热处理温度对PAN基炭纤维结构的影响

利用SEM观察了3种PAN基炭纤维（TX－63、T300、T700）热处理前和经不同温度热处理后的表面形貌，并测试了其石墨化度、Lc和d002值，以研究热处理温度对炭纤维表面和内部微观结构的影响。结果表明：TX－3、T300炭纤维表面本身有不规则沟槽、凸起和缺陷等，T700炭纤维表面比较圆滑，随着热处理温度升高，PAN基炭纤维的表面形貌发生明显的变化，尤其是2700℃处理后炭纤维表面的褶皱相对较浅而小；石墨化度与Lc随热处理温度升高而增大，d002值则呈减小趋势，说明热处理温度对炭纤维的表面和内部结构有显著影响。     

高频感应加热制备PAN基高模量炭纤维的研究

采用高频感应快速加热连续石墨化装置，制备ＰＡＮ基高模量炭纤维（ＨＭＣＦ）。结果表明，此法可以制备高模量炭纤维。当原料纤维抗拉强度在３．５ＧＰａ，模量在２３０ＧＰａ以下时，采用石墨化温度为２６００℃，可以得到与由传统石墨化炉相类似的结果。并对炭纤维的力学性能和结构参数进行了研究。     

微螺旋炭纤维结构性能的研究

微螺旋炭纤维因其特殊的三维手性结构,具有多种优异性能.综述了微螺旋炭纤维的微观形貌、力学性能、电性能、热性能、吸波性能和储气性能,并展望了螺旋炭纤维的应用前景,同时也总结了螺旋炭纤维研究中存在的问题.     

PAN基炭纤维经济规模分析

聚丙烯腈（Polyacrylonitrile缩写为PAN）基炭纤维市场需求旺盛,但由于我国PAN基炭纤维生产企业规模小、产品性能低,产品占领不了市场,企业效益欠佳。通过经济规模方法的分析,就国内现有技术状况和两个样本生产线,用工程技术法对PAN基炭纤维的经济规模进行分析,为我国炭纤维产业化发展提供参考。分析表明,国内PAN基炭纤维经济规模的起点为200t/a-275t/a。     

甲烷催化裂解制备毛线状炭纤维及其微观结构

以甲烷为碳源，硫酸亚铁为催化剂前驱体，通过化学气相沉积在石墨基板上制得毛线状炭纤维。扫描电子显微镜观察得知所制炭纤维具有毛线状结构，由许多直径更小的子纤维交叉合并而成。单束毛线状炭纤维的直径为4μm-8μm。高分辨透射电子显微镜显示构成纤维的碳层排列不平直，存在偏转角，有序排列的碳层被分割成许多有序微晶区域。进一步采用X射线衍射和激光拉曼光谱等分析手段对其微观结构进行表征，表明毛线状炭纤维中碳层排列有序度较高，石墨微晶尺寸较大（La≈5nm），层间距较小（d002=0．340nm）。推测毛线状炭纤维生长机理符合“吸附-扩散-析出”过程，形成毛线状结构主要由催化剂颗粒直径决定。     

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。     

电化学氧化处理对PAN基炭纤维表面浸润性的影响

以硫酸铵为电解质,对炭纤维进行连续电化学氧化处理,利用反气相色谱(IGC)研究电化学氧化处理前后的表面能变化,并联系SEM、AFM、XRD、Raman、XPS等测试结果综合分析电化学氧化处理对炭纤维表面性能的影响.研究表明,经电化学氧化处理后,纤维沿抽方向表面沟槽加深加宽,薄弱层被剥除,晶格择优取向遭到破坏;纤维表面活性官能团增多,氧和氮含量分别增加了180％和65％,提高了纤维与树脂的粘结性;纤维表面能提高了3.1倍,与树脂的浸润性得到改善;电化学氧化处理后其复合材料的ILSS达109MPa,已可充分满足实际应用需求.     

炭纤维表面化学的裂解气相色谱法研究

用裂解气相色谱法研究了炭纤维表面化学。与ＸＰＳ相结合,裂解色谱法可以反映炭纤维表面整个氧化层的状况。氧化后的炭纤维经５００℃裂解,色谱图中出现Ｃ３以内的气态烃及甲醛、丙酮等含氧化合物,表明炭纤维氧化后表面存在脂肪族结构。炭纤维的氧化方法或氧化时间不同,在其表面形成的化学结构也不同。     

CVD法制备微旋管状炭纤维的微观形貌

采用化学气相沉积（ＣＶＤ）法,使溶有少量杂质的乙炔在自制的过渡金属催化剂和Ｓ／Ｐ助剂的作用下热分解,合成了结构类似于ＤＮＡ的微旋管状炭纤维,且具有很好的再现性。微旋管状炭纤维是由两根炭纤维规则地二重旋郑匹合而成旋管,其直径约５ｕｍ。乙炔和氢气的比例及温度对产量及微观形貌有很大的影响。     

改进化学气相沉积法在炭纤维表面生长碳纳米管(英文)

采用一种改进的化学气相沉积法在炭纤维表面制备碳纳米管。为了提高炭纤维表面的润湿性能,炭纤维在浸渍之前先在CVD设备中在真空下973 K的高温处理,然后在硝酸和浓硫酸体积比为3∶1的混合酸中酸处理30 min。而改进的化学气相沉积法关键在于让催化剂的还原步骤和碳纳米管的生长步骤同时进行。这样通过减小过渡金属元素与炭纤维之间的接触时间从而降低了它们之间的相互扩散,在确保了炭纤维本身的力学性能下降程度明显小于用普通化学气相法制备的情况下生长出长且茂密的碳纳米管阵列。另外,经过对工艺参数的优化发现当用乙醇作溶剂,Fe(NO3)3.9H2O溶度为100 mmol/L,氢气和碳源气体比值为4/1,而生长时间为30 min时得到最好的碳纳米管阵列。     

利用感应加热技术进行炭纤维连续石墨化

采用感应加热技术研制出炭纤维连续高温热处理专用设备石墨化炉，最高使用温度3000℃。对PAN基炭纤维T300进行了连续石墨化处理，热处理温度为2000℃～3000℃，制备出力学性能相当于日本东丽公司M40的石墨纤维，验证了该设备的技术可行性。考察了热处理温度对炭纤维力学性能、密度和直径的影响，用SEM观察了石墨化前后炭纤维表面微观形态的变化。结果表明：随热处理温度的提高，炭纤维的密度增大、直径减小，弹性模量升高，而抗拉强度下降。经3000℃高温热处理后，纤维的弹性模量高达450GPa。     

石墨化温度对炭纤维微观结构及其力学性能的影响

以通用型PAN基炭纤维为原材料，通过1800℃～3000℃连续高温石墨化处理，制备了不同性能的炭(石墨)纤维；采用SEM、XRD、RAMAN、元素分析仪、万能材料测试机等分析手段研究了石墨化温度对炭(石墨)纤维微观结构、元素含量、表面形态及其力学性能的影响。实验表明：随着热处理温度的提高，炭纤维中非碳元素(氮、氢)的含量逐渐减少而碳元素质量分数却从92．62％增加到99．99％；纤维的微观结构也从二维乱层石墨结构向有序的三维层状结构发展，表现为石墨晶体层间距d。随处理温度的提升逐渐减小、d100和d110与La和Lc不断增大，纤维抗拉强度呈下降趋势、弹性模量呈上升趋势。     

Synthesis and characterization of Y-shaped carbon fibers by chemical vapor deposition

In this work, Y-shaped carbon fibers with high purity were successfully synthesized by CVD using copper tartrate as a catalyst precursor at low reaction temperature, 279 °C. A model has been proposed for interpreting the mechanism of the Y-shaped carbon fibers growth. It is suggested that the introduction of hydrogen is the key factor to the formation of three carbon fibers growth faces on every the agglomeration of copper monocrystalline catalyst particles and lead to the formation of Y-shaped carbon fibers subsequently. The Y-shaped carbon fibers were characterized by field emission scanning electron microscopy, transmission electron microscopy and X-ray diffraction.     

Effects of different acetylene/nitrogen ratios on characteristics of carbon coatings on optical fibers prepared by thermal chemical vapor deposition

The effects of C₂H₂/(C₂H₂ + N₂) ratios on the characteristics of carbon coatings on optical fibers prepared by thermal chemical vapor deposition are investigated. The C₂H₂/(C₂H₂ + N₂) ratios are set to 60, 70, 80, 90, and 100%. Additionally, the deposition temperature, working pressure, and mass flow rate are 1003 K, 133 kPa, and 40 sccm, respectively. The deposition rate, microstructure, and electrical resistivity of carbon coatings are measured. The low-temperature surface morphology of carbon-coated optical fibers is elucidated. Experimental results indicate that the deposition rate increases with increasing the C₂H₂/(C₂H₂ + N₂) ratio, and the deposition process is located at a surface controlled regime. As the deposition rate increases, the electrical resistivity of carbon coatings increases, while the ordered degree, nano-crystallite size, and sp² carbon atoms of the carbon coatings decrease. Additionally, the low-temperature surface morphology of the carbon coatings shows that if the carbon coating thickness is not smaller than 289 nm, decreasing the deposition rate is good for producing hermetic optical fiber coatings.     

The individual effect of coating thicknesses and deposition temperatures on Raman spectra of carbon films deposited on silica glass fibers by thermal chemical vapor deposition

Abstract

Carbon films are deposited on silica glass fibers by thermal chemical vapor deposition using pure methane as the precursor gas, and the individual effect of coating thicknesses and deposition temperatures on Raman spectra of carbon films is investigated. The results show that if the temperature is fixed at 950°C, the D peak position, the full‐width‐at‐half maximum of D band, and the integrated intensity ratio of the D band to the G band increase with increasing the coating thickness. This is because the size and number of particles grown on the carbon film surface increase with increasing the coating thickness and the carbon film becomes more disordered. Alternatively, if the coating thickness is fixed at 1200 nm, the D peak position, the full‐width‐at‐half maximum of D band, and the integrated intensity ratio of the D band to the G band decrease with increasing the deposition temperature. This indicates that the carbon film becomes more ordered and its nano‐grain size increases as the deposition temperature increases from 925 to 1025°C.     

聚丙烯腈基炭纤维中微孔的演变规律

利用二维小角X射线散射技术(SAXS),结合纤维孔结构解析理论及分形原理得到了炭纤维形成过程中纺丝、预氧化、低温和高温炭化等四个阶段样品的微孔结构信息。结果表明:原丝中孔隙沿纤维轴向择优取向,呈长梭状,其长轴与短轴的平均尺寸分别为24.3nm和19.2nm,长径比为1.27。遗留到预氧化阶段的原丝孔洞使得预氧化纤维出现高达1.85的长径比极大值,这可能与原丝线性结构向预氧丝耐热梯形结构转化有关。炭化阶段微孔尺寸迅速减小,长轴、短轴分别达到3.56nm和2.85nm左右,长径比也减小至1.24。分形状态研究表明:表面分形维数DS值介于2.42～2.88之间,且随工艺的进行逐渐增大,低温炭化阶段变化幅度较大,说明各级产品在微观结构上越来越复杂,亦证明低温炭化是促进炭纤维微观结构转变的重要的工艺段。     

Synthesis of carbon nanowalls by hot-wire chemical vapor deposition

Carbon nanowall (CNW) is a carbon nano-material which has a wall structure that stood on substrates. CNWs can be synthesized by hot-wire chemical vapor deposition (HWCVD) using methane without hydrogen dilution. The synthesis of CNWs by HWCVD is discussed along with reviewing the experimental results. The growth of CNWs is affected by hydrogen dilution ratio and substrate surface temperature. Based on these results, it is suggested that hydrogen radical density and substrate surface temperature are the important parameters for the synthesis of CNWs. The growth process of CNWs is also discussed.     

乙炔催化裂解制备碳纳米带及其结构表征

以乙炔（C2H2）为碳源,铁为催化剂,通过化学气相沉积技术在单晶硅衬底上制备了碳纳米带.采用场发射SEM、TEM、激光Raman光谱等先进分析手段对其形态和结构进行了表征.研究发现：碳纳米带是一种准二维材料,厚度约30nm,宽度在几百纳米,长度在100μm量级.碳纳米带的碳层沿着与其生长轴方向一致的（002）晶向排列,碳层的边缘都弯曲折叠成封闭结构.碳纳米带中碳层的排列不很平直,其中存在大量的层错.由此认为碳纳米带可用于能源等领域.     

Diode-like properties of as-grown chemical vapor deposited single-walled carbon nanotubes

Current rectification property of as-grown single-walled carbon nanotubes (SWNTs) is investigated. The SWNTs are grown by chemical vapor deposition (CVD) process. The process allowed to grow long strands of SWNT bundles, which are then used to fabricate multiple arrays of switching devices with the channel length of 3, 5, 7 and 10 microm on a 15 mm x 15 mm SiO2 on Si substrate. Regardless of the channel length, a majority of the fabricated devices show current rectification characteristics, with high throughput of current (I) in the forward bias (V) giving the forward and reverse current ratio (Ifor/Irev) of approximately 10(6). Atomic force microscopic (AFM) analysis of the device structure and surface topology of SWNT suggest the observed rectification of current to possibly result from (a) cross-tube junctions, (b) a mixture of metallic and semiconducting tubes in the SWNT bundles, and/or (c) chirality change along a single tube. The exact mechanism underlying the observed rectification could not be conclusively established. However, the analyses of the experimental results strongly suggest the observed rectification to result from Schottky-type diode properties of SWNTs with mixed chirality along the tube.