Surface characteristics of fluorine-modified PAN-based carbon fibers

Different fluorination methods were applied to modify the surface properties of carbon fibers. The relationship between the degree of fluorination and the physicochemical properties of carbon fibers was studied using a combination of mechanical tests, elemental analysis (EA), X-ray photoelectron spectrometry (XPS), and X-ray diffraction (XRD). EA and XPS analyses of fluorinated carbon fibers showed that treatment with mixtures of F₂/O₂ introduced a much higher fluorine concentration than that with F₂ only. However, XRD analysis showed that there was no increase in the interlayer distance, due to the mild fluorination condition applied. Consequently, the oxyfluorination was one of the more effective methods to increase surface polarity of carbon fibers, which probably played an important role in improving the tensile properties of the fibers in the epoxy resin system.     

Bulk and surface chemical functionalities of type III PAN-based carbon fibres

PAN-based carbon fibres carbonised at relatively low temperature, i.e. type III carbon fibres, were submitted to heat treatment at 2300 °C (GR) or oxidation in nitric acid. The samples were characterised by XPS, FTIR, wetting measurements, gas adsorption, elemental analysis and acid/base titration. While oxidation only slightly affects the nitrogen concentration, it produces an appreciable change in the nature of the chemical functions, namely the conversion of pyridine-type nitrogen and quaternary nitrogen into aliphatic functions. Oxidation treatment modifies all the material constituting the fibre, the oxygen concentration being about 1.5 times higher at the fibre external surface compared with the whole material. Three components (531.2, 532.6 and 533.8 eV) are clearly identified in the oxygen XPS peak, allowing a comparison to be made between the whole material and the external surface regarding chemical species. The acidic groups are mainly carboxyl. Fibres submitted to extensive oxidation also show a high basicity, attributed mainly to calcium carboxylate. Although the acidic and basic groups present in the whole material can be titrated with aqueous solutions, the fibres develop only a very small surface area and no microporosity as determined by krypton adsorption. The material may be viewed as a sponge, collapsed when dry but able to swell in water and developing a high cation-exchange capacity.     

Biopitch-based general purpose carbon fibers: Processing and properties

Eucalyptus tar pitches are generated on a large scale in Brazil as by-products of the charcoal manufacturing industry. They present a macromolecular structure constituted mainly of phenolic, guaiacyl, and siringyl units common to lignin. The low aromaticity (60-70%), high O/C atomic ratios (0.20-0.27%), and large molar mass distribution are peculiar features which make biopitches behave far differently from fossil pitches. In the present work, eucalyptus tar pitches are evaluated as precursors of general purpose carbon fibers (GPCF) through a four-step process: pitch pre-treatment and melt spinning, and fiber stabilization and carbonization. Homogeneous isotropic fibers with a diameter of 27 μm were obtained. The fibers had an apparent density of 1.84 g/cm³, an electrical resistivity of 2 × 10⁻⁴ Ω m, a tensile strength of 130 MPa, and a tensile modulus of 14 GPa. Although the tensile properties advise against using the produced fibers as structural reinforcement, other properties give rise to different potential applications, as for example in the manufacture of activated carbon fibers or felts for electrical insulation.     

Physical properties and biological effects of activated carbon fibers treated with the herbs

Activated carbon fibers (ACFs) were treated with various medicinal materials. The physical properties and biological effects of these ACFs were examined. In order to investigate the properties, adsorption isotherms, BET surface area and pore analysis for the herb material treated ACFs must be obtained. The pore size distribution of the samples was obtained by a regularization method on the basis of the non-local and smoothed density function theory approximation support these findings. To investigate the surface of treated ACFs, the surface morphology of the resulting samples by S.E.M. show that many of the treated herbs were distributed irregularly on the surface of the fiber. In results of biological effects in the treated herbs, most all of samples showed excellent antibacterial effects after 200-400 min.     

UV stabilization route for melt-processible PAN-based carbon fibers

Ultraviolet radiation-based stabilization routes were explored to produce carbon fibers from melt-processible PAN-based copolymers. An acrylonitrile/methyl acrylate (AN/MA) copolymer was melt-spun into fibers that were crosslinked using UV radiation. The fibers could then be stabilized by oxidative heat treatment, and subsequently carbonized. Physical and mechanical testing was performed to determine the degree of stabilization and the properties of the stabilized and carbonized fibers.     

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.     

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.     

Modified carbon nanotubes: an effective way to selective attachment of gold nanoparticles

Through various modifications of carbon nanotubes (CNTs), gold nanoparticles were selectively attached to the nanotube and the locations of functional groups were further confirmed. Using cationic polyethyleneamine or anionic citric acid as the dispersant, the surface properties of CNTs could be changed to yield a basic or acidic surface. By electrostatic interaction, the CNTs could be successfully coated with about 10 nm gold nanoparticles. After heat treatment in NH₃, about 1–2 nm gold nanocluster-filled nanotubes were achieved. This shows that the heat treatment with NH₃ could make CNTs open-ended and generate functional basic groups on the inner wall of the nanotubes.     

Surface chemistry of a viscose-based activated carbon cloth modified by treatment with ammonia and steam

The influence of ammonia treatment at 800 °C on the catalytic activity of a viscose-based activated carbon cloth (ACC) was evaluated for the oxidative retention of H₂S or SO₂ at room temperature. Change in the surface chemistry was observed by X-ray spectroscopy of nitrogen (N1s) and by temperature programmed desorption (TPD). Dynamic adsorption of H₂S or SO₂ in moist air onto a packed bed of activated carbon cloth was monitored by measurement of the breakthrough curves at room temperature. ACC modified by ammonia showed noteworthy enhanced SO₂ and H₂S loading relative to the untreated ACC. Improved SO₂ retention rate could be replicated several times after regeneration by washing at room temperature, in contrast to the case with H₂S. The likely reasons for the behavior of H₂S and SO₂ on the ammonia-treated ACC are discussed with reference to the recent literature.     

Short residence time graphitization of mesophase pitch-based carbon fibers

The effects of graphitization time and temperature on the properties of three mesophase pitch-based carbon fibers have been characterized. Graphitization temperatures studied were 2400, 2700, and 3000 °C and residence times ranged from 0.7 to 3600 s. Helium pycnometry, measurements of fiber tow resistance, and X-ray diffraction were employed to study fiber properties. As anticipated, substantial variations in fiber properties were noted for the range of graphitization conditions studied and among the three fiber types. Significant structural evolution and property development occurred even at the shortest furnace residence times. For example, for one of the fibers, a furnace residence time of 0.7 s at 3000 °C resulted in a degree of graphitization value of ∼50%, a density of 1.98 g/cm³, and an electrical resistivity of 6.3 μΩ m (corresponding thermal conductivity ∼200 W m⁻¹ K⁻¹). A simple energy consumption analysis suggests that short residence time graphitization at high temperature may result in both lower costs and substantially higher production rates for fibers prepared from mesophase pitch.     

Raman spectroscopy study of HM carbon fibres: effect of plasma treatment on the interfacial properties of single fibre/epoxy composites

The effect of an oxygen plasma treatment upon the structural and morphological properties of high-modulus carbon fibres has been studied by means of several characterisation techniques. Scanning electron microscopy showed that there were only minor changes of the morphology of the fibres following treatment. X-ray diffraction traces revealed that there were differences in structural parameters between the untreated fibres but no further modifications in the crystalline structure were detected after the plasma oxidation. Raman spectroscopy was used to follow the changes on the fibre surface structure following treatment. The peak positions and widths of the four main Raman bands (D, G, D′ and G′) were determined, with no significant changes observed after the surface treatment. A relationship between the width of the G band and the crystal parameter d₀₀₂ was found, with the magnitudes of both decreasing as the fibre modulus increased. A reference order parameter I_D/(I_D+I_G) ratio was calculated from the intensities of D and G bands. The treated fibres exhibited a more highly disordered surface structure that the untreated ones, as revealed by the increase of I_D/(I_D+I_G) after the plasma oxidation.     

Sulfonation of pyropolymeric fibers derived from phenol-formaldehyde resins

This research demonstrates that pyropolymeric fibers derived from phenol-formaldehyde resins can be successfully sulfonated providing advantages that are not currently available with traditional polymeric ion-exchangers. Benefits of this system include higher thermal stability, elimination of osmotic shock associated with beads, and enhanced ion-exchange capability. In this study, a series of thermally and chemically activated fibers were prepared by heating a phenolic precursor under inert atmosphere at temperatures between 350 and 600 °C. Subsequent sulfonation of the fibers in concentrated sulfuric acid incorporated sulfonic acid units as well as various oxygen-containing groups. The identification of functional groups and their thermal stability was carried out using elemental analysis (EA), diffuse reflectance Fourier transform infrared spectroscopy (DRIFTS), and thermal gravimetric analysis (TGA). The effect of sulfonation on pore volume and surface area is discussed. Functional groups added during the sulfonation process serve as either strong acid or weak acid cationic exchangers.     

A study of the electrical properties of carbon nanotube-NiFe2O4 composites: Effect of the surface treatment of the carbon nanotubes

Novel carbon nanotube-NiFe₂O₄ composite materials have been prepared for the first time by in situ chemical precipitation of metal hydroxides in ethanol in the presence of carbon nanotubes (CNTs) and followed by hydrothermal processing. The obtained composite powders were characterized using XRD, TEM and EDS. The effect of surface oxidation treatment of CNTs on their properties was investigated by FTIR, zeta potential and hydrodynamic radius distribution characterization. Electrical conductivity measurements show that surface oxidation treatment of CNTs can improve the electrical conductivity of the composites more pronouncedly than pristine CNTs do. With 10 wt.% addition of surface treated CNTs, the electrical conductivity is increased by 5 orders of magnitude. The surface oxidized CNTs are crucial for this significant increase in electrical conductivity, which provides strong adhesion between the nanotubes and the matrix to give a homogeneous carbon nanotube-NiFe₂O₄ composite.     

Grafted and crosslinked carbon black as an electrode material for double layer capacitors

Isocyanate prepolymers can readily react with oxidic functional groups on carbon black. Different prepolymers were examined for their grafting behaviour. In carbon black grafted with di-isocyanates, reactive isocyanate groups are available for cross-linking to a polyurethane system. This crosslinked carbon black was designed as a new active material for electrochemical electrodes. The successful crosslinking of carbon black was demonstrated by determinations of the grafted groups via titration and via thermogravimetric analysis. Products of this type were tested as an active material for electric double layer capacitor application. Active material for electric double layer capacitor electrodes was produced which had a specific capacitance of up to 200 F/g. Crosslinking efficiencies of up to 58% of the utilized polymers were achieved.     

Aqueous electrochemical intercalation of bromine into graphite fibers

For the first time, graphite fibers have been electrochemically intercalated with Br⁻ that have the same structure and properties as those intercalated from vapor phase Br₂. This was accomplished by intercalating pitch-based Thornel^® K-1100 graphite fibers at low temperature (near 0 °C) and high currents (2 A) for long times (6 h). The mechanism appears to be that Br⁻ is oxidized to aqueous Br₂ which, when sufficient local concentration builds up, intercalates the fiber. This was confirmed by intercalating K-1100 fiber in a saturated aqueous Br₂ solution without passing an electrical current. The applied voltage does apparently lower the activation energy of the reaction as evidenced by the observation that P-120 and P-100 fibers will not intercalate in aqueous Br₂ unless a voltage is applied.     

Molecular sieve properties obtained by cracking of methane on activated carbon fibers

Molecular sieve properties of activated carbon fibers modified by cracking treatment with methane are studied herein. The effect of methane treatment on the porous texture of the samples has been studied while varying temperature and time. These materials have been evaluated for their selectivity during CO₂ and CH₄ separation; their uptakes have been compared with non-treated activated carbon fibers (studied previously), which were considered suitable to be used as molecular sieves. Kinetics of CO₂ and CH₄ uptake have also been investigated in this research. The treatment produced materials exhibiting fast kinetics and high selectivity during CO₂ and CH₄ separation; at the same time however, the CO₂ uptake capacity was diminished.     

Mechanical properties of high-strength carbon fibres. Validation of an end-effect model for describing experimental data

The present contribution deals with the use of different models accounting for the mechanical response of high-strength (HT) carbon fibres. In particular, analytical models based on Weibull type of statistical distributions will be employed to analyse the dependence of the strength of carbon fibres on length. This dependence is relevant for interpreting the results of conventional fragmentation tests, which are traditionally performed to characterise the level of fibre/matrix adhesion in fibre reinforced composites. The objective of this work is to compare alternative models, such as the so-called “end-effect” model, for determining the tensile strength of HT carbon fibres at small gauge lengths. To validate these models, tensile tests were performed with five different HT, ex-PAN carbon fibres: a fresh, untreated sample, and four samples which were prepared after submitting the previous one to various surface treatments. Specifically, plasma oxidation was carried out under three different conditions of power and/or time of exposure. A sample oxidized by the manufacturer, presumably using an electrochemical treatment, was also included. Results showed that the end-effect model represents well the behaviour of the untreated and plasma treated under the mildest conditions carbon fibres. Overall, all treatments tend to decrease the tensile strength of the fibres, with the commercial treatment being the most damaging when compared to any of the plasma treatments carried out.     

Raman spectroscopy study of high-modulus carbon fibres: effect of plasma-treatment on the interfacial properties of single-fibre-epoxy composites: Part II: Characterisation of the fibre-matrix interface

High-modulus carbon fibres from different precursors were submitted to an oxygen plasma-treatment under similar conditions. Single-fibre epoxy composites were prepared from them, and fragmentation tests were performed in order to characterise fibre-matrix interfacial adhesion. Raman spectroscopy has been used in the present work to map the strain along the fibre during tensile loading of the matrix. The strain distributions obtained agreed well with the prediction of analytical models used conventionally to describe load transfer at interfaces. Interfacial shear stress distributions were then obtained from these distributions according to the conventional force-balance concept. The interfacial shear strength (IFSS) and frictional shear stress (τ_f) values were calculated to quantify the degree of fibre-matrix adhesion. It was found that both parameters increased dramatically after the surface treatment, confirming the ability of cold plasma oxidation to improve the adhesion of carbon fibre to epoxy matrices. A dependence of the IFSS on the degree of surface order, as given by the structural order parameter I_D/(I_D+I_G), calculated from the relative intensities of the D and G bands of Raman spectra, was found. This supports the role played by the graphitic structure in fibre-matrix adhesion.     

Flue gas desulphurization by activated carbon fibers obtained from polyacrylonitrile by-product

By pyrolysis of a polyacrylonitrile textile by-product, subsequent activation by CO₂ and treatment (at high temperature) with a N₂ flow containing a low percentage of O₂ or of NH₃, three carbonaceous matrices are obtained having a high surface area and surface sites with basic characteristics. The SO₂ sorption properties of these carbon samples (in the temperature range between 100 and 160 °C) from gaseous mixtures having a similar composition to flue gases, seems to be promoted by nitrogen bonded to carbon. The SO₂ adsorbed by the carbons can be divided, by suitable extraction with distilled water, into: (i) desorbable, such as SO₂ or H₂SO₃, (ii) desorbable, such as SO₃ or H₂SO₄, (iii) non-desorbable. Following 10 SO₂ adsorption and desorption cycles, the surface area values of the activated carbons remain practically constant, while both the content of the acidic surface sites and the amount of non-desorbable SO₂ increase; this results in the decrease in the SO₂ carbon sorption property seeming to be even more marked for the carbon sample containing nitrogen.