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     

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.     

The Effect of Abrasion Surface Treatment on the Bonding Behavior of Various Carbon Fiber-Reinforced Composites

Abstract

In this paper we show that current abrasion surface preparation practices do not perform equally on all composite surfaces. The effect of abrasion on the adhesive bond strength of various carbon fiber (CF) composites was investigated. Cyanate ester composites were fabricated using a low, a high and an ultra high modulus carbon fiber (T300, M55J, K13C2U). XPS and contact angle measurements showed that the surface energy of all three composites increased due to the removal of contaminants as well as increased in surface roughness. However, the lap shear strength degraded sharply for a number of cases, irrespective of roughness, depending on the fiber used. Composites utilizing lower modulus carbon fibers increased in adhesive bond strength following abrasion in comparison to composites with higher modulus fibers. As the modulus of the fiber and the abrasive grit size increased, the degree of degradation caused by abrasion was shown to increase significantly. Scanning electron microscopy (SEM) and profilometry measurements showed the development of an abrasion-affected zone that was especially prevalent for higher stiffness composites. The failures for the higher modulus specimens were caused by subsurface damage located a few fiber diameters below the abraded surface. However, an alternate technique using atmospheric plasma surface treatment exhibited efficient removal of contaminants while showing no degradation of bond quality when treating these ultra high modulus composites.     

Photografting of argon plasma-treated graphite/PEEK laminate to enhance its adhesion

Graphite/PEEK laminates were treated by argon plasma followed by air aging and then photografting of α- glycidyl ω- acrylate bisphenol A(GABA) to improve their adhesion characteristics. The effects of plasma time and power and photografting time on the epoxy bonded single lap shear joints between graphite/PEEK laminates were investigated. An optimum photografting time was found at which the single lap shear strength was optimized to 37 MPa compared to 28 MPa and 7 MPa obtained with air-aged argon plasma activated and pristine samples, respectively. Argon plasma treatment followed by air aging of graphite/PEEK laminate introduces surface peroxides and hydroperoxides and these when cleaved with ultraviolet (UV) light in the presence of the GABA monomer results in covalent grafting of the latter to PEEK/graphite laminate surface. The epoxy functionality of the GABA monomer then reacts with the epoxy adhesive. X-ray photoelectron spectroscopy (XPS) confirms the appearance of surface peroxides and hydroperoxides on air-aged argon plasma treated samples and disappearance of the same with UV irradiation. With UV irradiation of the air-aged argon plasma treated samples, XPS indicates the appearance of ester groups. Without the grafting monomer, UV irradiation in air cleaves the peroxide and causes oxidation resulting in the formation of surface esters. In the presence of the grafting monomer, UV irradiation results in covalent bonding of the monomer to the peroxide/hydroperoxide through the acrylate functionality resulting in increased concentration of ether linkages as confirmed by our XPS data; the ester functionality present in the grafted monomer caused the appearance of the ester peak in the XPS spectrum.     

Improved interfacial adhesion in carbon fiber/poly (ether ether ketone) composites with the sulfonated poly (ether ether ketone) sizing treatment

A water-soluble sulfonated poly (ether ether ketone) (SPEEK) sizing agent is prepared and applied to improve the interfacial adhesion of carbon fiber/poly (ether ether ketone) (CF/PEEK) composites. The surface morphology, surface roughness, surface chemistries, and surface free energy of SPEEK sized CF are obtained to understand the sizing effect. The results reveal the increased surface free energy and surface roughness of SPEEK sized CF. In addition, a chemical reaction between the CF surface and sizing layer is proved based on the results of XPS, IR, and ¹H NMR. The interfacial structure of CF/PEEK composites is further ascertained by AFM and the appearance of gradient interface could be verified for SPEEK sized CF/PEEK composites. The formation of the gradient interface is due to the chemical reaction between the CF and sizing agent as well as the improved compatibility between the sized CF and matrix, which benefits the improvement of interfacial adhesion.     

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.     

碳纤维经氧等离子/KH550处理后的表面形态和结构

碳纤维(CF)表面经氧等离子、KH550和 LiAlH_4处理后,其物理和化学性能得以改善.由于提高了 CF 和树脂间的联结,使 CF 复合材料的层间剪切强度提高50%以上,在湿热下的强度保留率达94%以上.使用纤维接触角测定仪,SEM 和 XPS 等对 CF 表面的浸润性、形态和化学组成进行了研究.实验指出:CF 经等离子和 KH550处理后,其临界表面能有了提高;CF 本身仅受氧离子刻蚀,故其拉伸强度的损失小于其他处理方法.     

Interfacial adhesion of plasma‐treated carbon fiber/poly(phthalazinone ether sulfone ketone) composite

Interfacial adhesion between fiber and matrix has a strong influence on composite mechanical performance. To exploit the reinforcement potential of the fibers in advance composite, it is necessary to reach a deeper understanding on the relation between fiber surface treatment and interfacial adhesion. In this study, air plasma was applied to modify carbon fiber (CF) surface, and the capability of plasma grafting for improving the interfacial adhesion in CF/thermoplastic composite was discussed and also the mechanism for composite interfacial adhesion was analyzed. Results indicated that air plasma treatment was capable of increasing surface roughness as well as introducing surface polar groups onto CF; both chemical bonding and mechanical interaction were efficient in enhancements of interlaminate shear strength of CF/PPESK composite, while mechanical interaction has a dominant effect on composite interfacial adhesion than chemical bonding interaction. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

The improved interface performance between carbon fiber and poly(ether-ether-ketone) by sulfonated polyether sulfone (s-PSF) sizing agent with different sulfonation degree

The effects of sulfonated polyether sulfone (s-PSF) with different sulfonation degrees on the interfacial properties of carbon fiber (CF)/poly(ether-ether-ketone) (PEEK) composites were investigated systematically. The performance of the modified CF and the corresponding CF/PEEK composites and was tested and characterized. Test results show that the CF surface polarity increases, the surface contact angle decreases, and the surface free energy increases with the increase in the s-PSF sulfonation degree. Scanning electron microscopy analysis shows that the increase in the sulfonation degree of s-PSF is beneficial to improve the interface between CF and PEEK. This condition can be ascribed to the hydrogen bonding force between the s-PSF sulfonic acid group and the polar functional group on the surface of the modified CF and the compatibility between s-PSF and PEEK. In terms of physical properties, the thermal and mechanical properties of CF/PEEK composite are improved with the increase in s-PSF sulfonation degree. The interlaminar shear strength, flexural strength, and modulus of CF/PEEK composites increase by 60.16%, 30.27%, and 19.30%, respectively.     

低温等离子体对UHMWPE纤维的表面改性

运用自行研制的常压低温等离子体设备对超高相对分子质量聚乙烯(UHMWPE)纤维进行了表面处理,选用正交试验法通过润湿性测试优化出不同工作气氛下的工艺条件,采用强力测试、扫描电镜(SEM)和光电子能谱仪(XPS)分析了等离子体处理前后UHMWPE纤维的性能变化。结果表明,常压低温等离子体在Ar携带丙烯酸和Ar／O2的气氛下处理UHMWPE纤维,表面改性效果良好。特别是选用Ar／O2流量比100:1,处理速度为5．8 m／min,输出功率189 W,可满足连续化生产。     

连续CF增强PEEK复合材料层压板的制备工艺

采用熔融浸渍法制备了连续碳纤维(CF)增强聚醚醚酮(PEEK)复合材料预浸带,并层压成型制备复合材料层压板。研究了成型温度、成型压力、成型时间、纤维含量等因素对复合材料层压板力学性能的影响。结果表明,在成型温度为370℃、成型压力为12 MPa、成型时间为70 min、纤维含量为61%的工艺条件下,连续CF增强PEEK复合材料层压板的力学性能达到最优值,弯曲强度和弯曲弹性模量分别达到(1 750.76±49.13)MPa和(107.54±6.35)GPa,层间剪切强度达到(100.04±6.88)MPa,缺口冲击强度为(84.44±1.54)k J/m2。随着冷却速率的增大,复合材料层压板的弯曲性能和层间剪切强度下降,而缺口冲击强度提高。SEM分析表明,复合材料层压板的界面粘结良好。     

Effect of the type of plasma on the polydimethylsiloxane/collagen composites adhesive properties

Polydimethylsiloxane (PDMS) films were treated with either oxygen (O₂), nitrogen (N₂) or argon (Ar) plasma between 40 W and 120 W for 5–15 min and their surface properties studied by contact angle measurements, infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and atomic force microscopy (AFM). Lower contact angles and increases in surface roughness, assessed by SEM and AFM, were observed for all used gases when plasma power and time increased, with argon treatment being the one that showed the most significant change in roughness.PDMS/collagen type I composites obtained after treating PDMS with oxygen at 80 W for 13 min or nitrogen and argon at 80 W for 14 min showed a peel strength of 0.1N/mm (oxygen plasma), 0.08 N/mm (nitrogen plasma) and 0.09 N/mm (argon plasma). In all cases, peel strength was higher than that measured for the untreated bilayer composite. An increase in adhesion strength, after oxygen and nitrogen plasma, was mostly attributed to chemical interaction between functional groups introduced on the PDMS surface and the functional groups on collagen as detected by FTIR. In contrast, the high peel strength observed on PDMS treated with argon plasma was attributed to its increased roughness which in turn increased mechanical interlocking. The properties of these composites render them suitable for adhesive free skin substitutes.     

Effect of various methods of pre-treatment of carbon fibers on the mechanical properties of PIP-based ceramics/carbon composites

The purpose of the work was to determine the conditions of CF preparation to obtain carbide composites with favorable mechanical response. The relationships between the interfacial properties of fiber/polymethylsiloxane composite, and mechanical properties of the resulting fiber/carbide composites were investigated. The CF/resin interfacial strength was modified by oxidation of CF surface with nitric acid, silanization, and depositing CNT or a pyrolytic carbon layer (PyC). The study of composite interphases (ILSS and SEM) and surface tests of the modified CF (XPS, FT-IR, wettability measurements) showed different nature of the bonding occurring at the fiber/resin and fiber/ceramics boundary. The CF silanization significantly improved the ILSS between CFs and resin by 38.5%, while reduced flexural properties of carbide composites. The most promising treatment method of CF for PIP-based ceramic composites was modification with PyC, which provided 2 times higher ILSS, 1.5 times higher flexural strength and improved work to fracture (WF) as compared to unmodified CF.     

Improvement of Interfacial Adhesion of Glass Fiber/Epoxy Composite by Using Plasma Polymerized Glass Fibers

This study intends to produce plasma polymer thin films of γ-glycidoxypropyltrimethoxysilane (γ-GPS) on glass fibers in order to improve interfacial adhesion of glass fiber-reinforced epoxy composites. A low frequency (LF) plasma generator was used for the plasma polymerization of γ-GPS on the surface of glass fibers at different plasma powers and exposure times. X-ray photoelectron spectroscopy (XPS) and SEM analyses of plasma polymerized glass fibers were conducted to obtain some information about surface properties of glass fibers. Interlaminar shear strength (ILSS) values and interfacial shear strength (IFSS) of composites reinforced with plasma polymerized glass fiber were evaluated. The ILSS and IFSS values of non-plasma polymerized glass fiber-reinforced epoxy composite were increased 110 and 53%, respectively, after plasma polymerization of γ-GPS at a plasma power of 60 W for 30 min. The improvement of interfacial adhesion was also confirmed by SEM observations of fractured surface of the composites.     

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     

PEEK的表面改性和表征

简要介绍了聚醚醚酮(PEEK)的一些特性及应用。综述了近年来用于PEEK薄膜表面改性的几种方法,包括等离子体处理、紫外辐照及湿化学法等。此外,简要概括了改性PEEK表面的表征方法,如扫描电子显微镜、X射线光电子能谱仪和原子力显微镜等。     

Preadhesion Laser Surface Treatment of Carbon Fiber Reinforced PEEK Composite

An excimer UV laser (193 nm) was used for preadhesion surface treatment of PEEK (polyetheretherketone) composite. This method presented an alternative to other limited and polluting conventional surface treatment methods. Experimental results indicated that laser preadhesion treatment significantly improved the shear and tensile adhesion strength of structural epoxy FM 300 2K bonded PEEK composite adherends compared with untreated and SiC blasted substrates. Best results were obtained with laser energies of 0.18 or 1 J/P cm.² Shear strength of laser-treated joints was improved by 450% compared with that of untreated PEEK composite and by 200% compared with SiC-blasted pretreatment at ambient and at extreme temperatures. An order of magnitude of improvement was found in the tensile strength-of laser-treated PEEK composite in a sandwich structure compared with non-treated or abraded sandwich joints. The mode of failure changed from adhesive to cohesive as the number of pulses or laser energy increased during treatment. The latter phenomenon was correlated with surface cleaning as revealed by XPS, with morphology changes as revealed by scanning electron microscopy, and by chemical modification as indicated by FTIR and XPS. The bulk of the PEEK composite adherend was not damaged by the laser irradiation during treatment as indicated by the identical flexural strength before and after laser treatment. It can be concluded that the excimer laser has a potential as a precise, clean and simple preadhesion surface treatment for PEEK composite.     

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.     

Adhesion Characteristics of Carbon Black Embedded Glass/Epoxy Composite

The surface of glass/epoxy composite material was embedded with carbon black which was dispersed in methyl ethyl ketone (MEK) during the curing process to enhance the adhesion strength of the glass/epoxy composite structure. The morphological effect of the carbon black on the surface of composite was observed using scanning electron microscopy (SEM) and atomic force microscopy (AFM). Quantitative chemical bonding analysis with X-ray photoelectron spectroscopy (XPS) was also performed to observe chemical bonding states on the surface. The lap shear strength of the glass/epoxy composite adhesive joints where composite adherends were embedded with carbon black was investigated with respect to the type and amount of embedment. Also, the tensile properties of the carbon black embedded glass/epoxy composites were measured to observe the mechanical degradation of the composite due to the MEK. The surface free energies of carbon black embedded composites were determined from the van Oss–Chaudhury–Good equation to correlate the lap shear strength of the adhesive joints with the surface free energies of composite adherends. From the experimental results, it was found that the carbon black embedment of the composite adherend improved much the bond strength due to the increased surface roughness on nano-scale as well as increased surface free energy.     

Characterization of diamond fluorinated by glow discharge plasma treatment

The surface fluorination of diamond by treatment in glow discharge plasmas of CF₄ for different times has been investigated. High quality diamond films were deposited onto silicon substrates using hot filament chemical vapor deposition (HFCVD). Subsequently, the films were exposed to a radiofrequency glow discharge plasma of CF₄ for times ranging from 5 min to 1 h. The effects of the plasma treatment on the surface morphology, diamond quality and elemental composition were investigated using atomic force microscopy (AFM), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS), respectively. Differences in film roughness caused by the plasma treatment were detected by AFM and confirmed by scanning electron microscopy (SEM). Raman spectroscopic analyses showed that the original diamond was of high quality and that the bulk of each film was unchanged by the plasma treatment. Analyses using XPS revealed increased surface fluorination of the films at longer treatment times. In addition, the density of free radicals in the films was probed using electron paramagnetic resonance spectroscopy (EPRS), revealing that untreated diamond possesses an appreciable density of free radicals (6×10¹² g⁻¹) which initially falls with treatment time in the CF₄ plasma but increases for long treatment times.