Evaluation of fiber surfaces treatment and sizing on the shear and transverse tensile strengths of carbon fiber-reinforced thermoset and thermoplastic matrix composites

The mechanical performance of advanced composite materials depends to a large extent on the adhesion between the fiber and matrix. This is especially true for maximizing the strength of unidirectional composites in off-axis directions. The materials of interest in this study were PAN-based carbon fibers (XA and A4) used in combination with a thermoset (EPON 828 epoxy) and a thermoplastic (liquid crystal poymer) matrix. The effect of surface treatment and sizing were evaluated by measuring the short-beam shear (SBS) and transverse flexural (TF) tensile strengths of unidirectional composites. Results indicated that fiber surface treatment improves the shear and trasverse tensile strengths for both thermosetting and thermoplastic matrix/carbon fiber-reinforced unidirectional composites. A small additional improvement in strengths was observed as the result of sizing treated fibers for the epoxy composites. Scanning electron microscope photomicrographs were used to determine the location of composite failure, relative to the fiber-matrix interface. Finally, the epoxy composites SBS and TF strengths appear to be limited to the maximum transeverse tensile strength of the epoxy matrix, while the thermoplastic composite SBS and TF strengths are limited by the LCP matrix shear and transverse tensile strengths, respectively.     

Plasma surface modification of carbon fibers: a review

The properties of the fiber/matrix interface in carbon fiber-reinforced composites play a dominant role in governing the overall performance of the composite materials. Understanding the surface characteristics of carbon fibers is a requirement for optimizing the fiber-matrix interfacial bond and for modifying fiber surfaces properly. Therefore, a variety of techniques for the surface treatment of carbon fibers have been developed to improve fiber-matrix adhesion as well as to enhance the processability and handling of these fibers. Many research groups have studied the effects of plasma treatments, correlating changes in surface chemistry with the interfacial shear strength. This article reviews the recent developments relative to the plasma surface modification of carbon fibers.     

Interfacial adhesion between ionic copolymers and high-modulus surface-treated carbon fibers

High-modulus carbon-fiber-reinforced thermoplastic composites typically fail at the interface due to poor adhesion between fiber and matrix. To increase interfacial strength, the research described herein focuses on modifying the fiber surface (via high-temperature acid treatment or zinc electrolysis) to facilitate chemical functional groups on the fiber that might increase fiber-matrix inter-actions. The thermoplastic matrix materials used in this study were random copolymers of ethylene and methacrylic acid in which the carboxyl groups in the methacrylic acid segments were neutralized with either sodium or zinc counterions. Mechanical tests were performed to determine the macroscopic effects of fiber pretreatment on the ultimate mechanical properties of the composites. Fabrication was designed such that fiber-matrix separation provides the dominant contribution to mechanical gracture. Composites containing fibers treated with nitric acid, or a mixture of nitric and sulfuric acids exhibit a 20 to 25 percent increase in transverse (tensile) fracture stress relative to composites fabricated with as-received fibers. Scanning electron microscopy of the fiber-matrix interface at fracture allows one to “zoom-in” and obtain qualitative details related to adhesion. Fracture surface micrographs of the above-mentioned acid-treated fiber-reinforced composites reveal an increase in the amount of matrix material that adhered to the fiber surface relative to the appearance of the fracture surface of composites fabricated with as-received fibers. The presence of acid functionality in the matrix, rather than the divalent nature of the zinc counterions, produces the largest relative enhancement of transverse (tensile) fracture stress in the above-mentioned composites containing surface-treated carbon fibers.     

Effect of chemical treatments of wood fibers on the physical strength of polypropylene based composites

Wood plastic composites attract great attention in various applications. Chemical modification of the wood fiber with NaOH and various coupling agents was performed for wood fiber composites. Wood fibers treated with NaOH, APTES, TEVS, and BC coupling agents were compounded with PP matrix for measuring physical properties. All those chemical treatments increased physical properties much compared to the untreated case because of the elimination of impurities by NaOH treatment and because of the introduction of compatible molecular structure onto the wood fiber surfaces. Especially, the TEVS case showed the best tensile strength, and it could be attributed to the chain structure having double bond of the molecules for high compatibility with PP matrix. The SEM morphology also demonstrated increased adhesion between wood fibers and PP matrix with chemical treatments. The adhesion between wood fiber and PP matrix would be a key parameter in achieving high physical properties of the composite materials.     

Influence of processing conditions on adhesion between carbon fibers and electron-beam-cured cationic matrices

Adhesion between an electron-beam-cured Diglycidyl Ether of Bisphenol A (DGEBA) epoxy matrix and AS4 carbon fibers has been evaluated with the microindentation test method and compared with similar thermally cured materials. The results indicate that the absence of amine compounds and of high temperature treatment associated with thermally cured epoxy matrices are detrimental to fiber-matrix adhesion in electron-beam-cured epoxy matrices when measured by the microindentation test. Electron beam processing was not found responsible for any adsorption and/or deactivation of the irradiated carbon fiber surface as determined by surface analysis with X-ray Photoelectron Spectroscopy (XPS). Moreover, the relationship between electron-beam processing conditions (namely, dose and dose increment) with the resulting matrix properties and the adhesion to carbon fiber have revealed a strong dependency of fiber-matrix adhesion on the bulk matrix properties independent of the electron beam processing history. Undercured electron-beam-processed matrices exhibit higher adhesion to carbon fibers that can be explained by a higher matrix shear modulus.     

INFLUENCE OF PROCESSING CONDITIONS ON ADHESION BETWEEN CARBON FIBERS AND ELECTRON-BEAM-CURED CATIONIC MATRICES

Adhesion between an electron-beam-cured Diglycidyl Ether of Bisphenol A (DGEBA) epoxy matrix and AS4 carbon fibers has been evaluated with the microindentation test method and compared with similar thermally cured materials. The results indicate that the absence of amine compounds and of high temperature treatment associated with thermally cured epoxy matrices are detrimental to fiber-matrix adhesion in electron-beam-cured epoxy matrices when measured by the microindentation test. Electron beam processing was not found responsible for any adsorption and/or deactivation of the irradiated carbon fiber surface as determined by surface analysis with X-ray Photoelectron Spectroscopy (XPS). Moreover, the relationship between electron-beam processing conditions (namely, dose and dose increment) with the resulting matrix properties and the adhesion to carbon fiber have revealed a strong dependency of fiber-matrix adhesion on the bulk matrix properties independent of the electron beam processing history. Undercured electron-beam-processed matrices exhibit higher adhesion to carbon fibers that can be explained by a higher matrix shear modulus.     

Comparative study of interlaminar fracture toughness of GFRP with different fiber surface treatments

This investigation is focused on the influence of glass fiber surface treatment on the interlaminar fracture toughness of unidrectional laminates. Three different fiber surface treatments were considered: polyethylene treated fibers to get poor adhesion, silance treated fibers to get good bond strength, and industrial fibers without special treatments with the coupling agents. The interlaminar fracture behavior of unidirectional glass fiber reinforced composites with different fiber surface treatments has been investigated in mode I, mode II, and for the fixed mixed mode I/II ratio 1.33. Double cantilever beam (DCB), end notched flexure (ENF), and mixed mode flexure (MMF) specimens were used. The data obtained from these tests were analyzed by using different analytical approaches and the finite element method. For the fibers treated with the silane coupling agent, a value about 2.5 times higher of mode II interlaminar fracture toughness for crack initiation was obtained in comparison with the polyethylene sized composite. For the composite made from the industrial fibers, a value about 2 times higher was obtained. Because of extensive fiber bridging and pullout in the composites with poor fiber/matrix adhesion, the results of mode I and mixed mode I/II tests did not characterize the interphase quality. In order to determine the interphase quality, the mode II tests are recommended.     

Acid-base interfaces in fiber-reinforced polymer composites

The role of Lewis acid-base interactions at the fiber-matrix interface in composites is studied with both glass and Teflon fibers. In the glass fiber case, surface chemistry is modified with amino-, methacryloxy- and glycidoxy-silane coupling agents (A-1100, A-174 and A-187, respectively). Silane adsorption mechanisms as well as the properties of filament-wound, unidirectional epoxy and polyester composites are explained by a combination of X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and flow microcalorimetry. The heats of adsorption of pyridine and phenol prove that the coupling agents add acidic sites to the glass fiber surface as well as stronger basic sites. The subsequent adhesion of the matrix polymers and the short beam shear strengths of composites are explained on this basis. The Teflon fibers are first etched with sodium naphthalene solutions, and then sequentially hydroborated and acetylated, producing approximately monofunctional hydroxyl (acidic) and ester (basic) groups on the surfaces, as determined by XPS, FTIR, and electrophoretic mobility analyses. Composites prepared with the acetylated fibers and a chlorinated polyvinyl chloride (acidic) matrix are superior in tensile properties, and SEM fractography shows PTFE fibrillation, indicative of good fiber-matrix adhesion and stress transfer, in this case only.     

Effect of fiber surface modification on the mechanical properties of sisal fiber‐reinforced benzoxazine/epoxy composites based on aliphatic diamine benzoxazine

Sisal fibers were incorporated into a mixture of benzoxazine and bisphenol A type epoxy resins to form a unidirectionally reinforced composite. Surface modifications of the sisal fibers were carried out with sodium hydroxide, γ‐aminopropyltrimethoxysilane, and γ‐glycidoxypropyltrimethoxysilane. The surface treatments led to changes in the morphology, chemical groups, and hydrophilicity of the fibers. The effect of the fiber surface treatments on the fiber–matrix interfacial adhesion and mechanical properties of the composites were also studied. The results showed that surface treatments with sodium hydroxide and a silane coupling agent led to improved fiber–matrix adhesion; this could be seen in the scanning electron micrographs of the fractured surfaces from mechanical testing and the reduction in the impact strength of the composites made from treated fibers. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

A comparative study on the influence of epoxy sizings on the mechanical performance of woven carbon fiber-epoxy composites

In the present work the effect of epoxy sizings on the fracture behavior of woven carbon fiber tetrafunctional epoxy composites has been investigated. Three-point flexural, short beam shear (SBS) and Mode-II interlaminar fracture toughness (ENF) tests have been carried out. Wettability and Atomic Force Microscopy (AFM) studies have been performed on commercial sized, desized and 0.7 wt% TGDDM and 0.7 wt% DGEBA sized carbon fibers. Dynamic mechanical thermal analysis and Scanning Electron Microscopy (SEM) studies were also carried out on the different carbon fiber/epoxy composites. The used sizing treatments provided composites with improved mechanical properties due to the enhancement achieved in the fiber-matrix adhesion. Polym. Compos. 25:319–330, 2004. © 2004 Society of Plastics Engineers.     

The effects of surface treatments of fibers on the interfacial properties in single-fiber composites

The interfacial properties between fibers and the matrix contribute to the overall properties in high performance composites. Plasma treatments (Ar, O₂, CF₄/O₂, N₂/H₂) have been performed on carbon fibers to improve the fiber-matrix interaction. The treatment efficiency was checked by the single-fiber technique, while the surface chemistry and morphology were characterized by X-ray photoelectron spectroscopy (XPS), static secondary ion mass spectroscopy (SSIMS), and scanning electron microscopy (SEM). The O₂- and N₂/H₂-plasma treatments proved most effective both for introducing oxygen-containing functionalities at the fiber surface and for improving the interfacial shear strength of carbon fiber/epoxy composites. A relationship between the oxygen concentration at the fiber surface and the interfacial shear strength is demonstrated.     

CO2 plasma modification of high-modulus carbon fibers and their adhesion to epoxy resins

Interfacial bond strength is often a performance-limiting factor of carbon-fiber-reinforced composites. This limitation is most prevalent when higher-modulus fibers or relatively unreactive matrix resins, such as engineering thermoplastics or high-temperature thermoset resin systems, are used. Radio-frequency (RF) glow discharge plasmas are an effective means of modifying carbon-fiber surface chemical characteristics to promote adhesion. It has been previously shown that oxidizing plasmas are especially effective compared with electro-oxidative treatments for treating carbon fiber surfaces as revealed by titrations, electron spectroscopy, wetting, and inverse gas chromatography measurements. This study evaluated the effectiveness of CO₂ plasmas on two experimental high-modulus carbon/graphite fibers and correlated the plasma surface modification with interfacial adhesion in an epoxy matrix composite system. The results show that CO₂ plasma treatment increased the surface oxygen content by nearly a factor of 2 over typical electro-oxidation treatments. The increased oxygen is mainly in the form of hydroxyl, ketone, and carboxyl-like moieties. Unidirectional composites were prepared from as-received and plasma-modified versions of each type of experimental fiber. The composites containing plasma-modified filaments exhibited 1.5-3.0 times the strength of composites fabricated with untreated or electro-oxidized filaments in transverse-flexural tests. Short-beam shear strength increased by two times over those with as-produced filaments and is equivalent to that of composites containing electro-oxidized filaments.     

Nanoscale toughening of carbon fiber‐reinforced epoxy composites through different surface treatments

Interests in improving poor interfacial adhesion in carbon fiber‐reinforced polymer (CFRP) composites has always been a hotspot. In this work, four physicochemical surface treatments for enhancing fiber/matrix adhesion are conducted on carbon fibers (CFs) including acid oxidation, sizing coating, silane coupling, and graphene oxide (GO) deposition. The surface characteristics of CFs are investigated by Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy, atomic force microscopy, scanning electron microscopy, interfacial shear strength, and interlaminar shear strength. The results showed that GO deposition can remarkably promote fiber/matrix bonding due to improved surface reactivity and irregularity. In comparison, epoxy sizing and acid oxidation afford enhancement of IFSS owing to effective molecular chemical contact and interlocking forces between the fiber and the matrix. Besides, limited covalent bonds between silane coupling and epoxy matrix cannot make up for the negative effects of excessive smoothness of modified CFs, endowing them inferior mechanical properties. Based on these results, three micro‐strengthening mechanisms are proposed to broadly categorize the interphase micro‐configuration of CFRP composite, namely, “Etching” “Coating”, and “Grafting” modifications, demonstrating that proper treatments should be chosen for combining optimum interfacial properties in CFRP composites. POLYM. ENG. SCI., 59:625–632, 2019. © 2018 Society of Plastics Engineers     

The influence of silane coupling agent composition on the surface characterization of fiber and on fiber-matrix interfacial shear strength

It is well known that the fiber-matrix interface in many composites has a profound influence on composite performance. The objective of this study is to understand the influence of composition and concentration of coupling agent on interface strength by coating E-glass fibers with solutions containing a mixture of hydrolyzed propyl trimethoxysilane (PTMS) and n -aminopropyl trimethoxysilane (APS). The failure behavior and strength of the fiber-matrix interface were assessed by the single-fiber fragmentation test (SFFT), while the structure of silane coupling agent was studied in terms of its thickness by ellipsometry, its morphology by atomic force microscopy, its chemical composition by diffuse reflectance infrared Fourier transform (DRIFT), and its wettability by contact angle measurement. Deposition of 4.5 ‐ 10 m 3 mol/L solution of coupling agent in water resulted in a heterogeneous surface with irregular morphology. The SFFT results suggest that the amount of adhesion between the glass fiber and epoxy is dependent not only on the type of coupling agent but also on the composition of the coupling agent mixture. As the concentration of APS in the mixture increased, the extent of interfacial bonding between the fiber and matrix increased and the mode of failure changed. For the APS coated glass epoxy system, matrix cracks were formed perpendicular to the fiber axis in addition to a sheath of debonded interface region along the fiber axis.     

Effect of surface treatment of carbon fiber on the electrical and mechanical properties of high-impact polystyrene composite

Carbon fiber (CF), PU(polyurethane)-coated carbon fiber (CF-PU) and Ni-coated fiber (NCF) treated with a coupling agent (CA) were used to prepare composites for high impact polystyrene (HIPS) by melt blending. The optimum concentration of the titanate CA is 1.5 phf (per hundred parts of filler) when coupled with the carbon fibers. A composite prepared by adding a CA directly into the matrix which was then reinforced with fibers was investigated for comparison. These composites were evaluated for electromagnetic interference shielding effectiveness, dispersion, and adhesion between the polymer and the filler by means of scanning electron microscopy (SEM). The addition of CA generally improved the shielding effectiveness; this is especially apparent when the matrix was pretreated with CA before compounding with the fibers. The tensile properties were also improved upon CA addition.     

Performance of pineapple leaf fiber–natural rubber composites: The effect of fiber surface treatments

Composites of natural rubber (NR) and short pineapple leaf fiber (PALF) were prepared on a laboratory two‐roll mill. The influences of untreated fiber content and orientation on the processing and mechanical properties of the composites were investigated. The dependence of extent of orientation on fiber concentration was also established. Sodium hydroxide (NaOH) solutions (1, 3, 5, and 7% w/v) and benzoyl peroxide (BPO) (1, 3, and 5 wt % of fiber) were used to treat the surfaces of PALFs. FTIR and scanning electron microscope (SEM) observations were made of the treatments in terms of chemical composition and surface structure. The tensile strength and elongation at break of the composites were later studied. The fiber–matrix adhesion was also investigated using SEM technique. It was found that all surface modifications enhanced adhesion and tensile properties. The treatments with 5% NaOH and 1% BPO provided the best improvement of composite strength (28 and 57% respectively) when compared with that of untreated fiber. The PALF‐NR composites also exhibited better resistance to aging than its gum vulcanizate, especially when combined with the treated fibers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1974–1984, 2006     

Effect of Organic Gas Plasmas on the Adhesion of Matrix Resins to Carbon Fibers

IM7 carbon fibers were surface treated in methane, ethylene, trifluoromethane and tetrafluoromethane plasmas. The surface chemical composition of the fibers was determined by X-ray photoelectron spectroscopy (XPS). The adhesion between as-received and plasma-treated carbon fibers and polyethersulfone (PES) and an epoxy resin was measured by the microbond pull-out test. XPS showed that the methane and ethylene plasmas deposited a thin layer of hydrocarbon on the fiber surface. The trifluoromethane plasma deposited a layer of fluorocarbon on the surface of the fibers. The tetrafluoromethane plasma etched the fibers and introduced a significant amount of fluorine on the surface. The microbond pull-out test results indicated that an etching plasma, such as the tetrafluoromethane plasma, improved the adhesion between carbon fibers and PES. These results are consistent with earlier work performed with ammonia plasma. The adhesion is believed to be due primarily to the differential thermal shrinkage between the fiber and the matrix. It was shown that in the case of a reactive matrix such as an epoxy resin, the fiber chemical composition plays a role in the fiber-matrix adhesion. However, this chemical effect is secondary to the cleaning effect of the surface treatment.     

Crystallization and fiber/matrix interaction during the molding of PEEK/carbon composites

The objective of this work was to investigate the effects of molding conditions (molding temperature, residence time at melt temperature, and cooling rate) on the crystallization behavior and the fiber/matrix interaction in PEEK/carbon composites made from both prepreg and commingled forms. In order to investigate the crystallization behavior of the PEEK matrix, the molding process was simulated by differential scanning calorimetric analysis, DSC. The results show that the prepreg and commingled systems do not have the same matrix morphology; prepreg tape was found to be at its maximum of crystallinity, whereas the commingled system was found to be only partially crystalline. The results show that processing must be carried out at a temperature sufficiently high to destroy the previous thermal history of the PEEK matrix; this is an essential requirement to produce efficient fiber/matrix adhesion in the commingled fabric system. Optical microscopic observations also suggest that matrix morphology near the fibers is dependent on the melting conditions; a well-defined transcrystalline structure at the interface is observed only when the melt temperature is sufficiently high. However, the high temperature of molding can easily result in degradation of the PEEK matrix such as chain scission and crosslinking reactions. Thermal degradation of the matrix during processing is found to affect the crystallization behavior of the composites, the fiber/matrix adhesion, and the matrix properties. This effect is more important in the case of a commingled system containing sized carbon fibers because the sizing agent decomposes in the molding temperature range of PEEK/carbon composites. This produces a decrease of the matrix crystallinity and an elimination of the nucleating ability of the carbon fibers. A transition between cohesive and adhesive fracture is observed when the cooling rate increases from 30°C/min to 71°C/min for the composite made from the commingled fabric. This critical cooling rate is found to closely correspond to a change in the mechanism of crystallization of the PEEK matrix.     

Stress-Strain and stress relaxation in oxidated short carbon fiber-thermoplastic elastomer composites

Stress-strain and stress relaxation properties are studied in composites consisting of a thermoplastic elastomer butadiene styrene copolymer (SBS) matrix and oxidated carbon fiber. The results obtained from samples at different degrees of oxidation are contrasted with those obtained from SBS filled with commercial carbon fiber. Carbon fiber oxidation with nitric acid gives rise to an increase in functional surface groups, which in turn enhance the capacity in the fiber to interact with the matrix. In the experimental composites, the increase in fiber-matrix interactions translates into proportionally greater strain necessary to reach the yield point, as well as into an increase in stress at the yield point. In addition, at initial strain below the strain at yield point, a slower stress relaxation rate is observed in oxidated fiber composites, as compared with those recorded for the matrix filled with commercial fiber. In the oxidated fiber composites, stress relaxation occurs in three stages, the first two of which may be associated to the fiber-matrix interface. © 1996 John Wiley & Sons, Inc.     

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.