短纤维增强C/C-SiC复合材料的微观结构与力学性能EI北大核心CSCD

综合原料的热物理性能分析和配比设计,实现了C/C复合材料载体孔隙体积的精细控制,采用热压-熔渗两步法在低温条件下制备了具有高致密、低残余Si含量特征的短碳纤维增强C/C-SiC复合材料。系统解析了C/C-SiC复合材料成型过程中的结构演变行为,研究了短纤维增强C/C-SiC复合材料的力学性能和失效机制。结果表明:多孔C/C复合材料载体孔隙的孔径呈双极分布特征,添加芳纶纤维可提高网络孔隙结构的连通性,具有显著的孔隙结构调控作用。SiC基体以网络骨架形态分布于C/C-SiC复合材料内部,与纤维束形成了强界面结合钉扎结构,高含量纤维协同作用下使C/C-SiC复合材料具有优异的综合力学性能,添加芳纶纤维可明显增加复合材料内部裂纹扩展路径,提高C/C-SiC复合材料的断裂韧性。碳纤维的面内各向同性分布及陶瓷相层间均匀分布对C/C-SiC复合材料承载、摩擦稳定性提升均具有积极作用。     

C/C复合材料在原子氧辐照下的结构性能演变

通过分析失重率、显微形貌变化讨论了原子氧辐照对C/C复合材料以及SiC基体改性C/C复合材料(C/C-SiC)的损伤机制; 并通过热膨胀系数(CTE)、热扩散率(TD)以及弯曲强度等性能的变化, 进一步讨论了原子氧辐照损伤对材料热物理及力学性能影响。结果表明, C/C复合材料受原子氧辐照损伤是物理化学综合作用, 属于冲击诱发-增强表面化学刻蚀; SiC组元表现出良好的抗原子氧侵蚀性能, 阻碍了原子氧向材料内部侵蚀, 但是SiC组元在更长时间辐照后出现机械破损; C/C复合材料在原子氧辐照下失重率呈线性增加, 而C/C-SiC复合材料失重率小于C/C复合材料且增长幅度越来越小; C/C复合材料和C/C-SiC复合材料的整体结构性能在辐照损伤后发生了一定变化。     

Process and wear behavior of monolithic SiC and short carbon fiber-SiC matrix composite

The process and wear behavior of monolithic SiC and 10 vol. % short carbon fiber-SiC matrix (C-SiC) composite have been studied. The results indicate that, among ethyl alcohol, acetone, n-hexane and n-octyl alcohol, n-octyl alcohol was the most effective dispersing agent in dispersing both SiC powder and short carbon fiber. Among AlN, Al₂O₃, B₄C, graphite, AlN/B₄C, AlN/graphite, B₄C/graphite and Al₂O₃/B₄C, the most effective sintering aid for the fabrication of SiC and C-SiC composite was a mixture of 2 wt% AlN and 0.5 wt% graphite. The monolithic SiC hot-pressed at 2100°C exhibited higher density but lower flexural strength than those hot-pressed at 2000°C due to a grain growth effect. For the C-SiC composite, both density and strength of the composite hot-pressed at 2100°C were generally higher than those hot-pressed at 2000°C. The density and strength of C-SiC composite were lower than those of monolithic SiC under the same hot pressing conditions due to a higher porosity level in the composite. When monolithic SiC slid against C-SiC composite, the weight losses of SiC and the composite were each less than that of self-mated SiC or self-mated C-SiC. In the self-mated SiC tribosystem, a mechanically stable film could not be established, resulting in an essentially constant wear rate. When sliding against C-SiC, a thin, smooth and adherent debris film was quickly formed on the SiC surface, resulting in a lower wear.     

Low-dimensional SiC nanostructures: Fabrication, luminescence, and electrical properties

Nanostructured silicon carbide has unique properties that make it useful in microelectronics, optoelectronics, and biomedical engineering. In this paper, the fabrication methods as well as optical and electrical characteristics of silicon carbide nanocrystals, nanowires, nanotubes, and nanosized films are reviewed. Silicon carbide nanocrystals are generally produced using two techniques, electrochemical etching of bulk materials to form porous SiC or embedding SiC crystallites in a matrix such as Si. Luminescence from SiC crystallites prepared by these two methods is generally believed to stem from surface or defect states. Stable colloidal 3C-SiC nanocrystals which exhibit intense visible photoluminescence arising from the quantum confinement effects have recently be produced. The field electron emission and photoluminescence characteristics of silicon carbide nanostructures as well as theoretical studies of the structural and electronic properties of the materials are described.     

High-temperature single-crystal 3C-SiC capacitive pressure sensor

Single-crystal 3C-silicon carbide (SiC) capacitive pressure sensors are proposed for high-temperature sensing applications. The prototype device consists of an edge-clamped circular 3C-SiC diaphragm with a radius of 400 /spl mu/m and a thickness of 0.5 /spl mu/m suspended over a 2-/spl mu/m sealed cavity on a silicon substrate. The 3C-SiC film is grown epitaxially on a 100-mm diameter <100> silicon substrate by atmospheric pressure chemical vapor deposition. The fabricated sensor demonstrates a high-temperature sensing capability up to 400/spl deg/C, limited by the test setup. At 400/spl deg/C, the device achieves a linear characteristic response between 1100 and 1760 torr with a sensitivity of 7.7 fF/torr, a linearity of 2.1%, and a hysterisis of 3.7% with a sensing repeatability of 39 torr (52 mbar). A wide range of sensor specifications, such as linear ranges, sensitivities, and capacitance values, can be achieved by choosing the proper device geometrical parameters.     

Study the formation mechanism of silicon carbide polytype by silicon carbide nanobelts sintered under high pressure

In this paper, in order to reveal the formation mechanism of SiC polytype, four SiC specimens sintered under high pressure has been investigated, after being prepared from SiC nanobelts as initial powders. The structure and morphology variation dependence of SiC specimens with temperature and pressure was studied based on experimental data obtained by XRD, SEM, and Raman. The results show that SiC lattice structure and the crystallite size are greatly affected by pressure between 2 and 4 GPa under different sintering temperatures of 800 and 1200 degrees C. At the largest applied pressure and temperature, 4 GPa and 1200 degrees C, 3C-SiC crystal structure can be changed into to R-SiC due to the stress resulted in dislocations instead of planar defects. Based on our results, the multiquantum-well structure based a single one-dimensional nanostructure can be achieved by applying high pressure at certain sintered temperature.     

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.     

机械搅拌器对C-SiC/Cu半固态浆料中石墨颗粒和SiCP的影响

利用直桨叶搅拌器在圆柱坩埚内机械搅拌C-SiC/Cu半固态浆料,研究搅拌速度为200 r/min、搅拌器上下移动速度为10 mm/s时C-SiC/Cu半固态浆料中石墨颗粒和SiC颗粒(SiC_P)的均匀性。结果表明:直桨叶与水平面的夹角γ与两种颗粒在坩埚顶部和底部含量偏差都存在二次关系,当γ=30°时石墨颗粒和SiC_P在坩埚中轴向分布均匀,但同一水平面内的SiC_P仍存在偏聚现象,说明SiC_P的偏聚是导致常规直桨叶机械搅拌C-SiC/Cu半固态浆料整体不均匀的主要原因;利用双层桨叶搅拌器代替常规直桨叶搅拌器,通过调整叶片层间距h,当h=10~20 mm时可以消除SiC_P的偏聚现象;通过对单层桨叶搅拌器和双层桨叶搅拌器机械搅拌铸造获得的C-SiC/Cu复合材料进行磨损试验发现,单层桨叶搅拌器不同部位磨损率存在差异,双层桨叶搅拌器磨损率几乎相同。说明SiC_P的偏聚可以通过增大机械搅拌剪切力度得以消除,利用双层桨叶搅拌器进行机械搅拌可以获得均质的C-SiC/Cu半固态浆料。      

CVI-GSI工艺制备C/C-SiC复合材料的组成结构与力学性能

采用密度为1.0g/cm~3的C/C素坯,联合化学气相渗透(CVI)和气相渗硅(GSI)2种工艺制备C/C-SiC复合材料,研究CVI C/C-SiC复合材料中间体的密度对CVI-GSI C/C-SiC复合材料物相组成、微观结构及力学性能的影响。结果表明:随着CVI C/C-SiC复合材料中间体密度的增大,CVI-GSI C/C-SiC复合材料C含量增多,残余Si含量减少,SiC含量先增多后减少,CVI-GSI C/C-SiC复合材料的密度先增大后减小;随着CVI C/C-SiC复合材料中间体的密度由1.27g/cm~3增加到1.63g/cm~3时,得到的CVI-GSI C/C-SiC复合材料的力学性能先升高后降低。当CVI C/C-SiC复合材料密度为1.42g/cm~3时,制得的CVI-GSI C/C-SiC复合材料力学性能最好,其弯曲强度为247.50MPa,弯曲模量为25.63GPa,断裂韧度为10.08MPa·m~(1/2)。     

Superconductivity in carrier-doped silicon carbide

Abstract

We report growth and characterization of heavily boron-doped 3C-SiC and 6H-SiC and Al-doped 3C-SiC. Both 3C-SiC:B and 6H-SiC:B reveal type-I superconductivity with a critical temperature T_c=1.5 K. On the other hand, Al-doped 3C-SiC (3C-SiC:Al) shows type-II superconductivity with T_c=1.4 K. Both SiC:Al and SiC:B exhibit zero resistivity and diamagnetic susceptibility below T_c with effective hole-carrier concentration n higher than 10²⁰ cm^?3. We interpret the different superconducting behavior in carrier-doped p-type semiconductors SiC:Al, SiC:B, Si:B and C:B in terms of the different ionization energies of their acceptors.     

Templated,carbothermal reduction synthesis of mesoporous silicon carbide from carbon nanotube–mesoporous silica core–shell composite

Mesoporous materials are the subject of extensive interest due to their large surface area and multiscale structural order. These properties are especially relevant for applications such as catalyst supports in both chemical and electrochemical systems. The first part of this study details the synthesis of carbon nanotube–mesoporous silica core–shell composites starting with single-walled carbon nanotubes (SWCNTs) and multi-walled carbon nanotubes (MWCNTs) through micellar self-assembly. The formation of such a composite structure was verified using scanning electron microscopy and further analysis was carried out through X-ray diffraction (XRD). The subsequent refinement of the diffraction pattern revealed the silica shell to be of the continuous cubic (Ia3d) MCM48 structure. The mesoporous silica–carbon nanotube core–shell composite was later subjected to high-temperature carbothermal reduction. Subsequent XRD analysis showed that the reduction product was mesoporous silicon carbide (SiC). Thus, this study details a novel synthesis method for mesoporous SiC, which is an attractive material for possible diverse applications such as catalyst supports, intercalation electrodes and other emerging high technology areas.     

Heteropolytype structures with SiC quantum dots

Epitaxial silicon carbide layers of 3C-SiC polytype with an array of nanodimensional SiC quantum dots (QDs) have been obtained for the first time using an improved method of sublimation epitaxy in vacuum. The X-ray topography and X-ray diffraction data unambiguously confirm the formation of a 3C-SiC epilayer with twinned regions on the surface of a 6H-SiC substrate. The surface topography of epilayers was studied by atomic force microscopy (AFM), and the microstructure of a near-surface layer of the deposit was investigated by transmission electron microscopy (TEM). Using the AFM and TEM data, the presence of QDs (representing SiC nanoislands) is established, and their average dimensions and concentration are evaluated.     

FeSi熔体中SiC晶须的VLS生长

在1500℃、 1600℃、 1650℃和1750℃氩气中保温3h, 使Fe-Si在石墨基板上熔化并敷展, 分别在熔层表面获得SiC颗粒层、 SiC颗粒与晶须混合层、 SiC晶须层和SiC腾空薄膜。XRD分析确定所有产物均为3C-SiC; TEM和SAED分析表明, SiC晶须为3C-SiC单晶, 生长方向为[111]。基于上述结果, 提出不同温度下C与熔体中的Si经不同反应路径, 生成不同形貌SiC的反应机理: 低温时(≤1500℃), Fe提高了熔体中C的饱和溶解度, 以液-固(LS)反应生成SiC颗粒; 较高温度时(1500~1750℃), 借助Fe的催化作用, 以气-液-固(VLS)机理生成SiC晶须; 更高温度时(≥1750℃), 气-液-固(VLS)变得无序, 生成SiC腾空连续膜。      

Formation of microcrystalline SiC films by chemical transport with a high-pressure glow plasma of pure hydrogen

The formation of microcrystalline 3C-SiC films on Si substrates by the plasma-enhanced chemical transport method was investigated using a pure hydrogen glow plasma at 0.027 MPa. In this method, no source gas was necessary. Instead, the erosion products of a sintered 3C-SiC plate in a hydrogen plasma were used as the deposition source. By Fourier transform infrared (FT-IR) absorption gas analysis, the species generated by the hydrogen etching of sintered SiC were found to be SiH₄ and CH₄, which can serve as precursors for SiC film formation. The etch rate of sintered SiC by hydrogen plasma decreased with increasing source temperature. The maximum etch rate of the sintered SiC was 450 nm/min at an input power of 47 W/cm². Films prepared by this method at substrate temperatures (T_sub) of 600 and 1073 K were analyzed by FT-IR absorption spectroscopy. An absorption peak at 800 cm^- 1 related to Si-C bonds was clearly observed, but no significant hydrogen-related absorption peaks, such as C-H and Si-H, were observed in the prepared films. The deposition rate of SiC was about 8 nm/min, independent of T_sub. The SiC films had a columnar structure, and their surface morphologies revealed faceted growth. With decreasing T_sub, the lateral grain size became large. The current-voltage characteristics of a prepared SiC/Si heterojunction np diode showed rectifying behavior, demonstrating that the doping of an SiC film can be achieved without a doping gas source. The dopant distribution near the SiC/Si interface deduced from capacitance-voltage measurements suggests that the precise control of the initial growth stage is important to obtain a good SiC/Si interface.     

MBE-growth of heteropolytypic low-dimensional structures of SiC

The controlled growth of SiC heteropolytypic structures consisting of hexagonal (-) and cubic (3C-) polytypes has been performed by solid-source molecular beam epitaxy. On on-axis substrates, 4H/3C/4H-SiC(0001) and 6H/3C/6H-SiC(0001) structures were obtained by first growing some nanometers thick 3C-SiC layer at lower temperatures (1550 K) and Si-rich conditions, and subsequent growth of -SiC on top of the 3C-SiC layer at higher temperatures (1600 K) under more C-rich conditions. On off-axis substrates, multi-heterostructures consisting of 4H/3C- or 6H/3C-stacking sequences were also obtained by first nucleating selectively wire-like 3C-SiC nuclei on the terraces of well-prepared off-axis -SiC(0001) substrates at low T (<1500 K). Next, SiC was grown further in a step-flow growth mode at higher T and Si-rich condition. After the growth many wire-like regions consisting of 3C-SiC were found within the hexagonal SiC layer material matrix indicating a simultaneous step-flow growth of both the cubic and the hexagonal SiC material.     

固体冲压发动机环境下C/C-SiC喷管的烧蚀行为及重复性使用分析

为探索C/C-SiC喷管在固体冲压发动机工作环境下烧蚀行为及重复使用的可行性,对固冲发动机C/CSiC复合材料喷管内层进行研究。研究结果表明:C/C-SiC复合材料喷管能够适应固体冲压发动机富氧、长时间的工作环境;C/C-SiC复合材料喷管收敛段的厚度有所下降,以热化学烧蚀和热机械侵蚀为主;喉部的厚度未发生明显变化,以热化学烧蚀为主;扩张段的厚度未发生变化,只有轻微的氧化。喷管内层的环向弯曲强度和轴向弯曲强度较试验前均有所降低,收敛段下降较多,而扩张段下降较少,但仍能满足重复使用要求;应对试验后喷管内层再进行分区化学气相沉积SiC涂层,提高喉部上游的抗氧化性能,提高其重复使用时的工作可靠性。     

Heteroepitaxial Growth and Characterization of 3C-SiC Films on Si Substrates Using LPVCVD

3C-SiC films have been deposited on Si (111) substrates by the low-pressure vertical chemical vapor deposition (LPVCVD) with gas mixtures of SiH4, C3Hg and H2- The growth mechanism of SiC films can be obtained through the observations using field emission scanning electron microscope (FESEM). It is found that the growth process varies from surface control to diffusion control when the deposition temperature increases from 1270 to 1350℃. The X-ray diffraction (XRD) patterns show that the SiC films have good crystallinity and strong preferred orientation. The results of the high resolution transmission electron microscopy (HRTEM) image and the transmission electron diffraction (TED) pattern indicate a peculiar superlattice structure of the film. The values of the binding energy in the high resolution X-ray photoelectron spectra (XPS) further confirm the formation of SiC.     

(C-SiC)f/C复合材料的烧蚀性能

将SiC纤维毡与C纤维毡交替层叠, 通过针刺工艺制备(C-SiC)_f/C预制体, 采用化学气相渗透与前驱体浸渍裂解复合工艺(CVI+PIP)制备(C-SiC)_f/C复合材料, 研究(C-SiC)_f/C复合材料H₂-O₂焰烧蚀性能。利用SEM、EDS和XRD对烧蚀前后材料的微观结构和物相组成进行分析, 探讨材料抗烧蚀机理。结果表明: (C-SiC)_f/C复合材料表现出更优异的耐烧蚀性能。烧蚀750 s后, (C-SiC)_f/C复合材料的线烧蚀率为1.88 μm/s, 质量烧蚀率为2.16 mg/s。与C/C复合材料相比, 其线烧蚀率降低了64.5%, 质量烧蚀率降低了73.5%; SiC纤维毡在烧蚀中心区表面形成的网络状保护膜可以有效抵御高温热流对材料的破坏; 在烧蚀过渡区和烧蚀边缘区形成的熔融SiO₂能够弥合材料的裂纹、孔洞等缺陷, 阻挡氧化性气氛进入材料内部, 使材料表现出优异的抗烧蚀性能。     

Oxidation Behavior of C/C-SiC Gradient Matrix Composites

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HREM Observations of Kinking in SiC Induced by Ball Milling

Kinking in SiC during ball milling (BM) at room temperature has been reported in this article. High-resolution electron microscopy (HREM) has been employed to characterize the microstructure at the atomic level. HREM observations show that partial dislocations can be introduced into SiC and glide on the primary (0001) planes under BM at room temperature. When numbers of the gliding partials are piled up along one direction, a kink boundary forms, which will initiate a crack. However, when gliding partials are not piled up, glide of the partials changes the stacking sequence and transformation from 6H-SiC→3C-SiC occurs.