Carbon fibers modified with carbon nanotubes

Carbon nanotubes were used to modify a polyacrylonitrile (PAN) polymer solution before the manufacture of the carbon fiber precursor. The modified PAN fibers were spun from a dimethylformamide solution containing a small amount of single-walled carbon nanotubes. The fibers were characterized by thermogravimetry and optical and scanning electron microscopy. Structure, morphology, and selected properties of the composite polymeric fibers and the fibers after carbonization are characterized. The mechanical properties of the fibers are examined. It is found that nanotubes in the PAN solution have a strong tendency to form agglomerates that inhibit suitable macromolecular chain orientation of the carbon fiber precursor. Fibers manufactured from such a solution have similar mechanical properties to those from a pure PAN precursor, and after carbonization the resultant carbon fibers are very weak. A comparison of pure carbon fibers and those containing nanotubes reveals slight differences in their structural ordering.     

化学改性对PAN原丝及预氧纤维结构性能的影响

在各种温度和时间条件下，将本实验室纺的KPAN原丝进行连续化学改性处理，借助IR光谱、DSC、TG、X射线衍射等分析方法，选出了最佳的改性温度和改性时间，并对化学改性的原丝、预氧丝的性能进行了初步探讨。得出结论：化学改性能缩短预氧环化时间，缓解纤维的放热和吸热，优质原丝应具有高纯度、高强度、高取向度性质。本课题希望通过对原丝进行化学改性的方法，获取具有在商业上有广泛应用前景的预氧化纤维和炭纤维。     

Carbon nanofibers prepared by a novel co-extrusion and melt-spinning of phenol formaldehyde-based core/sheath polymer blends

A novel route based on the solvent-free core/sheath melt-spinning of polypropylene/(phenol formaldehyde–polyethylene) [PP/(PF–PE)] to prepare the carbon nanofiber (CNF) has been demonstrated in this study. The approach consists of three main steps: co-extrusion of PP (core) and a polymer blend of PF and PE (sheath), followed by melt-spinning, to form the core/sheath fiber, stabilization of core/sheath fiber to form the carbon fiber precursor, and carbonization of carbon fiber precursor to form the final CNF. Both scanning electron microscopy and transmission electron microscopy images reveal long and winding CNF with diameter 100–600 nm and length greater than 80 μm. With a yield of ~45% based on its raw material PF, the CNF exhibits regularly oriented bundles which curl up to become rolls of wavy long fibers with clean and smooth surface. Results from X-ray diffractometry, Raman spectroscopy, and selected area electron diffraction pattern further reveal that the CNF exhibits a mixed-phase carbon material with graphitic particles embedded homogeneously in an amorphous carbon matrix.     

沥青基活性碳纤维研究：1.沥青纤维的不熔化处理

利用热分析，红外光谱研究了通用型沥青纤维的不熔化机理，同时对影响不熔化反应的诸因素进行了实验研究。结果表明，不熔化处理使沥青纤维碳氧基团含量增大，形成碳氧网络，使纤维熔点提高，强度上升。不熔化温度，时间，氧化剂深度及升温速率是不熔化处理的主要影响因素，它们影响不熔化纤维的结构与性能，影响沥青繁华纤维的碳化和活化。     

碳纤维制造过程中径向差异表征及演变机理

为优化PAN基碳纤维结构,采用AES表征PAN纤维在低温碳化与高温碳化后C,N,O沿纤维径向的分布,并用以阐明预氧化碳化过程径向差异的形成机理.结果表明:预氧丝径向结构不均匀,由外向内氧化程度降低;预氧时物理阻隔与化学阻隔导致径向形成氧浓度梯度,热物理传递与化学反应放热导致径向形成温度梯度.低温碳化时,热物理传递与化学反应放热形成温度梯度加剧了预氧时的径向差异;纤维分3部分,最外层氧含量低,由氧化程度高的预氧皮层外部强烈脱氮脱氧形成,最内层由氧化程度低的预氧芯层转化而成;中间是过渡层,一部分由氧化程度较高的预氧皮层内部少量脱氧脱氮而成,氧含量高,而后过渡到预氧程度低的低含氧量芯部.高碳丝径向组分差异变小,纤维分两部分,外层厚度仅为纤维直径的10%,是碳含量逐渐降低的过渡性皮层,其余部分为组成均一的芯层.     

The influences of silicone finishes on thermooxidative stabilization of PAN precursor fibers

The influences of functional polysiloxanes bearing epoxy or amino groups on the thermooxidative stabilization process of the PAN precursor fibers were studied. Structural changes were investigated by FT-IR spectroscopy. It was found that formation of the conjugated ladder structure in the precursor fiber was promoted by the functional polysiloxanes. Meanwhile heat releasing in the thermooxidative stabilization process was depressed. It seems that the coatings of the functional polysiloxanes on the fibers retarded oxygen diffusion into the PAN precursor fibers. The functional polysiloxanes did not affect carbonization in an inert atmosphere following the thermooxidative stabilization process.     

低温炭化温度梯度对聚丙烯腈预氧纤维结构演变及碳纤维性能的影响

聚丙烯腈(PAN)预氧纤维在低温炭化阶段经热裂解重组而转化为具有乱层石墨结构雏形的低温炭化纤维,此阶段的温度调控对最终碳纤维的结构与性能有着重要影响。采用¹³C固体核磁共振谱图(¹³C-NMR)、拉曼光谱(Raman)、X射线衍射(XRD)和力学性能分析等手段,研究预氧纤维在低温炭化阶段的反应进程、温度梯度调控对预氧纤维的结构演变和碳纤维结构及性能的影响。结果表明:PAN预氧纤维在低温炭化过程中,经450℃热处理后碳结构的支链化程度达到最大值0.99,当处理温度达到550℃后,以芳环链段的重组交联为主要反应。低温炭化温度梯度影响预氧纤维的结构演变进程,当采用350—450—650℃的梯度升温模式时,先经450℃处理的低碳纤维中—C—C基团的¹³C-NMR位移最大,表明纤维内的支化交联反应最多,再经650℃处理的纤维d₀₀₂以及相应高碳纤维的I_A/I_G达到最大,说明其无定形碳相对含量最多,因而最终碳纤维的力学性能最差;当采用350—550—650℃的梯度升温模式时,纤维内裂解与重组交联反应有序开展,低碳和高碳纤维的碳结构更优,最终碳纤维的致密性及力学性能得到提升。     

聚合物共混制备纳米和多孔碳纤维及性能研究

聚丙烯腈(PAN)和聚甲基丙烯酸甲酯(PMMA)共混膜的结构和尺寸可由两组分比例和分子量调整。以PAN为碳前驱体,PMMA为热分解聚合物,并控制m(PAN)/m(PMMA)为30/70和70/30,通过湿法纺丝制备了PAN/PMMA共混纤维。以m(PAN)/m(PMMA)为30/70和70/30的共混纤维为原丝经碳化后获得了纳米碳纤维(CNFs)和多孔碳纤维(PCFs)。利用扫描电镜观察了所得CNFs和PCFs的形貌,发现单根CNFs的直径为50～150nm,PCFs中孔的直径为0.1～1μm。由CNFs和PCFs的拉曼光谱分析了不同碳化温度对CNFs和PCFs石墨化程度的影响,结果表明随碳化温度升高,石墨化程度也增加,同时电导率也随之提高。     

Carbon nanofibers produced from modified electrospun PAN/hydroxyapatite precursors as scaffolds for bone tissue engineering

In the current study we have proposed a method to obtain a carbon/HAp bioactive nanofibrous scaffold. The modified carbon nanofibrous nonwoven' fabrics were obtained by the use of electrospinning and subsequent stabilization and carbonization processes. The modified with HAp powder nanofibrous PAN nonwovens were thermally stabilized using a multi-stage process in the temperature ranging from 100 °C to 300 °C in an oxidative environment and then carbonized at 1000 °C in argon atmosphere. The changes of properties of composite precursor membranes taking place during stabilization and carbonization processes were investigated using the methods of: DSC, TGA, FTIR, SEM, EDX, WAXD and mechanical tests. Bioactivity was determined by assessing the formation of crystalline apatite on the surface of membranes upon immersion in Simulated Body Fluid (SBF). The FTIR, SEM and WAXD investigation clearly prove that hydroxyapatite added to the electrospinning solution was present also in composites nanofibrous nonwovens after stabilization and carbonization process. It was found that due to HAp addition: the significant decrease of fibers average diameter occurs and that the average pore size for modified membranes is smaller than for the unmodified one. On the other hand it was shown that the ceramic additive protects fibers from mass reduction during the stabilization treatment. Finally a drastic increase of mineralization activity of nCF/HAp scaffolds as compared to their nCF counterparts has been proved.     

原丝浸渍硼酸对炭纤维结构与性能的影响

聚丙烯腈原丝(3K,1.1dtex)用硼酸进行浸渍,再分别进行间歇式预氧化和炭化。借助元素分析、X射线衍射、红外分析和扫描电镜等表征手段和力学性能测试,研究了硼酸浸渍对原丝结构、预氧化炭化过程及炭纤维结构与性能的影响。结果表明,硼能进入到原丝的内部,但只是物理吸附,在浸渍过程中不改变原丝结构,在预氧化过程,硼钝化了纤维的环化、氧化反应,起始温度推迟2.5℃。在炭化过程中,硼促进了纤维结构的有序化和完善,炭纤维的强度和模量都得到了提高。硼质量分数为1.376×10-4,张力为108 g时,炭纤维抗拉强度为2544 MPa,较同等条件未渗硼的提高约90%。     

Carbon Fibers from Polyethylene-Based Precursors

Polyethylene fibers are attractive as carbon fiber precursors due to their high carbon content and ease of manufacture. Also, highly ordered and oriented fibers with extraordinary physical and mechanical properties are available today. However, being thermoplastic fibers, they soften or melt at a fairly low temperature, losing their fiber form. These precursors have to be stabilized by introducing cross links in them so that they can withstand the higher temperatures of carbonization. Heating in a sulfuric acid bath was investigated as a possible means of stabilizing these fibers. The process of stabilization was studied using several characterization techniques, such as thermal analyses (DSC and TGA), color change, tensile properties, X-ray diffraction and electron microscopy. The fibers had a tendency to shrink to a great extent and the tension had a major role during the process of sulfonation. Some of the stabilized fibers were carbonized and their properties were evaluated     

中间相沥青基碳/碳复合材料的组织与性能

以3K PAN基碳纤维为增强体,以中间相沥青为基体前驱体,采用压力浸渍-碳化工艺制备出2D中间相沥青基碳/碳复合材料.研究分析了材料的偏光组织结构、弯曲性能及弯曲断口形貌,结果表明:基体碳的组织结构随碳化压力的不同而变化,低压时以小域组织为主,高压时以广域流线型组织为主;材料的抗弯强度、密度随碳化压力的增加而增高,最高抗弯强度可达278MPa;断裂特征与材料的密度、界面结合状况有关,密度较高、界面结合适中时,弯曲断口以纤维断裂、纤维拔出为主,材料具有韧性断裂特征.     

木质素制备低成本碳纤维的研究进展

随着石油资源的日益短缺,生物质资源的开发和利用显得尤为重要。木质素作为第二大天然高分子,来源广泛,价格低廉,其高达60%以上的含碳量,是制备碳纤维的理想原料。因此,基于木质素基碳纤维重要的应用价值和广阔的市场前景,文中详细综述了木质素为前驱体制备碳纤维的研究进展。木质素基碳纤维的制备包括:木质素的提取、前驱体的制备、原丝的预氧化和氧化原丝的碳化阶段,重点分析了木质素作为碳纤维前驱体存在的不足及解决方法。并对今后该领域的研究方向进行了展望。     

Influence of heat treatment conditions on the structure of hollow carbon fibers prepared from solid PVA fibers using iodine pretreatment

The influence of heating conditions on the structure of hollow carbon fibers (H-CFs) during their fabrication from solid poly(vinyl alcohol) (PVA) fibers is reported. The hollow structure of PVA-derived carbon was formed by selective iodination and subsequent stabilization of precursor PVA fiber close to the fiber surface followed by carbonization. The broadening of X-ray diffraction peaks due to disorder and the small size effects of the (002) plane were strongly reduced by increasing the heat treatment temperature (HTT) from 800 to 3000 °C, but the asymmetric shape of (10) and (110) reflections suggests turbostratic layer stacking. The increase of HTT to 3000 °C increased the degree of graphitization evident from the decrease of interplanar spacing from 0.360 to 0.338 nm and the intensity ratio of D to G bands in Raman spectra from 0.93 to 0.58. The crystallite size, orientation and electrical conductivity of the resultant H-CFs were also improved with higher HTT. Besides, the size of the hollow core was also influenced by the HTT and both wall thickness and carbon yield decreased with higher HTT. The core of the H-CFs could be easily filled with polymer by bulk polymerization of monomer.     

碳纤维碳化特征的SAM微观分析

本文应用SAM方法检测了由不同工艺条件造成的碳纤维的污染和产生的缺陷。对任意一根碳纤维,其表面和内部的碳俄歇峰、峰高和峰形都有差异,这一差异导致碳沿径向分布不均匀,并影响到碳纤维的力学性能。采用SAM的方法可监测予氧化和碳化过程中的工艺参数以便提高碳纤维的质量。      

由液化物树脂制备多孔碳纳米纤维及其表征

以壳粉为原料,在碱性条件下制备液化物树脂(LPF),经静电纺丝、固化、碳化得到多孔碳纳米纤维(PCNF)。探讨了聚乙烯醇(PVA)用量对纺丝液特性及纤维形貌的影响。同时,采用傅里叶变换红外光谱(FTIR)、热重分析仪(TG)、扫描电子显微镜(SEM)、X射线衍射仪(XRD)、全自动比表面积及孔隙分析仪(BET)等方法对不同碳化温度下的样品进行表征。结果表明:少量PVA可以明显提高LPF的纺丝性,且随PVA用量的增加,纤维的形貌更规整、直径更小;随着碳化温度的升高,LPF/PVA纤维逐渐裂解,多数官能团消失,基体为多苯稠环结构;同时,层间距d_((002))逐渐减小,平面尺寸L_c和L_c/d_((002))增加,纤维内部的类石墨结构逐渐向更规整、有序的石墨微晶结构转变;当碳化温度为800℃时,LPF/PVA的含碳量达55%以上,随着PVA用量的增加,纤维的比表面积明显增大且多以微孔为主,当PVA用量为8%时,得到比表面积为590m~2/g的多孔碳纳米纤维。     

Electrical properties of electrospun carbon nanofibers

Electrospun carbon nanofibers (ECNs) were prepared through stabilization and carbonization of electrospun polyacrylonitrile nanofibers as the precursor, and their morphological, structural, and electrical properties were evaluated. Temperature dependencies of resistivity of ECNs carbonized at several temperatures were investigated. The character of the temperature dependencies of resistivity was typical for semiconducting materials. The values of corresponding activation energies were obtained for ECN samples carbonized at different temperatures, and the results showed that the activation energy of ECNs decreased with the increase of carbonization temperature.     

SiCO-doped carbon fibers with unique dual superhydrophilicity/superoleophilicity and ductile and capacitance properties

Silicon oxycarbide (SiCO) glass-doped carbon fibers with an average diameter of 163 nm were successfully synthesized by electrospinning polymer mixtures of preceramic precursor polyureasilazane (PUS) and carbon precursor polyacrylonitrile (PAN) into fibers then converting to ceramic/carbon hybrid via cross-linking, stabilization, and pyrolysis at temperatures up to 1000 °C. The transformation of PUS/PAN polymer precursors to SiCO/carbon structures was confirmed by EDS and FTIR. Both carbon and SiCO/carbon fibers were amorphous and slightly oxidized. Doping with SiCO enhanced the thermal stability of carbon fibers and acquired new ductile behavior in the SiCO/carbon fibers with significantly improved flexibility and breaking elongation. Furthermore, the SiCO/carbon fibers exhibited dual superhydrophilicity and superoleophilicity with water and decane absorbing capacities of 873 and 608%, respectively. The cyclic voltammetry also showed that SiCO/carbon composite fibers possess better capacitor properties than carbon fibers.     

High‐Modulus Low‐Cost Carbon Fibers from Polyethylene Enabled by Boron Catalyzed Graphitization

Currently, carbon fibers (CFs) from the solution spinning, air oxidation, and carbonization of polyacrylonitrile impose a lower price limit of ≈$10 per lb, limiting the growth in industrial and automotive markets. Polyethylene is a promising precursor to enable a high‐volume industrial grade CF as it is low cost, melt spinnable and has high carbon content. However, sulfonated polyethylene (SPE)‐derived CFs have thus far fallen short of the 200 GPa tensile modulus threshold for industrial applicability. Here, a graphitization process is presented catalyzed by the addition of boron that produces carbon fiber with >400 GPa tensile modulus at 2400 °C. Wide angle X‐ray diffraction collected during carbonization reveals that the presence of boron reduces the onset of graphitization by nearly 400 °C, beginning around 1200 °C. The B‐doped SPE‐CFs herein attain 200 GPa tensile modulus and 2.4 GPa tensile strength at the practical carbonization temperature of 1800 °C.     

Novel high performance fibres

The need for high performance materials for aerospace and other structural engineering applications has led to the development of carbon fibres. At IIT Delhi, an attempt is being made to develop acrylic precursor fibres for manufacturing carbon fibres indigenously. The present study deals with the structural regulation of acrylic precursors during thermo-oxidative stabilization and subsequent carbonization. A new microporous acrylic fibre-acrysorb has also been developed which has high water imbibition and moisture sorption properties. Production of X-ray opaque and antistatic polyester fibres has also been high-lighted.