两种T700碳纤维的微观结构与性能研究

采用原子力显微镜(AFM)、扫描电镜(SEM)、拉曼光谱(Raman)、X射线衍射(XRD)和透射电镜(TEM)对国产JHT45-T700和日本东丽T700两种碳纤维的硬度相对大小、表面和断面形貌、石墨化程度和微晶结构进行了表征,分析了其中的差异。结果表明,东丽T700微区硬度大于国产JHT45-T700;国产JHT45-T700表面存在大量沟槽,而东丽T700表面光滑。因此,国产JHT45-T700与树脂基体的浸润性优于东丽T700。Raman与XRD分析表明,东丽T700石墨化程度、微晶尺寸和结构的有序程度均高于国产JHT45-T700;TEM显示,东丽T700晶格条纹比国产JHT45-T700更规整些,晶相较多,石墨微晶发育相对更完善。     

γ-巴豆酰内酯激发态动力学的共振拉曼光谱和完全活性空间自洽场(CASSCF)计算研究

采用共振拉曼光谱和完全活性空间自洽场(CASSCF)方法研究了γ-巴豆酰内酯的光吸收S2态的结构动力学和衰变机制.采用含时密度泛函理论方法结合光谱实验确认了紫外光谱和振动光谱.获得了涵盖A-带吸收的4个激发波长下的共振拉曼光谱.用CASSCF计算得到了S1,min,S2,min,T1,min,T2,min和T3,min及其相关势能面交叉点的结构与能量.研究了A-带共振拉曼光谱强度模式与S2,min和CI(S2/S1)交叉点结构的关系.借助El-Sayed规则分析了各系间窜跃路径的效率,提出了γ-巴豆酰内酯从S2,FC弛豫到基态S0的2条主要路径:内转换路径和系间窜跃路径.     

MnCl2/DMSO溶液的拉曼光谱和理论计算

利用拉曼光谱研究了不同温度和浓度MnCl₂/DMSO溶液体系离子的溶剂化作用, 结果表明, 在0~0.8 mol/L浓度范围内, 随着浓度增加, Mn²⁺与DMSO的相互作用逐渐增强, S=O伸缩振动峰向低波数移动, S=O双键减弱; C—S伸缩振动峰向高波数移动, C—S键增强. 温度升高, S=O双键和C—S键伸缩振动峰均向相反的方向移动, 溶剂化作用减弱. 56 ℃以上, 单体DMSO迅速增加, 与Mn²⁺溶剂化作用的DMSO迅速减少, 二聚体DMSO减少缓慢, 温度对溶剂化作用的影响大于溶剂自身的缔合. 利用密度泛函理论对可能存在的溶剂化构型[Mn(DMSO)_n]²⁺进行了优化、 热力学性质及理论拉曼光谱计算, 从理论上证实了Mn²⁺与DMSO存在相互作用, 导致DMSO的S=O键拉伸和C—S键收缩, 与实验光谱结果一致.     

PAN基碳纤维形成过程中热氧稳定化气氛对纤维径向结构演变的关联性研究

采用红外光谱、X射线能谱、激光显微共焦拉曼光谱、X射线衍射光谱和电子自旋共振等多种表征手段,定量探讨了热氧稳定化气氛中氧气浓度与聚丙烯腈纤维的径向结构转变以及与碳纤维结构和性能的关联.结果表明,随着氧气浓度的增大,氧气自皮层逐渐扩散到纤维内部,热氧稳定化纤维的径向结构趋于均质化.当热氧稳定化过程氧体积浓度(Vo)由20.38％增加到21.15％时,热氧稳定化纤维的皮芯结构逐渐减小,环化程度增幅显著,该过程对碳纤维皮部类石墨结构的形成具有促进作用,所得碳纤维的孔隙率减小,拉伸强度增大.当Vo大于21.34％时,热氧稳定化纤维的皮芯结构基本消失,但氧化程度过高且环化程度增幅缓慢,抑制了碳纤维皮部类石墨结构的形成,所得碳纤维的孔隙率增大,拉伸强度降低.控制Vo为21.15％ ～21.34％时,热氧稳定化纤维的环化和径向化学结构的均质化程度均得以提高,所得碳纤维在保持皮部较高石墨程度的同时促进了芯部类石墨结构的形成,此时拉伸强度最高,比在常规空气气氛条件下制备的碳纤维提高了12.22％.     

竹节状纳米碳纤维的制备及嵌锂性能研究

以泡沫镍为催化剂,在600和700℃下,以CVD法热解乙炔气体制备大量的纳米碳纤维.随着制备温度增加,纳米碳纤维直径变小,竹节状含量减少, d002值减小,微晶片层平面Lc和La值增大,碳材料的可逆容量则下降.分别用透射电镜、 X射线衍射和拉曼光谱观察和测定了纳米碳纤维的形貌、微结构,发现在不同条件下生长的纳米碳纤维有不同的形貌和结构.对纳米碳纤维的电化学嵌锂性能的研究表明,纳米碳纤维的结构对其电化学嵌锂容量和充放电循环寿命起重要影响,制备温度越低,纳米碳纤维的石墨化程度越差,可逆嵌锂容量相应要高一些.     

掺杂羧基化碳纳米管的纳米碳纤维前驱体的制备及表征

为获得结构完整、 性能优良的纳米碳纤维前驱体, 采用静电纺丝法制备了掺杂羧基化多壁碳纳米管(MWCNTs)的聚丙烯腈(PAN)纳米纤维. 用扫描电子显微镜、 偏振红外光谱、 透射电子显微镜、 拉曼光谱及拉伸性能测试等对杂化纳米纤维的微观结构和力学性能进行了研究, 分析了MWCNTs含量的影响. 实验结果表明, 5%(质量分数)的MWCNTs掺杂量为杂化纳米纤维直径的突变点, 且MWCNTs的加入有利于PAN分子链的取向, MWCNTs在PAN纤维中大体上沿纤维轴向取向分布. 3%MWCNTs/PAN杂化纳米纤维的拉伸强度和拉伸模量分别达到88.6 MPa和3.21 GPa.     

锂硫电池中碳酸乙烯酯与硫簇反应拉曼光谱的理论研究

通过密度泛函理论(DFT)计算了锂硫电池中多硫阴离子(S2-n)和碳酸乙烯酯(EC)的2种反应机理,并对其反应物和主要产物的拉曼光谱进行了理论分析.计算结果表明,2种反应路径中,S2-n进攻EC分子烷基碳所需活化能和Gibbs自由能均较低.多硫基团有很强的拉曼特征谱峰,与EC分子相关的部分拉曼谱亦发生显著变化.锂离子的存在影响反应产物的结构和拉曼光谱.密度泛函理论计算提供了锂硫电池中锂、多硫阴离子和电解液反应前后的结构变化和反应信息.     

拉曼光谱表征石墨烯材料的研究进展

石墨烯独特的二元化电子价键结构使其在纳米电子器件中具有良好的应用发展前景。拉曼光谱作为一种灵敏、便捷的技术,已被成功地用作表征石墨烯的结构和特性。本综述着重对沉积在不同基底以及掺杂的石墨烯拉曼光谱研究做了一个简单的总结。通过对铟锡氧化物、蓝宝石和玻璃基底上的石墨烯拉曼光谱进行观察,发现在不同基底上的石墨烯拉曼G峰与2D峰峰值会有不同程度的偏移,但2D峰峰值可判断石墨烯层数这一结论仍适用。掺杂可改变石墨烯的荷电状态,使石墨烯表现出空穴（p）型或电子（n）型掺杂特性,通过石墨烯拉曼光谱的变化可以定性石墨烯的掺杂类别并定量表征石墨烯的载流子浓度。     

4-硝基咪唑A-带激发态结构动力学

通过共振拉曼光谱实验和量子化学计算的方法研究了4-硝基咪唑(4NI)A-带激发态衰变动力学.对4NI的振动光谱、紫外电子吸收光谱、荧光光谱和共振拉曼光谱进行了指认.在全活化空间自洽场法(CASSCF)/6-31G(d)计算水平下获得了单重激发态S1(nOπ*)和S2(ππ*)和势能面交叉点S1(nOπ*)/S2(ππ*)的优化几何结构和能量,分析了A-带共振拉曼光谱的强度模式特征,获得了短时结构动力学,并结合全活化空间自洽场法(CASSCF)理论计算结果确定了4NI在S2(ππ*)态衰变通道主要是S2,FC→S2,min(ππ*)→S0辐射弛豫.     

拉曼光谱表征石墨烯材料研究进展

石墨烯独特的二元化电子价键结构使其在纳米电子器件中具有良好的应用前景。拉曼光谱作为一种灵敏、便捷的技术,已被成功用于表征石墨烯的结构和特性。本文主要介绍对沉积在不同基底以及掺杂的石墨烯所进行的拉曼光谱研究。通过对铟锡氧化物、蓝宝石和玻璃基底上石墨烯的拉曼光谱的观察,发现在不同基底上的石墨烯拉曼G峰与2D峰会有不同程度的位移,但2D峰峰值可判断石墨烯层数这一结论仍适用。掺杂可改变石墨烯的荷电状态,使石墨烯表现出空穴(p)型或电子(n)型掺杂特性,通过石墨烯拉曼光谱的变化可以定性石墨烯的掺杂类别并定量表征石墨烯的载流子浓度。     

Is the wall of a cellulose fiber saturated with liquid whether or not permeable with CO2 dissolved molecules? Application to bubble nucleation in champagne wines

In this paper, the transversal diffusion coefficient D perpendicular of CO2 dissolved molecules through the wall of a hydrated cellulose fiber was approached, from the liquid bulk diffusion coefficient of CO2 dissolved molecules modified by an obstruction factor. The porous network between the cellulose microfibrils of the fiber wall was assumed being saturated with liquid. We retrieved information from previous NMR experiments on the self-diffusion of water in cellulose fibers to reach an order of magnitude for the transversal diffusion coefficient of CO2 molecules through the fiber wall. A value of about D perpendicular approximately 0.2D0 was proposed, D0 being the diffusion coefficient of CO2 molecules in the liquid bulk. Because most of bubble nucleation sites in a glass poured with carbonated beverage are cellulose fibers cast off from paper or cloth which floated from the surrounding air, or remaining from the wiping process, this result directly applies to the kinetics of carbon dioxide bubble formation from champagne and sparkling wines. If the cellulose fiber wall was impermeable with regard to CO2 dissolved molecules, it was suggested that the kinetics of bubbling would be about three times less than it is.     

Properties,Morphology and Structure of BPDA/PPD/TFMB Polyimide Fibers

The mechanical properties of fibers were notably improved by incorporating 2,2′-bis(trifluoromethyl)- benzidine(TFMB) into 3,3′,4,4′-biphenyltetracarboxylic dianhydride(s-BPDA) and p-phenylenediamine(PPD) backbone. The best strength and modulus of BPDA/PPD/TFMB polyimide(PI) fiber(diamine molar ratio of PPD/TFMB= 90/10) were 1.60 and 90 GPa, respectively, which was over two times that of BPDA/PPD PI fiber. SEM image showed that the cross-section of fibers at each stage was round and voids free. Besides, the “skin-core” and microfibrillar structure were not observed. The thermal properties of PI fibers were also investigated. The results showed that the fibers owned excellent thermal stability, moreover, the structural homogeneity of fibers were significantly improved by heat-drawn stage. The T_g values were found to be around 300℃ by dynamic mechanical analysis(DMA). Wide angle X-ray diffraction(WAXD) and small angle X-ray scattering(SAXS) experiments indicated that the order degree of longitudinal and lateral stacks, the molecular orientation and the structural homogeneity of fibers were improved in the preparation process of fibers.     

Effect of Thermal Cycles on the Thermal Expansion Behavior of T700 Carbon Fiber Bundles

The relationships between the coefficient of thermal expansion(CTE) of T700 carbon fiber bundles(CFBs) and the thermal cycles were investigated. The microstructure of T700 CFBs was analyzed with Raman spectra and XRD before and after the thermomechanical test. The results indicated that the T700 CFBs exhibited negative expansion in the direction of parallel fibers in the temperature range of -150-150℃. The thermal strain that occurred during the heating and the cooling thermal cycle had an unclosed curve that served as the loop. When the experimental load was the same, the position of strain loop tended to move upward, and the length of the specimen increased continuously with the thermal cycles increasing. The microstructural analysis suggested that the degree of structural order and the degree of orientation along the fiber axis were improved with the increase of thermal cycles. The change of microstructure parameters could be the primary cause of the negative CTE's variation within the T700 CFBs.     

Carbon molecular sieves for air separation from Nomex aramid fibers

Activated carbon fibers prepared from aramid fibers have proved to possess outstanding homogeneity in pore size, most of all when Nomex aramid fiber is used as precursor. Taking advantage of this feature, microporous carbon molecular sieves for air separation have been prepared through carbon vapor deposition of benzene on Nomex-derived carbon fibers activated to two different burnoff degrees. Carbon molecular sieves with good selectivity for this separation and showing acceptable adsorption capacities were obtained from ACFs activated to the two burnoff degrees chosen.     

Determining the Surface Properties of Carbon Fiber in Contact Interaction with Polymeric Binders

Application of various criteria for evaluating the wettability of the surface of carbon fibers of Torayca T 300 3K brand was considered. A simulation of the carbon fiber impregnation in fabrication of a composite material was used to determine the thermodynamic parameters (surface energy, works of adhesion and cohesion) and the wetting angle for three kinds of promising polymeric binders. It was found that the best impregnation conditions for carbon fiber of Torayca T 300 3K brand (Cm12073 fabric) will be for the filament not subjected to thermal treatment because the capillary rise of the organic solvent simulating the polymeric binder decreases by 14% on removing the finishing oil. The presence of the Infutac layer fixer used to fabricate reflector segments raises the time of penetration of the polyurethane (with shape memory) and epoxy binders into the fabric sheet, makes the impregnation six times lower, and has no effect on the time of impregnation of carbon fibers with the silicone binder.     

煤焦油沥青基纤维状活性炭的吸附性能

煤焦油沥青基炭纤维（ＣＰＣＦ）价格低廉含炭量高、易于活化,是制备纤维状活性炭（ＣＰＡＣＦ）的优良原料。本文讨论了ＣＰＣＦ的抗拉强度和活化条件对ＣＰＡＣＦ比表面积的影响。并同石油系沥青基炭纤维（ＰＰＣＦ）进行了比较。考察了不同比表面积的ＣＰＡＣＦ、ＰＰＡＣＦ和商品用颗粒活性炭（ＡＣ）对０．１ｍｏｌ／Ｌ碘溶液、０．００５ｍｏｌ／Ｌ亚早兰溶液和２９３Ｋ下三氯甲烷饱和蒸汽的吸附性能,及以上三样品在２９３Ｋ     

Investigation of the Orientation in Composite Fibers of Polycarbonate with Multiwalled Carbon Nanotubes by Raman Microscopy

The superior association of the inherent good mechanical and electrical properties makes carbon nanotubes (CNT) exceptionally interesting for the production of composite fibers of thermoplastic polymers with CNT. Alignment of the CNT in the polymer fiber is important for improved mechanical properties. Especially the production of fibers makes it necessary to get a controlled orientation and/or alignment of the CNT. We applied transmission electron microscopy (TEM) and polarized Raman microscopy to quantify multiwalled carbon nanotubes (MWNT) orientation, alignment and crystallinity in polycarbonate (PC). The evaluation of the Raman measurements provided an improved alignment orientation of the MWNT in the fibers with increasing take-up velocity during melt spinning and that the crystal structure of the MWNT is not changed through melt spinning.     

Interfacial studies on the ozone and air‐oxidation‐modified carbon fiber reinforced PEEK composites

In this work, ozone modification method and air‐oxidationwere used for the surface treatment of polyacrylonitrile(PAN)‐based carbon fiber. The surface characteristics of carbon fibers were characterized by XPS. The interfacial properties of carbon fiber‐reinforced (polyetheretherketone) PEEK (CF/PEEK) composites were investigated by means of the single fiber pull‐out tests. As a result, it was found that IFSS (interfacial shear strength) values of the composites with ozone‐treated carbon fiber are increased by 60% compared to that without treatment. XPS results show that ozone treatment increases the amount of carboxyl groups on carbon fiber surface, thus the interfacial adhesion between carbon fiber and PEEK matrix is effectively promoted. The effect of surface treatment of carbon fibers on the tribological properties of CF/PEEKcomposites was comparativelyinvestigated. Experimental results revealed that surface treatment can effectively improve the interfacial adhesion between carbon fiber and PEEK matrix. Thus the wear resistance was significantly improved. Copyright © 2009 John Wiley & Sons, Ltd.     

Study of oriented polyethylene structures using a Raman longwave acoustic mode

This paper concerns the basics of using longwave (low-frequency) Raman spectroscopy in the region of a longitudinal acoustic mode for the study of structural features of polymers. Using ultrahighmolecular- weight polyethylene (UHMW PE)-based reactor powders, gels, and oriented fibers obtained by the gel technology, the length distribution of straight-chain segments and its relation to the morphology of the sample were analyzed. An important role of the low-frequency Raman spectroscopy in creating domestic gel technology for preparing ultrahigh-strength threads from polyethylene was demonstrated.     

Effect of the oxygen-induced modification of polyacrylonitrile fibers during thermal-oxidative stabilization on the radial microcrystalline structure of the resulting carbon fibers

The oxygen-induced modification of polyacrylonitrile (PAN) fibers during the final stage of thermal-oxidative stabilization is used to control the degree of chemical reactions and the radial structural homogeneity of fibers. A radial structure model for oxidized PAN fibers (OFs) and carbon fibers (CFs) has been established by Raman spectroscopy and wide angle X-ray diffraction. According to the model, the cross-section of OFs is divided into the internal and external regions; the oxygen-induced modification has a greater effect on the structural evolution of internal regions than that of external regions. When the oxygen volume content for the modification is 22.2%, the OFs possess the highest level value for degree of disorder (DD) in internal regions. This is inherited by the corresponding CFs with the best radial structure homogeneity and optimum mechanical properties; meanwhile, the coefficient of variation for DD is defined to characterize the radial homogeneity of CFs. The mechanism of the oxygen-induced modification demonstrates that the mechanical properties of the resulting CFs depend on the degrees of the intermolecular cyclization and oxidation which are beneficial to the decrease in CF crystallite size.