Grafted carbon fibers and their physicochemical properties. I. Grafting of methacrylic acid onto carbon fibers

A simple, reproducible method for grafting different carbon fibers (modified and unmodified, high‐modulus, and high‐tensile) with methacrylic acid is presented. The grafted carbon fibers were characterized by wetting measurements and electrokinetic studies. Scanning electron microscopy micrographs showed grafted polymer chains on all carbon fiber surfaces. The success of the grafting procedure depends on a suitable modification of the fiber surface. The amount and size of the grafted polymer chains on modified carbon fibers depend on the amount of initiator used. Contact angle measurements indicate an increase of the contact angle versus water and a decrease versus diiodomethane. The surface polarity calculated from the surface tensions obtained from contact angle values decreases for all systems under investigation. Zeta (ζ) potential measurements confirmed these results. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1175–1185, 1999     

Grafting of a liquid crystal polymer on carbon fibers

Covalent grafting of mesogenic chains on carbon fiber surfaces was attempted as part of a study on composite materials containing liquid crystal polymer matrices. Grafting in these composite systems is viewed not only as a mechanism to achieve interfacial bonding but also as an approach to modify the interphase physical structure. The synthetic approach to grafting involved the in-situ polymerization of monomers in the presence of functionalized fibers in order to grow chains covalently attached to the fibers. The chemical mechanism may be viewed as the “transesterification of car boxy lated fibers” with acetylated monomers. The monomers used were pimelic acid, p-acetoxybenzoic acid and diacetoxy hydroquinone which are known to yield upon condensation a chemically aperiodic nematic polymer. Evidence for grafting was obtained from X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) analysis on fibers retrieved from composite samples. Interestingly, SEM micrographs of fractured composite specimens containing the mesogen-grafted fibers reveal excellent wetting and interfacial bonding of a liquid crystalline matrix on the carbon surfaces. Based on theoretical considerations for end-adsorbed macromolecules and the nematogenic nature of the grafted chains we infer that dense layers of adsorbed polymer may form at the interfaces studied. From a materials point of view the in situ growth of liquid crystal polymer chains on fibers may offer mechanisms to control composite properties through both bonding and molecular orientation in interfacial regions.     

Induced orientational behavior of liquid crystal polymer by carbon fibers

Experimental results are presented that show that the structure of carbon fibers induces molecular orientation of liquid crystal polymers. X-ray diffraction data are used to demonstrate final collinearity of the polymer molecular axis and carbon fiber axis independent of fabrication approaches or prefabrication orientation of the polymer relative to the carbon fiber direction. The final degree of polymer molecular orientation approximately equals the degree of carbon basal plane orientation within the carbon fiber.     

Preparation of a carbon nanotube/carbon fiber multi-scale reinforcement by grafting multi-walled carbon nanotubes onto the fibers

To prepare a carbon nanotube (CNT)/carbon fiber multi-scale reinforcement (MSR), multi-walled carbon nanotubes (MWCNTs) functionalized at the end caps with hexamethylene diamine (HMD) are grafted onto the surfaces of carbon fibers treated with acyl chloride. The surface element concentrations, surface functional groups and morphology of the MSR were examined by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). XPS spectra indicate that sp² and sp³ carbon atoms are major components in the MSR surface, and the carbon fiber surface structure is not destroyed. There is 17.41% of C-NH_x in the surface of the MSR, which suggests that MWCNTs are covalently grafted onto carbon fiber surfaces. SEM shows that the grafted MWCNTs stick to the carbon fiber surface at different angles, and are uniformly distributed along the outer edges of the grooves in the fiber surface. The grafted MWCNTs are 50-200 nm in length and around 14 nm in diameter. It was found that the grafting increases the weight of carbon fiber by 1.2%, which implied that a considerable amount of MWCNTs were grafted onto carbon fiber surfaces.     

Plasma etching and plasma polymerization coating of carbon fibers. Part 1. Interfacial adhesion study

Unsized AS-4 carbon fibers were etched by RF plasma and then coated via plasma polymerization in order to enhance their adhesion to vinyl ester resin. Gases utilized for plasma etching were Ar, N₂ and O₂, while monomers used in plasma polymerization coating were acetylene, butadiene and acrylonitrile. Plasma etchings were carried out as a function of plasma power (30–70 W), treatment time (1–10 min) and gas pressure (20–40 mtorr). Plasma polymerizations were performed by varying the treatment time (15–60 s), plasma power (10–30 W) and gas pressure (20-40 mtorr). The conditions for plasma etching and plasma polymerization were optimized by measuring interfacial adhesion with vinyl ester resin via micro-droplet tests. Plasma etched and plasma polymer coated carbon fibers were characterized by SEM, XPS, FT-IR and α-Step, dynamic contact angle analyzer (DCA) and tensile strength measurements. In Part 1, interfacial adhesion of plasma etched and plasma polymer coated carbon fibers to vinyl ester resin is reported, while characterization results including tensile strength of carbon fibers are reported in Part 2. Among the treatment conditions, a combination of Ar plasma etching and acetylene plasma polymer coating provided greatly improved interfacial shear strength (IFSS) of 69 MPa, compared to 43 MPa obtained from as-received carbon fiber. Based on the SEM analysis of failure surfaces and load-displacement curves, the failure was found to occur at the interface between plasma polymer coating and vinyl ester resin.     

Plasma etching and plasma polymerization coating of carbon fibers. Part 2. Characterization of plasma polymer coated carbon fibers

Unsized AS-4 carbon fibers were subjected to RF plasma etching and/or plasma polymerization coating in order to enhance their adhesion to vinyl ester resin. Ar, N₂ and O₂ were utilized for plasma etching, and acetylene, butadiene and acrylonitrile were used for plasma polymerization coating. Etching and coating conditions were optimized in terms of plasma power, treatment time, and gas (or monomer) pressure by measuring the interfacial adhesion strength. Interfacial adhesion was evaluated using micro-droplet specimens prepared with vinyl ester resin and plasma etched and/or plasma polymer coated carbon fibers. Surface modified fibers were characterized by SEM, XPS, FT-IR, α-Step, dynamic contact angle analyzer (DCA) and tensile strength measurements. Interfacial adhesion between plasma etched and/or plasma polymer coated carbon fibers and vinyl ester resin was reported previously (Part 1), and characterization results are discussed is this paper (Part 2). Gas plasma etching resulted in preferential etching of the fiber surface along the draw direction and decreased the tensile strength, while plasma polymer coatings altered neither the surface topography of fibers nor the tensile strength. Water contact angle decreased with plasma etching, as well as with acrylonitrile and acetylene plasma polymer coatings, but did not change with butadiene plasma polymer coating. FT-IR and XPS analyses revealed the presence of functional groups in plasma polymer coatings.     

Direct growth of carbon nanotubes on carbon fibers: Effect of the CVD parameters on the degradation of mechanical properties of carbon fibers

Grafting carbon nanotubes (CNTs) directly on carbon fibers represents a promising approach in order to strengthen the weak interface between carbon fibers and polymer matrix in carbon fiber reinforced polymer composites (CFRCs). We have carried out direct growth of CNTs on carbon fibers by using two different catalytic chemical vapor deposition (CVD) processes, namely the conventional CVD process based on catalytic thermal decomposition of ethylene and the oxidative dehydrogenation reaction between acetylene and carbon dioxide. The effect of various CVD growth parameters, such as temperature, catalyst composition and process gas mixture, was for the first time systematically studied for both processes and correlated with the mechanical properties of carbon fibers derived from single-fiber tensile tests. The growth temperature was found to be the most critical parameter in the presence of catalyst particles and reactive gasses for both processes. The oxidative dehydrogenation reaction enabled decreasing CNT growth temperature as low as 500 °C and succeeded to grow CNTs without degradation of carbon fiber's mechanical properties. The Weibull modulus even increased indicating partial healing of present defects during the CVD process. The new insights gained in this study open a way towards simple, highly reproducible and up-scalable process of grafting CNTs on carbon fibers without inducing any damages during the CVD process. This represents an important step towards CNT-reinforced CFRCs with higher damage resistance.     

The influence of continuous stabilization on the properties of stabilized fibers and the final activated carbon fibers. Part I

This study found that, during continuous stabilization and carbonization, the shrinkage behavior of polyacrylonitrile (PAN) fibers affects the morphology and properties of the stabilized fibers, the carbon fibers, and the final activated carbon fibers. In the stabilized fibers, a higher shrinkage of the PAN fibers during the stabilization process increased the oxygen content and the core proportion and decreased the formation of ladder polymers. The effect of the shrinkage behavior of the PAN fibers on the fracture surfaces of the stabilized fibers is discussed. A microstructure model of stabilized fibers is presented, depicting fine radial structure at the fiber center. When stabilized fibers were carbonized during a continuous carbonization process, a hole structure was found in the fiber center at the temperature of 800°C, and a hollow core was found at the temperature of 1300°C. The shrinkage behaviors during the stabilization stage and the formation of the hole and the hollow core in the fiber's center during the carbonization stage are discussed. The carbon fibers developed from shrunk stabilized fibers have a lower density and lower preferred orientation than fibers developed from unshrunk stabilized fibers. But the fibers developed in this new process have greater nitrogen and oxygen content, and have a greater porosity than the traditionally-produced fibers. The mechanical properties df the new and the traditional fibers are comparable. These characteristics are very valuable in the production of activated carbon fibers, which will be described in our next paper.     

Coating of carbon fibers with adhesion-promoting thin poly(acrylic acid) and poly(hydroxyethylmethacrylate) layers using electrospray ionization

Thin coatings of poly(acrylic acid) (PAA) and poly(hydroxyethylmethacrylate) (PHEMA) were deposited onto carbon fibers by means of the electrospray ionization (ESI) technique in ambient air. These high-molecular weight polymer layers were used as adhesion promoters in carbon fiber–epoxy resin composites. Within the ESI process, the carbon fibers were completely enwrapped with polymer in the upper 10 plies of a carbon fiber roving. As identified with scanning electron microscopy also shadowed fibers in a bundle as well as backsides of fiber rovings were pinhole-free coated with polymers (‘electrophoretic effect’). Under the conditions used, the layers have a granular structure. Residual solvent was absent in the deposit. PAA and PHEMA films did not show any changes in composition and structure in comparison with the original polymers as analyzed by X-ray photo-electron spectroscopy and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. Single-fiber pullout tests of coated fibers embedded in epoxy resin showed significantly increased interfacial shear strength. It is assumed that chemical bonds between carbon fiber poly(acrylic acid) and epoxy resin contribute significantly to the improved interactions.     

Melt-spun liquid core fibers: physical and morphological characteristics

Application of different polymers and fillers in multi-component fibers has recently emerged as an effective approach in textile industries. Recent investigations have extensively demonstrated that hollow fibers can be melt-spun and subsequently filled with liquids; however, introduction of a liquid into a fiber core and filling it up with that liquid, specifically at extended lengths, remains challenging. In this study, based on the results previously obtained for the simulation and extrusion of polymer melt and liquid co-flowing, continuous production of the liquid core bi-component filaments via melt spinning through specially designed spinneret is discussed. In fact, core/shell bi-component filaments 50 μm in diameter consisting of polypropylene sheath and complex ester core were produced undergoing 1500 m/min continuous melt spinning with drawing ratio of 5. Physical properties of the developed fibers were investigated which were in acceptable condition with those of the reference solid and hollow fibers. Successful presence of a liquid in an eccentric channel 15 μm in diameter was demonstrated by microscopic observation. Furthermore, the ester oil was retained inside the fiber due to its low contact angle against polypropylene, thereby resolving the need for sealing the fiber’s outlet. Also, TGA and FTIR analysis confirmed the presence of liquid inside the bi-component fibers. DSC tests showed a similar crystallinity for liquid core and hollow fibers, which was about 37 %, while solid fiber had 5 % more crystallinity. Due to the vast available liquids and polymers with various properties, developed liquid core fibers will provide a suitable platform for a large number of applications in future.     

Syntheses and the Main Properties of Fiban Fibrous Ion Exchangers

The works on synthesis and main properties of fibrous ion exchangers are reviewed in the paper. The main attention is paid to the FIBAN materials found practical applications in water treatment and air purification processes. The following methods for preparation of ion exchange fibers have been considered: mechanical mixing of inert fiber‐forming polymer solutions or melts with finely dispersed ion‐exchangers with their following spinning into fibers; preparation of composite fibers containing polymeric reinforcement in the polyelectrolyte body; spinning of specially prepared polymers containing ionizable groups and having fiber‐forming properties; grafting of ionogenic polymers (or polymers in which ionogenic groups can be introduced after grafting) onto polymer chains of the existing polymer fiber; polymer analogues conversion of existing polymeric fibers by introducing in their structure ionizable functional groups. Conditions for preparation of ion exchange fibers with high exchange capacity, optimal swelling and acceptable mechanical properties have been outlined.     

Location of some typical vinyl polymers within radiation-grafted cotton fibers: An electron microscopical survey

Electron microscopical observations of radiation-induced rayon–styrene graft copolymers were published by Kaeppner and Huang in 1965. The present paper reports electron microscopical investigations on the relationship of the structure of vinyl–cotton graft polymers to the original morphology of the cotton fiber and into the distribution of the grafted vinyl polymer in the cotton fiber structure. The grafted vinyl monomers investigated in this study were acrylonitrile, styrene, methyl methacrylate, and vinyl acetate. Two radiation-induced procedures were used: simultaneous irradiation grafting and post-irradiation grafting. Ceric ion grafting of acrylonitrile to cotton was included for purposes of comparison. Distribution of the vinyl polymer within the cotton fiber is illustrated by a series of electron micrographs, selected as typical of the particular grafted species under consideration. Results indicate that the diffusion rate of monomer into the cellulose fiber plays an important role in the final distribution of polyacrylonitrile grafts within the fiber. Uniform distribution of polyacrylonitrile in the fiber was achieved by simultaneous irradiation grafting of acrylonitrile on a highly substituted cyanoethylated cotton. In samples of low degree of cyanoethylation the distribution of graft polymer was non-uniform. In grafting initiated by ceric ion the acrylonitrile graft polymer was evenly distributed. Polystyrene–cotton copolymers from grafts, made by simultaneous irradiation of cotton in methanol solutions of the styrene monomer, were uniform throughout the fiber but showed opening of structure associated with the amount of graft formed. Grafting of methyl methacrylate occurred only in the peripheral regions of the fiber; by contrast, grafting of vinyl acetate was uniform throughout the fiber wall. Important factors governing the successful irradiation grafting in cotton fibers are choice of solvent, ratio of monomer to cellulose, nature of prior chemical modification of the cellulose, and total irradiation dosage.     

Influence of surface morphology of the kraft pulp fibers on the growth of the transcrystalline layer of polypropylene

The objective of this study was to evaluate the influence of the wood fiber surface on the crystallization behavior of thermoplastic polymers. Unbleached and bleached kraft pulp fibers were used for this study with 100% polypropylene (PP), 95% PP/5% maleic anhydride polypropylene (MAPP), and 100% MAPP at 150°C. Nuclei were induced at the ends of the fibers and on damaged surfaces while poor crystallization behavior was observed on the fiber surfaces using 100% PP. Enhanced MAPP induced transcrystallization on the wood fiber surfaces; the nucleation density also increased with the addition of MAPP. Oxygen/carbon (O/C) ratios of smooth surfaces, damaged surfaces, and the ends of wood fibers also indicated that the oxidation process of both wood fiber and thermoplastic polymer affected the crystallization process without MAPP addition. It was observed that the MAPP played a role in increasing numbers of nuclei on the linear fiber surface to induce transcrystallization. Dynamic mechanical properties increased 52% with 100% MAPP compared to the use of 100% PP. Therefore, the increased thickness of transcrystalline layer and nucleation density on the surface of wood fiber positively correlated with the dynamic mechanical properties of wood fiber‐plastic composites. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Radiation-Induced graft copolymerization of methacrylic acid onto polypropylene fibers. IV. Thermal behavior

Thermal behavior of polypropylene-g-poly(methacrylic acid) fibers prepared by graft copolymerization of methacrylic acid onto polypropylene fibers, using simultaneous-irradiation technique, was evaluated by thermogravimetric analysis, differential scanning calorimetry, and limiting oxygen index measurements. In general, the thermal properties of polypropylene fiber were markedly improved by the grafting of methacrylic acid. The inherent crystallinity of polypropylene, as deduced from DSC, did not show any change in the grafted fibers, suggesting that the grafting occurs in the amorphous region, without disrupting the crystalline part of the polymer. The LOI of grafted fibers showed an increase over the original fiber.     

Surface Modification of Carbon Fibers by Free Radical Graft‐Polymerization of 2‐Hydroxyethyl Methacrylate for High Mechanical Strength Fiber–Matrix Composites

Free radical polymerization of vinylic monomers in the presence of carbon fibers results in the grafting of polymers onto the carbon fiber surface. Graft polymers cannot be removed by intense washing with good polymer solvents. The density and size of these structures are successfully controlled by reaction conditions. Grafting of the carbon fiber surface with hydroxyethyl methacrylate allows for introducing functional groups suitable for the reaction with an epoxy‐based resin. The resulting fiber‐reinforced composites show enhanced mechanical properties compared to samples prepared from carbon fibers equipped with a standard sizing for epoxy resins. Thus, tensile strength increases by 10%, while interlaminar shear strength improves by 20%.     

Photo-induced polymerization of methyl acrylate vapors on prewetted polyamide and polyester fibers

Photo-induced polymerization of methyl acrylate vapors on polyamide and polyester fibers occurred when these fibers were wetted with the polar solvents methanol, N,N-dimethylformamide, or dimethyl sulfoxide (neat or in aqueous solution). Polymer grafting was accompanied by homopolymer formation, with the amount of grafting and ratio of grafting to homopolymerization being dependent on the fiber type, the solvent used to wet the fiber, and the amount of water present in the wetting solution. Overall deposition of polymer was higher on polyamide than on polyester under all wetting conditions. Water present in the wetting agent had a limited effect on polymerization of poly(methyl acrylate) on polyamide, whereas water caused a rapid decrease in polymerization on polyester. The nature of polymer grafting on the fibers under various wetting conditions was examined by scanning electron microscopy and tensile property measurements, and the mode of polymer deposition was outlined in light of our findings.     

Direct electrochemical attachment of carbon nanotubes to carbon fiber surfaces

A novel electrochemical grafting of carbon nanotubes (CNTs) on the surfaces of carbon fibers using water as dispersive medium was achieved by the electrolysis of carboxylic acid-functionalized CNTs. The resulting CNT-hybridized carbon fibers showed a selective distribution of CNTs at active carbon sites on the fibers associated with the edge graphite layers and defects, without destroying the crystalline structure of carbon fibers. Such hybridized fibers should provide a potential for improving the mechanical properties of advanced composites by increasing the load transfer at fiber/matrix interfaces.     

In-situ composites: Evaluation of the adhesion between the thermoplastic matrix and the fibers of liquid crystalline polymer

Mechanical properties of fiber reinforced composites depend on the formation of stable adhesive bonds between the constituents. In order to evaluate quantitatively the adhesion between liquid crystal polymer (LCP) fibers and a thermoplastic matrix of polycarbonate, the single fiber composite test (SFC), utilized for testing glass or carbon fiber composites, has been used. Neither chemical nor physical interaction has been found: the PC and LCP phases are completely incompatible. However, a mechanical friction between PC and LCP was observed during the drawing of the sample when the neck of the matrix started.     

Producing high‐quality precursor polymer and fibers to achieve theoretical strength in carbon fibers: A review

The precursor fiber quality has a large impact on carbon fiber processing in terms of its performance, production yield, and cost. Polyacrylonitrile precursor fibers have been used commercially to produce strong carbon fibers with average tensile strength of 6.6 GPa. There is a scope to improve the average tensile strength of carbon fibers, since only 10% of their theoretical strength has been achieved thus far. Most attempts to increase the tensile strength of carbon fibers have been made during the conversion of precursor fiber to carbon fiber. This review highlights the potential opportunities to enhance the quality of the polyacrylonitrile‐based precursor fiber during polymer synthesis, spinning, and postspinning. These high‐quality precursor fibers can lead to new generation carbon fibers with improved tensile strength for high‐performance applications. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43963.     

Lyocell fibers as the precursor of carbon fibers

In this work, Lyocell fibers, used as carbon fiber precursors, were investigated. Lyocell fibers used for the carbon precursors and the carbon fibers themselves were produced in our laboratory. The mechanical properties morphology and structure of the precursors and the obtained carbon fibers were studied and compared to those of rayon. The results show that Lyocell fibers have higher tenacity and modulus, and better thermal stability than rayon fibers. Scanning electron microscopy (SEM) experiments show that Lyocell precursors have round cross‐sections and fewer defects in the fibers, while rayon fiber has an oval cross‐section and many defects. Wide angle X‐ray diffraction (WAXD) results for the Lyocell precursors indicate that the degree of crystallinity of the Lyocell precursor is higher than that of a rayon precursor. They also show that Lyocell based carbon fibers have better mechanical properties than those that are rayon‐based. WAXD data of the obtained carbon fibers show that the crystallinity of Lyocell‐based carbon fiber is higher than that of rayon‐based carbon fiber. It is concluded that the Lyocell fibers are better precursors for carbon fibers than rayon. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1941–1947, 2003