泡沫炭的成核机理及其复合增强机制

以中间相炭微球(MCMB)、聚丙烯腈基炭纤维(PAN-CF)和纳米氧化锆(Zr O2)为增强体,采用自发泡法制备出泡沫炭复合材料,并研究不同增强材料对中间相沥青基泡沫炭的发泡行为和压缩强度的影响。结果表明,中间相沥青在发泡过程中遵循热点成核机制;较PAN-CF、MCMB而言,Zr O2纳米颗粒(~100 nm)对泡沫炭具有更佳的增强效果。当在中间相沥青原料中添加30%的纳米Zr O2后,泡沫炭的压缩强度可由7.57 MPa提高到31.4 MPa。     

纳米碳管对泡沫炭的超临界发泡行为及其力学性能的影响机制

采用超声波?磁力搅拌的方法, 实现了纳米碳管(CNTs)在中间相沥青(MP)中的均匀分散, 并考察了CNTs对泡沫炭的超临界发泡行为及其压缩强度的影响. 研究结果表明: 在超临界发泡过程中, 处于过饱和状态的甲苯将优先在CNTs/MP固-液界面处成核, 进而不断扩散、聚集、膨胀和发泡, 导致泡沫炭孔结构的均一性得以提高; 当在中间相沥青中均匀分散3.5wt%的CNTs后, 所制泡沫炭的压缩强度由3.2MPa提高到4.7MPa, 升高了46.9%; CNTs良好的导热性能降低了基体碳在石墨化过程中的热应力差异, 使得微裂纹的数量减少, 并且其一维纳米结构使得石墨化泡沫炭的孔壁和韧带结构得以增强.     

超临界流体制备中间相沥青泡沫炭及其导热性能研究

以奈系中间相沥青为原料,在初始压力2.0～4.0MPa的范围内,利用甲苯作为超临界溶剂制备中间相沥青基泡沫,并经氧化炭化和石墨化获得了三维网状结构的泡沫炭,利用扫描电镜、x射线衍射、激光导热测定仪分析了泡沫碳的结构和导热性能,研究了泡沫炭结构与其导热性能的关系.结果表明,不同条件下所制备得到的泡沫炭泡孔结构和孔分布的不同对导热系数影响较大,在2350℃下石墨化后导热系数达到42(W/mK).     

中间相沥青基活性泡沫炭的制备及其电化学性能研究

以中间相沥青为前驱体,经自挥发发泡法、KOH活化法制备的中间相沥青基活性泡沫炭作为超级电容器电极材料。采用扫描电镜、X射线衍射和低温(77K)N2吸附法对中间相沥青基活性泡沫炭的表面形貌和微观结构进行表征。中间相沥青基活性泡沫炭的比表面积为2700m2/g,总孔孔容为1.487cm3/g。通过恒流充放电、循环伏安和交流阻抗测试,考察了中间相沥青基活性泡沫炭作为超级电容器电极材料的电化学性能。在电流密度为0.02A/g时,中间相沥青基活性泡沫炭的比容量为240.48F/g,能量密度为33.4Wh/kg;在电流密度为5A/g时,比容量为166.68F/g,具有良好的电化学特性。     

前驱体对炭泡沫孔结构的影响

分别以煤沥青、石油中间相沥青和AR沥青为前驱体制备炭泡沫材料。采用GPC测定前驱体分子量,SEM观察所制炭泡沫的孔结构,光学显微镜测量所制炭泡沫的孔径及其分布。结果发现,由于煤焦油沥青不含中间相,且QI含量较高,导致在实验条件下不能直接制备出合格的炭泡沫。以石油中间相沥青和AR沥青为原料均能制备出具有分布均匀开孔结构,且微观各向异性的炭泡沫。由AR沥青制备的炭泡沫呈现平均孔径较小(212μm)、孔壁较薄、孔径分布较窄(180μm~300μm)、开孔率较高、以及韧带排列较规整等特点,表明低QI含量、低分子量且分布较窄的前驱体有利于发泡。     

SiO2气凝胶/中间相沥青基泡沫炭复合材料的制备与表征

以正硅酸乙酯、乙醇和去离子水为原料,采用溶胶-凝胶法制备了SiO2溶胶;并以煤沥青为原料,采用自挥发发泡法制备了中间相沥青基泡沫炭。然后采用浸渍工艺将SiO2溶胶和中间相沥青基泡沫炭在常压下进行复合,制备了SiO2气凝胶/中间相沥青基泡沫炭复合隔热材料。利用XRD、SEM、热导仪和万能试验机等设备分别研究了SiO2气凝胶、中间相沥青基泡沫炭以及SiO2气凝胶/中间相沥青基泡沫炭复合材料的结构和性能。结果表明,所制备的复合材料具有一定的力学性能,同时其隔热性能优于单一泡沫炭的隔热性能,有望成为一种新型的隔热材料。     

CVD PyC对炭泡沫结构及性能的影响

以AR中间相沥青为原料,采用中间相沥青自发泡法在发泡压力为0.1、3.0MPa,发泡温度为450℃的条件下制备了两种不同体积密度的炭泡沫CF-1和CF-2.将CF-1经过10h和70h化学气相沉积热解炭(CVDPyC)处理后得到炭泡沫CF-1-PC1和CF-1-PC2.测定了炭泡沫的抗压强度和导热系数,利用SEM和光学显微镜观察了炭泡沫的孔结构,考察了CVD PyC对炭泡沫结构及性能的影响.研究结果表明,CVD PyC处理可以增加炭泡沫韧带宽度,封填孔壁微裂纹;沥青炭和热解炭之间无明显界面,结合良好;经过CVD PyC处理后得到的CF-1-PC1和CF-1-PC2的体积密度、抗压强度、导热系数分别为, 0.196g·cm-3、1.89MPa、0.314W·m-1·K-1和0.461g·cm-3、11.93MPa、1.581W·m-1·K-1.     

由中间相沥青制备泡沫炭:Fe(NO3)3的影响

以中间相沥青为前驱体制备高性能泡沫炭，在考察中间相沥青、Fe（NO3）3及其混合物热分解行为的基础上，着重研究了Fe（NO3）3对制备中间相沥青基泡沫炭的影响，揭示了Fe（NO3）3对泡沫炭孔泡结构的影响规律及其作用机制，初步研究了在泡沫炭炭化过程中形成的Fe／C之物相结构及其石墨化行为。结果表明，在不同的炭化温度下，Fe在泡沫炭中的存在形态各异；Fe物种的存在有利于提高泡沫炭的石墨化程度。     

中间相沥青基泡沫炭的气泡生长过程

以AR合成中间相沥青为原料,在不同的温度下发泡制得了泡沫炭.采用扫描电镜和光学显微镜等分析手段对中间相沥青基泡沫炭的气泡生长机理进行了初步研究,讨论了温度对泡孔结构的影响.结果表明,当温度从480℃升至540℃时,平均泡孔直径从500μm升到800μm.最初形成的泡沫在熔融沥青中分布不均匀,汇集在沥青的上表面;气泡在Z轴方向的形状是椭球形,在Z轴垂直方向为球形.中间相沥青基泡沫炭气孔的形状和泡沫的体积密度密切相关.形成的泡沫体在z轴方向存在明显的体积密度梯度.     

发泡温度对炭泡沫结构及性能的影响

以AR中间相沥青为原料,采用中间相沥青自发泡法在初始发泡压力为3MPa、发泡温度在390～450℃范围内制备了4种炭泡沫。利用SEM观察了炭泡沫的孔隙结构,并测定了其体积密度、抗压强度和导热系数,考察了发泡温度对炭泡沫结构及性能的影响。结果表明,采用较低的发泡温度(430℃)可以消除大的孔隙缺陷;当发泡温度为410℃时,炭泡沫导热系数最高,为0.256W/(m·K)。     

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.     

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.     

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。     

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。     

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。     

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.     

Activated carbon catalyzing the formation of carbon nanotubes

Activated carbon (AC), a common carbon material, is employed as catalyst to synthesize carbon nanotubes (CNTs) through chemical vapor deposition (CVD) and detonation-assisted CVD methods. The results show AC can effectively catalyze CNT formation. From the microscopic observations on morphologies and structures of the formed intermediates, it is found that carbon-catalyzed CNT formation follows particle-wire-tube stepwise evolution mechanism, in which carbon nanoparticles first assemble into wire-like nanostructures, then evolve into nanotubes via particle-particle coalescence and structural crystallization.     

Biodistribution of carbon single-wall carbon nanotubes in mice

Carbon nanotubes are promising for use in biomedical and pharmaceutical sciences. Therefore, it becomes imperative to know the basic biological properties of carbon nanotubes in vivo. We labeled the water-soluble hydroxylated carbon single-wall nanotubes with radioactive 125I atoms, and then the tracer was used to study the distribution of hydroxylated carbon single-wall nanotubes in mice. They moved easily among the compartments and tissues of the body, behaving as small active molecules though their apparent mean molecular weight is tremendously large. This study, for the first time, affords a quantitative analysis of carbon nanotubes accumulated in animal tissues.     

Vitreous joining of SiC-coated carbon/carbon composites

This paper investigated the feasibility of joining of carbon/carbon (C/C) composites by using a silicate as interlayer. A SiC coating was pre-prepared on C/C substrate by pack-cementation technique to improve the wettability of glass on C/C composites, then the joints were prepared by a one-shot and low cost way. Microstructure and morphologies of the as-received joints were characterized by XRD, SEM and EDS. The results indicated that the SiC coating not only had a strong bonding with C/C composites, but also had a good physical and chemical compatibility with silicate glass. The room-temperature shear strength of the joints gives encouraging results, which can be up to 26 MPa. The fracture mode and the fracture behavior were discussed also.