Plasma Modifications to the Interface in Carbon Fiber Reinforced Thermoplastic Matrices

Radio frequency glow discharge oxygen plasma was used to modify the surfaces of PAN-based and mesophase pitch-based carbon fibers. Surface chemical changes to the fibers were monitored by X-ray photoelectron spectroscopy and by fiber wetting studies evaluated in terms of dispersive-polar components of surface energy and acid-base contribution to the work of adhesion. Physical changes to these fibers were monitored by scanning electron microscopy. Stress transferability of these fibers was evaluated by the embedded single fiber test in poly(methyl methacrylate), poly(ethyl methacrylate), poly(methacrylonitrile) and poly(vinyl chloride) as these matrices offered varying degrees of dispersive-polar and acid-base character. Experimentally determined critical aspect ratios were compared to the theoretical work of adhesion determined by dispersive-polar interactions and with the Lewis acid-base nature of the matrices.     

The Effect of Surface Activation in Polymer Matrix-Carbon Fiber Interactions

Various carbon fibers (CF) were surface modified by chemical and electrochemical treatments for the purpose of establishing organic functional groups on the fiber surface. A series of fibers, surface oxidized for various periods of time, was prepared. The amounts of surface functionalities formed were assessed by means of contact angle measurements on single fibers. A suitable set of probe liquids was used to determine the LW (Lifshitz-van der Waals) and acid-base components of carbon fiber surfaces. Similar tests were made on commercial, sized carbon fibers, polystyrene (PS) and polymethyl methacrylate (PMMA), and their surface energies determined in terms of LW, surface acidity and surface basicity components. Work of adhesion values were calculated of all combinations of CF and polymer matrix couples by using these surface energies of both constituents. The calculated work of adhesion values were correlated to the ILSS values obtained from single fiber pull out tests with PS and PMMA as matrices.     

Surface modification of ultra-high molecular weight polyethylene fibers by γ-radiation-induced grafting

A technique for grafting acrylic polymers on the surface of ultra-high molecular weight polyethylene (UHMWPE) fibers utilizing ⁶⁰Co gamma radiation at low dose rates and low total dose has been developed. Unlike some of the more prevalent surface modification schemes, this technique achieves surface grafting with complete retention of the exceptional UHMWPE fiber mechanical properties. In particular, poly(butyl acrylate) and poly(cyclohexyl methacrylate) were successfully grafted onto UHMWPE fibers with no loss in tensile properties. The surface and tensile properties of the fibers were evaluated using Fourier transform infrared/photoacoustic spectroscopy (FTIR/PAS), X-ray photoelectron spectroscopy (XPS), and tensile tests. The reinforcement efficiency of untreated, polymer-grafted, and plasma-treated UHMWPE fibers in polystyrene and a poly(styrene-co-butyl acrylate-co-cyclohexyl methacrylate) statistical terpolymer was characterized using mechanical tensile tests. The thermoplastic matrix composites were prepared with 4 wt% discontinuous (10 mm), randomly distributed UHMWPE fibers. An approximate 30% increase in composite strength and modulus was observed for poly(cyclohexyl methacrylate)-grafted fibers in the terpolymer and polystyrene matrices. A comparable improvement was realized with the plasma-treated fibers. On the other hand, poly(butyl acrylate) grafts induced void formation, i.e. energy dissipation through plastic deformation and volume expansion at the fiber/matrix interface in terpolymer composites. The latter resulted in a 75% increase in the elongation to failure. The effect of polymer grafts on fiber/matrix adhesion is discussed in terms of the graft and matrix chain interactions and solubility, graft chain mobility, and fracture surface characteristics as determined by scanning electron microscopy (SEM).     

Acid–base interactions and covalent bonding at a fiber–matrix interface: contribution to the work of adhesion and measured adhesion strength

The work of adhesion, W _A, and the practical adhesion in terms of the interfacial shear strength, τ, in some polymer-fiber systems were determined to establish a correlation between these quantities. An attempt was made to analyze the contributions of various interfacial interactions (van der Waals forces, acid-base interaction, covalent bonding) to the 'fundamental' and 'practical' adhesion. The surface free energies of the fibers were altered using different coupling agents. To characterize the strength of an adhesion contact, the ultimate adhesion strength, τ_ult, was determined for the onset of contact failure. The adhesion of non-polar polymers occurs through van der Waals interaction only; therefore, fiber sizing does not affect the adhesion strength. For polar polymers, such as poly(acrylonitrile butadiene styrene) and polystyrene, adhesion is sensitive to fiber treatments: suppression of the acid-base interaction by using an electron-donor sizing agent γ-aminopropyltriethoxysilane results in a decrease of both 'fundamental' and 'practical' adhesion. In the case of epoxy resins, the main contribution to the work of adhesion is made by covalent bonds. Since the process of their formation is irreversible, the work of adhesion determined from micromechanical tests seems to be more reliable than indirect estimations, such as from wetting and inverse gas chromatography techniques. Fiber treatment by sizing agents results in considerable changes in the intensity of adhesional interaction with the epoxy matrix. A correlation between the work of adhesion, the ultimate interfacial shear strength, and the strength of macro-composites has been found.     

Enhancement of surface adhesion between thermoplastic resin and carbon fiber using polymer colloids

To enhance the interfacial adhesion between carbon fiber and thermoplastic resin, poly(methyl methacrylate) (PMMA) particles were adsorbed on the carbon fiber. It was found that positively charged PMMA particles were readily adsorbed on the carbon fiber, and the interfacial shear strength between the modified carbon fiber and the resin was enhanced. In addition, the interaction between the carbon fiber coated with particles to the PMMA resin would be improved, and the surface adhesion between them was strengthened.     

A Comparison of the Work of Adhesion Obtained from Wetting and Vapor Adsorption Measurements

Some of the limitations to determining experimental values of the work of adhesion are discussed. Wetting measurements appear to provide the most direct means of assessing the work of adhesion for a solid-liquid system, but they require the formation of a finite contact angle by the liquid against the solid of interest, and the need for independent knowledge of the equilibrium spreading pressure of the liquid's vapor on the solid further limits their applicability. Vapor adsorption measurement using the technique of inverse gas chromatoraphy (IGC) provides a promising alternative means of determining the work of adhesion not subject to these limitations. The measurements are, furthermore, amenable to solids which are difficult to use with wetting measurements, e.g., those which are porous or granular. An attempt is made here to compare values of the work of adhesion determined using both wetting and vapor adsorption measurements. Good agreement is attained between the two methods for diiodomethane in contact with poly (vinyl chloride), poly (methyl methacrylate), and chemi-thermo-mechanical wood pulp fibers, suggesting that the technique of IGC is particularly well-suited for rapid determination of the work of adhesion.     

Evidence of Acid-Base Interfacial Adducts in Various Polymer/Metal Systems by IRAS: Improvement of Adhesion

The physical interactions of polymers with inorganic substrates are determined by two major contributions: Van der Waals forces and acid-base interactions, taken in the most general “Lewis” electron acceptor-donor sense. The present work shows that the work of adhesion can be very appreciably increased by the creation of interfacial acid-base interactions. Practically, polymers such as poly(ethylene-co-vinyl acetate) (EVA), terpene-phenol resins (TPR), and their blends, were solution cast on basic and acidic substrates. The nature of the interfacial bonds and the enthalpy of adduct formation through electron exchange are evidenced by Fourier transform infrared reflection-absorption spectroscopy (IRAS). Moreover, it is shown that, on the one hand, modification of the electron donor ability of the polymer functionalities reveals the amphoteric character of the substrate and, on the other hand, modification of the electron donor ability of the substrate changes the nature of the species involved in interfacial adduct formation. Then, practical adhesion tests were carried out in order to correlate the nature and strength of interfacial acid-base bonds with simultaneous increases in adhesive strengths. Thermodynamic considerations allowed us to propose estimated values of the acid-base work of adhesion, W^ab, and of the density of acid-base sites, n^ab.     

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.     

Charaterization of UHMWPE fiber/matrix adhesion by dynamic mechanical spectrometry

The tensile and dynamic mechanical properties of polystyrene and a poly(styrene-co-buty1 acrylate-co-cyclohexy1 methacrylate) statistical terpolymer (terpolymer) reinforced by randomly oriented, discontinuous ultra-high molecular weight polyethylene (UHMWPE) fibers are presented in terms of the fiber/matrix interfacial properties. Using a thermomechanical block model based on the parallel rule of mixtures, the adhesion characteristics of poly(butyl acrylate) (PBA) and poly(cyclohexyl methacrylate) (PCHM) grafted, plasma treated, and untreated fibers were determined. The model successfully predicts the tan δ response of the composites including peak height variations and the development of additional loss dispersions associated with the interphase. Moreover, the model yields a fiber reinforcement efficiency factor, K, which gives a quantitative measure of adhesion. The contact angle of PBA and PCHM grafted high density polyethylene (HDPE) films are also included and are compared to the contact angle of plasma treated fibers. The results indicate that PBA and PCHM grafts enhance adhesion through polymer graft/matrix interactions, not simply by improved wetting.     

低温等离子体改性UHMWPE纤维的表面性能

采用空气低温等离子体改善超高相对分子质量聚乙烯(UHMWPE)短纤维的黏着性,设计正交试验对改性后纤维的黏着性进行测试与分析,确定出较优试验方案;然后对未处理和经较优方案改性后的UHMWPE短纤维的表面形貌、表面化学成分、表面润湿性和强伸性进行测试分析。结果表明:空气低温等离子体改性UHMWPE短纤维黏着性的较优处理条件为功率50 W、压强15 Pa、反应时间120 s,此时,纤维的剥离功是未处理的4.14倍,黏着性得到了大幅度的提升,且单纤维强力损失率仅为3.29%;经较优方案处理后,纤维表面的粗糙程度有所增加,表面润湿性有明显改善,纤维表面的C元素含量明显减少,O、N元素含量有所增加,且出现了相对含量为22.2%的C=O官能团,有利于UHMWPE短纤维黏着性的改善。     

Evidence of Acid-Base Interfacial Adducts in Various Polymer/Metal Systems by IRAS: Improvement of Adhesion

The physical interactions of polymers with inorganic substrates are determined by two major contributions: Van der Waals forces and acid-base interactions, taken in the most general “Lewis” electron acceptor-donor sense. The present work shows that the work of adhesion can be very appreciably increased by the creation of interfacial acid-base interactions. Practically, polymers such as poly(ethylene-co-vinyl acetate) (EVA), terpene-phenol resins (TPR), and their blends, were solution cast on basic and acidic substrates. The nature of the interfacial bonds and the enthalpy of adduct formation through electron exchange are evidenced by Fourier transform infrared reflection-absorption spectroscopy (IRAS). Moreover, it is shown that, on the one hand, modification of the electron donor ability of the polymer functionalities reveals the amphoteric character of the substrate and, on the other hand, modification of the electron donor ability of the substrate changes the nature of the species involved in interfacial adduct formation. Then, practical adhesion tests were carried out in order to correlate the nature and strength of interfacial acid-base bonds with simultaneous increases in adhesive strengths. Thermodynamic considerations allowed us to propose estimated values of the acid-base work of adhesion, W^ab , and of the density of acid-base sites, n^ab .     

A Comparison of the Work of Adhesion Obtained from Wetting and Vapor Adsorption Measurements

Some of the limitations to determining experimental values of the work of adhesion are discussed. Wetting measurements appear to provide the most direct means of assessing the work of adhesion for a solid-liquid system, but they require the formation of a finite contact angle by the liquid against the solid of interest, and the need for independent knowledge of the equilibrium spreading pressure of the liquid's vapor on the solid further limits their applicability. Vapor adsorption measurement using the technique of inverse gas chromatoraphy (IGC) provides a promising alternative means of determining the work of adhesion not subject to these limitations. The measurements are, furthermore, amenable to solids which are difficult to use with wetting measurements, e.g., those which are porous or granular. An attempt is made here to compare values of the work of adhesion determined using both wetting and vapor adsorption measurements. Good agreement is attained between the two methods for diiodomethane in contact with poly (vinyl chloride), poly (methyl methacrylate), and chemi-thermo-mechanical wood pulp fibers, suggesting that the technique of IGC is particularly well-suited for rapid determination of the work of adhesion.     

Improvement of the interfacial adhesion between PBO fibers and PPESK matrices using plasma‐induced coating

This work deals with the plasma‐induced coating process on the surface of PBO fibers to obtain a strong interfacial adhesion between the poly(p‐phenylene benzobisoxazole) (PBO) fibers and the poly(phthalazinone ether sulfone ketone) (PPESK) matrices. The process consisted of four steps: (a) plasma preactivation of PBO fibers; (b) immersion in an epoxy resin solution; (c) drying and then soaking with the PPESK solution; (d) shaped by compression molding technique. The orthogonal experiments used in this study enable the determination of the significant experimental parameters that influence efficiency of the process by comparing the values of ILSS. The order of their influences was the concentration > power > treating time > treating pressure. The results of the interlaminar shear strength (ILSS) and water absorption showed that the ILSS of the composite increased by 56.5% after coating, meanwhile the water absorption declined to 0.32%. The changes of the surface chemical composition, the surface morphology, and the surface free energy of fibers were studied by FTIR spectroscopy, atomic force microscope (AFM), and dynamic contact angle analysis (DCAA), respectively. Fracture mechanism of the composite was examined by scanning electron microscope (SEM). The results indicated that plasma‐induced coating process was an efficient method to enhance the interfacial adhesion of PBO fibers and PPESK matrices. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Acid-base character of carbon fiber surfaces

The acid-base character of the surfaces of commercially available carbon fibers used in advanced composites is determined using both pulsed and continuous flow microcalorimetry techniques. The carbon fibers investigated include unsized versions of AS4, IM6, IM7X, T300, and several Apollo fibers with different levels of surface treatment. All of these carbon fiber surfaces are amphoteric and energetically heterogeneous. In general, the heats of preferential adsorption in the pulsed flow mode of bases dissolved in n-heptane are larger than for acids. While most of the adsorbates used are reversibly and physically adsorbed onto the carbon fibers, some primary and secondary amines exhibit irreversible binding to a portion of the surface. In continuous flow experiments the adsorption heat isotherms for several bases on T300 display a sharp jump at low probe concentrations, reflecting the energetically heterogeneous nature of these surfaces. Comparisons between the flow microcalorimetry data and other measures of the surface chemistry are made. Pulsed flow adsorption heats correlate with the amount of oxidized carbon species on the fiber surfaces as detected using ESCA, and recently reported results of inverse gas chromatography and programmed thermal desorption (S. Wesson, Textile Research Institute). Calorimetry results are also compared with fracture mechanical measures of fiber-resin adhesion in manufactured composites. Adsorption heats of both acids and bases on selected carbon fibers correlate with edge delamination and 90° flexural strengths of composites composed of these fibers in both epoxy and bismaleimide resins. This supports a causal connection between carbon fiber surface adsorption heats and a practical measure of fiber-resin adhesion.     

Adhesion of Polypropylene Fiber to Cement Matrix

Abstract

In this research, the adhesion of polypropylene (PP) fibers to cementitious matrix has been investigated and the chemical bonding and mechanical interlocking between PP fiber and hardened cement paste has been studied. Furthermore, thermodynamic work of adhesion and loss-function (dissipation energy) has been calculated in the PP-cement matrix model system. To investigate the work of adhesion, the pull-out test has been used. Also, the surface free energy and contact angle of the PP monofilaments and cement matrix have been measured using a tensiometer and the fiber–cement interfacial interactions and thermodynamic work of adhesion and loss-function were calculated. Scanning electron microscopy (SEM) analysis was used to study the fiber–cement matrix interfacial transition zone (ITZ). The results showed that the application of theories of polymer–polymer adhesion in fiber–cement matrix systems was feasible. To verify the accuracy of the method, the adhesion of two other fibers (nylon 6,6 and acrylic polymer) was studied.     

Surface modification of ultra-high strength polyethylene fibers for enhanced adhesion to epoxy resins using intense pulsed high-power ion beam

The effects of intense pulsed high power ion beam (HPIB) treatment of ultra-high strength polyethylene (UHSPE) fibers on the fiber/epoxy resin interface strength were studied. For this study, argon ions were used to treat Spectra? 1000 (UHSPE) fibers in vacuum. Chemical and topographical changes of the fiber surfaces were characterized using Fourier transform infrared spectroscopy in attenuated total reflectance mode (FTIR-ATR), X-ray photoelectron spectroscopy (XPS), dynamic wettability measurements, and scanning electron microscopy (SEM). The fiber/epoxy resin interfacial shear strength (IFSS) was evaluated by the single fiber pull-out test. The FTIR-ATR and XPS data indicate that oxygen was incorporated onto the fiber surface as a result of the HPIB treatment. The wettability data indicate that the fibers became more polar after HPIB treatment and also more wettable. Although the total surface energy increased only slightly after treatment, the dispersive component decreased significantly while the acid-base component increased by a similar amount. SEM photomicrographs revealed that the surface roughness of the fibers increased following the HPIB treatment. The single fiber pull-out test results indicate that HPIB treatment significantly improved the IFSS of UHSPE fibers with epoxy resin. This enhancement in IFSS is attributed to increased roughness of the fiber surface resulting in mechanical bonding and in increased interface area, increased polar nature and wettability, and an improvement in the acid-base component of the surface energy after the HPIB treatment.     

Evaluation of Adhesion Property of UHMWPE Fibers/Nano-epoxy by a Pullout Test

Ultrahigh-molecular-weight polyethylene (UHMWPE) fibers have poor wetting and adhesion properties to polymer resins because of the inert surface of the fibers. In our previous study, a reactive nano-epoxy matrix, developed by making a modification on the matrix with reactive graphitic nanofibers (r-GNFs), showed improved wettability to UHMWPE fibers. In this work, fiber bundle pullout tests were conducted to evaluate the adhesion property between the UHMWPE fibers and the nano-epoxy matrices. Analysis of load-displacement curves from pullout tests shows that debonding initiation load and ultimate debonding load increased considerably, because of effective improvement of adhesion between the UHMWPE fibers and nano-epoxy matrix. Stress-controlled and energy-controlled models of interfacial debonding were applied for theoretical analyses. Results from ultimate IFSS, frictional shear stress, and critical energy-release rate are in good agreement with experimental results. Nano-epoxy matrix with 0.3 wt% r-GNFs shows effective improvement in terms of adhesion property between UHMWPE fiber and epoxy.     

Effect of Poly(methyl Methacrylate) Modified Water Hyacinth Fiber on Properties of Low Density Polyethylene/Natural Rubber/Water Hyacinth Fiber Composites

The effect of poly(methyl methacrylate) modified water hyacinth fiber on properties of low density polyethylene (LDPE)/natural rubber (NR)/water hyacinth fiber (WHF) composites were investigated. The composites were prepared with Z-blade mixer at 180°C and rotor speed of 50 rpm. The poly(methyl methacrylate) modified water hyacinth fibers in LDPE/NR composites (LDPE/NR/WHF-_PMMA) gave a greater value of tensile strength, Young's modulus, glass transition temperature (Tg), melting temperature (Tm), and % crystallinity compared to unmodified water hyacinth fibers in LDPE/NR composites (LDPE/NR/WHF). FTIR analysis shows the presence of ester carbonyl group and C-O ester group in poly (methyl methacrylate) modified water hyacinth fiber. The SEM micrograph also shows a better interfacial adhesion between the fibers and LDPE/NR matrixes for LDPE/NR/WHF-_PMMA composites than LDPE/NR/WHF composites. LDPE/NR/WHF-_PMMA composites had a lower value of interparticle spacing compared to LDPE/NR/WHF composites thatenhanced the interparticle interaction between fiber and LDPE/NR matrixes.     

玻璃纤维表面的聚甲基丙烯酸甲酯接枝

本文用臭氧对表面涂有ＭＡＣ试剂的玻璃纤维进行了处理，使玻纤表面产生活性中心，引发甲基丙烯酸甲酯在玻璃纤维表面上接枝聚合，接枝纤维的密度减小，对水的浸润性下降，红外光谱及扫描电镜观察证明玻璃纤维表面上有聚甲基丙烯酸存在。     

Influence of the fiber surface properties on the mechanical strength of unidirectional fiber composites

The influence of the thermodynamic adhesion between fibers and matrix on the mechanical properties of a continuous fiber reinforced composite is studied for two systems: carbon fiber reinforced poly(ether ether ketone) and glass fiber reinforced poly(ether imide). The fibers are modified chemically and characterized by measuring the contact angle formed by molten resin on the fibers. Various fiber treatments yield a wide range of contact angles, which are determined optically. Unidirectional fiber reinforced laminates are manufactured and transverse flexural strength is measured with the values reported as a function of the specific work of adhesion. It is shown that adhesion at the fiber-resin interface correlates with both the composite strength and the void morphology within the laminate after consolidation.