/s和0.5 mg/s;在烧蚀中心区,涂层试样的烧蚀以升华分解为主,同时还伴有氧化烧蚀和微区机械剥蚀;在烧蚀过渡区,涂层的烧蚀机制以热氧化和燃气冲刷为主;而在烧蚀边缘区,涂层的烧蚀则主要表现为弱氧化烧蚀。     

Preparation and characterization of biomorphic SiC hollow fibers from wood by chemical vapor infiltration

Biomorphic SiC hollow fibers were prepared by the reactive infiltration of SiO vapor into basswood-derived charcoal. Gaseous SiO was produced from a SiO₂/Si powder mixture in Ar at elevated temperatures. Scanning electron microscopy, energy dispersive X-ray spectroscopy, X-ray diffraction and Fourier transform-infrared spectroscopy were employed to characterize the structural morphology and phase compositions of the final products. The results show that the tubular cells in bulk charcoal are converted into lots of SiC hollow fibers with pore diameters of 10–50 μm and lengths ranging from hundreds of μm to several mm. Resulting SiC hollow fibers consist of β-SiC with a minute amount of α-SiC. The formation mechanism of SiC hollow fibers is based on the gas–solid reaction between SiO and carbon.     

Si3N4／SiC复合陶瓷粉末的研制

研究了添加晶种的碳热还原ＳｉＯ２法制取Ｓｉ３Ｎ４／ＳｉＣ复合粉末的工艺。发现反应温度的升高、反应时间的延长、原料ＳｉＯ２粉比表面的增大、添加Ｓｉ３Ｎ４晶种以及提高Ｎ２流速，均有利于Ｓｉ３Ｎ４、ＳｉＣ相含量的增加。当ＳｉＯ２：Ｃ为１：２，加入１０Ｗｔ％Ｓｉ３Ｎ４品种时，在１３５０℃下于Ｎ２流速为０．４ｍ３·ｈ－１气氛下反应４ｈ，可得到平均粒度为０．４６ｍ，含Ｎ２３．９ｗｔ％、Ｃ６．２５Ｗｔ％、Ｏ２．９０ｗｔ％的Ｓｉ３Ｎ４／ＳｉＣ超细复合粉末。     

Oxidation behavior of C/C composites with SiC/ZrSiO4–SiO2 coating

A SiC/ZrSiO₄–SiO₂ (SZS) coating was successfully fabricated on the carbon/carbon (C/C) composites by pack cementation, slurry painting and sintering to improve the anti-oxidation property and thermal shock resistance. The anti-oxidation properties under different oxygen partial pressures (OPP) and thermal shock resistance of the SZS coating were investigated. The results show that the SZS coated sample under low OPP, corresponding to the ambient air, during isothermal oxidation was 0.54% in mass gain after 111 h oxidation at 1500 °C and less than 0.03% in mass loss after 50 h oxidation in high OPP, corresponding to the air flow rate of 36 L/h. Additionally, the residual compressive strengths (RCS) of the SZS coated samples after oxidation for 50 h in high OPP and 80 h in low OPP remain about 70% and 72.5% of those of original C/C samples, respectively. Moreover, the mass loss of SZS coated samples subjected to the thermal cycle from 1500 °C in high OPP to boiling water for 30 times was merely 1.61%.     

W-SiC-C/C复合材料制备及等离子烧蚀性能

目的提高C/C复合材料在超高温下的抗烧蚀性能。方法采用化学气相沉积法,在C/C复合材料表面制备SiC过渡层,然后以惰性气体保护等离子喷涂工艺在带有SiC过渡层的C/C材料表面制备W涂层,研究所制备的W-SiC-C/C复合材料的微观形貌与结构特征。以200 kW超大功率等离子焰流,考核W-SiC-C/C材料的抗烧蚀性能,并与无涂层防护的C/C材料进行对比分析。结果W涂层主要为层状的柱状晶结构。W涂层与SiC过渡层、过渡层与基体界面呈镶嵌结构,结合良好。SiC过渡层阻止了W、C元素相互迁移与反应。在驻点压力为4.5 MPa、温度约5000 K、热流密度为36 MW/m²的烧蚀条件下,当烧蚀时间小于10 s时,涂层对C/C材料起到了较好的保护作用,W涂层发生氧化烧蚀,基体未发现烧蚀,平均线烧蚀率为0.0523 mm/s;当烧蚀时间超过15 s后,涂层防护作用基本失效,基体C/C材料发生烧蚀现象。结论以W涂层、SiC过渡层为防护的C/C复合材料,能够适用于短时间超高温的烧蚀环境,如固体火箭发动机等。W涂层的熔融吸热、氧化耗氧以及SiC过渡层的氧化熔融缓解涂层热应力和氧扩散阻碍的联合作用,提高了C/C材料的抗烧蚀性能。     

SiC 涂层对不同碳基体氧化防护行为的研究

为了提高碳材料的抗氧化性能,采用料浆烧结法在石墨和C/C复合材料上制备了SiC 抗氧化涂层.测试了SiC涂层在1200℃的高温下对不同碳基体的氧化防护能力,利用扫描电子显微镜 (SEM)、X-射线衍射仪(XRD)对涂层结构进行分析.结果表明:SiC涂层对不同碳材料的抗氧化防护行为有很大差异,在1200℃的高温下SiC涂层对石墨具有较好的抗氧化性能,而对C/C复合材料的氧化防护性能较差.     

富碳β-SiC的燃烧法合成及微波介电性能

以硅粉和炭黑为原料,利用燃烧合成法,在0.1MPa 的N_2气氛下合成了β-SiC粉体.对其进行拉曼光谱和SEM表征,结果表明:合成的SiC为含有C反位缺陷C_(si)和石墨态sp~2C的富C β-SiC固溶体.添加剂聚四氟乙烯(PTFE)含量为10%时合成的SiC粉体为等轴状团聚颗粒,粒径约为0.2μm,随着PTFE添加量的增加,SiC粉体颗粒的平均粒径增大.在8.2～12.4 GHz频率范围对所合成SiC的介电常数进行测试,发现15%PTFE时合成的SiC粉体具有较好的介电常数实部ε'、虚部ε"和介电损耗tanδ,对其微波损耗机理进行了讨论.     

Microstructure and oxidation of multi-layer MoSi2-CrSi2-Si coatings for SiC coated carbon/carbon composites

Multi-layer MoSi₂-CrSi₂-Si anti-oxidation coatings with different compositional ratios were prepared on the surface of SiC coated carbon/carbon (C/C) composites by a two-step pack cementation method. The microstructure and anti-oxidation performance of the coating were studied. The results show that the multi-layered coatings could protect the C/C composites from oxidation in air at 1773 K for 1000 h or 1873 K for 750 h, respectively. The anti-oxidation performance of the multi-layer MoSi₂-CrSi₂-Si coating is mainly attributed to their dense and microcrack-free structure, appropriate thermal expansion coefficient and the well dispersed MoSi₂ and CrSi₂ in the coating.     

Anti-oxidation behavior of chemical vapor reaction SiC coatings on different carbon materials at high temperatures

To protect carbon materials from oxidation, SiC coatings were prepared on carbon/carbon(C/C) composites and graphite by chemical vapor reaction. SEM and XRD analyses show that the coatings obtained are composed of SiC grains and micro-crystals. The influence of different carbon substrates on oxidation behavior of coated samples was investigated, and then their oxidation mechanisms were studied. Oxidation test shows that the SiC coated graphite has a better oxidation resistance than SiC coated C/C composites at high temperatures (1 623 K and 1 823 K). In the oxidation process, the oxidation curves of SiC coated C/C composites are linear, while those of SiC coated graphite follow a quasi-parabolic manner. The oxidation mechanism of the former is controlled by chemical reaction while the latter is controlled by oxygen diffusion based on the experimental results. The variation of oxidation behavior and mechanism of SiC coatings on two kinds of carbon substrates are primarily contributed to their structure differences.     

反应烧结SiC制备SiC/B4C复合材料的研究

基于反应烧结SiC制备出相对密度较高的SiC/B4C复合材料,并探讨原料中C含量对SiC/B4C复合材料物相、显微结构、体积密度、力学性能的影响。结果表明,SiC/B4C复合材料的相组成为B4C、SiC、Si、B13C2和B12.97Si0.03C2。SiC/B4C复合材料的显微组织为:SiC相和B4C相均匀分布,游离Si填充在B4C相和SiC相的空隙处,且形成了连续相。随着原料中C含量的增加,复合材料的力学性能整体呈现先增加后降低的趋势。原料中C最佳添加量为10%(质量分数),对应SiC/B4C复合材料的维氏硬度、抗弯强度和断裂韧性分别为24.4GPa、361.3MPa和4.41MPa·m1/2,复合材料开口气孔率和体积密度分别为0.19%和2.58g/cm3。     

碳/碳-碳化硅复合材料在舰载机尾流场中烧蚀性能研究

为了提高航空母舰燃气导流板的工作性能,将碳/碳-碳化硅复合材料（C/C-SiC）试件在舰载机尾流中做模拟起飞工况的多次重复烧蚀试验,测定试件的烧蚀率和抗热震性能;采用扫描电镜（SEM）和微CT观察试件烧蚀后的微观形貌,采用能谱分析（EDS）测量燃烧产物的成份,对试件的烧蚀机理和热震损伤机制进行分析。结果表明：试件的线烧蚀率约为0.0405mm/s,质量烧蚀率约为0.0349g/s。在热影响区,复合材料基体在热震的作用下出现裂纹,而氧化反应不明显;在过渡区,热震使试件发生氧化反应生成SiO2在碳纤维的周围沉积,形成包鞘结构,有效地阻滞了氧化反应向内部传递,降低了试件的烧蚀率;在烧蚀中心区,生成的SiO2易被高速气流吹除掉而无法大量沉积,对氧化反应的阻滞作用不大,试件在此处烧蚀成凹坑,碳纤维呈尖笋状分布;试件的损伤机制是裂纹和氧化共同作用的结果,复合材料总体表现出优异的抗烧蚀性能。