用RAMAN光谱研究碳纤维皮芯结构随热处理温度的演变规律

用Raman光谱研究碳纤维经不同温度热处理后其皮芯结构的演变规律。结果发现：随着热处理温度的提高,碳纤维表面和内部的Raman光谱具有相似的变化趋势。同时,表征碳纤维表面和内部石墨化程度的R_s与 R_c值均越来越小,且R_s值减小得更快,说明碳纤维的石墨化程度越来越高,并且表面的石墨化程度提高的更快,这是因为碳纤维表面和内部的碳有着不同的石墨化物性。前者接近于软碳,易于石墨化;后者接 近于硬碳,难于石墨化,可能是树脂碳。文章提出并采用皮芯结构因子R_sc(＝R_s/R_c)来表征了碳纤维的皮芯结构程度。当R_sc等于1时,碳纤维是完全均质的。随着热处理温度的升 高,碳纤维的R_sc趋向于零,说明其皮芯结构越来越严重。碳纤维的皮芯结构加重是最终导致其抗拉强度不断降低的原因之一。     

PAN基碳纤维在石墨化过程中的拉曼光谱

采用激光拉曼光谱研究了PAN基碳纤维在石墨化(2 000～3 000 ℃)过程中的结构变化;比较了石墨化前后纤维表面和断面拉曼光谱特征。结果表明：高温石墨化后,碳纤维的一级拉曼光谱有3个峰(D,G和D′),表征碳纤维结构有序程度的拉曼参数主要有D和G峰的半高宽(FWHM)、G峰的拉曼位移和D与G峰的积分强度比R(I_D/I_G)。随着热处理温度的提高,D和G峰的半高宽、G峰的拉曼位移和R值均逐渐减小,即使经过3 000 ℃高温处理后,D峰仍然存在,R值为0.19,说明纤维中仍存在无序结构。另外,R值与纤维中石墨微晶的基面宽度L_a成反比,石墨化后纤维取向性的增加使得表面和断面的拉曼光谱有明显的差异。因此,可利用激光拉曼光谱来定量表征碳纤维的石墨化程度和取向。     

阵列碳纳米管的石墨化程度

采用化学气相沉积法制备了阵列碳纳米管薄膜,对阵列碳纳米管的石墨化程度进行了系统研究。利用扫描电子显微镜(SEM)、拉曼光谱(Raman)对样品形貌以及结构进行了表征。探讨了不同实验参数对阵列碳纳米管石墨化程度影响的机理。结果发现,在一定催化剂浓度范围内,催化剂浓度过低时,阵列碳纳米管的石墨化程度较差,而随着催化剂浓度的增加,阵列碳纳米管的石墨化程度逐渐变好;生长石墨化程度较好的阵列碳纳米管需要合适的进液速度,进液速度过低或过高都会使得碳纳米管的石墨化程度变差;此外,生长石墨化程度较好的阵列碳纳米管也需要合适的生长温度,生长温度过低或过高都会使得碳纳米管的石墨化程度变差。     

PAN基碳纤维在表面处理中的拉曼光谱研究

采用激光拉曼光谱研究了PAN基碳纤维在表面处理中的微结构变化,分析了表面处理前后碳纤维的一级拉曼光谱特性。结果表明：拉曼光谱中主要的D峰和G峰的拉曼频移、半高宽以及各个不同拉曼频移位置对应肩峰的积分面积比是表征碳纤维物相结构变化的重要参数。经过不同的表面处理,PAN基碳纤维的一级拉曼光谱参数发生了一定程度变化,D峰和G峰的拉曼峰位向高波数偏移,表征石墨微晶尺寸的R值有所提高,这说明在表面处理后碳纤维的石墨微结构受到刻蚀,微晶尺寸有所减小,石墨微晶的边界活性增大;此外,表征碳纤维结构有序程度和缺陷多少的D峰和G峰的半高宽均有减小,表征无定型碳结构或某种有机官能团的A峰和D″峰的相对积分面积减小,这说明与乱层石墨结构相比,碳纤维中存在的无定型碳结构更容易被刻蚀,经过表面处理之后无定型碳的物相比例减小,这与碳纤维XRD图谱中表观结晶度提高的规律相一致。因此,利用激光拉曼光谱可研究碳纤维物相结构的变化规律。     

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 6 0 0和 70 0℃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 ,d0 0 2 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     

湖南砂矿金刚石中石墨包裹体拉曼光谱原位测定：形成条件及成因指示

石墨是天然金刚石中最常见的包裹体之一,按其形成顺序可分为原生、同生、次生,原生/同生与次生石墨包裹体的存在指示了金刚石形成的环境及形成后可能经历的变化。对湖南沅水流域产出的13粒宝石级-半宝石级砂矿金刚石中的原生/同生石墨包裹体及次生石墨包裹体进行显微激光拉曼光谱的原位测试。测试显示,湖南沅水流域金刚石中原生/同生石墨包裹体与次生石墨包裹体的G带与D带拉曼位移均存在漂移,其中原生/同生石墨包裹体G带的漂移范围为1 591～1 600 cm-1,次生石墨的漂移范围为1 575～1 588 cm-1,显示其形成压力较低,结晶压力变化范围大。原生/同生石墨漂移程度估算出该区域压力范围为4.01～5.88 GPa,估算结果与利用橄榄石包裹体拉曼位移估算的源区压力范围基本一致。该区域内金刚石中原生/同生石墨包裹体的D带拉曼位移在1 350～1 368 cm-1之间,D带与G带的强度比(I_D/I_G值)值位于0.36～0.82之间,具有较低有序度结构/结晶程度与橄榄岩型金刚石的高结晶度石墨明显不同指示该区域部分砂矿来源的金刚石的形成深度较浅,成因与榴辉岩关系更为密切,形成过程极可能曾位于石墨-金刚石稳定域附近。研究结果表明,金刚石石墨包裹体拉曼位移的漂移程度可成为探索金刚石原生源区形成环境的有效方法之一。     

保护介质对爆轰固相产物生成的影响

 通过爆轰合成超细金刚石实验，对装药在不同环境下引爆后得到的固相碳产物进行比较分析，研究不同介质如氮气、水、冰、遇热分解的盐等对爆轰产物中固相碳形成的影响，同时提出用石墨化程度来比较这种影响。结果显示，介质对爆轰产物中固相碳的石墨化和超细金刚石的保护有着重要的作用。几种介质中水的保护效果较好。     

FeCl_3对准东煤基多孔碳孔隙结构与石墨化协同调控

多孔碳制备过程中,孔结构的发展和石墨化的演变相互依存,且高的石墨化度往往导致孔隙结构衰减。为同时提高煤基多孔碳孔隙结构与石墨化程度,本文以我国大储量准东煤为原料,通过添加FeCl_3实现孔隙结构与石墨化度的协同调控,探究不同FeCl_3添加量的影响。结果表明:随着FeCl_3添加量增加,煤焦比表面积由346 m~2·g~(-1)增加到574m~2·g~(-1);石墨化程度逐渐增加,I_G/I_(All)由8.774%增加到9.328%。通过分析得出:FeCl_3水解及热解作用产生的铁氧化物与热解、活化过程产生的CO反应原位形成CO_2,对煤焦刻蚀,促进微孔的发展;煤焦中无定型碳与还原性Fe形成Fe_3C中间相,在碳不断"溶解析出"过程实现了催化石墨化的进行;酸洗过程释放了一部分中孔。由此可见,FeCl_3同时起着微孔造孔剂、中孔模板剂及催化石墨化促进剂的作用。     

石墨-六角氮化硼微晶混合物与水高压反应产物分析

 利用球磨法制备石墨-六角氮化硼微晶混合物，并在6.1 GPa、800~1 500 ℃条件下与水进行高压反应，以便研究用水作触媒合成B-C-N三元化合物的可能性。通过对反应产物的XRD、XPS谱分析发现：高压下随着温度的升高，反应产物中出现再结晶石墨，其晶化程度逐渐提高；但没有出现再结晶六角氮化硼，也未出现立方氮化硼。在球磨不充分条件下，石墨-六角氮化硼混合物的XRD谱没有完全弥散，它们与水高压反应时，能观察到石墨与立方氮化硼分别结晶的现象，但都没有形成B-C-N晶化结构。     

高煤级煤石墨化轨迹阶段性的XRD和Raman光谱表征

为了研究石墨化过程中煤的分子结构有序化轨迹,选取湖南、陕西19个不同变形-变质程度高煤级煤为研究对象,采用工业分析、元素分析、X射线衍射分析（XRD）和拉曼光谱分析（Raman）等手段,结合分峰拟合的数学方法,对系列样品分子结构参数（XRD结构参数,如石墨化度、延展度L_a、堆砌度L_c及面网间距d₀₀₂等;Raman参数,如P_G,P₁,R₁,R₂等）进行了统计与计算。研究结果表明：煤化作用阶段H/C随变质程度增加而逐渐减小,但在石墨化阶段以物理变化为主,其趋势变缓或不显著;XRD参数d₀₀₂,L_a,L_c,N及L_a/L_c等随变质程度呈现非线性连续（阶跃性）变化,拐点大致对应R_m=7.0%,d₀₀₂=0.338 nm,拐点之前L_a,L_c及N变化较小（或平稳增大）,拐点之后石墨晶体结构快速形成,微晶尺寸增大,拼叠作用开始并逐渐增强;L_a/L_c变化亦反映石墨化过程由缩合作用向拼叠作用转变。高煤级煤石墨化轨迹可按有序化增加的三阶段模型来表述,无定形碳（无烟煤）至变无烟煤阶段,G峰位、峰位差P₁变化显著,I_D1/I_G在表达无序程度时不服从TK关系;变无烟煤至半石墨阶段,即从石墨化开始结构演化轨迹呈现不同方向,R₁随着有序的增加呈现截然相反的轨迹,部分石墨组分演化服从TK关系,R₂在石墨化度为45%时呈现截然相反的轨迹;石墨阶段温、压作用导致微晶尺寸急剧增加（或阶跃）,I_D1/I_G减小服从TK关系。当不同石墨化程度的新生组分共存时,d₀₀₂不足以代表样品最大的演化程度,但其作为平均度量来标度高煤级煤石墨化过程中结构演化特征仍为较优的选择,且(002)和(γ)峰半峰宽能较好地区分石墨化煤的变质类型,H/C,I_D1/I_G亦随d₀₀₂演化轨迹不同,需利用d₀₀₂＜0.344 0 nm,R₁＜2.0,H/C＜0.12等综合指标判别石墨化的开始。由此可以看出,采用XRD和Raman光谱分析技术可以表征高煤级煤石墨化轨迹阶段性以及结构的差异性。     

The research on the interfacial compatibility of polypropylene composite filled with surface treated carbon fiber

Dielectric barrier discharges (DBD) in ambient air are used on carbon fiber to improve the fiber surface activity. Carbon fibers with length of 75 μm are placed into the plasma configuration. The interaction between modified carbon fibers and polypropylene (PP) was studied by three-point bending (TPB) test. The chemical changes induced by the treatments on carbon fiber surface are examined using X-ray photoelectron spectroscopy (XPS). XPS results reveal that the carbon fiber modified with the DBD at atmospheric pressure show a significant increase in oxygen and nitrogen concentration. These results demonstrate that the surface of the carbon fiber is more active and hydrophilic after plasma treatments using a DBD operating in ambient air.     

Preparation of vertically aligned carbon nanotube arrays grown onto carbon fiber fabric and evaluating its wettability on effect of composite

Vertically aligned carbon nanotube (CNT) arrays have been grown onto the carbon fiber fabric using a catalytic chemical vapor deposition (CCVD) method. The as-synthesized CNT arrays are about 20 μm in height, and the nanotube has a mean inner and outer diameter of 2.6 nm, 5.5 nm, respectively. The CNT-grafted carbon fabric shows a hydrophobic property with a contact angle over 145°, and the single CNT-grafted carbon fiber shows a sharp increase of dynamic contact angle in de-ionized water from original 71.70° to about 103°, but a little increase does in diiodomethane or E-51 epoxy resin. However, the total surface energy of carbon nanotube-grafted carbon fiber is almost as same as that of as-received carbon fiber. After CNTs growth, single fiber tensile tests indicated a slight tensile strength degradation within 10% for all different lengths of fibers, while the fiber modulus has not been significantly damaged. Compared with the as-received carbon fibers, a nearly 110% increase of interfacial shear strength (IFSS) from 65 to 135 MPa has been identified by single fiber pull-out tests for the micro-droplet composite, which is reinforced by as-received carbon fiber or CNT-grafted carbon fiber.     

Intense electron emission from carbon fiber cathodes

We studied the emission properties of carbon fiber cathodes. These cathodes were made either of a single carbon fiber or of carbon fabric, or of an array of carbon fiber bundles. It was found that an intense emission of electrons occurs from a plasma which is formed on the carbon fiber surface as a result of a flashover process. In addition, the time delay in the appearance of the electron emission with respect to the start of the accelerating voltage pulse was found to depend strongly on the voltage growth rate. A simple model of the plasma formation is suggested. Received 12 March 2001     

Dimensional changes of carbon fiber fabrics reinforced phenolic resin-based carbon/carbon composites during pyrolysis

The dimensional changes of two-dimensional phenolic resin-based carbon/carbon composites during pyrolysis were investigated. The carbon/carbon composites were obtained by pyrolyzing the carbon fiber/phenolic resin composites that were fabricated using a vacuum bag hot pressing technique. Length, width and thickness of the rectangular composite samples were measured carefully before and after pyrolysis. The effects of heat treatment temperature and fiber pre-heat treatment on the dimensional changes of carbon/carbon composites were investigated. The measurement results indicated that different behavior in dimensional changes could be obtained for carbon/carbon composites with different fiber–matrix bonding in the interface.     

碳纤维阴极的电子发射机制

 建立了金属阴极和碳纤维阴极的电子发射机制模型，发射后的阴极和碳纤维阴极的微观照片证实了模型的正确性。实验结果与分析表明：一种优化的阴极应该具备多种电子发射机制，整个阴极的电子发射更均匀，碳纤维阴极的电子发射不仅具有尖端的场发射，而且伴随着侧向的表面闪络(随纹)。此外和金属阴极相比较，处理后碳纤维阴极具有较慢的等离子体膨胀速度(≤1 cm/μs)并使该实验用微波源具有较宽的微波脉冲输出(≥200 ns)。     

利用飞秒激光加工碳纤维(英文)

为验证光学加工碳纤维材料的可行性,利用飞秒激光和连续激光对碳纤维块体材料进行了加工。获得了利用飞秒和连续激光加工的表面形貌。与连续激光加工相比,利用脉宽40fs的激光加工效率较高,加工区边缘形貌较好,加工质量较高。通过不同激光功率下加工孔径尺寸的研究获得了飞秒激光加工阈值在1012W/cm2量级。研究结果证明了光学加工碳纤维体材料的可行性。     

Interfacial interaction in carbon fiber/thermoplastic composites

This work was undertaken in order to increase the understanding of the mechanism responsible for fiber/matrix interaction in carbon fiber/thermoplastic composite. From results of previous study on carbon fiber/PEEK composite, which suggested that the formation of the fiber/ matrix interaction was primarily related to a chemisorption mechanism, a study was done of the conditions required to obtain efficient fiber/matrix interaction in PA-12 and PP/carbon fiber composites. The interest in studying carbon fiber composite based on PP and PA-12 was that these two matrices are very different in terms of reactivity, polyamide having many more reactive groups than polypropylene. As expected, due to the non-reactive chemical structure of the polypropylene, fiber/matrix interaction in carbon fiber/PP composite occurred only when the matrix was thermally degraded, i.e. when the composite was molded at high temperature or under long residence time at the melt temperature. For the carbon fiber/PA-12 composite, strong fiber/matrix interaction occurred readily at relatively low molding temperature, i.e. well before thermal degradation of the matrix. It was also found that the short beam shear strength in these composites seems to evolve with molding temperature, and a maximum interfacial strength was observed at a molding temperature corresponding to the thermal degradation of the matrix. This indicates that although matrix degradation often results in strong reduction in the composite performance, some matrix degradation can be beneficial in terms of interfacial mechanical properties. Finally, this work demonstrated that while the formation of fiber/matrix interaction seems to be primarily related to a chemisorption mechanism, the contribution of interphase crystallinity to the interfacial strength is not negligible. In fact, interfacial crystallinity was found to be essential to ensure optimum interfacial strength.     

Surface modification of polyacrylonitrile-based carbon fiber and its interaction with imide

In this work, sized polyacrylonitrile (PAN)-based carbon fibers were chemically modified with nitric acid and maleic anhydride (MA) in order to improve the interaction between carbon fiber surface and polyimide matrix. Bismaleimide (BMI) was selected as a model compound of polyimide to react with modified carbon fiber. The surface characteristic changing after modification and surface reaction was investigated by element analysis (EA), scanning electron microscopy (SEM), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and surface enhanced Raman scattering (SERS). The results indicated that the modification of carbon fiber surface with MA might follow the Diels Alder reaction mechanism. In the surface reaction between modified fibers and BMI, among the various surface functional groups, the hydroxyl group provided from phenolic hydroxyl group and bridged structure on carbon fiber may be the most effective group reacted with imide structure. The results may shed some light on the design of the appropriate surface structure, which could react with polyimide, and the manufacture of the carbon fiber-reinforced polyimide matrix composites.     

碳纤维阴极发射均匀性的实验研究

 分别用自制浸渍碘化铯（CsI）针式环状碳纤维阴极和环状不锈钢阴极所产生的电子束轰击尼龙目击靶，研究碳纤维阴极发射均匀性。在碳纤维阴极电子束轰击的目击靶上得到了均匀的烧蚀痕迹，而不锈钢阴极电子束轰击的目击靶上烧蚀痕迹不均匀，表明碳纤维阴极发射电子束的均匀性优于不锈钢阴极。分析认为两阴极不同的发射机制及其所特有的材料性质和结构导致其发射电子束均匀性的差异。用光学显微镜和电子显微镜对不锈钢阴极尖端和碳纤维阴极尖端和侧面进行扫描，发现不锈钢阴极仅尖端处被烧蚀，而碳纤维阴极尖端和侧面都有烧蚀痕迹，验证了碳纤维阴极由场发射和表面闪络共同作用的发射机制的假设分析。     

Radical grafting from carbon fiber surface: graft polymerization of vinyl monomers initiated by azo groups introduced onto the surface

This paper describes the radical graft polymerizations of vinyl monomers from carbon fiber surface initiated by azo groups introduced onto the fiber surface. The carbon fiber used in this experiment was the polyacrylonitrile type. The introduction of azo groups onto the carbon fiber surface was achieved by the reaction of 4,4'-azobis (4-cyanopentanoic acid) with isocyanate groups which were previously attached onto the surface by the treatment of the fiber with tolylene 2,4-diisocyanate. The amount of surface azo groups introduced onto nitric acid-treated carbon fiber was determined to be 0.60 x 10^-5 mol 9^-1 by nitrogen analysis. The radical graft polymerization of methyl methacrylate (MMA) was tried. Though the thermal polymerization of MMA proceeded slightly in the absence or in the presence of untreated carbon fiber, the rate of the polymerization was considerably low. In contrast, the graft polymerization of MMA was initiated in the presence of the carbon fiber having surface azo groups, and part of resultant poly(MMA) grafted onto the surface. The percentage of grafting increased with an increase in polymerization time and reached 42.8% after 24 h. The graft polymerizations of other monomers, such as styrene, vinyl acetate, and acrylic acid, were also initiated by the surface azo groups attached onto the carbon fiber, and the corresponding polymer effectively grafted onto the surface.