Conversion of acrylonitrile-based precursor fibres to carbon fibres

The physical and morphological aspects of the conversion of acrylonitrile-based precursors to carbon fibres are reviewed. The development of structure through the different stages of the process, namely precursor fibre formation, oxidative stabilization and carbonization, is described. The interactive contributions of process conditions and the precursor structures to the morphology and the properties of carbon fibres are discussed.     

Structure and properties of mesophase pitch carbon fibre with a skin-core structure carbonized under strain

Coal tar mesophase pitch fibres stabilized at 270° C to different extents were carbonized under strain by the constant load or constant length, using different heating rates, and further graphitized at 2500° C. Shallow and moderate stabilization provided a skin-core structure in the resultant fibres which exhibited higher orientation, tensile modulus, and better graphitizability after calcination at 1300° C and graphitization at 2500° C than deep stabilization. The tensile strength and modulus of the graphitized fibre was significantly improved through the strained carbonization when the stabilization was performed to a moderate extent. The strain tended to give an onion-like alignment in the fibre to improve the preferred orientation of carbon planes. Larger load and more rapid heating during carbonization modified the structure and properties of resultant fibres through a significant longitudinal elongation. The stabilization extent of pitch fibres governs the mobility or fusibility of mesogen molecules at the carbonization which allows their better alignment by the strain.     

Effiziente Herstellung von Kohlenstofffasern

Efficient production of carbon fibres using new technologies Innovative process technologies for carbonization of precursor fibres, which can substitute conventional oven technologies and raise the efficiency of carbon fibre production are presented. The process technologies are based on the substitution of convective heat transfer by microwave plasma or direct fiber heating. In microwave-assisted plasma treatment, the heating of the fibres is carried out both by microwave absorption in the fibre volume and energy input into the fibre surface by means of the plasma species. During electrical carbonization, the fibres are heated by means of an electrical current flow. The processes can be used separately, one after the other (also in combination with conventional furnace technology) or as hybrid processes.     

Carbon fibres from cellulosic precursors: a review

The focus of this review is primarily on the sequence of structural changes at micro and molecular level during carbonization of cellulosic fibres. The influence of various operational parameters such as the pyrolytic temperature and the stabilization agents also discussed as is the effect of the initial properties of the cellulose fibre on the final properties of the carbon fibre.     

Conversion of acrylonitrile-based precursors to carbon fibres

The progress of stabilization of two compositions of acrylic fibres with various orientations has been followed by a variety of techniques. The thermooxidative treatments for stabilization have been carried out in a continuous process and also in a batch process under free shrinkage, constant length and constant tension conditions. The morphological model of acrylic fibres consists of an alternating sequence of laterally ordered and laterally disordered regions along the fibre direction. This structure is consistent with the observations based on small-angle X-ray scattering of copper- impregnated precursor fibres and thermomechanical response, thermal stress development, calorimetry, wide- and small-angle X-ray scattering and sonic modu-lus measured at different extents of stabilization. Lateral as well as orientational order in these fibres can be increased markedly through a high-temperature deformation process prior to stabilization. An increase in perfection and extent of order is observed in the early stages of stabilization. There is also a simultaneous decrease in the orientation of the disordered phase at this stage and the extent of this decrease depends on the axial constraints imposed on the fibre. Little difference in the rate of stabilization is observed as measured by density or oxygen uptake for fibres with different extents of orientation, lateral order or restraint. Fibres containing itaconic add, a stabilization catalyst did show an increased rate of stabilization. Inferences have been drawn regarding additional research pertaining to achieving high order in precursor fibres, minimizing orientational relaxation during oxidative stabilization, and the techniques for monitoring the extents of the stabilization treatment and the changes in relevant morphological parameters.     

Production of carbon fibres from a pyrolysed and graphitised liquid crystalline cellulose fibre precursor

Regenerated cellulose fibres, spun from a liquid crystalline precursor, were pyrolysed at temperatures in the range 400–2,500?°C. Raman spectroscopy and X-ray diffraction showed that the degree of graphitisation of the fibre increased with increasing temperature. Electron microscopy, however, suggested that the fibres have a skin–core structure. This observation was confirmed by micro-Raman analysis, whereupon the ratio of the intensities of the D and G bands shows that the skin consists of a graphitised structure, whereas the core consists of significantly less graphitised material. The contributions of the graphitised skin and the inner core to the potential mechanical properties of the fibres were also assessed by following the position of the 2D Raman band during tensile deformation of the fibre. The Raman band shift rate against strain was used to evaluate the fibre modulus, which suggested a modulus of ~140 GPa for the skin and 40?GPa for the core, respectively. If this incomplete graphitisation could be overcome, then there is potential to produce carbon fibres from these novel precursor materials.     

Some factors for the high performances of mesophase pitch based carbon fibre

The tensile strength and Young's modulus of the carbon fibres prepared from naphthalene derived mesophase pitch were studied by varying the spinning temperature, heating rate and final temperature of the stabilization and graphitization temperatures to find the best properties obtainable from the particular pitch. The heating rate was very influential on the tensile strength of the fibre; a slow heating of 0.5° C min^–1, provided the highest strength, as high as 5 GPa at the optimum final temperature of stabilization. A higher or lower final temperature reduced the strength. Insufficient oxygen uptake or decomposition of oxygen groups at the surface of the fibre could induce defects, reducing the strength. In contrast, Young's modulus of the fibres was rather insensitive to preparation conditions. The carbonization and graphitization temperature influenced the mechanical properties as follows: the strength increased stepwise with the carbonization temperature, whereas the modulus increased sharply with the graphitization temperature. The structural factors most influential differed with these properties.     

Continuous Nanoscale Carbon Fibers with Superior Mechanical Strength

Continuous nanoscale carbon fibers can be developed by stabilization and carbonization of highly aligned and extensively stretched electrospun polyacrylonitrile copolymer nanofiber precursor under optimal tension. These carbon fibers, with diameters of tens of nanometers, are expected to possess a superior mechanical strength that is unlikely to be achieved through conventional approaches. This is because i) the innovative precursor, with a fiber diameter approximately 100 times smaller than that of conventional counterparts, possesses an extremely high degree of macromolecular orientation and a significantly reduced amount of structural imperfections, and ii) the ultrasmall fiber diameter also effectively prevents the formation of structural inhomogeneity, particularly sheath/core structures during stabilization and carbonization.     

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.     

Oxidative stabilization of acrylic fibres

When acrylic fibres are heat treated for various times at 220 to 250° C, they form dark, insoluble structures of uncertain chemical character which are inert to many strong oxidizing and reducing agents. The heat-treated fibres are, however, rapidly decoloured by warm alkaline hypochlorite solutions. When fibres which have undergone short-time heat treatment are subjected to the hypochlorite, incubation periods are observed before decolouration is noted; and a swollen acrylic network remains after decolouration is complete. The acrylic network is primarily unreacted precursor units save for a small amount of hydrolyzed material. The decoloured reaction is zero order, indicating a reaction at the surface. The rate of the decolouration reaction also increases with increasing duration of the stabilization heat treatment. In fibres which have undergone partial diffusion-controlled stabilization, a dark mantle surrounds a lightly coloured core. The rate of decolouration is unaffected as the decolouration interface passes from the mantle to the core, indicating that the decolouration reaction is not influenced by the occurance of any sequent reactions. The existence of the acrylic residue indicates that the prefatory reactions are continuing in both mantle and core during the course of stabilization.¹³C-NMR spectra of the acrylic residue show the same triad methine peak areas as those obtained on the untreated fibre; hence the stereoregularity of the nitrile groups has no influence on the rate of nitrile polymerization. The mechanisms of nitrile initiation and of decolouration are discussed. The residue obtained by sulphuric acid etch is different from that obtained by hypochlorite treatment. These results suggest that during the early-to-intermediate stages of stabilization, the fibre consists of interpenetrating networks of original material, i.e., fibre which has undergone only the prefatory reactions and fibre which has undergone the sequent reactions.     

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.     

Thermal stability and oxidation resistance of novel carbon-silicon alloy fibres

The effect of thermal treatment on the properties and structure of carbon-silicon alloy fibres produced from a novel silicon-containing carbon precursor is reported. The precursor, containing about 22 wt% Si, was melt spun into fibres and then oxidatively stabilized under different conditions to render the fibres infusible. The fibres were pyrolysed and heat treated to 1600 °C in inert atmosphere. The extent of stabilization was found to be critical to the development of mechanical strength of the fibres which varied with heat treatment temperature, showing a maximum at 1200 °C when the strength was 1.2–1.4 GPa. Moduli were low because of the lack of orientation of the carbon layer planes along the fibre axis. The maximum strength and the thermal stability at high temperatures is considerably reduced if the fibres are excessively oxidized at the stabilization stage. Optimally stabilized fibres show a drop in strength at 1300 °C but this stabilizes at about 600 MPa over the range 1300–1600 °C. These strengths are remarkably good considering the low modulus which is due to the quite high failure strains. The fibres can show excellent resistance to oxidation if given an initial short exposure to oxygen at high temperature. This is considered to be due to an imperceptible layer of silica.     

Scanning tunnelling microscopy study of activated carbon fibres

Scanning tunnelling microscopy (STM) has been used to study isotropic pitch-based carbon fibres before and after steam activation. The results show that the present carbon fibre precursor exhibits a particulate surface which is very favourable for the formation of activated carbon fibre. After activation, the carbon fibre surface becomes much more porous and rougher, and the mesopores are evidently present on the surface. Because the scale is down to atomic resolution, the STM observations offer direct evidence for the existence of micropores on the surface of the activated carbon fibres. In addition, the surface textures of both fibres are presented and discussed.     

Preparation of hollow carbon nanospheres via explosive detonation

Hollow carbon nanospheres were prepared via a rapid detonation technique, by using negative-oxygen balance explosive trinitrotoluene and nickel powder as starting materials and inorganic acid as solvent. The carbon/metal nanocomposite particles precursor with core-shell structure was engendered firstly during detonation, and then the metal nickel core was dissolved through inorganic acid to attain the hollow carbon nanospheres. High-Resolution Transmission Electron Microscope, X-ray diffraction and Raman spectrum were used to characterize the precursor and the as-synthesized samples respectively. The results show that the external diameter of the hollow carbon nanospheres is 25-150 nm and the thickness of the wall is about 2-10 nm. The surface of hollow carbon nanosphere displays multilayer wall in structure with 0.35 nm space between the layers. Based on the experimental results, possible formation mechanism was also proposed.     

磷掺杂中空碳球的制备及其电容性能EI北大核心CSCD

以酚醛预聚体和苯乙烯为原料通过水热法一步合成中空聚合物球(HPS),再以三氯化磷为反应剂通过傅-克反应对HPS处理得到含磷交联聚合物,经高温炭化和KOH活化制备磷掺杂中空碳球(AP-HCS)。采用FT-IR,TG,SEM,TEM,Raman,BET,XPS等手段对含磷聚合物和碳材料的组成、结构与形貌进行表征,测试碳材料在1 mol/L H2SO4介质中的电容性能。结果表明:AP-HCS的比表面积可达2177 m2/g,在1 A/g电流密度下,比电容为288 F/g,5 A/g电流密度下经循环充放电5000次后比电容值仍能保持88.9%,具备良好的电容性能。     

Blending mesophase pitch to improve its properties as a precursor for carbon fibre Part 1 Blending of PVC pitch into coal tar and petroleum-derived mesophase pitches

The blending of mesophase pitch with isotropic PVC pitch was studied to improve their properties as a precursor for carbon fibre. PVC pitch prepared at 420° C which remained almost isotropic was found to be miscible with coal tar-derived mesophase pitch without reducing the anisotropic content and spinnability. The tensile strength of pitch fibres remained unchanged by the blending; however, the reactivity for stabilization was enhanced. The resultant carbon fibres from the blend exhibited slightly higher tensile strength. In contrast, petroleum-derived mesophase pitch failed to dissolve the PVC pitch, leaving a number of isotropic droplets. The structural factors of mesophase pitches with regard to their compatibility with PVC pitches are briefly discussed.     

Effects of fibre content on mechanical properties and fracture behaviour of short carbon fibre reinforced geopolymer matrix composites

Geopolymer matrix composites reinforced with different volume fractions of short carbon fibres (C_f/geopolymer composites) were prepared and the mechanical properties, fracture behaviour and microstructure of as-prepared composites were studied and correlated with fibre content. The results show that short carbon fibres have a great strengthening and toughening effect at low volume percentages of fibres (3·5 and 4·5 vol.%). With the increase of fibre content, the strengthening and toughening effect of short carbon fibres reduce, possibly due to fibre damage, formation of high shear stresses at intersect between fibres and strong interface cohesion of fibre/matrix under higher forming pressure. The property improvements are primarily based on the network structure of short carbon fibre preform and the predominant strengthening and toughening mechanisms are attributed to the apparent fibre bridging and pulling-out effect.     

Structure of mesophase pitch-based carbon fibres

The structure of five samples of commercially available carbon fibres with ultra-high modulus produced from mesophase pitch was studied by the complementary techniques of high resolution electronmicroscopy, X-ray diffraction and transverse magnetoresistance effect. The fibres with high strength and elongation to failure were found to be composed of turbostratic carbon structure, which was different from the three-dimensional graphite structure in ultra-high modulus carbon fibres. Transmission electron microscope examination revealed that the mesophase pitch-based fibres with high strength have a basic structure unit with folded sheets arranged nearly parallel to the fibre axis similar to those of high modulus carbon fibres produced from PAN. The present fold structure was suggested to contribute consequently to the lower graphitizability of the fibres and to the strong effects on the fibre strength. By controlling the microstructure, it is expected that the crystallographic as well as the mechanical properties could be improved significantly even from the same kind of precursor materials such as mesophase pitch.     

Scanning electron microscopic study of acacia and eucalyptus wood chars

SEM studies of acacia and eucalyptus wood chars, prepared under different carbonization conditions, were undertaken to provide information on what happens in the transformation of wood to chars. The material normally lost as volatiles contributes totally to the formation of pores, cracks and pyrolytic carbon. Both woods exhibited similar devolatilization behaviour in pore structure development, crack formation and pyrolytic carbon deposition, showing a decrease in pore size with an increase in carbonization temperature and cracks/voids formation during rapid carbonization at higher temperatures (i.e. 800–1050 °C). Slow carbonization led to pyrolytic carbon deposition in resulting wood char structures and did not disturb the fibrous nature and cell structures of the wood, even at a high carbonization temperature of 1200 °C. Prolonged heating at carbonization (slow) temperatures of 800 and 1000 °C caused sintering of the adjacent fibres resulting in the formation of compacted mass.     

Synthesis of carbon hollow particles by a simple inverse-emulsion method

Morphology-controlled carbon hollow particles have been successfully prepared via carbonization of the resorcinol-formaldehyde (RF) hollow particles synthesized from O/W/O inverse-emulsion system. Various morphologies of carbon hollow particles such as hollow spheres, bowl-like structure, and capsules were tailored by adjusting the pH values of RF precursor. The obtained carbon hollow particles exhibited similar microporous properties with specific surface areas of 526-659 m² g^− 1 and pore volumes of 0.26-0.43 cm³ g^− 1. Based on these results, it was proposed that the low initial pH value of RF precursor and the stability of inverse-emulsion system were crucial in fabricating morphology-controlled carbon hollow particles.