Resonant frequency study of tensile and shear elasticity moduli of carbon fibre reinforced composites (CFRC)

The dynamic elastic properties are important characteristics of composite materials. They control the vibrational behaviour of composite structures and are also an ideal tool for monitoring of the development of CFRCs’ mechanical properties during their processing (heat treatment, densification). The present studies have been performed to explore relations between the dynamic tensile and shear moduli and some structural features (viz., fibre fraction, fibre type, porosity, weave pattern of woven reinforcement) of various unidirectional or bi-directional fibre reinforced carbon/carbon composites, made out of PAN- or pitch-based fibres as reinforcements and phenolic resin or coal tar pitch as matrix precursors. The dynamic tensile and in-plane shear moduli were determined from resonant frequencies of a beam with free ends. The longitudinal dynamic Young’s modulus of unidirectional CFRC composites – besides its dependence on the original fibre modulus and fibre volume contents – also reflects changes induced in matrix and fibres by heat treatment. The in-plane shear modulus does not depend on the fibre type but there exists its distinct tendency to increase with increasing fibre fraction. For bi-directionally reinforced composites, the longitudinal tensile modulus is more sensitive to the fabric weave pattern than to the fibre type. Tensile modulus of diagonally cut specimens and in-plane shear modulus of longitudinally cut ones are mutually correlated and, therefore, simultaneously controlled by densification steps and graphitisation heat treatment.     

Effects of high-temperature heat treatment on the mechanical properties of unidirectional carbon fiber reinforced geopolymer composites

Unidirectional carbon fiber reinforced geopolymer composite (C_uf/geopolymer) is prepared by a simple ultrasonic-assisted slurry infiltration method, and then heat treated at elevated temperatures. Effects of high-temperature heat treatment on the microstructure and mechanical properties of the composites are studied. Mechanical properties and fracture behavior are correlated with their microstructure evolution including fiber/matrix interface change. When the composites are heat treated in a temperature range from 1100 to 1300 °C, it is found that mechanical properties can be greatly improved. For the composite heat treated at 1100 °C, flexural strength, work of fracture and Young's modulus reach their highest values increasing by 76%, 15% and 75%, respectively, relative to their original state before heat treatment. The property improvement can be attributed to the densified and crystallized matrix, and the enhanced fiber/matrix interface bonding based on the fine-integrity of carbon fibers. In contrast, for composite heat treated at 1400 °C, the mechanical properties lower substantially and it tends to fracture in a very brittle manner owing to the seriously degraded carbon fibers together with matrix melting and crystal phases dissolve.     

Effect of heat treatment on synthetic carbon precursors

Carbonaceous materials obtained from polyethyleneterephthalate (PET), a potential precursor for polymer-based carbon, were studied after heat treatment at 750, 900 and 1200 °C in an inert atmosphere. The carbon content increases to more than 95% (w/w) already at the lowest temperature applied. The surface area decreases from 242 to 14.7 m²/g between 750 and 1200 °C, causing also a reduced pore volume and the conversion of open to closed pores. The pore structure exhibits a gate effect. The carbon matrix contains both amorphous and semicrystalline regions. The spatial extent of the latter can be described by a Maxwellian distribution with a maximum of 12 Å at the lowest and 17 Å at the highest temperature values. Increasing the temperature from 900 to 1200 °C does not increase the size of these domains but yields a more ordered carbon skeleton. In the WAXS spectrum a flat diffuse peak about 3.5-4.0 Å corroborates that the graphitic domains are of colloidal size. The immersional wetting enthalpies determined in water, methanol and benzene indicate that the surface has an amphoteric character and that the carbon structure and surface chemistry are strongly affected by the heat treatment processes.     

Coalescence of single-walled carbon nanotubes and formation of multi-walled carbon nanotubes under high-temperature treatments

Electric arc-discharge single-wall carbon nanotubes are annealed between 1600 and 2800 °C under argon flow. Their stability and evolution are studied by coupling TEM, X-ray diffraction and Raman spectroscopy. The first modifications appear at 1800 °C with a significant decrease of the crystalline order. It is due to SWNTs coalescence leading to smaller bundles but with an increase of the tube diameters from 2 to 4 nm. From 2200 °C, SWNTs progressively disappear to the benefit of MWNTs having at first two to three carbon layers then reaching 7 nm external diameter. The possible mechanisms responsible for the SWNTs coalescence and instability and their transformation in MWNTs are discussed.     

Carbon/carbon composites based on a polyimide matrix with coal tar pitch

Blending of coal tar pitch with a polyimide precursor based on acetyl derivatives of aromatic diamines during its synthesis leads to a homogeneous, highly thermostable matrix for carbon fibre reinforced composites. If the weight content of the pitch in the polyimide matrix does not exceed 40%, the mechanical properties (flexural strength, shear modulus and fracture toughness) of these composites are comparable to those of similar composites based on a pure polyimide matrix. Carbonisation and graphitisation of the composites with a properly blended matrix precursor leads to carbon fibre reinforced carbon composites with lower open porosity and higher density, elastic modulus and flexural strength than those of composites based on a pure polyimide matrix.     

The key role of microtexture in the graphitisation of PBO fibre chars as seen by X-ray scattering and transmission electron microscopy

Poly(p-phenylene benzobisoxazole) (PBO) fibres, heat-treated between 900 and 2700 °C, were studied by both small- and wide-angle X-ray scattering, and by HRTEM. As directly imaged by HRTEM, the material treated at 900 °C consists of nanometre-sized graphitic domains with a microtexture that resembles non-graphitisable carbon. However, above 2000 °C, these elongated structures coalesce, yielding highly graphitised lamellar carbon. This graphitisation mode is very different from the conventional progressive graphitisation of lamellar carbon. It is similar to that of polyimide films, and is characterized by a preferential planar orientation of the polyaromatic structural units inherited from the pristine fibre microtexture.     

Nanographite structures formed during annealing of disordered carbon containing finely-dispersed carbon nanocapsules with iron carbide cores

Disordered carbon containing finely-dispersed carbon nanocapsules with iron carbide cores were synthesized by a modified method in which low-current plasma discharge was generated in liquid ethanol with ultrasonic irradiation. The structure of nanographite forms prepared by the annealing at 900 °C for 2 h of disordered carbon containing finely-dispersed carbon nanocapsules was studied. Transmission electron microscopy (TEM) studies of the powder sample after annealing revealed most part of disordered carbon was transformed into nanographite ribbons, hollow polyhedral graphitic cages and thick carbon shells with the turbostratic structure of carbon layers. TEM observations of the carbon layers revealed stacking defects. Selected-area diffraction and fast Fourier transforms of digitized images revealed that carbon inter-layer spacings vary from 3.4 to 3.5 Å. XRD analysis showed that annealing of the powder sample at 900 °C for 2 h resulted in the decompositions of iron carbide cores and a well-defined broad carbon peak (0 0 2) centered at 2θ ≈ 25.9° (d₀₀₂ = 3.44 Å) was detected. The growth of the I_D/I_G ratio and shift of the D peak to a lower wavenumber may indicate increase in size the graphite clusters and ordering carbon structure, i.e. appearance of nanographite structures.     

Microstructure difference between core and skin of T700 carbon fibers in heat-treated carbon/carbon composites

The core and skin microstructure of T700 carbon fibers in carbon/carbon composites, prepared with chemical vapor infiltration (CVI) at 1000 °C and heat treated at 2300 and 2800 °C, have been studied by means of high-resolution transmission electron microscopy (HRTEM). The orientation angles of the graphitic basal planes obtained from selected-area electron-diffraction patterns show that the structure difference between the core and skin is a change of the degree of preferred orientation of the graphitic basal planes which decreases gradually from the skin region to the core region after CVI at 1000 °C. With increasing heat-treatment temperature, the basal planes orient parallel to the fiber axis, first in the skin region and then in the core region. In addition, the diameter of the core region decreases considerably from about 3.3 to 2.2 μm after heat treatment at 2800 °C. HRTEM lattice-fringe images show that the graphitic crystallite size increases significantly both in the core and skin, but more in the skin. Moreover, with increasing crystallite size, pores of nanometer scale start to form in the fiber.     

Effect of carbon fiber surface functional groups on the mechanical properties of carbon-carbon composites with HTT

The present investigation describes the quantitative measurement of surface functional groups present on commercially available different PAN based carbon fibers, their effect on the development of interface with resol-type phenol formaldehyde resin matrix and its effect on the physico-mechanical properties of carbon-carbon composites at various stages of heat treatment. An ESCA study of the carbon fibers has revealed that high strength (ST-3) carbon fibers possess almost 10% reactive functional groups as compared to 5.5 and 4.5% in case of intermediate modulus (IM-500) and high modulus (HM-45) carbon fibers, respectively. As a result, ST-3 carbon fibers are in a position to make strong interactions with phenolic resin matrix and HM-45 carbon fibers make weak interactions, while IM-500 carbon fibers make intermediate interactions. This observation is also confirmed from the pyrolysis data (volume shrinkage) of the composites. Bulk density and kerosene density more or less increase in all the composites with heat treatment up to 2600 °C. It is further observed that bulk density is minimum and kerosene density is maximum upon heat treatment at 2600 °C in case of ST-3 based composites compared to HM-45 and IM-500 composites. It has been found for the first time that the deflection temperature (temperature at which the properties of the material start to decrease or increase) of flexural strength as well as interlaminar shear strength is different for the three composites (A, B and C) and is determined by the severity of interactions established at the polymer stage. Above this temperature, flexural strength and interlaminar shear strength increase in all the composites up to 2600 °C. The maximum value of flexural strength at 2600 °C is obtained for HM-45 composites and that of ILSS for ST-3 composites.     

The thermal and mechanical properties of a polyurethane/multi-walled carbon nanotube composite

A polyurethane/multi-walled carbon nanotube elastomer composite was synthesized. The microstructure of the composite was examined by field-emission scanning electron microscopy and transmission electron microscopy. The thermal and mechanical properties of the composite were characterized by dynamic mechanical thermal analysis, thermogravimetric analysis and tensile testing. The chemical linkage of carbon nanotubes with polyurethane matrix was confirmed by Fourier transform infrared spectra. The study on the structure of the composite showed that carbon nanotubes could be dispersed in the polymer matrix well apart from a few of clusters. The results from thermal analysis indicated that the glass transition temperature of the composite was increased by about 10 °C and its thermal stability was obviously improved, in comparison with pure polyurethane. The investigation on the mechanical properties showed that the modulus and tensile strength could be obviously increased by adding 2 wt% (by weight) CNT to the matrix.     

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.     

Dielectric effects on positive temperature coefficient composites of polyethylene and short carbon fibers

By adding the short carbon fibers to the polyethylene matrix, excellent positive temperature coefficient (PTC) effect was achieved. Alternating current (AC) electrical properties of this PTC composite were studied as a function of frequency. The analysis of AC electrical conductivity and dielectric permittivity was done by using a micro-morphology model, which included conductive carbon fiber-aggregates in series with an equivalent circuit of resistor-capacitor parallel that represent the blends at these contact regions. The observed electrical properties of PTC composites were due to the breakage of the conduction networks caused by thermal expansion. The dielectric behaviors of the interfacial polarization between polyethylene matrix and carbon fibers could be described by Maxwell-Wagner-Sillars relaxation when the composite was heated above 116 °C. The analysis of the electric modulus in the frequency range from 100 Hz to 10 MHz revealed that the interfacial relaxation followed the Cole-Davidson distribution of relaxation time.     

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.     

Nanocomposite matrix for increased fibre composite strength

A new type of three-phase thermoplastic composite has been made, consisting of a main reinforcing phase of woven glass or carbon fibres and a PA6 nanocomposite matrix. Nanocomposites have the potential to improve the matrix dominated flexural and compressive strength by increasing the matrix modulus. Good quality fibre composites have been made with several types of PA6 nanocomposite and unfilled PA6 in combination with glass and carbon fibre reinforcement. Flexural tests on commercial PA6 fibre composites have shown the decrease of the flexural strength upon increasing temperature and this has been compared with the decrease of the matrix modulus. The nanocomposites used in this research have moduli that are much higher than unfilled PA6, also above T_g and in moisture conditioned samples. The strength of glass fibre composites can be increased by more than 40% at elevated temperatures and the temperature range at which a certain minimum strength is present can be increased by 40-50 °C. Carbon fibre composites also show significant improvements at elevated temperatures, although not at room temperature. The advantage of the use of nanocomposites instead of other polymers to improve the fibre composite properties is that the properties can be improved without any change in the processing conditions.     

Stabilization and carbonization of gel spun polyacrylonitrile/single wall carbon nanotube composite fibers

Gel spun polyacrylonitrile (PAN) and PAN/single wall carbon nanotube (SWNT) composite fibers have been stabilized in air and subsequently carbonized in argon at 1100 °C. Differential scanning calorimetry (DSC) and infrared spectroscopy suggests that the presence of single wall carbon nanotube affects PAN stabilization. Carbonized PAN/SWNT fibers exhibited 10-30 nm diameter fibrils embedded in brittle carbon matrix, while the control PAN carbonized under the same conditions exhibited brittle fracture with no fibrils. High resolution transmission electron microscopy and Raman spectroscopy suggest the existence of well developed graphitic regions in carbonized PAN/SWNT and mostly disordered carbon in carbonized PAN. Tensile modulus and strength of the carbonized fibers were as high as 250 N/tex and 1.8 N/tex for the composite fibers and 168 N/tex and 1.1 N/tex for the control PAN based carbon fibers, respectively. The addition of 1 wt% carbon nanotubes enhanced the carbon fiber modulus by 49% and strength by 64%.     

TEM and electron tomography studies of carbon nanospheres for lithium secondary batteries

The structure of carbon nanospheres of 100-200 nm diameter, which showed superior high-speed charge-discharge behavior as the negative electrode in a lithium ion battery, was investigated with XRD, SEM and TEM with an electron tomography attachment. Observation of carbon 0 0 2 lattice images, as well as electron diffraction patterns, illustrated that heterogeneous microtexture was formed as the polyhedronization of the particle proceeded with heat-treatment. The outside region of the particle heat-treated at 2800 °C has stacking structure of aromatic layers with some distribution of d₀₀₂, while the center region consisted of non-graphitic. Structure defects seemed to be concentrated along the ridgelines of the polyhedronized particles after heat-treatment. The electron tomography technique clarified the morphology of the graphitized particles, although the images should be understood with other crystallographic measurements. A slice image computed in the 3D-reconstruction process showed the inner texture of the graphitized particles more clearly than the conventional TEM bright-field image.     

Improved activated carbon by thermal treatment in methane and steam: Physicochemical influences on MIB sorption capacity

Thermal treatment by steam or by methane plus steam altered the physicochemical properties of a commercial lignite-based activated carbon; and improved the carbon’s sorption capacity for the odorant 2-methylisoborneol (MIB). Rapid small scale column tests (RSSCTs) revealed that favorable thermal treatment allowed an activated carbon to remove this odorant for up to six times longer before initial MIB breakthrough than did its commercial lignite counterpart. For these RSSCTs (135 ppt), clarified water from a water treatment plant (2.07 mg/L TOC) was spiked with ¹⁴C-MIB; and liquid scintillation protocols facilitated ¹⁴C-MIB detection at 1-3 ppt. The more favorable thermal treatment at 1000 °C increased pore volumes with 5-400 Å widths by twofold; and the bed volume to initial MIB breakthrough correlated fairly well (R² = 0.9) with pore volume in the range of 5-60 or 5-400 Å. Thermal tailoring altered the carbon’s apparent point of zero charge: from pH 6.5 for the commercial lignite carbon, to pH 9.2 for tailored carbon. When methane and steam were used together, the C, H, N and O contents were virtually the same as for the commercial lignite. In contrast, when steam was employed alone, the percent of oxygen increased, and the percent of H, C and N therefore decreased slightly.     

Improvement of oxidation resistance of unidirectional Cf/SiO2 composites by the addition of SiCp

Unidirectional carbon fiber reinforced fused silica composites (uni-C_f/SiO₂) with addition of different contents of SiC particle (SiC_p) were prepared by slurry infiltrating and hot-pressing. The model of oxygen infiltrating into the composite was supposed according to the characterization of fiber/matrix interface observed by transmission electronic microscope (TEM). The oxidation process of the composite was analyzed by thermo-gravimetry and differential scanning calorimeter (TG-DSC) method and the oxidation resistance was evaluated by the residual flexural strength and the fracture surface of the composite after heat treatment at elevated temperatures method. The results showed that the oxidation of carbon fiber started at 480 °C and ended at 800 °C and the oxidation of SiC_p started at above 1000 °C in the composite. The addition of 20 wt.% SiC_p had a better oxidation resistance. According to the characterization of fiber/matrix interface observed by TEM, gaps existed at the fiber/matrix interface which resulted from the CTE mismatch of carbon fiber and SiO₂ matrix. While the CTE mismatch between SiC_p and SiO₂ matrix could also result in the pre-existing gaps in the matrix. The oxygen penetrated along the gaps and simultaneously reacted with carbon fiber ends and SiC_p, which filled the gaps at the fiber/matrix interface and the pre-existing gaps in the matrix and subsequently prevented oxygen from infiltrating inward.     

Structural changes in carbon aerogels with high temperature treatment

The structural change of carbon aerogels at high temperatures up to 2800°C has been investigated. Change in microtexture of fine particles, which constitute carbon aerogels derived from phenolic resin, was of a typical non-graphitized carbon. The microporosity decreased with an increase of heat-treatment temperature, and disappeared at 2000°C. The mesoporosity still remained even after heat-treatment up to 2800°C, though 50% of mesopore volume was lost because of the fusion of the particles with the change of carbon microtexture.     

Fabrication and superhydrophobicity of fluorinated carbon fabrics with micro/nanoscaled two-tier roughness

Superhydrophobic carbon fabric with micro/nanoscaled two-tier roughness was fabricated by decorating carbon nanotubes (CNTs) onto microsized carbon fibers, using a catalytic chemical vapor deposition and subsequent fluorination surface treatment. The superhydrophobic surfaces are based on the regularly ordered carbon fibers (8-10 μm in diameter) that are decorated by CNTs with an average size of 20-40 nm. The contact angle of water significantly increases from 148.2 ± 2.1° to 169.7 ± 2.2° through the introduction of CNTs. This confirms that the wettability of carbon fabric changes from hydrophobicity to superhydrophobicity due to structural transformation. This finding sheds light on how the two-tier roughness surface induces superhydrophobicity of rough surfaces, and how the presence of CNTs reduces the area fraction of a water droplet in contact with the carbon surface with two-tier roughness.