Influence of oxygen plasma treatment on interfacial properties of poly(p‐phenylene benzobisoxazole) fiber‐reinforced poly(phthalazinone ether sulfone ketone) composite

The influence of oxygen plasma treatment on both surface properties of poly(p‐phenylene benzobisoxazole) (PBO) fibers and interfacial properties of PBO fiber reinforced poly(phthalazinone ether sulfone ketone) (PPESK) composite were investigated. Surface chemical composition, surface roughness, and surface morphologies of PBO fibers were analyzed by X‐ray photoelectron spectroscopy (XPS), Atomic force microscopy (AFM), and scanning electron microscopy (SEM), respectively. Surface free energy of the fibers was characterized by dynamic contact angle analysis (DCAA). The interlaminar shear strength (ILSS) and water absorption of PBO fiber‐reinforced PPESK composite were measured. Fracture mechanisms of the composite were examined by SEM. The results indicated that oxygen plasma treatment significantly improved the interfacial adhesion of PBO fiber‐reinforced PPESK composite by introducing some polar or oxygen‐containing groups to PBO fiber surfaces and by fiber surface roughening. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and characterization of poly(γ‐methacryloxypropyltrimethoxysilane)‐grafted silica hybrid nanoparticles prepared by surface‐initiated atom transfer radical polymerization

Poly(γ‐methacryloxypropyltrimethoxysilane) (PMPTS)‐grafted silica hybrid nanoparticles were prepared by surface‐initiated atom transfer radical polymerization (SI‐ATRP). The resulting PMPTS‐grafted silica hybrid nanoparticles were characterized using Fourier transform infrared spectroscopy (FTIRS), nuclear magnetic resonance (NMR), gel permeation chromatography (GPC), X‐ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), scanning electron microscopy (SEM), static water contact angle (WCA) measurement, and thermogravimetric analysis (TGA). Combined FTIRS, NMR, XPS, SEM, and TGA studies confirmed that these hybrid nanoparticles were successfully prepared by surface‐initiated ATRP. SEM and AFM studies revealed that the surfaces of the nanoparticles were rough at the nanoscale. In addition, the results of the static WCA measurements showed that the nanoparticles are of low surface energy and their surface energy reaches as low as 6.10 mN m^?1. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Surface ammonification of the mutual‐irradiated aramid fibers in 1,4‐dichlorobutane for improving interfacial properties with epoxy resin

The mutual irradiated aramid fibers in 1,4‐dichlorobutane was ammoniated by ammonia/alcohol solution, in an attempt to improve the interfacial properties between aramid fibers and epoxy matrix. Scanning electron microscopy (SEM), X‐ray photoelectron spectroscopy (XPS), dynamic contact angle analysis (DCA), interfacial shear strength (IFSS), and single fiber tensile testing were carried out to investigate the functionalization process of aramid fibers and the interfacial properties of the composites. Experimental results showed that the fiber surface elements content changed obviously as well as the roughness through the radiation and chemical reaction. The surface energy and IFSS of aramid fibers increased distinctly after the ammonification, respectively. The amino groups generated by ammonification enhanced the interfacial adhesion of composites effectively by participating in the epoxy resin curing. Moreover, benefited by the appropriate radiation, the tensile strength of aramid fibers was not affected at all. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44924.     

Poplar wood–methylol urea composites prepared by in situ polymerization. II. Characterization of the mechanism of wood modification by methylol urea

A prepolymer was used to prepare wood/prepolymer composites by a pulse‐dipping machine. The mechanical properties and dimensional stability were evaluated. The characterization of natural and modified woods was performed by Fourier transform infrared spectroscopy, ¹³C‐NMR spectroscopy, X‐ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM) with energy‐dispersive X‐ray analysis (EDXA). Cross‐polarization/magic‐angle spinning ¹³C‐NMR analysis revealed that the in situ polymerization between the prepolymer and the hydroxyls in the wood structure took place with the reduction of hydroxyl groups. XPS analysis indicated that the content of carbon decreased, whereas the content of oxygen increased. SEM–EDXA indicated a good dispersion of the modifier in the wood fiber and other vertical cells. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42406.     

UV photo‐stabilization of tetrabutyl titanate for aramid fibers via sol–gel surface modification

Tetrabutyl titanate was used as sol–gel precursor of a nanosized TiO₂ coating to improve the photo‐stability of aramid fibers. The nanosized TiO₂ coating was characterized by XRD and XPS. The influence of the TiO₂ coating on photo‐stability of aramid fibers was investigated by an accelerated photo‐ageing method. The photo‐stability of aramid fiber showed obvious improvement after coating. After 156 h of UV exposure, the coated fibers showed less deterioration in mechanical properties with the retained tensile strength and elongation at break greater than 36 and 50% of the original values, respectively, whereas the uncoated fibers degraded completely and became powdery. SEM analysis showed no significant surface morphological change on the coated fiber after the exposure, while some latitudinal crack fractures appeared on the uncoated aramid fiber. The effect of the nanosized TiO₂ coating was also well demonstrated by examining the difference of distributions of C1s in XPS deconvolution analysis on the surface of uncoated/coated fibers with increasing UV exposure time. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3113–3119, 2007     

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     

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.     

Effects of XeCl excimer laser treatment of Vectran® fibers and their adhesion to epoxy resin

Vectran^® fibers, made using liquid crystalline polyester, were treated with pulsed XeCl excimer laser (308 nm) to alter their surface characteristics and, thus, improve their adhesion to epoxy resin. The treatments were carried out in air using varying numbers of pulses at different laser fluences. The effects of laser treatment on the fiber surface topography, chemistry and wettability have been investigated. Fiber/epoxy resin interfacial shear strength was measured using the microbead test. The surface roughness was characterized qualitatively and quantitatively using scanning electron microscopy (SEM) and atomic force microscopy (AFM), respectively. Changes in the surface energy were characterized using the Wilhelmy technique. Based on the SEM micrographs, the threshold fluence for the formation of surface structure was found to be less than 36 mJ/(pulse ? cm²). The laser treatments at fluences higher than the threshold fluence introduced periodic roll (wavy) structures on the fiber surface transverse to the fiber axis. From the AFM results, the fiber surface roughness was found to increase by up to 3.5 times the control fiber after the laser treatment. The dispersion component of the surface energy decreased, while the acid–base component of the surface energy increased significantly from 0 to 8.8 mJ/m² after the laser treatment. The Vectran^® fiber/epoxy resin IFSS increased by up to 75% after the laser treatment. This improvement is mainly attributed to higher surface roughness of the fiber.     

Atomic force microscopy,X-ray diffraction,X-ray photoelectron spectroscopy and thermal studies of the new melamine fiber

This paper reports the characterization of unaged and aged melamine fibers using various characterization techniques including atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), scanning electron microscopy (SEM) and thermal analysis. Since melamine fiber is a relatively new fiber, very few studies on its characterization have been made. Morphological studies of the fiber surface using SEM display die lines running along the filament surface, which are characteristics of synthetic fibers and generally occur during spinning of the molten prepolymer through the spinnerets. AFM studies show that the surface of a melamine fiber filament contains a large number of hills and valleys, which are triangular in shape. AFM roughness analysis shows that melamine fiber surface is considerably rough which may aid in adhesion of the fiber with polymeric matrices. Ageing causes an increase in the surface roughness with simultaneous increase in the crystallinity of the fiber from 19.4% to 22.6%. In XPS studies, high concentrations of carbonyl and hydroxyl groups on the filament surface have been detected. Ageing causes a reduction in the hydroxyl group concentration and an increase in the carbonyl group concentration due to surface oxidation. The reduction in the surface hydroxyl groups due to ageing has also been detected in the Fourier-Transform infrared (FT-IR) spectra of the aged fibers. Thermogravimetric (TG) studies reveal a high thermal stability of the melamine fiber even in an oxidative environment such as air.     

Energy filtered low voltage “in lens detector” SEM and XPS of natural fiber surfaces

Most analyses of natural fibers give the average composition of the fiber and not the nature and distribution of surface species present. The nature of the fiber surface is important since it governs interfacial adhesion between fiber and matrix and the transfer of stress to the fiber in composite materials. The surface of caustic treated flax fibers is analyzed using X‐ray photoelectron spectroscopy (XPS) and a low voltage scanning electron microscopy (SEM) technique that uses a filtered in‐lens electron detector. XPS shows that the fiber surface is not composed of a single polymer but is a mixture of materials, probably degraded lignin and hemicellulose and extractives. The SEM technique shows patches of material on the surface with different contrast and this contrast is shown to result from different average atomic number (Z). The variation in surface composition has obvious implication in variable interfacial properties in composites made using natural fibers. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39572.     

Development of composites based on recycled polyethylene/sugarcane bagasse fibers

In this work, sugarcane bagasse fibers were used as filler in composites having recycled high‐density polyethylene (PEr) as matrix. Because of the poor interaction between fibers surface and the PEr, the surface of bagasse was chemically modified. This modification consists of washing with water at 80°C, a mercerization process using sodium hydroxide and acetylation reaction with acetic anhydride. The chemical modification was characterized by Fourier transform infrared–horizontal attenuated total reflectance (FTIR‐HATR) and ¹³C nuclear magnetic resonance spectroscopies (NMR), thermogravimetric analysis (TGA), and scanning electronic microscopy (SEM). The composites were prepared from modified and unmodified fibers into PEr matrix, containing 5, 10, and 20% (w/w) of fiber. The samples were processed by extrusion and molds were prepared by injection process in order to perform mechanical tests. These materials were analyzed by SEM, TGA, and the water uptake was evaluated. Also, their mechanical properties were analyzed. Morphological analysis indicated that the chemical modification of sugarcane bagasse increased the compatibility between matrix and reinforcement. Tensile, flexural, and impact tests showed that the mechanical properties of the composite were improved compared to PEr due to the presence of the fibers. POLYM. COMPOS., 35:768–774, 2014. © 2013 Society of Plastics Engineers     

Preparation and property of waterborne UV‐curable chain‐extended polyurethane surface sizing agent: Strengthening and waterproofing mechanism for cellulose fiber paper

Waterborne UV‐curable polyurethane (UWPU) dispersions with different hydrophilicity and functionalities were prepared by varying the content of dimethylol butanoic acid (DMBA) and pentaerythritol triacrylate (PETA). And linear and cyclic chain extenders with different functionalities were also incorporated into the UWPU backbone, including isophorone diamine (IPDA), diethylene triamine (DETA), and ethylene diamine (EDA). Effects of DMBA content, PETA content, photoinitiator content, UV curing time, chain extender on the properties of UWPU dispersions and films, as well as the properties of the unsized and sized paper were investigated. The water resistance and mechanical properties of sized paper were greatly relied on the particle size, the molecular weight, the croslinking density, and penetrability of UWPU. UWPU dispersion chain extended with IPDA (IPDA‐UWPU) displayed smaller particle size than that of UWPU. The paper sized with IPDA‐UWPU was endowed with best water resistance, tensile strength, folding strength and surface strength. XPS depth analysis revealed that IPDA‐UWPU exhibited better penetrability into the paper substrate than UWPU. SEM and AFM demonstrated that the smoothness of sized paper was improved, and the bond strength between fibers was enhanced. The obtained UWPU could be directly used as an effective and fast drying surface sizing agent for cellulose fiber paper. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42354.     

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.     

Surface immobilization of polymer brushes onto porous poly(vinylidene fluoride) membrane by electron beam to improve the hydrophilicity and fouling resistance

Poly(vinylidene fluoride) (PVDF) membrane was pre-irradiated by electron beam, and then poly(ethylene glycol) methyl ether methacrylate (PEGMA) was grafted onto the membrane surface in the aqueous solution. The degree of grafting was significantly influenced by the pH value of the reaction solution. The surface chemical changes were characterized by the Fourier transform infrared attenuated total reflection spectroscopy (FTIR-ATR) and X-ray photoelectron spectroscopy (XPS). Combining with the analysis of the nuclear magnetic resonance proton and carbon spectra (¹H NMR and ¹³C NMR), PEGMA was mainly grafted onto the membrane surface. Morphological changes were characterized by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The porosity and bulk mean pore size changes were determined by a mercury porosimeter. The surface and bulk hydrophilicity were evaluated on the basis of static water contact angle, dynamic water contact angle and the dynamic adsorption process. Furthermore, relative high permeation fluxes of pure water and protein solution were obtained. All these results demonstrate that both hydrophilicity and fouling resistance of the PVDF membrane can be improved by the immobilization of hydrophilic comb-like polymer brushes on the membrane surface.     

Fabrication of superhydrophobic fabric coating using microphase‐separated dodecafluoroheptyl‐containing polyacrylate and nanosilica

Superhydrophobic coating was developed on cotton fabric in this article using a dodecafluoroheptyl‐containing polyacrylate (DFPA) and nanosilica. Film morphology of DFPA on cotton fibers/fabrics and chemical compositions of the treated cotton fabric were investigated using scanning electron microscopy (SEM), atomic force microscopy (AFM), and X‐ray photoelectron spectroscopy (XPS), respectively. DFPA could form a relatively even film on the cotton fabric/fiber under SEM observation; however, it presented a rough and microphase‐separated pattern under AFM observation. There were many mountain‐like protuberances. The height of the protuberances and the root mean square roughness (R_ms) of the film reached about 20–50 nm and 12.511 nm in 2 × 2‐μm² scanning field (as the scale data was 100 nm). XPS analysis indicated that the perfluoroalkyl groups had the tendency to enrich at the film–air interface. DFPA could make the treated cotton fabric with a water contact angle (WCA) at about 138.5°. Cotton fabric was previously roughened using a 1 wt % silica sol with an average particle size of 20–30 nm and then finished by DFPA; hydrophobicity of the resultant cotton fabric was strongly improved, and WCA could reach 153.6°. The color of this superhydrophobic fabric would not be influenced, but its softness decreased compared to untreated fabric. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effect of plasma duty cycle on silver nanoparticles loading of cotton fabrics for durable antibacterial properties

A facile method for strongly anchoring silver nanoparticles (AgNPs) onto cotton fabrics was reported. It consists in loading AgNPs onto the cotton fiber preliminary coated with maleic anhydride plasma polymer layer. This results in hydrolyzis and ring opening of anhydride groups followed by electrovalent bonding of silver ions and reduction in NaBH₄. X‐ray photoelectron spectroscopy (XPS), infrared spectroscopy, and scanning electron microscope (SEM) were used to analyze changes in the surface chemical composition and morphology of the plasma modified fibers. The presence of AgNPs was confirmed by UV–Visible spectroscopy and atomic force microscopy (AFM) images. Remarkably, varying plasma duty cycle for plasma polymer deposition allowed tailoring the amount of loaded AgNPs. The highest amount of AgNPs was obtained with the lowest duty cycle values. Qualitative tests showed that silver containing plasma modified cotton displays significant antibacterial activity. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41279.     

A study on Xe excilamp treatment of wool fibers

A Xe excilamp (λ = 172 nm) was applied to photo irradiate and surface modify wool fibers. The scanning electron microscopy (SEM) showed that the outer surface of the fibers was etched after excilamp treatment, and some microcracks emerged on the surface scales. X‐ray photoelectron spectroscopy (XPS) analysis indicated that the excilamp‐treated fibers possessed high concentration of oxygen, sulfur, and nitrogen, as well as increased hydrophilic groups, such as hydroxyl group, carboxyl group, and sulphur oxide species on the surface. Fourier transform infrared spectroscopy with attenuated total internal reflectance (FTIR‐ATR) mode measurement showed that the sulphur oxide species was mainly composed of cysteic acid and S‐sulphonate together with a small amount of cystine monoxide and cystine dioxide on the outer surface of excilamp‐treated wool fiber. The contact angle of water on the excilamp‐treated fiber decreased about 110°. Using an acid dye, deeper hue was achieved in dyeing the treated fibers, evidenced by improved relative color strength (K/S) and brightness (L^*) values. And the directional friction effect (DFE) of the wool fibers in wet obviously decreased after the excilamp treatment. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Enhancing the Interfacial Properties of Composites by Grafting Polyethylene Glycol and Polyvinyl Alcohol Onto a CF Surface

In this study, a carboxy esterification reaction was used to graft the hydrophilic polymers polyethylene glycol (PEG) and polyvinyl alcohol (PVA) onto the surface of carbon fibers (CFs). The properties of the grafted CFs were investigated by scanning electron microscopy (SEM), atomic force microscopy (AFM), X‐ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TG) and through the measurement of interlaminar shear strength (ILSS). SEM enabled the graft morphology on CF surfaces to be determined. In comparisons of grafted and non‐grafted CFs, AFM indicated that the roughness was significantly improved; XPS showed that the concentration of oxygen‐containing functional groups increased by 186.1%; TG showed that the grafting rate of CF‐grafted PEG (CF‐g‐PEG) was 0.5%, and that of CF‐grafted PVA (CF‐g‐PVA) was 2.0%; and the ILSS of CF‐g‐PEG and CF‐g‐PVA increased by 22.7% and 43.0%, respectively. We conclude that esterification grafting is an effective method for modifying the physicochemical properties of CFs and improving the interfacial adhesion of composites. POLYM. ENG. SCI., 59:1043–1050, 2019. © 2019 Society of Plastics Engineers     

Surface modification of aramid fibers with γ‐ray radiation for improving interfacial bonding strength with epoxy resin

Co⁶⁰ γ‐ray radiation as a simple and convenient method for surface modification of Armos aramid fibers was introduced in this article. Two kinds of gas mediums, N₂ and air, were chosen to modify aramid fiber surface by γ‐ray irradiation. After fiber surface treatment, the interlaminar shear strength values of aramid/epoxy composites were enhanced by about 17.7 and 15.8%, respectively. Surface elements of aramid fibers were determined by XPS, the analysis of which showed that the ratio of oxygen/carbon was increased. The crystalline state of aramid fibers was determined by X‐ray diffraction instrument. The surface topography of fibers was analyzed by atomic force microscopy and scanning electron microscope. The degree of surface roughness and the wettability of fiber surface were both enhanced by γ‐ray radiation. The results indicated that γ‐ray irradiation technique, which is a suitable way of batch process for industrialization, can significantly improve the surface properties of aramid fibers reinforced epoxy resin matrix composites. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Improvement of interfacial properties in bismaleimide composites using functionalized graphene oxide grafted carbon fiber

A hierarchical reinforcement, which was used to improve the interfacial properties of bismaleimide (BMI) composites, was prepared by grafting functionalized graphene oxide (GO) onto a carbon fiber surface. The GO and carbon fibers were first functionalized separately to create interactional functional groups on their surfaces. The grafting process was then realized by an amidation reaction of the amine and acyl chloride function groups formed on GO and carbon fibers, respectively. The surface groups of functionalized GO and carbon fibers were identified by an X‐ray photoelectron spectroscopy (XPS). The resulting reinforcement was further characterized by scanning electron microscopy (SEM), atomic force microscopy (AFM) and dynamic contact angle analysis. Experimental results showed that the functionalized GO were successfully grafted onto the carbon fibers surfaces and significantly increased the surface energy of carbon fibers. The study also indicated that the prepared hierarchical reinforcement could significantly improve the interfacial adhesion of resulting BMI composite. POLYM. ENG. SCI., 58:886–893, 2018. © 2017 Society of Plastics Engineers