Direct growth of core-shell SiC-SiO(2) nanowires and field emission characteristics

A simple, direct synthesis method was used to grow core-shell SiC-SiO(2) nanowires by heating NiO-catalysed silicon substrates. A carbothermal reduction of WO(3) provided a reductive environment and carbon source to synthesize crystalline SiC nanowires covered with SiO(2) sheaths at the growth temperature of 1000-1100?°C. Transmission electron microscopy showed that the SiC core was 15-25?nm in diameter and the SiO(2) shell layer was an average of 20?nm in thickness. The thickness of the SiO(2) shell layer could be controlled using hydrofluoric acid (HF) etching. Field emission results of core-shell SiC-SiO(2) and bare SiC nanowires showed that the SiC nanowires coated with an optimum SiO(2) thickness (10?nm) have a higher field emission current than the bare SiC nanowires.     

界面涂层与基体对先进CVI-SiC/SiC复合材料性能的影响

对含有几种典型界面结构和SiC纳米线的CVI-SiC/SiC复合材料的弯曲性能和断裂韧性进行了比较研究. 研究表明: 界面涂层对SiC/SiC的力学性能至关重要, 120nm厚的碳界面涂层使材料的强度与韧性都增加一倍; 在用140nm厚的SiC层将该碳层分为更薄的两层, 形成C/SiC/C多层界面涂层时, 材料的强度没有明显的变化, 而断裂韧性则略有提高. 对基体中弥散分布有SiC纳米线的SiC/SiC的力学性能研究表明, SiC纳米线具有非常高的强化效率, 使SiC/SiC复合材料具有更高的强度和韧性.     

SiC Nanowires Toughed HfC Ablative Coating for C/C Composites

In order to improve ablation resistance of carbon/carbon(C/C) composites,SiC nanowires were prepared on C/C composites surface in prior through chemical vapor reaction before HfC coating.SiC nanowires grew randomly and had good combination with HfC coating.SiC nanowires toughed HfC coating had lower linear and mass ablation rates than original HfC coating.The surface was much flatter and exhibited smaller cracks in center region.The ablation mechanism of HfC coating has been changed by SiC nanowires.Thicker HfO2 fused layer was formed on the surface of the toughed HfC coating,which could provide efficient protection for C/C composites.Therefore,SiC nanowires toughed HfC coating behaved in better ablation resistance.     

核壳结构SiC/SiO2纳米线的低温合成与表征

以酚醛树脂(PF)作为碳源, 纳米SiO₂为硅源, 在1300℃氩气气氛下通过碳热还原反应, 制备出具有核壳结构的SiC/SiO₂纳米线。采用X射线分析衍射仪(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、高分辨率透射电子显微镜(HRTEM)、拉曼光谱(Raman)对产物的组成、形貌、微观结构等进行了表征。结果表明; SiC/SiO₂纳米线长可达数毫米, 单根SiC/SiO₂纳米线由直径30 nm的β-SiC晶体为内核和厚度约12 nm的无定形SiO₂壳层组成; 室温下SiC/SiO₂纳米线的PL发光峰与β-SiC单晶的发光特征峰相比有蓝移。最后, 讨论了核壳结构SiC/SiO₂纳米线的生成机制。     

碳纤维表面改性增强Fe3Al-Al2O3复合材料的制备及组织性能

采用溶胶-凝胶分散和热压烧结制备了短切碳纤维（CF_s）/Fe₃Al-Al₂O₃复合材料。分别通过电化学镀Cu和化学气相沉积SiC对CF_s表面修饰和改性,研究了Cu镀层和SiC涂层对CF_s/Fe₃Al-Al₂O₃复合材料显微组织、相组成、力学性能及断裂行为的影响。结果表明,未修饰的CF_s在Fe₃Al-Al₂O₃基体中受到严重侵蚀,CF_s/Fe₃Al-Al₂O₃复合材料致密度低,抗弯强度仅为239.0 MPa,与Fe₃Al-Al₂O₃强度相当;表面镀Cu可有效保护CF_s不被侵蚀,同时提高了CF_s/Fe₃Al-Al₂O₃复合材料的烧结致密性和界面结合强度,从而明显提高了复合材料的断裂强度,但断裂过程中纤维拔出较短;CF_s表面沉积SiC的CF_s/Fe₃Al-Al₂O₃复合材料组织均匀致密,表面涂层完整,且与纤维及基体之间结合力相当,断裂过程中,涂层既可随纤维一起拔出基体,也可与CF_s分离而留在基体之中,SiC涂层与纤维及基体之间的弱相互作用很大程度上促进了纤维脱黏和拔出,从而促进CF_s/Fe₃Al-Al₂O₃复合材料韧化所需的渐进破坏机制。      

Study of the growth,and effects of filament to substrate distance on the structural and optical properties of Si/SiC core–shell nanowires synthesized by hot-wire chemical vapor deposition

Silicon/silicon carbide (Si/SiC) core–shell nanowires grown on quartz substrates by hot-wire chemical vapor deposition were studied. Nickel was used as a catalyst to induce the growth of these core–shell nanowires followed by the vapor–solid–solid growth mechanism. The nanowires were grown by varying substrate-to-filament distance; d_s-f from 1.9 to 3.1 cm with an interval of 0.4 cm. Lower d_s-f produced a high density of straight core–shell nanowires. A highly crystalline single crystal Si core of the nanowires was produced at lower d_s-f as well. Presence of Si and SiC nano-crystallites embedded within an amorphous matrix in the shell of the nanowires exhibited a high intensity of photoluminescence emission spectra from 600 to 1000 nm. The effects of the d_s-f on the structural and optical properties of the nanowires are discussed.     

Interfacial control of uni-directional SiCf/SiC composites based on electrophoretic deposition and their mechanical properties

Interfacial control of uni-directional SiC_f/SiC composites were performed by EPD, and their mechanical properties at room temperature were evaluated. The effect of the thickness of carbon interphase on SiC fibers by EPD on mechanical properties of uni-directional SiC_f/SiC composites was also investigated. The average thickness of carbon coating on SiC fibers increased from 42 nm to 164 nm with an increase in the concentration of colloidal graphite suspension for EPD. Dense SiC_f/SiC composites were achieved and their fiber volume fraction was 47–51%. The SiC_f/SiC composites had a bending strength of 210–240 MPa. As the thickness of carbon coating was below 100 nm, the SiC_f/SiC composites (SC01 and SC02) fractured in almost brittle manner. In contrast, the SiC_f/SiC composites (SC03) showed a pseudo-ductile fracture behavior with a large number of fiber pullout as the thickness of carbon coating was above 100 nm. The fracture energy of SC03 was 3–4 times as high as those of SC01 and SC02 and the value was about 1.7 kJ/m². In consideration of the results of mechanical properties, the thickness of carbon coating on SiC fibers should be at least 100 nm to obtain high-performance SiC_f/SiC composites. The fabrication process based on EPD method is expected to be an effective way to control the interfaces of SiC_f/SiC composites and to obtain high-performance SiC_f/SiC composites.     

Effects of trace amount of nanometric SiC additives with wire or particle shapes on the mechanical and thermal properties of alumina matrix composites

SiC nanowires (SiCNWs) are suitable candidates used as additives to improve the thermal conductivity of alumina, since they exhibit superior properties such as high chemical and thermal stability. In this study, alumina matrix composites reinforced with very small amount of β-SiC/SiO₂ core–shell nanowires were fabricated by hot-pressing. They were first characterized and compared with alumina matrix specimens containing SiC nanopowder. It was found out that with 0.2 wt% SiC additives, the grain sizes of the alumina specimens were reduced by 20 % of that of the monolithic one, regardless of the shape of the SiC additives. Vickers hardness of specimen containing both SiCNWs and SiC nanopowders slightly increased, while fracture toughness decreased more than that of the monolithic alumina. Thermal conductivity of the specimens increased with increased amount of SiCNWs and was better than those of the specimens containing SiC nanopowders. The alumina composite containing 0.2 wt% SiCNWs had higher thermal conductivity than that of the monolithic alumina by as much as 45 %. From these results, it is clear that only small amount of nanosized SiC as an additive material, particularly SiCNWs, has a significant effect on the properties of alumina matrix composites.     

Selective growth of SiC nanowires in interlaminar matrix for improving in-plane strengths of laminated Carbon/Carbon composites

β-SiC nanowires(SiCNWs) were selectively grown in the interlaminar matrix with a volume fraction of0.65% by applying a pyrocarbon coating on carbon fibers, which realizes the proper reinforcement of C/C composites. The thickness of the pyrocarbon is optimized to 0.5 μm based on the analysis of in-situ fiber strengths with the fracture mirror method. The pyrocarbon coating increased the in-situ fiber strength by~7% and prevent brittle fracture of the composites. Compared with C/C, the interlaminar shear and flexural strength of SiCNW-C/C(10.06 MPa and 162.44 MPa) increase by 158% and 57%. Incorporating SiCNWs changes the crystallite orientations and refines the crystallite size of pyrocarbon matrix. The functions of SiCNWs vary with their loading density. When SiCNWs are sufficient in the matrix, they help reinforcing and improving the critical failure stress of the matrix. When their density decreases to a certain degree, SiCNWs help changing the crystallite orientations of pyrocarbon and toughening the matrix.     

Scalable fabrication of novel SiC nanowire nonwoven fabric

Flexible papers constructed by one-dimensional nanowires have attracted much attention due to their various applications. Herein, a novel nonwoven fabric with paper-like qualities composed of zinc blende SiC (β-SiC) nanowires was fabricated by a scalable rolling process. The SiC nanowires were synthesized by the carbothermal reduction reaction of the carbon fiber and carbonaceous silica xerogel. The crystal phase, morphology and microscopic structure of the as-prepared SiC nanowires were characterized by field emission scanning electron microscope, X-ray diffraction and high-resolution transmission electron microscopy. The nanowire vapor–solid growth mechanism and preparation process for SiC nanowire nonwoven fabric were also discussed. The freestanding SiC nanowire nonwoven fabric exhibited high flexibility, high mechanical strength, excellent refractory performance and thermal stability. With high flexibility, high mechanical strength, superior nonflammability and thermal stability, the flexible paper-like 3C-SiC nanowire nonwoven fabric materials would be expected to have some potential applications, such as ceramic matrix composites, metal matrix composites, energy storage, catalyst supports, radiation-proof fabric, filtration and separation.     

Ceramic composites: roles of fiber and interface

Results are presented that elucidate: (a) the effects of fiber coating on retained fiber strength and mechanical properties of Nicalon-fiber-reinforced SiC matrix composites; and (b) the role of residual stresses in the interfacial bond strength of SiC-fiber-reinforced reaction-bonded Si₃N₄ matrix composites. For Nicalon-fiber-reinforced SiC matrix composites that were fractured in a flexural mode, retained in-situ fiber strength, ultimate strength and work-of-fracture (WOF) of the composites increased with increasing thickness of the fiber coating and reached maximum values at a coating thickness of ≈0.3 μm. A direct correlation between the variation of in-situ fiber strength and the variation of ultimate strength and WOF of the composites clearly indicates the critical role of the retained in-situ strength of reinforcing fibers in composites. Fiber pushout tests performed on SiC-fiber-reinforced reaction-bonded Si₃N₄ matrix composites indicate that both debonding and frictional shear stresses decreased with increasing fiber content. These variations are consistent with the variation of residual radial stress on fibers, as measured by neutron diffraction, i.e. residual stresses decreased with increasing fiber content. Because fracture behavior is strongly controlled by interfacial bond strength, which is proportional to the residual radial stress, appropriate control of residual stresses is critical in the design of composites with desired fracture properties.     

MoSi2-SiC 抗氧化涂层对碳/碳复合材料弯曲性能的影响

在C/C 复合材料表面制备了MoSi₂-SiC 抗氧化涂层, 分析了涂层工艺对C/C 复合材料组织的影响, 测试了材料的室温弯曲力学性能。结果表明, 该工艺在C/C 复合材料表面生成抗氧化涂层的同时, 基材内部的层间和纤维束界面, 以及孔隙周围也被硅化。C/C 复合材料经涂层工艺处理后, 弯曲断裂行为发生改变, 弯曲强度明显升高,塑性有一定程度的降低。      

Evaluation of the efficiency of TiB2 and TiC as protective coatings for SiC monofilament in titanium-based composites

The vigorous interfacial reactions in SiC/Ti-6Al-4V composites at elevated temperatures lead to the deterioration of the mechanical properties of the composites. TiB₂ and TiC were selected as potential protective coatings for SiC fibres in titanium-based composites. These coatings were deposited on to fibres by the chemical vapour deposition technique. Comparisons and evaluations have been made of the effectiveness of these ceramics as protective coatings for SiC fibres by incorporating the coated fibres into a Ti-6Al-4V matrix using the diffusion bonding method. Emphasis has been placed on the chemical compatibility of the candidate coating with SiC and Ti-6Al-4V by examining the interfaces of the fibre/coating/matrix using microscopic methods and chemical analysis. A stoichiometric TiB₂ coating was found to be stable with SiC and has proved an effective barrier to prevent the SiC fibre from reacting with the Ti-6Al-4V. The TiC coating showed no apparent reaction with a titanium-alloy matrix under the conditions studied, but was found to react with the SiC fibre substrate.     

Core-shell morphology and characterization of carbon nanotube nanowires click coupled with polypyrrole

Core-shell nanowires having multiwalled carbon nanotubes (MWNT) as a core and polypyrrole (PPy) as a shell were synthesized using Cu(I)-catalyzed azide-alkyne cycloaddition click chemistry. According to transmission electron microscopy measurements, the uniform PPy layers of 10-20 nm in thickness were formed well on the MWNT's surface. In particular 'grafting from' click coupling was more effective in obtaining uniform and stable core-shell nanowires as well as in the reaction yield, compared to 'grafting to' click coupling. This is due to chemical bond formation between PPy and MWNT in equal intervals along the longitudinal direction of the MWNT, achieved by 'grafting from' click coupling. As a result, the core-shell nanowires were very stable even in the sonication of nanowires and showed an enhanced electrical conductivity of 80 S cm(-1), due to the synergetic interaction between MWNTs and PPy, which is higher than the conductivity of pure MWNTs and pure PPy. In addition, the core-shell nanowires could show better NO2 gas sensing properties compared to pure MWNTs and pure PPy as well as MWNT/PPy composites prepared by in situ polymerization. The synthesized core-shell nanowires would play an important role in preparing electrical and sensing devices.     

Structure-property relations for silicon nitride matrix composites reinforced with pyrolytic carbon pre-coated Hi-Nicalon fibers

Si₃N₄ matrix composites reinforced with pyrolytic carbon pre-coated Hi-Nicalon (SiC) fibers, were studied using tensile testing and transmission electron microscopy. Three types of samples were evaluated all with a nominal coating thickness of 200 nm. The composites were densified by hot pressing at 1550 °C (type I and II) and at 1600 °C (type III). The fibers were coated with pyrolytic carbon via CVD with identical (sample I) and opposite (samples II and III) directions of the gas flow and of the fiber movement through the reactor. Tensile testing indicated for the three sample types respectively: brittle behaviour with huge pull out of the fibers, pseudo-plastic behaviour and brittle behaviour with little pull out. TEM indicated for the three sample types debonding typically at the fiber/coating interface, at the coating/matrix interface and in the coating, respectively. The relation between processing, structure, particularly of the coating and its interfaces with the matrix and the fibers and mechanical properties is addressed.     

碳/碳复合材料SiC/MoSi_2/ZrO_2涂层体系氧化烧蚀性能

抗氧化涂层技术是解决碳/碳复合材料高温抗氧化性的最有效技术途径之一。为了提高材料在1 800℃以上的高温抗氧化性能,首次采用包埋法、涂刷法和等离子喷涂法在碳/碳复合材料表面制备出SiC/MoSi_2/ZrO_2梯度抗氧化涂层体系。采用SEM/EDS、结合力和粗糙度测试对涂层表面及断面形貌进行微观分析,利用等离子风洞对整个涂层体系进行氧化试验。结果表明:基体、过渡层和高温抗氧化层之间结合力良好,高温抗氧化层厚度均匀、结构致密。经等离子风洞氧化600s后,涂层表面温度达到1 850℃,氧化质量失重速率仅为3.15×10~(-6) g/(cm~2·s)。表明SiC/MOSi_2/ZrO_2梯度抗氧化涂层体系在1 800℃以上的高温环境下具有很好的抗氧化性能。     

C/C复合材料Ta2O5-TaC/SiC抗氧化抗烧蚀涂层研究

采用包埋法和低压化学气相沉积(CVD)法在碳/碳(C/C)复合材料表面依次制备了Ta2O5-TaC内涂层和SiC外涂层,用X射线衍射分析(XRD)、扫描电镜(SEM)及电子能谱(EDS)对涂层的相组成、微观形貌和元素组成进行了分析,研究了涂覆涂层后C/C复合材料在1 500℃静态空气中的防氧化性能及在氧-乙炔烧蚀中的抗烧蚀性能。结果表明:采用两步法制得的Ta2O5-TaC/SiC复合涂层结构致密,该复合涂层有效提高了C/C复合材料的抗氧化和抗烧蚀性能;Ta2O5-TaC/SiC复合涂层在1 500℃静态空气环境下可对C/C复合材料有效保护100 h以上;涂层试样在氧乙炔烧蚀环境中烧蚀60 s表明涂层可将C/C复合材料的线烧蚀率降低47.07%,质量烧蚀率降低29.20%。     

Preparation and characterization of SiC nanowires and nanoparticles from filter paper by sol–gel and carbothermal reduction processing

The carbothermal reduction of SiO₂ gel containing filter paper (as carbon precursors) in argon was used to prepare SiC nanowires and nanoparticles. The resulting SiC ceramic, as well as the conversion mechanism of carbon/silica composites to SiC nanowires and nanoparticles, have been investigated by scanning electron microscopy (SEM), Transmission electron microscopy (TEM), x-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and thermogravimetric analysis (TG) techniques. XRD and IR studies show that the materials, obtained from reaction at 1550 °C for 1 h in static argon atmosphere, are β-SiC. SEM and TEM reveal that SiC nanowires is single crystal wires with diameters ranging from 50–200 nm and their lengths over several tens of microns. According to thermodynamic analysis, SiC nanowires and SiC nanoparticles in the resulting SiC ceramic are formed by gas-gas reaction of SiO (g) and CO (g).     

Surface chemical composition of SiC-cored nanowires investigated at room and elevated temperatures in ultra-high vacuum

Nanowires with SiC core were produced via Si/PTFE combustion synthesis in air and deposited from 1,2-dichloroethane suspension on an Au (111) surface. The dependence of the chemical bonding states on temperature (300-673 K) between different elements being a building material of nanowires' sidewalls was investigated by X-ray photoelectron spectroscopy (XPS) in ultra-high vacuum (UHV) conditions. Apart from silicon and carbon, the presence of oxygen and nitrogen was observed. Moreover, Si₃N₄ seems to be the second most important compound (after SiC) forming the amorphous outer shell of SiC nanowires. It is shown that carbon-containing compounds (oxides, nitrides, hydrocarbons) are substantially removed under annealing. It is also reported that a noticeable part of subsurface oxygen in the outer shell reacts with nitrogen at 473-573 K forming stable N-O bonds on nanowires' surface.     

Synthesis of the tube-brush-shaped SiC nanowire array on carbon fiber and its photoluminescence properties

Tube-brush-shaped nanostructure of SiC nanowires was synthesized on polyacrylonitrile-based carbon fibers. The morphology and microstructure of the nanowires were characterized by X-ray powder diffraction, field emission scanning electron microscopy and high-resolution transmission electron microscopy. A quasi-periodically twin structure with (111) plane as the boundary along the SiC nanowires was observed. The vapor-solid growth mechanism of the SiC nanowire brush is also discussed. Moreover, some separated blue-shifted photoluminescence peaks around 469 nm were measured. The separated blue-shifted emission peaks are attributed to the quantum confinement of nanoscaled twin segments along each nanowire rather than the apparent diameters of the nanowires. The SiC nanowire brushes hopefully can find potential applications in nanotechnology.