炭/炭复合材料抗氧化研究现状

总结了炭/炭复合材料抗氧化研究现状,重点介绍了抗氧化涂层的制备方法,包括包埋浸渍法、化学气相沉积(CVD)、溶胶-凝胶法(Sol-Gel)和水热电沉积法以及近几年针对抗氧化涂层开裂问题各国学者的最新研究成果。提出了炭/炭复合材料抗氧化研究今后努力的方向。     

化学气相沉积炭/炭复合材料研究进展

炭/炭复合材料被成功用于许多领域,主要用作抗烧蚀、热防护和刹车材料,如飞机的刹车盘、导弹的头锥等.化学气相沉积是制备炭/炭复合材料的关键技术,本文阐述了炭/炭复合材料化学气相沉积工艺原理,论述了化学气相沉积热解炭机理的研究现状,介绍了不同种类化学气相沉积工艺的特点,以及化学气相沉积工艺计算机数值模拟技术的研究进展.提出了炭/炭复合材料化学气相沉积技术的研究方向和发展趋势.     

炭／炭复合材料SiC／Mo（Six，Al1-x）2涂层形成机理与抗高温氧化性能

采用高温包渗技术在炭／炭复合材料表面制备了SiC／Mo（Six,Al1-x）2复合涂层,采用两步反应法研究了复合涂层的生成机理。发现复合涂层是由Si、Al2O3、SiC、MoSi2原始粉末材料与基体炭材料经过复杂化学反应生成的SiC、Mo（SixAl1-x）2以及微量Mo4．8Si3C0．6固溶体组成。在较低温度下（〈1750℃）,单质硅与基体碳的液-固相反应,经过2小时后可以在炭／炭复合材料表面和内部孔隙表面生成致密的SiC过渡涂层;在较高温度下（≤2000℃）,SiC、Al2O3和MoSi2间的反应较为复杂,其主要过程为SiC与Al2O3间生成液体硅、液体铝和气态SiO、Al2O的多相反应,该反应生成的液体铝能够与MoSi2颗粒发生置换反应,生成熔点降低的Mo（Six,Al1-x）2转移涂层;同时,生成的液体硅与CO反应生成晶须状β—SiC,并与Mo（Six,Al1-x）2形成增强型复合涂层。本文还研究了过量单质Si和SiC对Mo（Six,Al1-x）2的还原反应,化学反应推论与实验结果相吻合。以新提出的涂层生成机理为指导,以粉末原料质量组成为Si10％,Al2O3 10％,SiC54％和MoSi226％时所制得了致密并且无粘结的复合涂层材料,并研究了封孔处理后复合材料的抗氧化性能。     

以环己烷为前驱体制备炭/炭复合材料

以环己烷为前驱体利用化学液气相沉积工艺,采用针刺炭纤维毡为预制体,制备了具有光滑层和粗糙层结构的炭/炭复合材料。利用金相显微镜、高分辨扫描电子显微镜进行了材料的微观组织结构的分析,分析了在不同位置不同织构热解炭的形成机理。同时阐述了化学液气相沉积工艺原理。实验结果表明,通过调整工艺参数,利用化学液气相沉积工艺可以制备具有不同微观组织结构的炭/炭复合材料。     

炭-炭复合膜制备的探索研究

以煤沥青基炭分离膜为支撑体，采用聚合物溶液涂层或浸渍制备出了炭－炭复合分离膜，测试了高纯H2，CO2，N2和O2单组分在炭－炭基复合分离膜上的渗透速率，计算了各气体组分的理想分离系数。结果显示以聚乙二醇水溶液进行表面涂层制备的炭－炭复合膜，其气体分离性能与炭分离膜相比稍有提高，以酚醛树脂N，N－二甲基乙酰胺溶液和加有分散剂的酚醛树脂乙醇溶液涂层制备的炭－炭复合膜在分离性能上都有较大提高，尤其加有分散剂的酚醛树脂乙醇溶液涂层后可使H2／CO2的分离系数达16．0左右，而采用酚醛树脂乙醇溶液涂层和浸渍得到的炭－炭基复合膜的气体渗透速率和分离系数均下降。     

新型炭纤维/泡沫炭预制体的制备及致密化研究

由炭纤维/酚醛树脂经过发泡、固化和炭化制备出4种不同炭纤维含量(3%,7%,10%和15%)的泡沫炭作为制备炭/炭复合材料新型预制体,通过等温化学气相沉积对预制体进行致密化处理。研究了炭纤维含量对预制体微观结构、致密化过程及力学性能的影响。结果表明:炭纤维含量增加,使预制体产生更多的微裂纹,并有更多的炭纤维裸露在泡沫炭韧带外,有助于提高化学气相沉积的沉积速率。炭纤维/泡沫炭预制体炭/炭复合材料压缩强度随着预制体中炭纤维含量的增加而增加,当炭纤维体积分数为10%时,压缩强度达到峰值,为43MPa。     

镍催化制备炭/炭复合材料

利用催化化学气相沉积法制备炭／炭复合材料，研究了反应温度、前驱体气体含量、催化剂含量和时间对所制备的炭／炭复合材料密度的影响，采用扫描电镜观察分析了基体碳的形貌。结果表明，利用催化剂镍可制取密度达1．594g／cm^3的炭／炭复合材料，并有晶须状基体碳生成。在各种工艺参数中，对炭／炭复合材料的密度影响最大的是温度和前驱体气体，其次为催化剂含量，最后是时间。     

C/C复合材料SiC-SiO_2/ZrO_2-SiC复合抗氧化涂层

为了提高C/C复合材料在高温有氧环境的抗氧化性,在SiC抗氧化涂层防护的基础上,采用气相沉积法及溶胶凝胶吸附冷凝热蒸汽法在C/C复合材料表面制备出了SiC-SiO2/ZrO2-SiC复合涂层。利用扫描电镜、能谱质谱测试及X射线衍射等检测方法对涂层各层进行了分析。结果表明,溶胶吸附ZrCl4蒸汽法制备ZrO2涂层,不仅能够在高温自动修复单层SiC涂层的裂纹缺陷,还起到了在制备外层SiC涂层过程中缓冲应力的作用。这种多层复合涂层在高温下具有良好的抗氧化性,在1 800℃等离子焰动态空气氧化120 s后,计算得出该涂层失重速率仅为0.4 g/(m2·s),表明该涂层具有卓越的抗氧化性。     

炭/炭复合材料化学液气相沉积致密化技术研究

介绍了炭/炭复合材料化学液气相沉积工艺的基本原理.化学液气相沉积工艺与热梯度化学气相沉积工艺在本质上是相同的,不同之处是化学液气相沉积用液态烃作前驱体,提高了原料的利用率,加快热解炭沉积的速率.研究了不同沉积温度对炭/炭复合材料微观组织结构的影响.采用偏光显微镜观察了材料的粗糙层、光滑层热解炭微观组织结构.研究发现用环己烷作前驱体当沉积温度为1 100℃时可以得到粗糙层结构的热解炭.     

炭/炭复合刹车材料的防氧化技术研究进展

从炭／炭复合材料氧化特点、抗氧化要求出发，综述了基体改性技术和涂层技术，对炭／炭复合材料防氧化研究进展进行了详细的介绍，提出了对其高温抗氧化研究方向的一些观点。     

碳/碳复合材料表面SiC/c-AlPO_4复合涂层及其抗氧化机制

采用二次包埋法和水热电泳沉积法相结合的工艺在碳纤维增强碳复合材料表面制得SiC/方石英型磷酸铝(cristobalite aluminum phosphate,c-AlPO4)复合涂层。借助X射线衍射仪和扫描电镜对复合涂层的晶相组成和显微结构进行了表征。研究了复合涂层的高温氧化性能,讨论了复合涂层氧化、失效的机理。结果表明:复合涂层具有双层结构,包埋的SiC内层主要由α-SiC,β-SiC和少量的游离硅组成,外层由c-AlPO4颗粒构成,内外层结合紧密。复合涂层在1300～1500℃范围内具有良好的抗氧化性能,其氧化激活能为117.2kJ/mol,氧化过程主要受氧在c-AlPO4层中的体扩散速率所控制;氧化气体逸出留下的孔洞是复合涂层防氧化失效的主要原因。     

A double layer nanostructure SiC coating for anti-oxidation protection of carbon/carbon composites prepared by chemical vapor reaction and chemical vapor deposition

A double layer nanostructure SiC coating was prepared by chemical vapor reaction and chemical vapor deposition to protect carbon/carbon composites from oxidation. The obtained dense coating reveals a typical crystalline structure and combines well with the substrate. The outer layer of the coating consists of SiC nanocrystals and nanowires, whereas the inner layer is mainly composed of SiC microcrystals, nanocrystals and nanowires. The oxidation and cyclic thermal shock test performed at 1400 °C in air demonstrates that the prepared dense nanostructure coating has excellent anti-oxidation behavior and thermal shock resistance at high temperature. After 400 h oxidation and 34 cycles of thermal shock from 1400 °C to room temperature, the weight loss of the coated sample is only 1.67%. In the oxidation process, the amorphous silica formed at the beginning of the oxidation crystallizes to cristobalite as oxidation time increased. The formation of cristobalite resulted in micro-cracks formed along grain boundaries in the cyclic thermal shock test. As only cracks are formed on the coating surface, it can be concluded that the formation of the penetration cracks may be the reason for the weight loss of the SiC coated composite.     

HfC nanowires to improve the toughness and oxidation resistance of Si-Mo-Cr/SiC coating for C/C composites

To improve the oxidation resistance of carbon/carbon (C/C) composites, a dense HfC nanowire-toughened Si-Mo-Cr/SiC multilayer coating was prepared by chemical vapor deposition (CVD) and pack cementation. The microstructure, thermal shock and isothermal oxidation resistance of the coating were investigated. HfC nanowires could improve the toughness of the coating and suppress the coating cracking. After incorporating HfC nanowires in the coating, both of the thermal shock and isothermal oxidation resistance of the coating were obviously improved. The multilayer coating with HfC nanowires could effectively protect C/C composites at 1773 K for 270 h, whose weight loss is only 0.19%. The good oxidation resistance is mainly attributed to the formation of a compound glass layer containing SiO₂ and Cr₂O₃.     

Oxidation behavior of oxidation protective coatings for PIP-C/SiC composites at 1500 °C

Three-dimensional carbon fiber reinforced silicon carbide (C/SiC) composites were fabricated by precursor infiltration and pyrolysis (PIP) with polycarbosilane as the matrix precursor, SiC coating prepared by chemical vapor deposition (CVD) and ZrB₂-SiC/SiC coating prepared by CVD with slurry painting were applied on C/SiC composites, respectively. The oxidation of three samples at 1500 °C was compared and their microstructures and mechanical properties were investigated. The results show that the C/SiC without coating is distorted quickly. The mass loss of SiC coating coated sample is 4.6% after 2 h oxidation and the sample with ZrB₂-SiC/SiC multilayer coating only has 0.4% mass loss even after oxidation. ZrB₂-SiC/SiC multilayer coating can provide longtime protection for C/SiC composites. The mode of the fracture behavior of C/SiC composites was also changed. When with coating, the fracture mode of C/SiC composites became brittle. When after oxidation, the fracture mode of C/SiC composites without and with coating also became brittle.     

Electron beam assisted physical vapor deposition of very hard TiCN coating with nanoscale characters

The work concerns electron beam assisted physical vapor deposition (EB-PVD) of titanium carbo-nitride (TiCN) on D2 tool steel. First, D2 steel substrate was heat treated to support and improve the load bearing capacity of the coating. To reduce the intrinsic gap between D2 substrate and TiCN coating and to improve the adhesive strength of the coating, a thin bond coat of Ti was EB-PV deposited on D2 steel prior to TiCN coating. The deposited coating was characterized in depth using XRD, SEM, AFM, profilometry and nanoindentation; its performance was assessed by the wear tests. The results demonstrated that EB-PVD process is successful in uniform deposition of nanograined (5.7 nm) TiCN coating; this character of the coating enhances its mechanical responses and cohesive strength. AFM topographic characterization confirms nanoscale smoothness of the TiCN coating which is a key factor in upgrading the wear resistance and tribological behavior of the coating. Nanoindentation results showed that the deposited coating is very hard; it is also tough enough. The hardness of the TiCN in this work is too much higher than those reported in the literature by similar works. AFM and nanoindentation results showed that a TiCN coating with thickness of 1.6 μm and roughness of 22 nm exhibits a hardness of 3552 HV which is much higher than those hardnesses reported in previous works. The wear tests showed that the deposited TiCN coating has a higher wear resistance than the D2 steel as well as TiN coating; this better performance is attributed to the modifications made in the coating process and its nanoscale characters.     

炭/炭复合材料MoSi2/SiC抗氧化涂层的研究

采用包埋法制备C／C复合材料抗氧化MoSi2／SiC梯度涂层，同时对抗氧化涂层的形成、组织结构以及抗氧化性能与渗料的关系和抗氧化机理进行了研究。结果表明：采用包埋法制备的C／C复合材料抗氧化MoSi2／SiC梯度涂层致密，但有少量裂纹，涂层有良好的抗氧化效果。当Si与SiC保持一定的比例时，渗料中MoSi2的含量为50％时，涂层具有最好的抗氧化效果；当MoSi2与SiC保持一定的比例时，渗料中Si的含量为20％时，涂层具有最好的抗氧化效果。     

Thermal Barrier Coatings Design with Increased Reflectivity and Lower Thermal Conductivity for High-Temperature Turbine Applications

High reflectance thermal barrier coatings consisting of 7% Yittria-Stabilized Zirconia (7YSZ) and Al₂O₃ were deposited by co-evaporation using electron beam physical vapor deposition (EB-PVD). Multilayer 7YSZ and Al₂O₃ coatings with fixed layer spacing showed a 73% infrared reflectance maxima at 1.85 μm wavelength. The variable 7YSZ and Al₂O₃ multilayer coatings showed an increase in reflection spectrum from 1 to 2.75 μm. Preliminary results suggest that coating reflectance can be tailored to achieve increased reflectance over a desired wavelength range by controlling the thickness of the individual layers. In addition, microstructural enhancements were also used to produce low thermal conductive and high hemispherical reflective thermal barrier coatings (TBCs) in which the coating flux was periodically interrupted creating modulated strain fields within the TBC. TBC showed no macrostructural differences in the grain size or faceted surface morphology at low magnification as compared with standard TBC. The residual stress state was determined to be compressive in all of the TBC samples, and was found to decrease with increasing number of modulations. The average thermal conductivity was shown to decrease approximately 30% from 1.8 to 1.2 W/m-K for the 20-layer monolithic TBC after 2 h of testing at 1316°C. Monolithic modulated TBC also resulted in a 28% increase in the hemispherical reflectance, and increased with increasing total number of modulations.     

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.     

SiCn/SiC oxidation protective coating for carbon/carbon composites

Nano-SiC (SiC_n) coating was deposited on SiC pre-coated C/C composites by a hydrothermal electrophoretic deposition. The phase compositions, surface and cross-section microstructures, and anti-oxidation properties of the multilayer coatings were investigated. Results show that hydrothermal electrophoretic deposition is an effective route to prepare smooth and homogeneous SiC_n coating on SiC-C/C composites. The as-prepared SiC_n/SiC multilayer coatings can effectively protect C/C composites from oxidation in air at 1773 K for 202 h with a weight loss of 0.79% and at 1873 K for 64 h with a weight loss of 1.3%.     

Wetting,infiltration and interaction behavior of CMAS towards columnar YSZ coatings deposited by plasma spray physical vapor

Thermal barrier coatings (TBCs) produced by electron beam physical vapor deposition (EB-PVD) or plasma spray (PS) usually suffer from molten calcium-magnesium-alumino-silicate (CMAS) attack. In this study, columnar structured YSZ coatings were fabricated by plasma spray physical vapor deposition (PS-PVD). The coatings were CMAS-infiltrated at 1250?°C for short terms (1, 5, 30?min). The wetting and spreading dynamics of CMAS melt on the coating surface was in-situ investigated using a heating microscope. The results indicate that the spreading evolution of CMAS melt can be described in terms of two stages with varied time intervals and spreading velocities. Besides, the PS-PVD columnar coating (～100?μm thick) was fully penetrated by CMAS melt within 1?min. After the CMAS attack for 30?min, the original feathered-YSZ grains (tetragonal phase) in both PS-PVD and EB-PVD coatings were replaced by globular shaped monoclinic ZrO₂ grains in the interaction regions.