The Tribological Properties of Polypropylene Composite Filled with DBD-Treated Carbon Fiber

Dielectric barrier discharges (DBD) in ambient air are used on carbon fiber to improve the carbon fiber surface activity. Carbon fibers with length of 75 um are placed into the plasma configuration. The tribological properties of polypropylene filled with untreated and DBD treated carbon fiber are comparatively investigated. Results show that DBD treatment greatly improve the friction and wear properties of carbon fiber reinforced polypropylene composite (CF/PP).     

Wettability assessment of plasma-treated PBO fibers based on thermogravimetric analysis

Changes in the surface wettability of poly(p-phenylene benzobisoxazole) (PBO) fibers were investigated by thermogravimetric analysis (TGA) following an air dielectric barrier discharge (DBD) plasma treatment. The results were then supplemented and confirmed by scanning electron microscopy (SEM), dynamic contact angle analysis (DCAA), X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) measurements. After exposure to the DBD plasma at a pre-determined power level, TGA analysis showed that the residual rates retained by the PBO composites decreased, which meant an increase in the amount of resin coating the PBO fibers in the composites. Observations by SEM confirmed that there was more resin adhering to the treated PBO fibers and the wetting behavior of resin on the fibers was greatly improved. Meanwhile, DCAA for the treated fibers showed a significant enhancement in fiber surface free energy. XPS and AFM were performed in order to reveal any variations in fiber surface activity and surface morphology resulting from the surface treatment. The resulting data showed that increases in oxygen-containing polar groups and surface roughness on the plasma-treated PBO fibers contributed to the above improved wetting behavior. With comprehensive analyses, it was concluded that TGA could be used as a supporting method assessing the surface wettability of PBO fibers before and after air DBD plasma treatment.     

Hydrophobic recovery of repeatedly plasma-treated silicone rubber. Part 2. A comparison of the hydrophobic recovery in air,water, or liquid nitrogen

Surfaces of medical grade silicone rubber (Q7-4750, Dow Corning) were modified by repeated (six times) RF plasma treatments using various discharge gases: oxygen, argon, carbon dioxide, and ammonia. The treated samples were stored for a period of 3 months in ambient air, water, or liquid nitrogen. Subsequently, the temporal behavior of the effects of the plasma treatment on the physicochemical surface properties of the silicone rubber was investigated using water contact angle measurements and X-ray photoelectron spectroscopy (XPS). Hydrophobic recovery during 3 months storage in ambient air was considerable and nearly complete for all four plasmas used. Hydrophobic recovery was almost completely suppressed during storage in liquid nitrogen, and only a minor increase of around 10° in advancing water contact angle was observed for all four plasma treatments. Also during storage of treated samples in water, hydrophobic recovery was minimal and initiated again by returning the treated samples to ambient air. XPS analyses showed that argon, carbon dioxide, and ammonia plasma-treated silicone rubber all had increased carbon percentages at the expense of oxygen and silicon after storage in water, or in liquid nitrogen, compared with after storage in ambient air. Interestingly, the carbon content of oxygen plasma-treated silicone rubber decreased during storage in water, or in liquid nitrogen, compared with storage in ambient air, while its oxygen and silicon percentages increased.     

A study of the effect of oxygen plasma treatment on the interfacial properties of carbon fiber/epoxy composites

In this work, effects of the interface modification on the carbon fiber‐reinforced epoxy composites were studied. For this purpose, the surface of carbon fibers were modified by oxygen plasma treatment. The surface characteristics of carbon fibers were studied by X‐ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), dynamic contact angle analysis (DCAA), and dynamic mechanical thermal analysis (DMTA), respectively. The interlaminar shear strength (ILSS) was also measured. XPS and AFM analyses indicated that the oxygen plasma treatment successfully increased some oxygen‐containing functional groups concentration on the carbon fiber surfaces, the surface roughness of carbon fibers was enhanced by plasma etching and oxidative reactions. DCAA and DMTA analyses show that the surface energy of carbon fibers increased 44.9% after plasma treatment for 3 min and the interfacial bonding intensities A and α also reached minimum and maximum value respectively. The composites exhibited the highest value of ILSS after oxgen plasma treated for 3 min. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Influence of plasma surface treatments on kink band formation in PBO fibers during compression

The effect of nitrogen and oxygen plasma surface treatments on the compressive strength of PBO fibers has been studied. To this end, the nucleation and propagation of compression‐induced kink bands was carefully monitored by means of in situ bending tests inside a scanning electron microscope. The micromechanisms of deformation were identical irrespective of fiber surface condition (either as‐received or modified by plasma) but the critical stress necessary to induce irreversible damage in compression in the nitrogen‐plasma treated fibers was 40% higher than in the as‐received fibers. This improvement occurred without any reduction in the fiber tensile properties. The source of this behavior is discussed in the light of the morphological and chemical changes induced by the plasma treatments on the fiber surface, as studied by AFM and XPS. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

XPS study of the PET film surface modified by CO2 plasma: effects of the plasma parameters and ageing

Chemical modification of the PET surface by carbon dioxide plasma treatment has been studied using X-ray photoelectron spectroscopy (XPS). The plasma process results mainly in the formation of carbonyl, carboxyl, and carbonate groups at the PET surface. Under rather mild treatment conditions (low plasma power combined with a short treatment time), the formation of C-O bonds was found to be dominant, whereas the formation of highly oxidized carbon or double-bonded oxygen-containing groups required a high plasma power or a relatively long treatment time. The treatments performed under excessive conditions frequently led to degradation at the polymer surface. Angle-resolved XPS analyses performed on a freshly modified PET film showed a slight decrease in the O/C atomic ratio when the take-off angle (TOA) increased, indicating a relatively uniform distribution of oxygen within the sampling depth (estimated to be about 8 nm at 80° TOA). The chemical composition of the plasma-modified surface was found to be relatively stable on extended storage in air under ambient conditions. The decrease in oxygen-containing groups at the carbon dioxide-plasma-treated PET surface upon ageing is mainly ascribed to the surface rearrangement of macromolecular segments, the loss of oxygen-containing moieties introduced by the plasma treatment, and the possible migration of non-affected PET chains from the bulk to the surface region.     

Wetting and adhesion behavior of armos fibers after dielectric barrier discharge plasma treatment

To investigate the influence of atmospheric plasma treatment on aramid fiber wetting and adhesion behavior, an air dielectric barrier discharge (DBD) was applied to the Armos aramid fiber surface at different discharge power densities. Dynamic contact angle analysis indicated that the total surface free energy was increased from 49.6 to 68.3 mJ/m 2 , an increment of 37.7%, whereas the single-fiber tensile strength testing showed that the mechanical properties of the Armos fibers were almost unaffected. With the enhancement of fiber surface wettability, the interlaminar shear strength, which was used to determine the interfacial adhesion in Armos-fiber-reinforced thermoplastic poly(phthalazinone ether sulfone ketone) composites, increased by 17.2% to 71.4 MPa. Scanning electron microscopy photos showed that the predominant failure mode of the composites changed from interface failure to matrix and/or fiber failure after the plasma treatment. Taken together, these results suggest that the air DBD plasma was an effective technique for improving the surface and interfacial performance of the Armos fibers without damaging their bulk properties. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Surface Characterization of Plasma Treated Carbon Fibers and Adhesion to a Thermoplastic Polymer

The surface chemistry of IM7 carbon fibers was characterized by x-ray photoelectron spectroscopy (XPS). The fiber surface energetics were determined from a two-liquid tensiometric method. The adhesion between as-received and plasma-treated carbon fibers and polyethersulfone (PES) was measured by the microbond pull-out test.

The surface characterization techniques showed that the effect of any plasma treatment is attained within less than 15 seconds. It was found that both argon and air plasmas increased the oxidation state of the fiber surface and that they reduced the dispersive component (γ_s ^d) of the fiber surface free energy considerably. The ammonia plasma treatment resulted in a cleaning of the surface. This plasma treatment was also effective in improving the fiber/matrix adhesion of quenched samples. A similar adhesion enhancement between as-received fibers and PES is obtained by annealing the samples above the Tg of the polymer. The air plasma treatment did not have any significant effect on the fiber/matrix adhesion.     

Surface composition of carbon fibers subjected to oxidation in nitric acid followed by oxygen plasma

Type II, PAN-based carbon fibers (unsized and commercially treated) have been exposed to nitric acid and oxygen plasma individually and also to combined nitric acid/oxygen plasma treatments and the surface compositions have been determined using angle-resolved X-ray photoelectron spectroscopy (ARXPS) and ion scattering spectroscopy (ISS). Most of the oxygen on the as-received carbon fibers resides within the outermost 10-15 Å of the surface. Fiber exposure to nitric acid at 115°C for 20-90 min enhances the oxygen surface concentration to a point of saturation and the oxygen depth distribution is increased and becomes more uniform within the maximum XPS sampling depth (~60-100 Å). In addition, the fiber surface area is believed to be increased. After treating fibers to various degrees in nitric acid, subsequent exposure to oxygen plasma yields an additional increase in the surface oxygen content, particularly in the outermost fiber layers (10-15 Å). Under the conditions of the investigation, the maximum amount of surface oxidation occurs after sequential fiber exposure to nitric acid at 25°C for 30 s and oxygen plasma. As the extent of initial nitric acid treatment is increased, the synergism with subsequent plasma oxidation decreases, and the oxygen concentration becomes more uniform within the outer layers of the oxidized fibers. Overall, the data are consistent with a proposed oxidation mechanism in which oxygen plasma acts to enhance the surface density of oxygen on roughened and pitted nitric acid-oxidized fiber surfaces. As the duration of nitric acid exposure is increased, it is hypothesized that subsequent exposure to oxygen plasma smoothes the fiber surfaces but the surface density of oxygen remains essentially constant.     

Surface modification of ultra high modulus polyethylene fibers by an atmospheric pressure plasma jet

To improve their adhesion properties, ultra high modulus polyethylene (UHMPE) fibers were treated by an atmospheric pressure helium plasma jet (APPJ), which was operated at radio frequency (13.56 MHz). The surface properties of the fibers were investigated by X‐ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and contact angle measurement. The surface dyeability improvement after plasma treatments was investigated using laser scanning confocal microscopy (LSCM). The adhesion strengths of the fibers with epoxy were evaluated by microbond tests. In addition, the influence of operational parameters of the plasma treatment including power input and treatment temperature was studied. XPS analysis showed a significant increase in the surface oxygen content. LSCM results showed that the plasma treatments greatly increased fluorescence dye concentrations on the surface and higher diffusion rate to the fiber center. The tensile strength of UHMPE fiber either remained unchanged or decreased by 10–13.6% after plasma treatment. The contact angle exhibited a characteristic increase in wettability, due to the polar groups introduced by plasma treatment. The microbond test showed that the interfacial shear strengths (IFSS) increase significantly (57–139%) after plasma treatment for all groups and the optimum activation is obtained at 100°C and 5 W power input. SEM analysis showed roughened surfaces after the plasma treatments. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Surface Characterization of Plasma Treated Carbon Fibers and Adhesion to a Thermoplastic Polymer

The surface chemistry of IM7 carbon fibers was characterized by x-ray photoelectron spectroscopy (XPS). The fiber surface energetics were determined from a two-liquid tensiometric method. The adhesion between as-received and plasma-treated carbon fibers and polyethersulfone (PES) was measured by the microbond pull-out test.

The surface characterization techniques showed that the effect of any plasma treatment is attained within less than 15 seconds. It was found that both argon and air plasmas increased the oxidation state of the fiber surface and that they reduced the dispersive component (γ_s^d) of the fiber surface free energy considerably. The ammonia plasma treatment resulted in a cleaning of the surface. This plasma treatment was also effective in improving the fiber/matrix adhesion of quenched samples. A similar adhesion enhancement between as-received fibers and PES is obtained by annealing the samples above the Tg of the polymer. The air plasma treatment did not have any significant effect on the fiber/matrix adhesion.     

Highly Hydrophobic Wood Surfaces Prepared by Treatment With Atmospheric Pressure Dielectric Barrier Discharges

Atmospheric dielectric barrier discharge (DBD) treatments of wood were done to attain water repellency on wood surfaces. A specially designed frequency controlled parallel-plate DBD reactor was utilized to produce the discharges. Ethylene, methane, chlorotrifluoroethylene and hexafluoropropylene were used as DBD reagents. Contact angle, water absorption, X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) measurements on the modified surfaces were performed. For methane and ethylene, XPS data showed an increased surface atomic concentration of carbon from 72.7% on untreated samples up to 80.7 and 96%, respectively, whereas nearly 50% fluorine concentration was observed with fluorinated reagents. The C_1s spectrum of hexafluoropropylene-DBD-treated wood sample showed that the CF₃ group was introduced in a relative amount of 19%. AFM images showed distinct features for each of the DBD treatments, such as a deposit of a thin uniform film in the case of ethylene-DBD treatment, whereas the hexafluoropropylene-DBD treatment resulted in the nucleation of plasma-derived entities at the fiber surface and the subsequent growth of a film. Under optimized conditions the water contact angle was in the range of 139°–145°. The combination of depositing a low surface energy polymer on an already rough surface gave the surface-treated wood a highly hydrophobic character.     

Surface treatments of vapor-grown carbon fibers produced on a substrate

Vapor-grown carbon fibers (VGCF) were grown from a methane-hydrogen mixture on a reconstituted graphite support using different catalyst precursors, the [Fe₃(CO)₁₂] complex being found to be the most efficient for the production of VGCF. The fibers thus produced were characterized and submitted to different oxidative treatments, namely nitric acid, plasma, air and carbon dioxide. From analysis performed by scanning electron microscopy (SEM), nitrogen adsorption (BET) and X-ray photon spectroscopy (XPS) it appears that the air and carbon dioxide treatments do not lead to significant increase either of the surface area, or of the quantity of surface oxygen containing groups, despite the considerable weight loss attained (50%). This peculiar observation has been interpreted by considering the presence of traces of iron at the fibers surface, which can catalyze the gasification of carbon. The presence of iron on the VGCF has been evidenced for the first time by the time-of-flight secondary ion mass spectrometry technique. The cleansing of the fibers surface with concentrated hydrochloric acid results in the removal of the iron and leads, after CO₂ activation, to an improvement of the BET surface area. The use of nitric acid or plasma as oxidation agents does not affect significantly the surface morphology of the fibers, but greatly increases the number of surface oxygen functions.     

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.     

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.     

Effect of Atmospheric Plasma Treatment on Carbon Fiber/Epoxy Interfacial Adhesion

In this work the effect of atmospheric plasma treatment on carbon fiber has been studied. The carbon fibers were treated for 1, 3 and 5 min with a He/O₂ dielectric barrier discharge atmospheric pressure plasma. The fiber surface morphology, surface chemical composition and interfacial shear strength between the carbon fiber and epoxy resin were investigated using atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and the single fiber composite fragmentation test. Compared to untreated carbon fibers, the plasma treated fiber surfaces exhibited surface morphological and surface composition changes. The fiber surfaces were found to be roughened, the oxygen content on the fiber surfaces increased, and the interfacial shear strength (IFSS) improved after the atmospheric pressure plasma treatment. The fiber strength showed no significant changes after the plasma treatment.     

Analysis of Among-Species Variability in Wood Fiber Surface Using DRIFTS and XPS: Effects on Esterification Efficiency

Abstract

Variability in the chemical composition of surface properties of various wood fibers (eastern white cedar, jack pine, black spruce, and bark) was investigated using diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and X-ray photoelectron spectroscopy (XPS). Both DRIFTS and XPS showed high variability in fiber surface composition between species and between fiber types (sapwood, heartwood, and bark). Fiber surface was modified by esterification reaction using a maleic anhydride polyethylene (MAPE) treatment. DRIFTS failed to assess surface modification, whereas XPS results showed that MAPE treatment increased the surface hydrocarbon concentration of jack pine wood fiber, indicated by a decrease in oxygen–carbon ratio and an increase in relative intensity of the C1 component in the C1s signal. Lignin concentration variability on the fiber surface was determined as the major factor that prevents esterification from taking place.     

Effects of Microwave Processing on Fiber-Matrix Adhesion. II. Enhanced Chemical Bonding of Epoxy to Carbon Fibers

The effect of microwave processing on the chemical interactions occurring between the carbon fiber surface and the epoxy matrix constituents was investigated using X-ray Photoelectron Spectroscopy (XPS). Monofunctional model compounds selected to duplicate the matrix constituents were exposed to the carbon fibers at temperatures similar to those encountered during composite processing. After solvent extraction, chemisorbed species were quantified by XPS. Differences were apparent in the C 1s and O 1s core electron regions of the microwave treated samples when referenced to the same elemental regions of thermally (convection) treated samples. Specifically, the atomic percentage of oxygen (in the form of carbon oxides) was increased to a greater degree when using the microwave treatment as opposed to the thermal treatments. The microwave treatment resulted in a substantial increase in the amount of chemical interaction between the fiber surface and the epoxy resin and amine components of the matrix. An epoxy resin/amine hardener adduct compound was also used to investigate the possible interaction of the adduct hydroxyl group with the carbon fiber surface. XPS results indicate a low to insignificant interaction of the hydroxyl with the carbon fiber surface under the conditions used in this study.     

Effects of Microwave Processing on Fiber-Matrix Adhesion. II. Enhanced Chemical Bonding of Epoxy to Carbon Fibers

The effect of microwave processing on the chemical interactions occurring between the carbon fiber surface and the epoxy matrix constituents was investigated using X-ray Photoelectron Spectroscopy (XPS). Monofunctional model compounds selected to duplicate the matrix constituents were exposed to the carbon fibers at temperatures similar to those encountered during composite processing. After solvent extraction, chemisorbed species were quantified by XPS. Differences were apparent in the C 1s and O 1s core electron regions of the microwave treated samples when referenced to the same elemental regions of thermally (convection) treated samples. Specifically, the atomic percentage of oxygen (in the form of carbon oxides) was increased to a greater degree when using the microwave treatment as opposed to the thermal treatments. The microwave treatment resulted in a substantial increase in the amount of chemical interaction between the fiber surface and the epoxy resin and amine components of the matrix. An epoxy resin/amine hardener adduct compound was also used to investigate the possible interaction of the adduct hydroxyl group with the carbon fiber surface. XPS results indicate a low to insignificant interaction of the hydroxyl with the carbon fiber surface under the conditions used in this study.     

Influence of oxygen plasma treatment parameters on the properties of carbon fiber

This study is focused on the impact of oxygen plasma treatment on properties of carbon fibers and interfacial adhesion behavior between the carbon fibers and epoxy resin. The influences of the main parameters of plasma treatment process, including duration, power, and flow rate of oxygen gas were studied in detail using interlaminar shear strength (ILSS) of carbon fiber composites. The ILSS of composites made of carbon fibers treated by oxygen plasma for 1 min, at power of 125 W, and oxygen flow rate of 100 sccm presented a maximum increase of 28% compared to composites made of untreated carbon fibers. Furthermore, carbon fibers were characterized by scanning electron microscopy (SEM), tensile strength test, attenuated total reflectance Fourier transform infrared (ATR-FTIR), and Raman spectroscopy analyses. It was found that the concentration of reactive functional groups on the fiber surface was increased after the plasma modification, as well the surface roughness, which finally improved the interfacial adhesion between carbon fibers and epoxy resin. However, high power and long exposure times could partly damage the surface of carbon fibers and decrease the tensile strength of filaments and ILSS of treated fiber composites.