用不同催化剂制备纳米炭纤维的生长机理

研究了以Fe或Ni的催化剂采用有机物催化热解法制备的纳米炭纤维的形貌和结构。发现在两种情况下纳米炭纤维的生长机理安全不同;以Fe为催化剂纳米炭纤维基本符合气-液-固（VLS）催化生长机制（也称溶解扩散机制）,而以Ni为催化剂纳米炭纤维则符合固相催化生长机制。     

硅化处理对炭纤维石墨化度的影响

对炭纤维在真空炉中进行2100℃硅化处理.用SEM分析了炭纤维在硅化处理前后表面形貌的变化,利用能谱测定了其硅化处理后的成分变化并加以分析,用X射线衍射分析了热处理和硅化处理后的炭纤维石墨化度的变化.结果表明:处理后的炭纤维出现富C的SiC表层,内部为含有SiC的C芯,并伴随有类球状SiC颗粒的形成.沿炭纤维径向分布的SiC含量呈现梯度分布,其芯部的SiC含量为2.46%(质量分数,下同),靠近表层的SiC含量增加到7.53%,表面的SiC含量达到13.25%;纤维表面的类球状颗粒为含C的SiC颗粒,其中SiC的含量为30.55%.在2100℃热处理的炭纤维石墨化度几乎为0,而在2100℃硅化处理的炭纤维石墨化度高达48.5%.     

Cr颗粒含量对Ni-Cr纳米复合镀层组织结构的影响

使用Ni与纳米Cr颗粒共沉积方法制备Ni-Cr纳米复合镀层,研究了镀液中Cr颗粒浓度、搅拌强度和阴极电流密度等工艺参数对镀层中沉积Cr量的影响.结果表明:镀层中纳米Cr颗粒的复合改变了电沉积Ni的生长方向,Ni晶粒由原来沿(200)晶面取向生长,转变为沿(200)、(111)和(220)晶面均匀生长.镀层中Cr复合量越多,Ni晶粒的形核位置越多,Ni晶粒越细化.也探讨了Ni-Cr纳米复合镀的沉积机理.     

化学气相沉积法合成高强度纳米炭纤维/蜂窝堇青石复合材料

以C2H4为碳源、Ni-Cu合金作催化剂,采用化学气相沉积法在蜂窝状堇青石表面生长纳米炭纤维(CNFs),获得压缩强度为50.0 MPa的纳米炭纤维/蜂窝堇青石复合材料.在堇青石表面蜂窝腔内生长的CNFs直径为20nm～30nm,CNFs之间相互交织形成5μm厚的纤维层,CNFs的质量分数为25.3％.金属Cu的掺杂对Ni-Cu合金的颗粒尺寸产生重要影响,进而影响CNFs的生长速率、纤维层厚度及其微结构.所合成CNFs的石墨化程度不高,在蜂窝堇青石中生长纳米炭纤维可以把其压缩强度从10MPa增加到50 MPa.     

甲烷在Ni/Al2O3催化剂上积碳与失活行为研究

采用浸渍法制备Ni/Al2O3催化剂,研究反应条件对甲烷裂解生成碳产物形貌的影响和催化剂的失活机制.结果表明:在40Ni/Al2O3催化剂上碳生成物的沉积形式均呈纤维状结构,反应温度越高、空速越大,碳纤维的直径越小;碳在金属颗粒体相中的扩散是碳纳米纤维生长过程的速率控制步骤,当碳的生成速率低于碳在Ni中的体相扩散和迁移速率,生成的炭以纤维状结构生长.     

镁-镍合金催化剂制备及纳米碳管生长模式研究

采用多元醇法制备镁-镍合金纳米粉末,并以此为催化剂制备纳米碳管,利用比表面和孔径分布测定仪、X射线衍射仪和透射电镜,研究镁-镍合金催化剂的性能和纳米碳管的生长模式。结果表明:Mg∶Ni值对镁-镍合金催化剂特性影响较大,其中Mg∶Ni为1的催化剂颗粒比表面积较大且平均粒径较小;聚乙烯吡咯烷酮(PVP)用量增大,有利于提高催化剂颗粒的比表面积、减小平均粒径,但用量过大不利于Mg2Ni合成。在以镁-镍合金为催化剂制备碳纳米管的过程中,首先在催化剂表面形成碳膜,随后形成的碳膜将前期形成的碳膜及催化剂颗粒向外推挤,催化剂颗粒移动后遗留下中空隧道,最终形成碳管,由于纳米碳管尖端的催化剂颗粒反应后失去催化活性,碳管的生长动力主要来自碳管根部。     

原位生长纳米炭纤维/硅复合材料及其储锂性能

采用催化化学气相沉积法在微米硅颗粒表面原位生长纳米炭纤维得到纳米炭纤维/硅复合材料.利用SEM,TEM和XRD表征了复合材料的表面形态和微观结构,并考察了其作为锂离子电池负极材料的循环性能.电化学测试表明:与纳米纤维/硅机械混合物相比,原位生长纳米炭纤维/硅复合材料具有更高的可逆容量(1042mAh/g)和更好的循环稳定性.根据SEM和交流阻抗分析结果,分析了纳米炭纤维/硅复合材料在充放电过程中的结构演变机制,其优异的电化学性能主要来源于原位生长纳米炭纤维与硅颗粒之间良好的接触性能.     

二氧化硅纳米颗粒增强炭纤维/环氧树脂界面性能

纤维与基体间的界面性能是决定纤维增强树脂基复合材料力学性能的关键因素。采用单纤维断裂实验方法研究二氧化硅纳米颗粒对炭纤维/环氧树脂复合材料界面的增强作用。实验结果表明,涂覆在炭纤维表面和均匀分散在环氧树脂基体中的二氧化硅纳米颗粒含量分别为4.9g/m2和25%(质量分数)时,复合材料界面性能均得到改善,界面抗剪强度相比纯树脂体系分别提高了10.0%和15.0%。通过对纤维断点处双折射光斑和样品断面形貌等信息分析,可知纳米颗粒均匀分散并镶嵌到炭纤维表面沟槽中形成的锁扣结构是界面性能提高的重要原因。     

变截面形状螺旋形炭纤维的制备和生长机理

以镍为催化剂,通过控制碳源气体乙炔的流速,在1 013 K-1 053 K温度下,制备了纤维截面形状在生长过程中由扁平形变为圆形的螺旋炭纤维,同时螺旋直径也相应的由4.2 μm变化为6.0 μm,这种变截面螺旋炭纤维的发现,为微机械系统提供了一种新型弹簧.提出了变截面螺旋炭纤维的生长机理,认为催化剂颗粒的各向异性不仅影响螺旋炭纤维螺径的大小,还影响纤维的截面形状.随着生长过程中反应条件的改变,催化剂各向异性也发生改变,长方形催化剂既可以生长扁平形也可以生长圆形截面螺旋形炭纤维,但是立方形催化剂只能生长圆形截面螺旋形炭纤维.该机制的提出不仅有助于加深对双螺旋炭纤维生长本质的认识,还对指导螺旋形炭纤维的控制生长具有重要意义.     

乙烯催化裂解法选择性合成纳米炭纤维

通过采用不同金属催化剂进行乙烯催化裂解制备了具有不同微观结构的纳米炭纤维。利用纳米二氧化硅负载的铁、镍以及铁镍合金催化剂在适当的反应条件下分别制备了管状、实心鱼骨状以及空心鱼骨状的纳米炭纤维。由于金属催化剂与纳米二氧化硅间的强相互作用导致在低反应温度下也能达到高的反应活性，所以能够合成出高收率、小直径而且分布均匀的纳米炭纤维。不同结构的纳米炭纤维归因于金属催化剂的不同分散性以及不同的生长机理。通常利用铁催化剂进行乙烯裂解制备纳米炭纤维需要高于650℃，但是在我们的实验中发现500℃低温下利用纳米二氧化硅负载的铁催化剂进行乙烯裂解就能够合成出管状纳米炭纤维。     

短切炭纤维增强沥青基C/C复合材料的力学性能

利用模压半炭化成型工艺在大气环境下制备出了短切炭纤维增强沥青基C／C复合材料（简称SCFRC）。研究了短切炭纤维的体积分数对SCFRC材料的体积密度和力学性能的影响规律。借助光学显微镜和扫描电镜对其微观组织和断口形貌进行了观察，分析了短切炭纤维对SCFRC材料的增强机制。结果表明，当短切炭纤维的体积分数由0％增大到11．8％时，SCFRC材料的力学性能随之呈线性增加；短切炭纤维增强SCFRC材料的机制主要有裂纹偏转效应、桥联效应以及脱粘和拔出效应。     

短切炭纤维增强沥青基C/C复合材料的组织特征

利用新型、高效的模压半炭化成型工艺，在大气环境下制备出了短切炭纤维增强沥青基C／C复合材料制品，并借助光学显做镜和扫描电镜对其微观组织和断口形貌进行了观察。通过分析，解释了短切炭纤维增强沥青基C／C复合材料中炭纤维损伤的形成机制，提出了作为增强体相的短切炭纤维和焦炭颗粒与基体炭之间独特的界而结构模型。研究还表明：复合材料中明显存在着基体相和颗粒相一基体相的显微结构不仅呈层片状，而且层片状的结构好像数层桔子皮，将颗粒相包裹起来，这种“桔皮包裹”式的结构与炭纤维表面的POG结构基本相似。     

Kinetics of chemical vapor infiltration of carbon nanofiber-reinforced carbon/carbon composites

Preforms containing 0, 5, 10, 15 and 20 wt.% carbon nanofibers (CNFs) were fabricated by spreading layers of carbon cloth, and infiltrated by using the technique of isothermal chemical vapor infiltration (ICVI) at the temperature of 1100 °C under the total pressure of 1 kPa and with the flow of the mixture of propane/nitrogen in a ratio of 13:1. The infiltration rates increased with the rising of CNF content, and after 580 h of infiltration, the achievable degree of pore filling was the highest when the CNF content was 5 wt.%, but the composite could not be densified efficiently as the CNF content ranged from 10 to 20 wt.%. An analysis of the results, based on the effective diffusion coefficient and on the in-pore deposition rates, shows that the CNFs, due to their higher aspect ratio, accelerate overgrowth at pore entrances and thus lead to incomplete pore filling.     

Hierarchical carbon nanostructure design: ultra-long carbon nanofibers decorated with carbon nanotubes

Hierarchical carbon nanostructures based on ultra-long carbon nanofibers (CNF) decorated with carbon nanotubes (CNT) have been prepared using plasma processes. The nickel/carbon composite nanofibers, used as a support for the growth of CNT, were deposited on nanopatterned silicon substrate by a hybrid plasma process, combining magnetron sputtering and plasma-enhanced chemical vapor deposition (PECVD). Transmission electron microscopy revealed the presence of spherical nanoparticles randomly dispersed within the carbon nanofibers. The nickel nanoparticles have been used as a catalyst to initiate the growth of CNT by PECVD at 600°C. After the growth of CNT onto the ultra-long CNF, SEM imaging revealed the formation of hierarchical carbon nanostructures which consist of CNF sheathed with CNTs. Furthermore, we demonstrate that reducing the growth temperature of CNT to less than 500°C leads to the formation of carbon nanowalls on the CNF instead of CNT. This simple fabrication method allows an easy preparation of hierarchical carbon nanostructures over a large surface area, as well as a simple manipulation of such material in order to integrate it into nanodevices.     

Diamond formation on carbon/carbon composite

A carbon/carbon composite was used as substrate for low-pressure diamond deposition. To enhanced diamond nucleation on carbon/carbon composites, a total of ten surface preparation methods have been investigated. These methods involved the use of atomic hydrogen etching, mechanical polishing, sonication, or coating. Diamond nucleation was found to occur on either the defects of the carbon/carbon composite substrates or diamond particulate left on the substrates. The defects were created primarily by atomic hydrogen etching during the coating process. Seeding with diamond powders was performed by dip coating, sonication, or spray-coating processes. It was found that these seeding processes resulted in excellent nucleation of diamond.     

软硬混编预制体增强沥青基4D-C/C材料的拉伸破坏行为

以X-Y平面依次铺设炭纤维束、Z向穿插炭棒的4D软硬混编为预制体,采用沥青液相常压、高压浸渍/炭化-石墨化循环致密工艺制备4D-C/C复合材料。通过该材料Z向(炭棒方向)的拉伸实验,测定其拉伸性能和力学行为,并采用SEM分析试样表面及断口形貌。结果表明:宏观上拉伸试样以炭棒整体拔出的形式破坏;细观尺度上,试样表面形成了与载荷方向垂直的贯穿性裂纹,裂纹以2 mm左右的距离呈等间距分布;材料进一步的破坏过程中,基体裂纹在X-Y向纤维束中呈线性扩展,快速分割了基体材料,使4D-C/C复合材料的拉伸破坏演变为1D-C/C复合材料的破坏模式,由于炭棒与基体炭界面结合弱,炭棒以拔出方式失效和破坏。     

Graphitization behaviour of carbon fibre-glassy carbon composites

Carbon fibre-carbon composites were fabricated by aligning PAN-based carbon fibre unidirectionally in furfuryl alcohol resin char. The graphitization behaviour was investigated by an X-ray diffraction technique and by the measurement of magnetoresistance. The time-temperature superimposition study for interlayer spacing resulted in an activation energy of 242±35 kcal mol⁻¹. The kinetic study on magnetoresistance agreed with the result of X-ray measurement. The activation energy is that for the graphitization of the layer structure formed in the glassy carbon matrix of the composites. The graphitization mechanism of the layer structure is the same as that of soft carbons.     

Development of titanium-doped carbon–carbon composites

The development of titanium-doped carbon matrix–carbon fibre reinforced composites (CCCs) via liquid impregnation of carbon fibre preforms using mesophase pitch is studied. Two different approaches for introducing the dopant into the carbon material are investigated. One consists of doping the matrix precursor followed by the densification of the preform with the doped precursor. The second approach consists of doping the porous preform prior to densification with the undoped mesophase pitch. Titanium-doped CCCs with a very fine distribution of dopant (in the nanometric scale) are obtained by adding TiC nanoparticles to the matrix precursor. Thermal decomposition of titanium butoxide on the carbon preform prior to densification yields doped CCCs with higher titanium content, although with larger dopant size. The combination of these two methods shows the best results in terms of dopant content.     

Mesoscale evolution of non-graphitizing pyrolytic carbon in aligned carbon nanotube carbon matrix nanocomposites

Polymer-derived pyrolytic carbons (PyCs) are highly desirable building blocks for high-strength low-density ceramic meta-materials, and reinforcement with nanofibers is of interest to address brittleness and tailor multi-functional properties. The properties of carbon nanotubes (CNTs) make them leading candidates for nanocomposite reinforcement, but how CNT confinement influences the structural evolution of the PyC matrix is unknown. Here, the influence of aligned CNT proximity interactions on nano- and mesoscale structural evolution of phenol-formaldehyde-derived PyCs is established as a function of pyrolysis temperature (\(T_{\mathrm {p}}\)) using X-ray diffraction, Raman spectroscopy, and Fourier transform infrared spectroscopy. Aligned CNT PyC matrix nanocomposites are found to evolve faster at the mesoscale by plateauing in crystallite size at \(T_{\mathrm {p}}\) \(\sim\)800 \(^{\circ }\hbox {C}\), which is more than \(200\,\,^{\circ }\hbox {C}\) below that of unconfined PyCs. Since the aligned CNTs used here exhibit \(\sim\)80 nm average separations and \(\sim\)8 nm diameters, confinement effects are surprisingly not found to influence PyC structure on the atomic-scale at \(T_{\mathrm {p}}\) \(\le \)1400 \(^{\circ }\hbox {C}\). Since CNT confinement could lead to anisotropic crystallite growth in PyCs synthesized below \(\sim\)1000 \(^{\circ }\hbox {C}\), and recent modeling indicates that more slender crystallites increase PyC hardness, these results inform fabrication of PyC-based meta-materials with unrivaled specific mechanical properties.