Microstructure of carbon/carbon composites reinforced with pitch-based ribbon-shape carbon fibers

Carbon/carbon composites were prepared with ribbon-shape pitch-based carbon fibers serving as reinforcement and thermosetting PFA resin and thermoplastic pitch as matrix precursors. The composites were heat treated to 1000, 1600 and 2700 °C. Microstructural transformations taking place in the reinforcement, carbon matrix, and the interface were studied using polarized optical and scanning electron microscopy. The fiber/matrix bond and ordering of the carbon matrix in heat-treated composites was found to vary depending on the heat treatment temperature of the fibers. Stabilized fiber cleaved during carbonization of resin-derived composites. In contrast, fibers retain their shape during carbonization of pitch matrix composites. Optical activity was observed in composites made with carbonized fibers; the extent decreases with increased heat treatment of the fibers. Studies at various heat treatment temperatures indicate that ribbon-shape fibers developed ordered structure at 1600 °C when co-carbonized with thermosetting resin or thermoplastic pitches.     

A TEM study of microstructure of carbon fiber/polycarbosilane-derived SiC composites

The structures of two types of mesophase pitch-based carbon fibers (M30 and M70) reinforced SiC composites, prepared by the polycarbosilane impregnation-pyrolysis process, were investigated using transmission electron microscopy (TEM). It was found that M70 possessed a highly-ordered graphite structure despite occasional misorientation of some crystallites. However, the skin of M70 was less ordered than the interior of M70. The structure of M30 was uniform throughout, and was less ordered than that of M70. The fiber and matrix in M70/SiC bonded weakly, whereas the fiber and matrix in M30/SiC bonded tightly and locked together. This difference in the interface feature originates from the difference of the surface crystalline structures of M30 and M70, and is formed during the first impregnation-pyrolysis cycle of polycarbosilane.     

Fracture toughness of PAN-based carbon fibers estimated from strength-mirror size relation

Fracture toughness (K_IC) of representative high-strength type PAN (polyacrylonitrile)-based carbon fibers, Torayca™ T300 and T800H, with or without artificial surface defects, were estimated to be ca. 1 MPam^1/2 from the tensile strength vs. fracture mirror size relation, assuming a constant crack-to-mirror size ratio. The corresponding critical energy release rate (Γ) was ca. 7.4 J m⁻², which was close to the value derived from the reported surface energies for a graphite crystal. Similar K_IC values were obtained for the old-type PAN-based carbon fibers from the reported data by the use of the present estimation procedure.     

Carbon/carbon-boron nitride composites with improved wear resistance compared to carbon/carbon

This paper describes the fabrication of a carbon fiber reinforced/carbon-boron nitride (C/C-BN) hybrid matrix composite for possible use in aircraft brakes. These composites were fabricated via liquid infiltration of a liquid crystalline borazine oligomer into a low-density carbon fiber/carbon matrix (C/C) composite. The friction and wear properties of the C/C-BN were explored over the entire energy spectrum for aircraft braking using an inertial brake dynamometer. The C/C-BN composites with densities of 1.55 g/cc displayed wear rates 50% lower than values observed with C/C samples with densities of approximately 1.75-1.8 g/cc. This includes the near elimination of wear from 300 to 600 kJ/kg, which represents the normal landing regime for aircraft brakes. This encouraging behavior is attributed in part to the improved oxidation resistance of the BN at high energy levels and the ability of the BN to facilitate formation of a stable wear film at lower energy levels. The coefficient of friction, while being slightly lower than the values for C/C, appeared much less sensitive to changes in energy level.     

Compressive strength of three-dimensionally reinforced carbon/carbon composite

Compressive behavior of three-dimensionally reinforced carbon/carbon composite (3D-C/C) was examined from room temperature to elevated temperatures up to about 3000 K. Three-dimensionally reinforced C/C was found to have an inclination to induce kinks at the ends of specimens due to extremely low shear strength. In order to avoid this type of premature fracture and to conduct high-temperature tests, discussion was made on specimen geometry and testing procedure, and the combination of a dumbbell-shape specimen and test configuration without a supporting jig were found to be suitable for the present study. Using this set-up, the compressive strength of a 3D-C/C was evaluated as a function of temperature up to about 3000 K. The compressive strength of the 3D-C/C monotonically increased with the increase in temperature up to 2300 K, but decreased above this temperature. The strength enhancement was suggested to be caused by improvement in the fiber/matrix interfacial bonding, and the degradation over 2300 K was by softening of the matrix at high temperatures.     

Ultra high thermal conductivity polymer composites

Epoxy composites based on vapor grown carbon fiber (VGCF) were fabricated and analyzed for room temperature thermophysical properties. An unprecedented high thermal conductivity of 695 W/m K for polymer matrix composites was obtained. The densities of all the composites are lower than 1.5 g/cc. In addition the high value of coefficient of thermal expansion (CTE) of the polymer material was largely reduced by the incorporation of VGCF. Also, unlike metal matrix composite (MMC), the epoxy composite has an electrically insulating surface. Based on the composite thermal conductivities, the room temperature thermal conductivity of VGCF, heat-treated at 2600°C, was estimated to be 1260 W/m K. Furthermore, the longitudinal CTE of the heat-treated VGCF was determined, for the first time, to be −1.5 ppm/K.     

Effect of carbonization rate on the properties of a PAN/phenolic-based carbon/carbon composite

The effect of carbonization rate in a wide range (1, 100 and 1000 °C/min) on the properties of a PAN/phenolic-based carbon/carbon (C/C) composite was studied. The results indicated that the composite processed at a higher carbonization rate had a higher porosity level, more large pores and a more graphitic structure than that processed at a lower carbonization rate. After second graphitization the bending properties of composites carbonized at 1 °C/min and 1000 °C/min were comparable. The composite carbonized at 1000 °C/min had the highest fracture energy. The composite carbonized at 100 °C/min showed the worst mechanical performance among three. The large increase in carbonization rate can be beneficial to the industry from an economic point of view.     

Well-aligned polyaniline/carbon-nanotube composite films grown by in-situ aniline polymerization

Multiwalled carbon nanotubes (MWNTs) encapsulated by polyaniline (PANI) of nanometer size have been synthesized by in-situ polymerization, and are found to be orientationally ordered by the aligned MWNTs. Procedures are demonstrated for the preparation of nanocomposite-tube (NCT) films with controlled organization. Changes in the dimensions of the nanocomposites were measured using SEM and TEM techniques. The interaction between PANI and MWNTs and the nature of chain growth have been investigated and explained according to the results of FT-IR analysis. The improvement of thermal stability and crystallinity of the nanocomposites have been evaluated by using TGA and XRD. The mechanism of charge transport in these composites has also been studied by measuring the DC conductivity of all samples and examining the temperature-conductivity relations. MWNT alignment should be possible with other nanometer-sized building composites films, offering a general route for controlled assembly of organized nanomaterials and devices.     

Analysis of gas leakage through C/C composites

Gas leakage through carbon-fiber-reinforced carbon matrix composites (C/Cs) was examined with respect to the application of C/Cs in heat exchangers in an engine system for a future space plane. Because C/Cs have many cracks and pores, gas readily leaks through them. To predict and prevent this gas flow through the C/Cs, leakage rates were measured as a function of pressure, and gas flow paths were identified by microscopic observations of C/Cs. Several analytical models were then used to clarify the principal mechanisms yielding gas-flow resistance. Laminar flow models in tubes and slits were found to give excellent leak-rate predictions compared with experimental results for unidirectionally and three-dimensionally reinforced C/Cs, respectively. A model based on adiabatic expansion and compression, which is used for gas leaks through labyrinth seals, resulted in reasonable agreement with the leak rates through a cross-ply laminated C/C.     

Mechanical behavior of two-dimensional carbon/carbon composites with interfacial carbon layers

Effect of interfacial carbon layers on the mechanical properties and fracture behavior of two-dimensional carbon fiber fabrics reinforced carbon matrix composites were investigated. Phenolic resin reinforced with two-dimensional plain woven carbon fiber fabrics was used as starting materials for carbon/carbon composites and was prepared using vacuum bag hot pressing technique. In order to study the effect of interfacial bonding, a carbon layer was applied to the carbon fabrics in advance. The carbon layers were prepared using petroleum pitch with different concentrations as precursors. The experimental results indicate that the carbon/carbon composites with interfacial carbon layers possess higher fracture energy than that without carbon layers after carbonization at 1000°C. For a pitch concentration of 0.15 g/ml, the carbon/carbon composites have both higher flexural strength and fracture energy than composites without carbon layers. Both flexural strength and fracture energy increased for composites with and without carbon layers after graphitization. The amount of increase in fracture energy was more significant for composites with interfacial carbon layers. Results indicate that a suitable pitch concentration should be used in order to tailor the mechanical behavior of carbon/carbon composites with interfacial carbon layers.     

Preparation of an activated carbon artifact: oxidative modification of coconut shell-based carbon to improve the strength

Coconut shell-based activated carbon was oxidized in aq. H₂SO₄, HNO₃ and H₂O₂ to induce surface oxygen functional groups on its surface and to increase the mechanical strength of the resultant activated carbon artifact with PVB as a binder. Although all oxidation was confirmed to significantly increase the strength, aq. H₂O₂ was found to be most effective, giving strength as high as 6000 kPa, which is believed to be sufficient for the electrode of an electric double layer capacitor (EDLC). The increase of CO₂ evolving groups induced on the surface of activated carbon appears to be responsible for the strength increase. There was an optimum extent of oxidation for the strength as well as the performance of the electrode. Too much oxidation reduces the electrical conductivity of the activated carbon. Facile oxidation by aq. H₂O₂ can be recommended as a practical modification of the surface since it takes place safely below 100°C without releasing any harmful gas.     

Comparison of 2D and 3D carbon/carbon composites with respect to damage and fracture resistance

The static mechanical responses of two- and three-dimensionally reinforced carbon/carbon composites (2D- and 3D-C/Cs) were compared. The mechanical properties examined included tensile and shear stress-strain (S-S) relations, and fracture behavior using compact tension and double edge notch configurations. Compared with 2D-C/Cs, 3D-C/Cs were shown to possess a similar tensile S-S relation, lower shear strength, higher ultimate deformation in shear, and much higher fracture resistance. The differences in shear and fracture resistance were shown to be derived from a weaker fiber/matrix interface and weaker bonding between fiber bundles in the 3D-C/Cs. These weak interface characteristics of 3D-C/Cs are due to the high value of residual stresses caused by the three-dimensional fiber constraint of 3D-C/Cs.     

The tensile behavior of carbon fibers at high temperatures up to 2400 °C

The tensile behavior of four different brands of carbon fibers (a rayon-based, a PAN-based, and 2 pitch-based fibers) has been investigated at various temperatures up to 2400 °C. The tests were carried out using an original fiber testing apparatus. Various mechanical properties including strength and Young's modulus, as well as Weibull statistical parameters were extracted from test data. Typical tensile behaviors were evidenced such as an essentially linear elastic behavior at room temperature and intermediate temperatures up to 1400-1800 °C, then a nonlinear elastic delayed response at higher temperatures and ultimately an inelastic response with permanent deformations at very high temperatures. Such unusual nonlinear responses for homogeneous materials were related to structure and texture features at the nanometer scale, that were described through an X-ray diffraction technique.     

Microscopic study of failure mechanisms in infiltrated carbon fiber felts

Failure mechanisms in infiltrated carbon fiber felts have been studied by optical light microscopy, transmission electron microscopy and scanning electron microscopy combined with mechanical testing experiments. A model is presented which describes crack generation and propagation at layer-layer and fiber-matrix interfaces as well as within matrix carbon layers with different textures. Intensive cracking occurs within high- and less frequently in medium- and low-textured pyrolytic carbon layers. In particular, fracture does not occur directly at the fiber-matrix interface but within the low-textured matrix layer deposited on the fiber. Crack deflection in interface regions between layers with different textures, crack deflection along boundaries of columnar grains in high -textured layers and at interfaces between polyhedral nanoparticles, and finally crack bridging within high -textured lamellae are cooperative failure mechanisms contributing to the toughness enhancement.     

Studies on the mechanical and mechanical interfacial properties of carbon–carbon composites impregnated with an oxidation inhibitor

In this work, the relationships between work of adhesion and fracture toughness parameters, such as work of fracture (W_f), the critical stress intensity factor (K_IC), and the specific fracture energy (G_IC), of carbon–carbon composites (C/C composites) were investigated. The impact properties of the composites were also studied in the context of differentiating between the initiation and propagation energies for failure behavior. Composites consisting of different contents of the oxidation inhibitor MoSi₂ displayed an increase of the work of adhesion between the fibers and the matrix, which improved both the fracture toughness and impact properties of the composites. The 12 wt% MoSi₂ composites exhibited the highest mechanical and mechanical interfacial properties. This was probably due to the improvement of the London dispersive component, W_A^L, of the work of adhesion, resulting in an increase in the interfacial adhesion force among the fibers, filler, and matrix in this system.     

Sharp indentation behavior of carbon/carbon composites and varieties of carbon

Sharp indentation tests on carbon fiber and carbon matrix composites (C/C composite) were carried out over a wide load range from 0 to 2 N on three different cross sections: normal, parallel and inclined to the fiber axis. For comparison purposes, a variety of carbons including HOPG, glassy C, and pyrocarbon films was also examined. Both the fibers and the matrices displayed first a purely elastic response and second crack-induced damage. A purely elastic behavior was also observed with most of the varieties of carbon considered. Young’s modulus was extracted from the indentation curves either at maximum or at various forces, using the Sneddon equation of elastic response on loading (elastic indentation) or a classical equation based on elastic recovery on unloading (elastoplastic indentation). Results are discussed with respect to features of structure and heterogeneity of material in the stressed volume.     

Preparation of an activated carbon artifact: factors influencing strength when using a thermoplastic polymer as binder

An activated carbon artifact was prepared through mixing, moulding, curing and carbonizing, using polyvinylbutyral resin (PVB) as the binder, dibutyl phthalate (DBP) as a plasticizing agent and isocyanuric acid ester as a cross-linking agent to clarify influential factors on its strength. Preparation conditions such as moulding pressure, temperature and time of curing, carbonization and the amount of cross-linking agent were varied to find their influences on the strength of the resultant form. The form was observed under SEM of wide scope to find correlations between its morphology and strength. The closed packing of the activated carbon filler and the plastic binder was always favorable to develop the strength of the form. The curing extent of PVB, which was influenced by curing atmosphere, temperature and time, and cross-linking agent, was found to govern the strength of the forms. Air or oxygen is very essential for the curing. The optimum temperature was found to be 200°C and longer curing time is beneficial to improve the strength. The cross-linking agent improved the strength of the form up to 7000 kPa through accelerating the cross-linkage of PVB resin. Sufficient curing allows the rapid heating up to 10°C/min for the development of the strength by maintaining the shape of the form. The thermoplastic powders are highly dispersed onto the surface of activated carbons and are cured sufficiently there to adhere the activated carbon grains. Sufficient curing stabilizes the thermoplastic polymer to be thermosetting, anchoring the grains through the carbon bond for higher strength of the carbonized form. PVB resin is cured into heat-resisting cross-linked chains through oxidative condensation onto the activated carbon surface where the oxygen functional groups appear to play important roles in the curing.