Kohlenstoff-Fäden und deren Verwendung in Verbundwerkstoffen

Carbon fibres and carbon fibre composite materials. Carbon fibres are a new reinforcement for high performance composite materials. Their most interesting property is the high Young's modulus. The tensile strength of carbon fibres exceeds 200 kp/mm², the Young's modulus 50,000 kp/mm². Carbon fibre reinforced plastics are mainly used where high stiffness is needed. In most cases, carbon fibre composite components are manufactured by filament winding burt also by lamination and moulding. Data about the different processes for the production of carbon fibres as well as mechanical properties are given. In addition to the different manufacturing methods of composite materials a survey about the today applications is given.     

Carbon/Carbon – an inverse composite structure

Carbon/carbon composites are a type of material, which combines the refractory properties of carbon with the high strength and stiffness of carbon fibres. Although one could not expect a reinforcement by the combination of a carbon matrix with carbon fibres the fibre properties can be used. Additionally the material shows a pseudoplastic fracture behaviour in spite of its ceramic nature. Explanations for this inverse behaviour in comparison to other composite structures will be presented including mechanical viewpoints, interactions at the interface between fibre and matrix, their influence to the fracture characteristics and micromechanical behaviour as well as the interactions between modulus and microstructure. Furtheron examples for some industrial applications are described.     

Amorphous carbon fibres from linear low density polyethylene

Carbon fibres with good mechanical properties have been produced from linear low density polyethylene (LLDPE). The melt-spun LLDPE fibres were made infusible by treatment with chlorosulphonic acid. The cross-linked fibres were pyrolysed at temperatures between 600 and 1100 °C under tension, in a nitrogen atmosphere, within 5 min. Carbon fibres prepared at 900 °C had a tensile strength of 1.15 GPa and a Young's modulus of 60 GPa. The elongation at break was extremely high, up to 3%. The carbon yield of the process was 72 to 75%.     

Anorganische Fasern. Herstellung,Eigenschaften und Verwendung

Inorganic Fibres – Fabrication, Properties and Application Glass- and carbon fibres are preferred reinforcement materials for composites with polymer matrix. Basing on an analysis of their properties it is shown that other inorganic fibres can combine the advantages of both, and avoid their disadvantages. Boron-, siliconcarbide- and alumina-fibres are discussed in detail. The boron fibre has a YOUNG's modulus up to 45 MN/m² and a strength of 3000–4000 MN/m² as well as high compressive and shear strength. Therefore the boron fibres are superior to the carbon fibres as high modulus reinforcement material. The disadvantages of the boron fibres are their complicated fabrication process (chemical vapour deposition on a tungsten monofilament), and their only availability in form of monofilaments with diameters of at least 60 μm. The boron fibre recristallizes at 6000 °C and reacts also with the tungsten substrat. Thus, its application at elevated temperatures is limited. The SiC-fibre shows the same mechanical properties as the boron fibre but it can be fabricated by chemical vapour deposition also on a carbon monofilament. The advantages are the chemical compatibility with carbon substrat and the resistance against oxidation. The disadvantage is the higher density compared with that of boron (3,5 against 2,6 · 10³ kg/m³) Carbon yarns (with 10 000 monofilaments of 10 μm diameter) with SiC coatings of 0,5 μm can be seen as an alternative to the relatively thick SiC-monofilaments with 60 μm diameter. The advantage of such coated carbon yarn is a better applicability in fibre reinforced composite materials. There exists a further alternative preparation process for SiC-yarn, namely the spinning of polycarbosilanes with subsequent formation of SiC by pyrolysis treatment. Al₂O₃-fibres are chemically inert against most oxidic and metallic matrix materials, and promises to be candidate reinforcement materials for aluminium. They can be prepared by melt-spinning process as well as by a hydrolysis-process starting from aluminium organic compounds with subsequent heat treatment for thermal decomposition. The properties of all these fibre materials are compared with those of glass-, polyamid- and carbon-fibres as well as with metal wires.     

Effective reinforcement in carbon nanotube-polymer composites

Carbon nanotubes have mechanical properties that are far in excess of conventional fibrous materials used in engineering polymer composites. Effective reinforcement of polymers using carbon nanotubes is difficult due to poor dispersion and alignment of the nanotubes along the same axis as the applied force during composite loading. This paper reviews the mechanical properties of carbon nanotubes and their polymer composites to highlight how many previously prepared composites do not effectively use the excellent mechanical behaviour of the reinforcement. Nanomechanical tests using atomic force microscopy are carried out on simple uniaxially aligned carbon nanotube-reinforced polyvinyl alcohol (PVA) fibres prepared using electrospinning processes. Dispersion of the carbon nanotubes within the polymer is achieved using a surfactant. Young's modulus of these simple composites is shown to approach theoretically predicted values, indicating that the carbon nanotubes are effective reinforcements. However, the use of dispersant is also shown to lower Young's modulus of the electrospun PVA fibres.     

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.     

Chemical vapor deposition of titanium nitride on carbon fibres as a protective layer in metal matrix composites

The significance of carbon fibres for reinforcing metals has increased in the last years, because of their excellent mechanical properties. However, to avoid the weakening reaction during MMC fabrication between the fibre and the liquid metal, a protective coating has to be applied. Continuous carbon fibre roving with 6000 filaments were coated with TiN by thermal induced chemical vapour deposition (CVD) using a gas mixture of TiCl₄, N₂ and H₂ as a precursor. The deposition process in the reactor was simulated by a modified Phoenics-CVD software program using a 2D-axisymmetric model. Carbon fibres reinforced magnesium matrix composites are fabricated by a pressure infiltration casting process. The mechanical properties of the MMCs can be used to demonstrate the efficacy of the coated fibre approach. The rule of mixture is realized to 98% for the coated fibre, and only 48% for the uncoated system. The infiltration pressure during the processing of composites was lowered from 10 to 1 MPa for the TiN coated system.     

Conversion of acrylonitrile-based precursors to carbon fibres

The effects of stabilization conditions on the formation of a consolidated carbon fibre structure from two acrylonitrile-based precursor fibres, one containing itaconic acid as comonomer and the other a commercial precursor, have been studied. The progression of changes in elemental composition and properties such as sonic modulus, electrical resistance and density in a continuous, low temperature (1200° C) carbonization process are reported for the first time. A criterion based on attaining a composition dependent critical density in stabilization is proposed for avoiding the formation of a hollow core in carbon fibres processed continuously at reasonably rapid rates. Aspects related to the development of open and closed micropores in the carbon fibre structure and the possible mechanisms for the formation of a hollow core in carbonization are also discussed.     

Small-scale heat-treatment of rayon precursors for stress-graphitization

A method for the routine stabilization and heat-treatment of rayons to prepare them for carbonization and graphitization has been developed. After treatment by this method, which employs either air or pure oxygen, the yarn is suitable for fast, continuous stress-carbonization and stress-graphitization. Routine processing conditions yield “carbon fibres” with a filament modulus of fifty million psi. This procedure, which produces a carbon yield between 16 and 21 %, has been successfully applied to rayons produced by five different manufacturers. The steps necessary to accommodate the process to different sources of precursor materials are discussed, and the final product properties obtained are presented.     

On Young’s modulus of multi-walled carbon nanotubes

Carbon nanotubes (CNTs) were discovered by Iijima in 1991 as the fourth form of carbon. Carbon nanotubes are the ultimate carbon fibres because of their high Young’s modulus of ≈ 1 TPa which is very useful for load transfer in nanocomposites. In the present work, CNT/Al nanocomposites were fabricated by the powder metallurgy technique and after extrusion of the nanocomposites bright field transmission electron microscopic (TEM) studies were carried out. From the TEM images so obtained, a novel method of ascertaining the Young’s modulus of multi-walled carbon nanotubes is worked out in the present paper which turns out to be 0·9 TPa which is consistent with the experimental results.     

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.     

Polymere Nanoverbundwerkstoffe: Chancen,Risiken und Potenzial zur Verbesserung der mechanischen und physikalischen Eigenschaften

Polymer Nanocomposites: chances, risks and potential to improve the mechanical and physical properties The development of nano‐particle reinforced polymer composites is presently seen as one of the most promising approaches of materials for future engineering applications. The unique properties of at least some types of the nano‐particles (e.g., Carbon Nanotubes or Carbon Black) and the possibility of combining them with conventional materials and reinforcements (e.g., carbon‐, glass‐ or aramid‐fibres), has led to an intense research in the field of nanocomposites. Especially Carbon Nanotubes have shown a high potential for an improvement of the properties of polymers. Besides an increase in the electrical conductivity even at an extremely low nanotube content the improvement of the mechanical properties is of special interest. The exceptionally high aspect ratio in combination with a low density and a high strength and stiffness make the carbon nanotubes a most interesting candidate for a reinforcement of polymeric materials. The electrical, mechanical and thermal properties of Carbon Nanotubes open up new perspectives also for their use as multifunctional materials, e.g. conductive polymers with improved mechanical performance. The problem, however, is to transfer the interesting potential regarding the mechanical, thermal and electrical properties to the polymer. Two main issues have to be addressed for a significant improvement of the properties of polymers by adding Carbon Nanotubes: the interfacial bonding and, especially also, a proper dispersion of the individual Carbon Nanotubes in the polymeric matrix.     

中介相沥青基碳纤维的性能

本文较系统地论述了中介相沥青基碳纤维的五种优异性能，包括力学性能、耐高温性能、热导及电导性能、尺寸稳定性能及编织性能；探讨了杨氏模量、热导率与电阻率之间的定性或定量关系；还综述了中介相沥青原料、温度和纤维形状对碳纤维电阻率的重要影响；指出中介相沥青基碳纤维是综合性能最优的高性能纤维之一。     

Oberflächenbehandlung von Kohlenstoffasern und mechanische Eigenschaften von Laminaten

Surface Treatment of Carbon Fibres and Resulting Composite Properties In composites carbon fibres are used as reinforcing fibres with thermosetting and thermoplastic resins as martices. These carbon fibres differ strong in their micro-structure and therefrom in fibre properties. To achieve sufficiant composite properties special carbon fibre surface treatment methods are necessary. This paper describes a systematic study on oxidative surface treatment of carbon fibres by wet-, dry- and anodic oxidation. Further investigations by matrix variation show us the influence of matrix strength on the mechanical composite properties. Finally it is shown that in case of impact load composite fracture behaviour is controlled only by the fibre itself.     

Development of sizing-free multi-functional carbon fibre nanocomposites

High quality multi-walled carbon nanotubes (CNTs) grown at high density using a low temperature growth method are used as an alternative material to polymer sizing and is utilised in a series of epoxy composites reinforced with carbon fibres to provide improved physical and electrical properties. We report improvements for sizing-sensitive mechanical and physical properties, such as the interfacial adhesion, shear properties and handling of the fibres, whilst retaining resin-infusion capability. Following fibre volume fraction normalisation, the carbon nanotube-modified carbon fibre composite offers improvements of 146% increase in Young’s modulus; 20% increase in ultimate shear stress; 74% increase in shear chord modulus and an 83% improvement in the initial fracture toughness. The addition of CNTs imparts electrical functionalisation to the composite, enhancements in the surface direction are 400%, demonstrating a suitable route to sizing-free composites with enhanced mechanical and electrical functionality.     

Effect of fibre coating and geometry on the tensile properties of hybrid carbon nanotube coated carbon fibre reinforced composite

Hierarchically structured hybrid composites are ideal engineered materials to carry loads and stresses due to their high in-plane specific mechanical properties. Growing carbon nanotubes (CNTs) on the surface of high performance carbon fibres (CFs) provides a means to tailor the mechanical properties of the fibre–resin interface of a composite. The growth of CNT on CF was conducted via floating catalyst chemical vapor deposition (CVD). The mechanical properties of the resultant fibres, carbon nanotube (CNT) density and alignment morphology were shown to depend on the CNT growth temperature, growth time, carrier gas flow rate, catalyst amount, and atmospheric conditions within the CVD chamber. Carbon nanotube coated carbon fibre reinforced polypropylene (CNT-CF/PP) composites were fabricated and characterized. A combination of Halpin–Tsai equations, Voigt–Reuss model, rule of mixture and Krenchel approach were used in hierarchy to predict the mechanical properties of randomly oriented short fibre reinforced composite. A fractographic analysis was carried out in which the fibre orientation distribution has been analyzed on the composite fracture surfaces with Scanning Electron Microscope (SEM) and image processing software. Finally, the discrepancies between the predicted and experimental values are explained.     

Multifunctional brushes made from carbon nanotubes

Brushes are common tools for use in industry and our daily life, performing a variety of tasks such as cleaning, scraping, applying and electrical contacts. Typical materials for constructing brush bristles include animal hairs, synthetic polymer fibres and metal wires (see, for example, ref. 1). The performance of these bristles has been limited by the oxidation and degradation of metal wires, poor strength of natural hairs, and low thermal stability of synthetic fibres. Carbon nanotubes, having a typical one-dimensional nanostructure, have excellent mechanical properties, such as high modulus and strength, high elasticity and resilience, thermal conductivity and large surface area (50-200 m2 g(-1)). Here we construct multifunctional, conductive brushes with carbon nanotube bristles grafted on fibre handles, and demonstrate their several unique tasks such as cleaning of nanoparticles from narrow spaces, coating of the inside of holes, selective chemical adsorption, and as movable electromechanical brush contacts and switches. The nanotube bristles can also be chemically functionalized for selective removal of heavy metal ions.     

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.     

A review of the development of three generations of small diameter silicon carbide fibres

Three generations of small diameter ceramic fibres based on polycrystalline silicon carbide have been developed over a period of thirty years. This has been possible due to studies into the relationships between the microstructures and properties of the fibres. A variety of techniques have been employed by research teams on three continents. The fibres are made by the conversion of polymer precursors to ceramic fibres and all three generations are presently produced commercially. The nature of the precursor and the techniques used for cross-linking have been varied in order to optimise both properties and cost of manufacture. It has been possible to improve the characteristics of the fibres as the processes involved in the cross-linking of the precursor fibres have been better understood and the mechanisms governing both room temperature and high temperature behaviour determined. The result is that, although first generation fibres were limited by a low Young's modulus at room temperature and by creep and instability of the structure at temperatures far lower than those limiting the behaviour of bulk silicon carbide, the third generation fibres shows many of the characteristics of stoichiometric silicon carbide. This remarkable improvement in characteristics has been due to a thorough understanding of the materials science governing the behaviour of these fibres which are reinforcements for ceramic matrix composite materials.     

The role of a polyamide interphase on carbon fibres reinforcing an epoxy matrix

Carbon fibres were pretreated by means of an interfacial in-situ polyamidation technique resulting in a polyamide coating of the fibres. The procedure followed involved successive application to the carbon fibres of two immiscible solutions of hexamethylenediamine and adipoyl chloride. Previous work conducted in our laboratory on chrysotile/epoxy composites coated with Nylon 6,6 provided interesting results when the tensile performance was evaluated. This behaviour was attributed to the improved affinity between matrix and asbestos fibres as a result of the well-known compatibility between polyamide and the epoxy phase. In this study emphasis is given to the coating of long carbon fibres such as are used for the preparation of unidirectional carbon/epoxy composites. The mechanical properties of uniaxial laminates with varying fibre volume fractions and polyamide contents are then compared with those of uncoated carbon fibres.