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。     

等离子喷涂制备ZrB2/SiC/Ta2O5涂层抗烧蚀性能研究

为了提高C/C复合材料的抗烧蚀性能,通过等离子喷涂法在C/C表面制备了SiC/Al₂O₃内层和ZrB₂/SiC/Ta₂O₅外层的双层涂层,通过XRD,SEM和EDS分析了涂层烧蚀前后的物相组成、微观结构和成分分布。烧蚀前涂层表面没有裂纹并且内层与基体、内层与外层之间结合良好。元素Zr、Si、Ta在涂层表面的分布相近,涂层表面成分分布均匀性良好。通过氧乙炔火焰在1800 ℃下对涂层的抗烧蚀性能进行考核。烧蚀过程中形成的镶嵌结构有利于阻挡氧气的渗入,Ta-Si-O玻璃层的形成封填了涂层孔隙,对基体有良好的保护效果,涂层表现出了较好的抗烧蚀性能。     

SiC-Glass涂层碳/碳复合材料的中低温氧化行为及机制研究

为揭示具有良好高温(1300～1600 ℃)抗氧化性能的SiC-Glass涂层在中低温(500～1200 ℃)条件下的氧化防护性能,对SiC-Glass涂层碳/碳(C/C)复合材料的中低温氧化行为和机制进行了系统研究.结果表明,SiC-Glass涂层C/C复合材料的中低温氧化失重服从直线规律,但氧化机制存在温度依赖性,可分为2个区段:(1) 低温区(500～800 ℃),氧化失重速率与温度服从Arrhenius关系,氧化主要受控于氧在涂层缺陷内的扩散速率;(2) 在中温区(800～1200 ℃),氧化失重速率与温度不服从Arrhenius关系,氧化过程受氧在涂层缺陷中的扩散、SiC内涂层材料的氧化、Glass外涂层的部分熔融愈合等多种因素联合控制.对比分析表明,SiC-Glass涂层的中低温抗氧化性能不及其高温抗氧化性能优异.中低温下,涂层缺陷愈合不充分是导致这一现象的主要原因.     

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.     

碳／碳复合材料表面等离子喷涂陶瓷涂层的抗氧化性能

研究了有涂层与无涂层的碳／碳复合材料的高温氧化行为。等离子喷涂的陶瓷涂层，在氧化温度不大于１０００℃条件下，对碳／碳复合材料有良好的保护作用，无涂层的碳／碳复合材料在６００￣９００℃温度范围内的氧化机制相同；而有涂层时，氧化机制在７６０℃左右发生变化。碳毡增强碳基复合材料的氧化从表面碳毡开始，碳毡的氧化速率较基体碳的氧化速率大。     

碳毡体密度对碳/碳复合材料抗氧化性能的影响

采用自加热化学液相沉积法制备碳/碳复合材料。考察了不同材料在不同温度、时间下的氧化失重率,研究了碳毡体密度与碳/碳复合材料氧化行为的关系。探讨了氧化温度和氧化时间对材料氧化侵蚀的影响机理。结果表明,毡体密度大的碳/碳复合材料具有更好的抗氧化性。扫描电镜观察材料氧化前后的显微形貌发现,基体碳更易被氧化。     

高铌γ-TiAl合金表面微弧氧化陶瓷涂层的耐蚀性及高温氧化行为

利用微弧氧化技术（MAO）在硅酸钠和氢氧化钾溶液中对高铌γ-TiAl合金表面原位生长陶瓷涂层以提高γ-TiAl合金的抗高温氧化性能。采用扫描电子显微镜（SEM）、X射线衍射仪（XRD）、X射线光电子能谱（XPS）、电化学工作站和箱式电阻炉高温氧化测试分析涂层的表面及截面形貌、相组成、元素化学结合状态、耐蚀性和高温氧化行为。XRD和XPS结果表明,陶瓷涂层主要由Al₂TiO₅、SiO₂和Nb₂O₅组成。涂层与基体界面结合良好,厚度约2.15 μm。高铌γ-TiAl合金经微弧氧化处理后,在3.5%NaCl溶液中的腐蚀电流降低近1个数量级。微弧氧化处理试样在800~900 ℃中的氧化增重仅为基体的8.9%~37.5%。微弧氧化陶瓷涂层将基体的氧化激活能从247.79 kJ/mol增加到涂层试样的574.41 kJ/mol。     

人工机械心瓣热解碳 / 石墨界面结合强度分析

目的研究人工心瓣热解碳涂层与基体结合强度的影响因素,从而分析提高人工心瓣寿命的途径。方法通过改进的剪切试验法,得到人工机械心瓣热解碳涂层/石墨基体的平均界面剪切结合强度。利用有限元分析软件ANSYS建立三维模型,对人工机械心瓣热解碳涂层/石墨基体的界面剪切应力进行分析,将分析结果与试验结果进行对比。利用ANSYS验证不同涂层厚度以及不同涂层弹性模量的情况下,界面剪切应力的变化情况。结果试验所得的平均界面剪切结合强度为5.535 MPa,有限元分析得到的平均结合强度值为5.98 MPa。随着涂层厚度的增加,涂层与基体结合强度降低;随着涂层弹性模量的增加,涂层与基体结合强度增大,但弹性模量并非越大越好,应有一个合适的值。结论 ANSYS分析是准确的。制备热解碳涂层时,应尽量薄一些,热解碳的弹性模量相对石墨应尽量大一些。     

热喷涂可磨耗涂层的三维显微结构

采用超音速火焰喷涂和大气等离子喷涂在高温合金表面制备由金属粘结层NiCoCrAlYTa和陶瓷面层Dy₂O₃稳定的ZrO₂组成的可磨耗涂层,利用X射线显微镜（XRM）对涂层三维微观结构进行表征,结合扫描电子显微镜对经高温后的涂层孔隙、界面及裂纹演变进行研究。结果表明：在1100 ℃高温氧化条件下,随着氧化时间增加,粘结层中的富Ta相逐渐溶解并向晶界扩散,60 h后Ta元素完全固溶;粘结层/面层界面处形成双氧化层,由较致密均匀的氧化铝内层和混合氧化物外层构成;涂层的剥落失效主要由涂层中的裂纹缺陷导致,其在高温下优先沿界面、贯穿孔隙扩展。     

SiC/MoSi2高温抗氧化涂层的制备及性能探究

采用磁控溅射法在C/C复合材料表面制备SiC/MoSi2抗氧化涂层,并利用SEM、XRD以及EDS等测试手段对涂层的组织结构、抗氧化性能以及抗氧化机制进行了研究。结果表明,所得涂层结构致密、厚度均匀可控,呈柱状晶。在1500℃静态氧化60min后,涂层试样表现出了较优异的抗氧化性能,氧化质量损失仅为3.2x10-2g/cm-2。导致C/C基体被氧化失重的主要原因是涂层中沿晶界产生的贯穿裂纹为氧气进入基体表面提供了通道。     

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.     

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–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.     

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.     

工艺因素对水热改性C/C复合材料抗氧化性能的影响

以一定配比的Al_2O_3粉和磷酸溶液组成的悬浮液作为水热处理前驱体,采用水热法对C/C复合材料基体进行了防氧化改性.采用X射线衍射(XRD)仪、扫描电子显微镜(SEM)和能量色散谱(EDS)仪分别对改性试样的物相组成、显微结构及化学元素组成进行表征.重点研究了水热反应时间、水热反应釜填充比等工艺因素对改性C/C复合材料的物相组成、微观形貌及抗氧化性能的影响.结果表明:水热改性方法是一种行之有效的提高C/C复合材料基体抗氧化性能的手段.经过水热改性处理,试样的抗氧化性能明显提高;延长水热反应时间和增大水热釜填充比都有利于基体抗氧化性能的提高;在水热釜填充比为70%、水热温度为200 ℃的条件下,改性处理72 h的C/C复合材料在700 ℃的静态空气中恒温氧化10 h后氧化失重仅为2.31%.     

Effect of carbon on cavity formation during the high-temperature oxidation of Ni

Ni containing 0.00002 to 0.003 wt.% carbon was oxidized in 1 atm O₂ at 700 to 1270°C for 1 min to 20 hr. Cavity formation in the metal and oxide and at the oxide-metal interface was affected by the carbon content. Extensive cavitation developed at the grain boundaries of Ni containing as little as 0.0001 wt.% carbon but no cavitation occurred in decarburized Ni. Metal cavitation is dependent on the local concentration of carbon segregated at the Ni grain boundaries rather than on the overall carbon content. The cavities arise from hot deformation or creep of the metal substrate induced by the oxidation process. The cavities in the oxide formed on decarburized Ni remain near the oxide-metal interface; on Ni containing appreciable carbon the oxide cavities migrate outward by a dissociative mechanism assisted by the gaseous transfer of oxygen across the cavities with CO-CO₂ acting as the carrier.     

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。     

Oxidation Behavior of Ni-3,6, 10 wt.% Al Alloys at 800°C

The oxidation behavior of Ni and Ni-3, 6, and 10Al alloys at 800°C in an N₂–O₂ gas mixture was investigated. The mass gain of each alloy depended on both the oxidation periods and Al content. NiO scale was formed on all alloy substrates accompanied by internal oxides of Al₂O₃. Many cavities were formed at the NiO/substrate interface at shorter oxidation times, and these cavities were found to be filled by metallic Ni(Al) from the matrix in the internal-oxidation zone by the development of internal oxides. The filling of cavities by Ni(Al) was more significant on higher Al alloys, which had a higher density of internal Al₂O₃. Once metallic Ni(Al) formed along the entire NiO/substrate interface, the oxidation kinetics became the same as pure Ni. It was concluded that pure Ni filling the cavities at the interface provided a diffusion path of Ni from the substrate to the NiO scale, and that controlled the oxidation kinetics.     

Effect of tin addition on Nb–Si-based in situ composites. Part II: Oxidation behaviour

This paper reports the effects of adding from 2 to 8 at.% tin on the oxidation behaviour of Nb/Nb₅Si₃ composites at 815 °C and at higher temperatures (1100 and 1200 °C). The role of tin in the elimination of pesting and in the oxidation process at high temperatures was established. The consumption of elements with a higher affinity for oxygen than Sn induces the accumulation of tin at the oxide/internal oxidation zone boundary. Low melting point phases (NbSn₂ and/or pure Sn) form at 815 °C, whereas a layer of M₅Si₃ and Nb₅SiSn₂ forms at 1100 and 1200 °C. Once these products are formed, they generate an oxygen diffusion barrier and allow the elimination of pesting. However, for long oxidation processes at 1100 °C, the oxidation rate of Nb/Nb₅Si₃ composites containing tin should be higher than that for tin-free composites. Moreover, some oxidation results have suggested that the presence of A15-(Nb,Ti)₃(Sn,Ti) in the microstructure of composites with at.%Sn > 2 can severely impact the low temperature fracture toughness of these composites.     

Microstructure and anti-oxidation property of Si-W-Cr coating for SiC coated carbon-carbon composites

To protect carbon/carbon (C/C) composites from oxidation at high temperature, a Si-W-Cr coating was prepared on the surface of SiC coated C/C composites by a simple pack cementation technique. The microstructure and phase composition of the as-received multi-coating were examined by SEM, XRD and EDS. The coating obtained by first step pack cementation was porous α-SiC structure. New phases of WSi₂ and CrSi₂ together with α-SiC deposited on the porous SiC inner layer. Oxidation test shows that the weight loss of single SiC coated C/C is up to 8.21% after 9 h in air at 1773 K, while the weight loss of Si-W-Cr/SiC coated C/C composites is only 2.26% after 51 h. After thermal cycling between 1773 K and room temperature for 40 times, the weight loss is only 3.36%. The weight loss of coated C/C composites was primarily due to the reaction of C/C matrix and oxygen diffusing through the penetrable cracks in the coating.