三级化学气相沉积法制备SiC纤维及拉伸性能测试

以甲基三氯硅烷为先驱体,用直流电热三级化学气相沉积法制备了带有碳涂层的钨芯SiC纤维,测定了纤维的室温拉伸强度,并用Weibull分布对纤维的拉伸强度进行了评价.利用扫描电镜(SEM)、X射线衍射仪(XRD)和透射电镜(TEM)分析了纤维的断口形貌、相结构组成和W/SiC界面反应层的微观结构.结果显示,三级化学气相沉积法制备SiC纤维拥有两层β-SiC和均匀的表面碳涂层,钨芯和SiC之间存在厚度约为0.35μm的界面反应层,纤维的平均拉伸强度和Weibull模数分别达到3266MPa和16.3,并对纤维的断裂机理进行了分析和讨论.     

无压浸渗法制备氧化态SiC颗粒增强铝基复合材料

研究了SiC颗粒在1000~1200℃的氧化行为, 其氧化增重率与保温时间符合抛物线规律, 氧化增重受扩散过程控制, 氧化激活能为219 kJ/mol. 采用预氧化处理的SiC颗粒为增强体, 含Si、Mg的铝合金为基体, 通过无压浸渗方法制备了SiC_p/Al复合材料, 分析了复合材料的微观组织与界面形貌, 探讨了无压浸渗机理. 复合材料中颗粒分布均匀, 无偏聚现象. 材料制备过程中存在界面反应, SiC颗粒表面的氧化层与铝合金中的Mg、Al反应形成了一定数量的MgAl₂O₄. 界面反应的存在提高了润湿性, 促进了无压自发浸渗.     

Cf/ZrC-ZrB2-SiC-C超高温陶瓷复合材料的显微结构表征

利用X-射线衍射、扫描电子显微镜和透射电子显微镜对Cf/ZrC-ZrB2-SiC-C超高温陶瓷复合材料的相组成、纤维/热解碳层的界面特征和超高温陶瓷基体的显微结构特征进行了表征。在碳纤维表面有一层厚度为2～3μm石墨化程度较高的热解碳界面层,该界面层可以避免采用PIP工艺制备超高温陶瓷基体时可能对碳纤维造成的损伤。热解碳层与碳纤维之间为弱机械结合,其界面间分布着20～30 nm的ZrC纳米颗粒。Cf/ZrC-ZrB2-SiC-C超高温陶瓷复合材料基体主要由ZrC,ZrB2,SiC和石墨相(Cg)组成。基体中石墨的(002)面沿着ZrC,ZrB2或SiC的表面生长。在石墨与ZrB2和石墨与SiC的界面没有观察到取向关系,界面处既没有反应层也没有非晶相存在。在石墨与ZrC之间存在ZrC(111)∥Cg(002),ZrC[110]∥Cg[010]的取向关系。ZrB2和SiC之间也没有界面反应和非晶层存在。     

BN/SiC复合界面层对SiC纤维和PIP-Mini复合材料力学性能的影响

采用化学气相渗透(CVI)工艺, 在SiC纤维表面沉积BN和BN/SiC复合界面层, 对沉积界面层前后纤维的力学性能进行了评价。采用聚合物浸渍裂解(PIP)工艺进行致密化, 制得以原纤维、BN界面层和BN/SiC界面层纤维增强的三种Mini-SiC_f/SiC复合材料, 研究其微观结构和拉伸性能。结果表明: 采用CVI工艺制得的界面层厚度均匀、结构致密, 其中BN界面层中存在六方相, 晶体尺寸为1.76 nm; SiC界面层结晶性较好, 晶粒尺寸为18.73 nm; 沉积界面层后SiC纤维的弹性模量基本保持不变, 拉伸强度降低。与SiC_f/SiC相比, PIP工艺制备的SiC_f/BN/SiC和SiC_f/(BN/SiC)/SiC-Mini复合材料所能承受的最大拉伸载荷和断裂应变明显提升, BN界面层起主要作用。由断面形貌分析可以看出, SiC_f/BN/SiC和SiC_f/(BN/SiC)/SiC复合材料的纤维拔出明显, 说明在断裂时消耗的能量增加, 可承受的最大载荷增大。     

C涂层对SiC纤维增强Ti基复合材料界面的影响

采用透射电镜和扫描电镜研究了SiC纤维增强Ti基复合材料的界面反应,重点分析了C涂层对界面行为的影响.结果表明,C涂层可以明显改善纤维和基体之间的界面结合状况;SiC/C/Ti-6Al-4V复合材料的界面反应产物是主要为TiC,而无C涂层SiC/Ti-6Al-4V的界面反应产物为TiC,Ti5Si3和Ti3SiC2界面反应层生长受扩散控制,其厚度增长满足抛物线生长规律,SiC/C/Ti-6Al-4V由于C涂层消耗完毕前后的不同情况,其界面反应层生长并不完全符合这一规律,C涂层的存在可以有效的抑制界面反应的进行.     

SiC纤维增强钛基复合材料界面反应机理

本文应用相图和扩散通道理论分析了SiC/Ti复合材料界面反应的过程及界面区微观形貌,SiC纤维的表面状态直接影响着SiC/Ti界面反应的扩散通道。在SiC纤维表面涂覆TiC,或涂覆碳基涂层使Ti₃SiC₂层优先形成,能有效地控制界面反应,保护SiC纤维,界面区中反应产物层的排列顺序不一定与扩散通道所示的相顺序一一对应。      

不同界面SiC/SiC复合材料的断裂行为研究

碳化硅纤维增强碳化硅复合材料(SiC/SiC)是极具前景的高温结构材料。通过先驱体浸渍裂解(PIP)工艺分别制备了PyC界面和CNTs界面SiC/SiC复合材料, 对两种SiC/SiC复合材料的整体力学性能以及界面剪切强度等进行了测试表征, 并对材料中裂纹的产生与扩展进行了原位观测。结果表明, 两种界面SiC/SiC复合材料弯曲强度相近, 但PyC界面SiC/SiC复合材料的断裂韧性约为CNTs界面SiC/SiC复合材料的两倍。在PyC界面SiC/SiC复合材料中, 裂纹沿纤维-基体界面扩展, PyC涂层能够偏转或阻止裂纹, 材料呈现伪塑性断裂特征; 而在CNTs界面SiC/SiC复合材料中, 裂纹在扩展路径上遇到界面并不偏转, 初始裂纹最终发展为主裂纹, 材料呈现脆性断裂模式。     

PyC层对SiC纤维束及MiniSiC/SiC复合材料拉伸性能和强度分布的影响

采用等温等压化学气相浸渗法(ICVI),对原始的SiC纤维束和沉积有PyC层的SiC纤维束浸渗SiC基体,制备了纤维束复合材料SiC/SiC(Mini SiC/SiC)。分析了SiC纤维束和Mini SiC/SiC复合材料的拉伸性能,同时利用两参数Weibull分布研究了强度分布。结果表明,PyC层具有修复纤维表面缺陷的作用,SiC纤维束沉积PyC层后,纤维表面光滑而致密,表面缺陷减少,其拉伸强度、延伸率和Weibull模数分别比原始SiC纤维束提高了25%、12%和288%;且由其增强复合材料的拉伸强度、延伸率和Weibull模数分别比由原始SiC纤维束增强复合材料提高了103%、83%和340%。PyC界面层对SiC纤维表面缺陷的修复作用和对SiC纤维的保护作用以及降低复合材料裂纹敏感性的作用提高了Mini SiC/SiC复合材料的拉伸性能和Weibull模数。     

SiCP/ZL 109 复合材料中SiC 的界面行为

以常规TEM 为工具, 研究了SiCP/ ZL 109 复合材料中数十个SiC 颗粒及其界面,Si 优先在SiC 表面上形核、长大, 形成界面Si, 并形成大量SiC/S i 界面。靠近SiC 界面的Al 基体中, 普遍存在一层厚度小于1Lm 的“亚晶铝带”, 其内有大量位错。SiC 与Al、SiC 与Si 之间虽然没有固定的晶体学位向关系, 但是存在下列优先关系: (1103) _SiC//(111)_Al, [1120]_SiC//[110]_Al; (1101) _SiC//(111) _Si; [1120]_SiC//[112]_Si。      

SiCf/Ti-6Al-4V复合材料界面反应动力学

SiC纤维增强Ti基复合材料(SiCf/Ti)容易发生界面反应,从而影响其力学性能.开展界面反应和动力学的研究,对于SiCf/Ti复合材料的制备和服役具有指导意义.采用扫描电镜、透射电镜和X射线衍射分析了SiCf/Ti-6Al-4V复合材料的界面反应及其动力学,发现SiC纤维的C涂层与Ti-6Al-4V反应形成粗晶粒的和细晶粒的TiC,长期高温热处理使得界面反应加剧,TiC层加厚,当C涂层完全消耗后,界面反应层中除了TiC外,还出现了Ti3Si2.研究表明,界面反应层的加厚受元素扩散控制,服从抛物线规律,求出的动力学参数Q为268.8kJ/mol,k0为0.0057m/s1/2.     

Preparation of silicon carbide nanowires via a rapid heating process

Silicon carbide (SiC) nanowires were fabricated in a large quantity by a rapid heating carbothermal reduction of a novel resorcinol-formaldehyde (RF)/SiO₂ hybrid aerogel in this study. SiC nanowires were grown at 1500 °C for 2 h in an argon atmosphere without any catalyst via vapor-solid (V-S) process. The β-SiC nanowires were characterized by field-emission scanning electron microscope (FE-SEM), X-ray diffraction (XRD), transmission electron microscope (TEM), high-resolution transmission electron microscope (HRTEM) equipped with energy dispersive X-ray (EDX) facility, Fourier transformed infrared spectroscopy (FTIR), and thermogravimetric analysis (TGA). The analysis results show that the aspect ratio of the SiC nanowires via the rapid heating process is much larger than that of the sample produced via gradual heating process. The SiC nanowires are single crystalline β-SiC phase with diameters of about 20-80 nm and lengths of about several tens of micrometers, growing along the [1 1 1] direction with a fringe spacing of 0.25 nm. The role of the interpenetrating network of RF/SiO₂ hybrid aerogel in the carbothermal reduction was discussed and the possible growth mechanism of the nanowires is analyzed.     

固相烧结SiC陶瓷

实验采用α-SiC,β-SiC和（1％αSiC＋99％β-SiC作为起始粉末,以B,C为添加剂,热压烧结SiC陶瓷,其烧结过程中尽管发生多型体之转的转变,但其现现形式为α-SiC的6H→4H,和β-SiC的3C→6H两种形式,尽管有大量的长柱颗粒生成,但是由于没有弱的界面结合,不能原位增强。     

Analysis of Microstructure of Silicon Carbide Fiber by Raman Spectroscopy

The SiC fiber was prepared by chemical vapour depostion, which consists of tungsten core, SiC layer and carbon coating. The microstructure of the fiber was investigated using Raman spectroscopy, illustrating SiC variation in different region of the fiber. The result shows that the SiC layer can be subdivided into two parts in the morphologies of SiC grains; their sizes increase and their orientations become order with increasing distance from the fiber center. It is demonstrated that the mount of free carbon in the fiber is responsible for the variation of SiC grains in sizes and morphologies. The analysis of Raman spectra shows that the predominant β-SiC has extensive stacking faults within the crystallites and mixes other polytypes and amorphous SiC into the structure in the fiber.     

Study on W/SiC interface of SiC fiber fabricated by chemical vapor deposition on tungsten filament

SiC fiber was fabricated by chemical vapor deposition on tungsten filament heated by direct current in a CH₃SiCl₃-H₂ gas system. Microstructure of W/SiC interfacial reaction zone in the fiber was identified by means of scanning electron microscope and transmission electron microscope. Results showed that the thickness of the interfacial reaction zone is between 350 and 390 nm, and two reaction products of W₅Si₃ and WC were formed during fabricating SiC fiber. Electron diffraction analysis and composition detection indicated that W₅Si₃ is adjacent to tungsten core and WC is adjacent to SiC sheath, and the W/SiC interface can be described as W/W₅Si₃/WC/SiC. Furthermore, the formation mechanism of the interfacial reaction zone is discussed.     

Mechanism of SiC crystals growth on {100} and {111} diamond surfaces upon microwave heating

The subject of this work is focused on characterization of the microstructures and orientations of SiC crystals synthesized in diamond–SiC–Si composites using reactive microwave sintering. The SiC crystals grown on the surfaces of diamonds have either shapes of cubes or hexagonal prisms, dependent on crystallographic orientation of diamond. The selection of a specified plane in diamond lattice for the TEM investigations enabled a direct comparison of SiC orientations against two types of diamond facets. On the {111} diamond faces a 200 nm layer of 30–80 nm flat β-SiC grains was found having a semi-coherent interface with diamond at an orientation: (111)[112]SiC║(111)[110]C. On the {100} diamond faces β-SiC forms a 300 nm intermediate layer of 20–80 nm grains and an outer 1.2 µm layer on top of it. Surprisingly, the SiC lattice of the outer layer is aligned with the diamond lattice: (111)[110]SiC║(111)[110]C.     

先驱体法制备的含铝SiC纤维的组成和结构研究

先驱体聚铝碳硅烷经熔融纺丝、空气预氧化处理、1300℃烧成可制得SiC(OAl)纤维(称为KD-A), 该纤?维再经1800℃烧结转变为SiC(Al)纤维(称 为KD-SA). 采用了元素分析、AES、SEM、XRD、RMS以及²⁹Si、¹³C、²⁷Al魔角自?旋固体核磁共振等测试方法对纤维的组成和结构进行了研究. 元素分析结果表?明KD-A的化学组成为SiC_1/31O_0.25Al_0.018, KD-SA为SiC_1.03O_0.013Al_0.024. AES表明, KD-A和KD-SA的表面和内部组成 不同. SEM表明KD-A、KD-SA表面光滑平坦, ?没出现孔洞、裂纹、沟槽等表面缺陷. XRD、RMS以及²⁹Si、¹³C、²⁷Al核磁共振的分析结果表明: KD-A包含较多的不定形游离C, O以不?定形SiC_xO_y复合相的形式存在, Al与复合相中的O相连存在于复合相中, 复合相在纤维中是连续相, 少量 的β-SiC微晶分散在其中, 是非晶SiC纤维; KD-SA含有大量的β-SiC晶粒, 少量的α-SiC和Al₂O₃, 是近化学计量比的多晶SiC纤维.     

SiC nanofibers by pyrolysis of electrospun preceramic polymers

Silicon carbide (SiC) nanofibers of diameters as low as 20 nm are reported. The fibers were produced through the electrostatic spinning of the preceramic poly(carbomethylsilane) with pyrolysis to ceramic. A new technique was used where the preceramic was blended with polystyrene and, subsequent to electrospinning, was exposed to UV to crosslink the PS and prevent fiber flowing during pyrolysis. Electrospun SiC fibers were characterized by Fourier transform infrared spectroscopy, thermo gravimetric analysis-differential thermal analysis, scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and electron diffraction. Fibers were shown to be polycrystalline and nanograined with β-SiC 4H polytype being dominant, where commercial methods produce α-SiC 3C. Pyrolysis of the bulk polymer blend to SiC produced α-SiC 15R as the dominant polytype with larger grains showing that electrospinning nanofibers affects resultant crystallinity. Fibers produced were shown to have a core–shell structure of an oxide scale that was variable by pyrolysis conditions.     

Formation of SiC nanowhiskers by carbothermic reduction of silica with activated carbon

The silicon carbide (SiC) nanowhiskers were obtained by a carbothermic reduction of silica (SiO₂) with activated carbon at 1450 °C. The products were characterized by X-ray diffraction (XRD), Fourier transformed infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FE-SEM) and high resolution transmission electron microscopy (HR-TEM). The SiC nanowhiskers were grown as crystalline β-SiC with the diameter ranging from 20 to 150 nm grew along (111) direction with the length up to several tens of micrometers. Yield of β-SiC is very high with the moderate amount of un-reacted SiO₂. This is the first report on the synthesis of high yield of β-SiC by simple direct heating method.     

SiC空心球的制备与表征

以炭黑和粉煤灰为原料,通过微波加热碳热还原法制备了SiC空心球.制备工艺为:将粉煤灰与炭黑球模板按n(C)∶n(SiO2)=4.2配料,在1300℃氢气气氛下恒温0.5h.采用扫描电子显微镜、能谱仪、X射线衍射和拉曼光谱对SiC空心球进行了表征,结果表明,SiC空心球球壳由带有缺陷的β-SiC线组成,β-SiC线的直径为50～500nm.     

原位增强SiC陶瓷

实验采用β-SiC为起始原料,Y₂O₃、A1₂O₃为烧结助剂,通过适当的烧结控制,获得了具有长柱状晶粒结构的α－SiC陶瓷,材料以液相烧结机制密化,在烧结过程中发生了与柱状晶形成有关的SiC晶粒3C→4H相变．材料的力学性能与晶粒的形态即长径比存在一定的依从关系,并显示出原位增强的特性．在较佳工艺条件下,材料的强度和韧性最大值分别达到620MPa、6．1MPa.m^1/2．压痕裂纹扩展的途径表明,裂纹偏转和晶粒桥联是主要的增韧机理,这得益于其弱的界面结合．