掺杂难熔金属碳化物对炭/炭复合材料烧蚀机理的影响

通过对炭／炭复合材料（C／C）和添加难熔金属碳化物炭／炭复合材料（C／C＋MC）的微观结构对比分析，研究了二者在电弧加热器上的烧蚀机理。结果表明，难熔金属化合物（MC）在烧蚀过程中进入到距表层几个微米之内的纤维和基体炭微晶内，明显影响了相邻微晶的形貌。MC的存在，一方面，加大了机械剥蚀等力学因素引起的质量损失，增大了试样表面粗糙度，从而进一步加重了烧蚀；另一方面，MC具有降低碳的升华总量的效应。从综合效应来看，C／C＋MC复合材料的烧蚀速率比C／C复合材料高。     

基于神经网络的炭/炭复合材料烧蚀性能预测

采用人工神经网络(ANN)对炭/炭复合材料烧蚀性能进行了预测。确定了炭/炭复合材料的密度、 石墨化程度和基体炭类型为其烧蚀性能的关键控制因素, 通过人工神经网络表征了炭/炭复合材料的密度、 石墨化程度与其烧蚀性能之间的关系。在大量实验基础上对神经网络结构与参数发生变化时的网络性能进行了评估。结果表明, 当网络训练集规模、 隐层节点数、 初始学习率与动量项等参数的取值分别为35、 7、 0.5和0.2时网络预测性能达到最佳状态, 在此基础之上对炭/炭复合材料的质量烧蚀率进行了预测与评价。实践证明, 采用人工神经网络对炭/炭复合材料的烧蚀性能进行预测时误差小于11％, 满足工程实践的精度要求。      

纤维含量和热处理对炭/炭复合材料性能的影响

研究了炭纤维体积分数和预制体热处理温度对炭/炭复合材料力学性能的影响.结果表明,随着预制体中炭纤维体积分数的增加炭/炭复合材料的硬度逐渐增加,但当炭纤维的体积分数大于30%时,炭/炭复合材料硬度增加的幅度减小.炭纤维体积分数的增加对炭/炭复合材料硬度的影响有两个相反的作用,纤维的增强作用将使硬度增大,而孔隙率的增加将导致硬度的减小.炭/炭复合材料的抗弯强度随着纤维体积分数的增加而增加,但因纤维体积分数的增加会导致孔隙减小.致使热解炭不能充分地渗透填充到纤维间的孔隙内,抗弯强度下降,所以随着纤维体积分数的增加,材料的弯曲强度会出现拐点.随着预制体热处理温度的不同,炭/炭复合材料有脆性断裂、整束纤维拔出的假塑性断裂和部分炭纤维拔出的假塑性断裂三种断裂机制.     

纤维种类对炭/炭复合材料微观结构和力学性能的影响(英文)

采用6 K的预氧丝和炭纤维制备预制体,通过化学气相渗积制备炭/炭复合材料。通过偏光显微镜、拉曼光谱、纳米硬度和三点弯曲等手段研究其微观结构和力学性能。结果表明,预氧丝复合材料的基体为暗层和粗糙层炭,厚度分别为1.4-2.6μm和10.2-11.6μm;而炭纤维复合材料的基体为光滑层和粗糙层炭,厚度分别为8μm和4.4μm;预氧丝纤维的模量和硬度明显小于炭纤维,同时基体的模量和硬度随消光角的增加而降低;低模量的基体和纤维导致预氧丝复合材料的拉伸强度、拉伸模量、弯曲强度和模量分别降低了14.5%-24.2%、9.7%-19.8%、7.3%-15.4%和15.1%-18.6%;但其韧性指数却提高了224%-235%,这是高含量的粗糙层炭和纤维的石墨化收缩所致;同时提出了一个三单元复合模型用来模拟复合材料的拉伸模量,模拟误差小于9.9%。     

掺杂难熔金属碳化物对炭/炭复合材料烧蚀微观结构的影响

详细分析和比较了3D炭／炭复合材料及其添加难熔金属碳化物的试样在三种烧蚀条件下的烧蚀结果、微观结构及形貌。SEM观察结果显示，纤维与基体间的界面优先烧蚀现象对纯炭／炭试样是普遍存在的，相反，对难熔金属碳化物掺杂的炭／炭试样而言，纤维却总是优先被烧蚀；纤维单丝相对基体优先烧蚀越明显，材料宏观烧蚀率越大。对纯炭／炭试样烧蚀表层区的TEM观察结果表明，在烧蚀过程中炭纤维和基体炭均发生明显的微观结构变化，具体表现为炭纤维的微晶尺寸显著长大，而基体炭原有层片区则出现柱状炭。烧蚀测试条件对材料宏观和微观形貌及烧蚀机理都有影响：     

碳化铪改性炭/炭复合材料喉衬的热化学烧蚀

采用小型固体火箭发动机研究了碳化铪(HfC)改性炭/炭复合材料喉衬的热化学烧蚀.借助基于最小自由能原理的NASA-CEA程序计算了燃气组成,借助化学热力学软件FactSage计算了燃气组分与碳、HfC的化学反应.结果表明,燃气中的H2O、CO2和OH是碳和HfC的主要氧化组分,使材料发生热化学烧蚀;纤维-基体界面是烧蚀的薄弱环节,烧蚀沿着界面分别向碳纤维和基体方向推进.热化学作用(氧化)造成纤维变细,顶端呈锥状,基体变薄,呈壳状.     

热解炭结构对C/C复合材料烧蚀性能的影响

采用电弧驻点烧蚀试验方法测试了具有典型光滑层和粗糙层热解炭结构的两种C/C复合材料的烧蚀率,研究了热解炭结构对C/C复合材料烧蚀性能的影响.结果表明:热解炭结构对C/C复合材料烧蚀性能有较大的影响.具有粗糙层结构的C/C复合材料石墨化度高,不同炭结构之间结合好,线烧蚀率和质量烧蚀率较小,烧蚀性能较好;具有光滑层结构的C/C复合材料石墨化度低,烧蚀性能较差.     

表面多孔炭/炭复合材料骨组织改建支架的生物学性能及其表征(英文)

采用炭/炭复合材料制备了骨组织改建支架,并对所制支架进行了表面形貌观察、痕量元素分析和体内生物学性能评价。结果表明:所制支架能够有效实现对自体移植骨的支撑和骨性融合,生物相容性良好。亦即,表面多孔炭/炭复合材料能够满足作为骨组织改建支架材料的成分要求。     

炭/炭复合材料表面C/SiC/Si-Mo-Cr多层复合防氧化涂层研究(英文)

为提高炭/炭(C/C)复合材料的高温抗氧化性能,采用料浆涂刷法首先在C/C复合材料表面制备了预炭层,然后以Si粉及石墨粉(Si粉与石墨粉的质量配比为:60～80:10～25)为原材料采用包埋法经高温热处理获得C/SiC内涂层,最后在涂有C/SiC内涂层的C/C复合材料表面采用包埋法制备Si-Mo-Cr外涂层。借助扫描电镜、X射线衍射、电子能谱等分析测试手段对涂层试样的微观结构进行了分析,研究了涂层C/C复合材料在1 873 K和1 973 K下的氧化行为。结果表明:由于涂层氧化过程中表面生成了SiO2和Cr2O3复合玻璃层,其在1 873 K温度下表现出优异的防氧化性能,可以有效保护C/C复合材料达135 h。当氧化温度提高至1 973 K并氧化30 h后,该复合涂层氧化过程玻璃层完整性被破坏,涂层失效。     

抗烧蚀C/C复合材料研究进展

C/C复合材料因优异的高温性能被认为是高温结构件的理想材料。然而,C/C复合材料在高温高速粒子冲刷环境下的氧化烧蚀问题严重制约其应用。因此,如何提高C/C复合材料的抗烧蚀性能显得尤为重要。笔者综述C/C复合材料抗烧蚀的研究现状。目前,提高C/C复合材料抗烧蚀性能的途径主要集中于优化炭纤维预制体结构、控制热解炭织构、基体中陶瓷掺杂改性和表面涂覆抗烧蚀涂层等4种方法。主要介绍以上4种方法的研究现状,重点介绍基体改性和抗烧蚀涂层的最新研究进展。其中,涂层和基体改性是提高C/C复合材料抗烧蚀性能的两种有效方法。未来C/C复合材料抗烧蚀研究的潜在方向主要集中于降低制造成本、控制热解炭织构、优化掺杂的陶瓷相以及将基体改性和涂层技术相结合。     

High performance carbon-carbon composites

Carbon-carbon composites rank first among ceramic composite materials with a spectrum of properties and applications in various sectors. These composites are made of fibres in various directions and carbonaceous polymers and hydrocarbons as matrix precursors. Their density and properties depend on the type and volume fraction of reinforcement, matrix precursor used and end heat treatment temperature. Composites made with thermosetting resins as matrix precursors possess low densities (1.55–1.75g/cm³) and well-distributed microporosity whereas those made with pitch as the matrix precursor, after densification exhibit densities of 1.8–2.0g/cm³ with some mesopores, and those made by the CVD technique with hydrocarbon gases, possess intermediate densities and matrices with close porosities. The former (resin-based) composites exhibit high flexural strength, low toughness and low thermal conductivity, whereas the latter (pitch- and CVD-based) can be made with very high thermal conductivity (400–700 W/MK) in the fibre direction. Carbon-carbon composites are used in a variety of sectors requiring high mechanical properties at elevated temperatures, good frictional properties for brake pads in high speed vehicles or high thermal conductivity for thermal management applications. However, for extended life applications, these composites need to be protected against oxidation either through matrix modification with Si, Zr, Hf etc. or by multilayer oxidation protection coatings consisting of SiC, silica, zircon etc.     

炭/炭复合材料新型热梯度制备工艺

对传统的热梯度化学气相渗透工艺进行了改进.把高热导率(55W/(m·℃))的48k炭纤维束穿入针刺炭毡预制体中心.利用炭纤维束和炭毡预制体热导率(0.15W/(m·℃))的差异,在预制体内部产生热梯度.在900℃～1200℃下,天然气首先在预制体中心的48k炭纤维处热解,致密化沿径向由中心向外部推进,67 h后材料的密度达1.778 g/cm3.研究了炉内输入电压、电阻、致密化时间、沉积层位置等工艺参数对材料性能的影响.通过偏光显微镜和扫描电子显微镜研究了基体热解碳的微观结构,并对炭纤维体积含量为10%的炭/炭试样进行了烧蚀性能测试.     

Surface structures of PAN-based carbon fibers and their influences on the interface formation and mechanical properties of carbon-carbon composites

Defects and microvoids in the surface region not only influenced the tensile strength and strain of carbon fibers but also affected the interface formation with pyrocarbon. The interface formation in carbon-carbon composites was closely correlated to rearrangement of carbon atoms and the evolution of surface structure of carbon fiber. Half-open elliptic microvoids or edge planes at the fiber surface were beneficial to the mechanical interlocking as well as chemical bonding with pyrocarbon, contributing to a compatible interface with high interlaminar shear strength of the composites. The closed microvoids in the surface region of carbon fiber would hardly open up to bond with pyrocarbon, which brought negative effects to the mechanical properties of composites. Carbon fiber without obvious microvoids or surface defects tended to have better tensile strain but form weak interface with pyrocarbon, leading to a better pseudo-ductility and ability to absorb more fracture energy under load.     

炭/炭复合材料高温抗氧化涂层的研究进展

阐述了近年来国内外炭/炭复合材料高温抗氧化涂层在玻璃、贵金属、陶瓷以及复合涂层等涂层体系方面的新近展,总结了炭/炭复合材料高温抗氧化涂层在已有制备工艺的完善以及新工艺的开发等方面的最新研究成果,结合涂层炭/炭复合材料在航空、航天以及军事领域的应用背景对高温抗氧化涂层的下一步发展趋势进行了展望.指出：目前的研究结果尚达不到严酷环境下的应用要求,炭/炭复合材料高温抗氧化涂层下一阶段将向着长寿命、耐高温、抗冲刷和低成本的方向发展;涂层新工艺的开发和涂层与基体结合研究将是下一步的研究重点;多相复合涂层和梯度陶瓷涂层有望取得在高温冲刷环境下长时间应用的突破性进展.     

Effects of fluctuation of fibre orientation on tensile properties of flax sliver-reinforced green composites

Plant-based natural fibres are often used as a reinforcing material for environmentally friendly green composites. Especially, the form of slivers of natural fibres is anticipated for increasing their stiffness and strength. However, the sliver structure has fluctuations in fibre orientation, which decreases their mechanical properties. This paper describes the effects of such fibre orientation fluctuation on tensile properties of fibre-reinforced fully green composites. The composites were reinforced with slivers of high-strength flax fibres, for which a fabrication method called ‘direct method’ was applied. To quantify the morphology of the fibre orientation, fibre orientation angles were measured on fine segments, which were divided into 1 mm × 1 mm squares on a photograph of the whole composite surface. Although it is well-known that tensile strength of unidirectional composites decreases with increasing fibre orientation angle, the tensile strength obtained here did not show any appreciable relation to the statistical properties of measured fibre orientation angles such as average and standard deviation. The concept of two-dimensional (2D) autocorrelation was used in the present study to express the degree of similarity between fibre orientation angles in two different local areas. Results show that, if high 2D autocorrelation coefficients occupy more area on a composite surface, then this composite possesses more regular fibre orientation and tends to exhibit higher tensile strength. This tendency is stronger in the composites close to on-axis alignment, whereas it became weak in the off-axis composites angled more than 15° because of shear fracture.     

One-step amino-functionalization of milled carbon fibre for enhancement of thermo-physical properties of epoxy composites

Development of new chemical approaches for preparation of engineered carbon-based fillers is critical for high-performance applications. Herein, an efficient method for covalent functionalization of polyacrylonitrile-based carbon fibre through azo radical addition under mild condition is demonstrated. In this way, isobutyronitrile radicals in situ produced from thermal decomposition of 2,2′-azobisisobutyronitrile (AIBN), were covalently grafted on milled carbon fibre (MCF) surface, assisted by microwave irradiation, as evidenced by FTIR, Raman, and TGA analysis. The grafted isobutyronitriles on MCF surface (n-MCF) were applied for further MCF amino-functionalization (a-MCF) via nucleophilic reaction of an amine-rich compound. Then, both pure MCF and a-MCF were incorporated into epoxy matrix; and its curing process and thermo-physical properties were investigated using DSC, rheometry, DMA, TGA, and flexural analysis. The T_g and flexural strength of epoxy/a-MCF composites, compared to epoxy/MCF, increased by ∼3.5% and ∼10.2%, resulting from good adhesion between a-MCF and epoxy matrix which confirmed by SEM observations.     

Effect of load on tribological behaviour of carbon-carbon composites

The effect of load on the tribological behaviour of three different two-dimensional carbon-carbon composites, including polyacrylonitrile (PAN) fibre-pitch matrix, PAN fibre-chemical vapour infiltrated (CVI) matrix, and pitch fibre-resin/CVI hybrid matrix composites has been compared. Results indicated that friction and wear rate variations with slide distance depended on load and the type of composite. The worn surface morphology was categorized into three types (I, II and III). The friction coefficient, wear rate and temperature all increased sharply when the transition from type I to type II occurred. When the powdery type II debris was compacted to form the lubricative type III debris, the friction coefficient and wear rate declined, although never approached their initial type I levels. For all composites, a higher load can accelerate the transition from type I to type II, but impedes the transition from type II to type III. Under 2.4 MPa, the type II morphology was never observed to transform into type III morphology in this study.     

碳化铪含量对C/C复合材料喉衬烧蚀性能的影响

将炭毡浸渍于饱和的HfOCl2.8H2O乙醇溶液中,经600℃热处理形成HfO2/C复合材料,然后采用热梯度化学气相沉积工艺在2100℃进行致密化和石墨化处理使HfO2转化为HfC而得到碳化铪(HfC)改性、整体炭毡增强的炭/炭(HfC-C/C)复合材料整体喉衬。利用小型固体火箭发动机试车台装置,在7MPa、3200℃烧蚀3s以测定HfC含量对喉衬烧蚀性能的影响。结果表明,HfC质量分数为5.7%的HfC-C/C喉衬线烧蚀率减小了25.2%;HfC质量分数为8.7%的HfC-C/C喉衬线烧蚀率减小了49.6%。同时,当HfC质量分数为5.7%时,HfC-C/C喉衬出现了以恒定线烧蚀率为特征的稳态烧蚀阶段,且该阶段的持续时间随HfC含量的增加而增加。     

Effect of fibre volume fraction on fatigue behaviour of glass fibre reinforced composite

The aim of this paper is to study the fatigue behavior of GFRP composites manufactured by vacuum bagging process by varying the volume fraction. Constant‐amplitude flexural fatigue tests were performed at zero mean stress, i.e. a cyclic stress ratio R=?1 by varying the frequency of the testing machine. The relationship between stiffness degradation rate and fibre volume fraction, was observed, and the influence of volume fraction on the tensile strength was also investigated. The results show that, as the volume fraction increases the stiffness degradation rate initially decreases and then increases after reaching a certain limit for the volume fraction. Graph between volume fraction and Young's modulus shows that as the volume fraction increases Young's modulus also increases and reaches a limit and then it decreases with further increase in volume fraction, due to the increase in fibre content which changes the material properties of the composite material. The obtained results are in agreement with the available results.     

A novel image analysis procedure for measuring fibre misalignment in unidirectional fibre composites

A novel image analysis procedure named Fourier transform misalignment analysis (FTMA) for measuring fibre misalignment in unidirectional fibre composites is presented. Existing methods are briefly illustrated and evaluated. The FTMA-method is presented, describing the specimen preparation and elaborating how the image analysis algorithm uses Fourier transformation and a least squares method to compute single fibre orientations. On the basis of parameter investigations the robustness of the FTMA-method is investigated. Software generated micrographs with known fibre misalignment are used to determine the precision of the method. The precision is used, along with computation time and memory usage, to benchmark the FTMA-method against the existing multiple field image analysis (MFIA) method. It is found that the FTMA-method is at least as accurate as existing methods. Furthermore, the FTMA-method is much faster than the existing methods, completing a typical analysis in approximately 1 min. Overall, it is concluded that the FTMA-method is a robust, precise and time efficient tool for determining fibre misalignment in unidirectional fibre composites, offering a higher degree of detail than the existing MFIA-method.