常压等离子射流表面改性超高模量聚乙烯纤维

利用常压等离子射流(APPJ)方法对超高模量聚乙烯(UHMPE)纤维进行表面改性处理。研究了处理前后UHMPE纤维的力学性能、表面形貌、化学成分、表面粘结性能的变化。结果表明,常压等离子射流处理后,UHMPE纤维的强度未发生显著变化,纤维表面粗糙度增加,表面氧元素的含量增加,表面极性基团增加,纤维与环氧树脂之间的粘结性能得到显著的改善。     

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     

The role of additional silane coupling agent treatment in oxygen plasma-treated UHMPE fiber/vinylester composites

Ultra-high modulus polyethylene (UHMPE) fiber was treated with oxygen plasma and a silane coupling agent in order to improve the interfacial adhesion between the UHMPE fiber and vinylester resin. The oxygen plasma and γ-methylmethacryloxypropyltrimethoxysilane (γ-MPS)-treated UHMPE fiber/vinylester composites showed a slightly higher interlaminar shear strength than the oxygen plasma-treated UHMPE fiber/vinylester composites. The interfacial adhesion of the oxygen plasma-treated UHMPE fiber/vinylester composites in this study is mainly due to mechanical interlocking between the micropits formed by the oxygen plasma treatment and the vinylester resin. The γ-MPS molecules adsorbed onto the UHMPE fiber surface neither affected the morphology of the UHMPE fiber surface, nor reduced the extent of mechanical interlocking. The improved interfacial adhesion by the γ-MPS treatment is due to enhanced wettability and chemical interaction through the chemically adsorbed γ-MPS molecules, as detected by Fourier-transform infrared (FT-IR) spectroscopy. The γ-MPS molecules adsorbed onto the ultra-high molecular weight polyethylene (UHMWPE) plate surface also reduced the aging effect of the oxygen plasma-treated UHMWPE surface.     

Modified shear lag model for fibers and fillers with irregular cross-sectional shapes

For fibers with irregular cross sections such as ultrahigh modulus polyethylene (UHMPE) fibers and ribbon-like carbon fibers, the original shear lag model would not provide accurate calculations for interfacial shear stress because it assumes a circular fiber cross section. In this study, a modified shear lag model is proposed to calculate the interfacial shear stress that reflects the change of fiber cross-sectional shape. Microbond test on a UHMPE fiber/epoxy system was used for verification of the model. The difference between the interfacial shear strength (IFSS) calculated using the modified model and that using the original model assuming an equivalent fiber diameter was found to be as high as 15% and it linearly increased as the irregularity of the cross-sectional shape increased. When the irregularity constant exceeds 1.12, the error in IFSS involved in using the original shear lag model and an equivalent fiber diameter is greater than 10%.     

Effect of Glycerol Coating on the Atmospheric Pressure Plasma Treatment of UHMWPE Fibers

In order to investigate how coatings of glycerol affects atmospheric pressure plasma treatment, ultra high molecular weight polyethylene (UHMWPE) fibers were first pretreated with 0.2 and 0.6 mol/l glycerol solutions, respectively, and then were modified by an atmospheric pressure plasma jet (APPJ) using helium as the carrier gas with a flow rate of 20 l/min, discharge power of 30 W and a radio frequency of 13.56 MHz. After the plasma treatment, scanning electron microscopy (SEM) and atomic force microscopy (AFM) analysis revealed that the glycerol coated-APPJ treated samples possessed smoother surface than the APPJ directly treated samples. The X-ray photoelectron spectroscopy (XPS) analysis indicated that the changed content of oxygen containing groups on the surface of the glycerol coated groups compared with the non-glycerol coated group was mainly due to the remaining glycerol on the fiber surfaces. The water contact angle test revealed that the wettability of the glycerol coated-APPJ treated fibers decreased slightly in comparison with the APPJ directly treated fibers. Furthermore, the microbond pull-out test indicated that the interfacial bonding of the fiber to epoxy resin decreased when the fiber was pretreated with glycerol before plasma treatment. Therefore, it was concluded that the presence of glycerol on fiber surface weakened the effectiveness of APPJ treatment of UHMWPE fibers in improving the interfacial bonding to epoxy. This was mainly attributed to the consumption of plasma energy in etching the glycerol layer on the fiber surface and a weak interfacial layer due to the presence of residual glycerol.     

Atmospheric-pressure plasma treatment of polyamide 6 composites for bonding with polyurethane

An atmospheric-pressure plasma jet (APPJ)-based surface treatment process was investigated for the structural (τ_B > 15 MPa) adhesive bonding of polyamide 6 (PA6) composites. The treated surfaces were examined by contact angle measurement, X-ray photoelectron spectroscopy, and atomic force microscopy (AFM). Additionally, the shear strengths of single lap specimens were determined as a function of different plasma intensities and polyurethane adhesives. Our results show that APPJ leads to an increase of the surface free energy, oxygen concentration, and number of functional groups. Furthermore, the topography of the surface was significantly modified by exposure to APPJ. AFM measurements show that special attention has to be paid to the intensity of the plasma treatment to avoid melting and flattening of the PA6 surface on the nanometer scale. With optimized multiple APPJ treatments, lap shear strength of 20 MPa was achieved for the first time for this material system, allowing the material system to be employed in future automobile applications.     

常压等离子体改善高性能纤维粘结性的研究

以氦气为载气,氧气为反应气体,对高强度聚乙烯和Twaron 1000芳纶两种高性能纤维进行常压等离子体处理,来改善纤维的粘结性能;采用单纤维抽拔实验测定等离子体处理前后纤维与环氧树脂之间的界面剪切力;利用原子力显微镜和X射线光电子能谱仪分析等离子体处理前后纤维表面形态和化学成分的变化。结果表明:高强度聚乙烯纤维和芳纶经常压等离子体处理后,纤维表面粗糙度增加,纤维表面碳元素含量下降,羟基、羧基等含氧或氮的极性基团增加,纤维粘结性能得到提高,但其强度无明显变化。     

Influence of temperature and relative humidity on aging of atmospheric plasma jet treatment effect on ultrahigh-modulus polyethylene fibers

The aging effects of atmospheric pressure plasma treated fiber surfaces are important for storage and processing of the fibers. One of the high-performance fibers, ultrahigh modulus polyethylene (UHMPE) fiber, was chosen as a model system to investigate the aging process of atmospheric pressure plasma jet (APPJ) treated fibers surfaces 0, 7, 15 and 30 days after initial plasma treatment. The fiber was first plasma-treated and then stored at temperatures varying from ?80 to 80°C on the same relative humidity (RH, 0%) and on RH of 0%, 65% and 100% at the same temperature of 20°C. Immediately after the plasma treatment, scanning electron microscope (SEM) showed the roughened fiber surface. X-ray photoelectron spectroscopy analysis showed changed surface chemical compositions. Contact-angle measurement showed increased surface wettability and microbond test showed an increase in IFSS. With increasing relative humidity or decreasing temperature, the IFSS value decreased and the contact angle increased more slowly. However, after 30 days, the IFSS values and contact angles reached a similar level for all groups. Moisture showed no effect on the single fiber tensile strengths during aging. The reasons for the observed aging behavior could be that decreasing temperature or increasing relative humidity hindered the surface rearrangement of polymer chains after plasma treatment.     

Impact behavior of carbon fiber/ultra-high modulus polyethylene fiber hybrid composites

Carbon fiber (CF)/ultra-high modulus polyethylene (UHMPE) fiber hybrid composites were fabricated using vinyl ester resin as a matrix. Interfacial adhesion of carbon fiber/vinyl ester composites and UHMPE fiber/vinyl ester composites as model composites was optimized using low temperature plasma treatment. Interlaminar shear strengths of carbon fiber/vinyl ester and UHMPE fiber/vinyl ester homocomposite were greatly increased by plasma and silane coupling agent treatment. From the result of the impact test, total absorbed energy of carbon fiber/UHMPE fiber hybrid composites was correlated with laminating sequences at optimized interfacial adhesion between the reinforcing fiber and matrix resin. UHMPE fiber layers of hybrid composites played an important role in absorbing energy. Elastic and plastic deformation of UHMPE fiber layers also played a key role in improving the impact properties of carbon fiber/UHMPE fiber hybrid composites.     

Application of the microbond technique. IV. Improved fiber–matrix adhesion by RF plasma treatment of organic fibers

The microbond technique is a modification of the single-fiber pullout test for measuring interfacial shear strength. Briefly, a cured microdroplet of material is debonded in shear from a single fiber. Ultra-high modulus polyethylene (Spectra) fibers and aramid fibers (Kevlar) were treated using a radio frequency plasma in order to increase the interfacial bond between the fibers and an epoxy resin. The treated fiber surface was subsequently analyzed by X-ray photoelectron spectroscopy (XPS). Plasma treatment resulted in an increased concentration of oxygen containing functionalities on the fiber surface. The interfacial shear strength as determined by the microbond test increased by 118% for the Spectra fibers and by 45% for the Kevlar fibers with the same epoxy resin. Scanning electron microscopy indicated little change of the surface topography of either fiber following plasma treatment. Effects of friction and surface composition of the plasma-treated fibers is discussed. © 1993 John Wiley & Sons, Inc.     

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.     

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.     

低温等离子体对PBO纤维表面的改性

采用硅烷偶联剂处理聚对苯撑苯并双噁唑(PBO)纤维,利用常压射频低温等离子体对PBO纤维进行了表面处理,通过扫描电镜、红外光谱、光学显微镜等研究了处理时间对PBO纤维表面官能团和表面形貌的影响规律,通过单丝拔出实验测定PBO纤维基复合材料的界面剪切强度。结果表明:经过常压射频低温等离子体处理后,PBO纤维的表面形成了大量的极性基团,表面产生明显的凹坑,PBO纤维与树脂的粘接性能提高50%,纤维的拉伸强度下降5%。     

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.     

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.     

Surface modification of UHSPE fibers through allylamine plasma deposition. II. Effect on fiber and fiber/epoxy interface

The surface of ultra-high strength polyethylene (UHSPE) fibers was modified using allylamine plasma deposition to improve their adhesion to epoxy resins. Allylamine plasma polymerization was investigated at different power inputs and polymerization times. The adhesion of treated fibers to epoxy resin was studied by single-fiber, pull-out tests. A special silicon rubber mold was developed to embed the single fiber in epoxy resin. The results show that the interfacial shear strength (IFSS) increased by a factor of 2 to 3 after allylamine plasma treatments. The greatest improvement, by a factor of 3.25, was obtained at 30 W for 10 min. Scanning electron microscopy (SEM) was also used to study the surface topography of fibers pulled from the epoxy resin. In most cases, it was observed that pull-out failure occurred at the interface, as evidenced from clean fiber surfaces. In a few cases, however, fibrils were peeled from fibers. The fiber strength decreased, but initial modulus increased after the plasma treatments. The decrease in fiber strength was insignificant for treatments at a lower power input, but was significant at higher power inputs. Treatment time, however, had no significant effect on fiber strength.     

Aging of hydrophobized surfaces of ramie fibers induced by atmospheric pressure plasma treatment with ethanol pretreatment

In order to investigate hydrophilic recovery of hydrophobic treatment of cellulose fibers, ramie fibers are ethanol-pretreated followed by atmospheric pressure plasma jet (APPJ) treatment using helium as the treatment gas and age for up to 150?days in 20?°C and 65% relative humidity. Scanning electron microscopy shows the fiber surfaces of the ethanol-pretreated?+?APPJ-treated group of freshly prepared, aged for 30?days, and aged for 150?days are covered with polypropylene matrix after fiber pullout tests. X-ray photoelectron spectroscopy shows that the freshly prepared ethanol-pretreated?+?APPJ-treated group has a 31% reduction in atomic ratio of oxygen to carbon and maintains at a similar level even after 150?days of aging. Water contact angle measurement demonstrates that the wettability of fiber surface of the freshly prepared ethanol-pretreated?+?APPJ-treated group drastically decreases and remains at the same lever after aging. Interfacial shear strength test reveals that the interfacial adhesion between PP matrix and ramie fiber for the freshly prepared ethanol-pretreated?+?APPJ-treated group increases 26% and remains substantially higher than that of the control group over time. These results indicate that the ethanol pretreatment followed by APPJ treatment is a permanent surface treatment with negligible aging for at least five months.     

Relationship Between Some Mechanical Strengths of CFRP and Interfacial Properties

The relationships between microscopic properties such as interfacial shear strength (IFSS) and macroscopic properties such as flexural strength were investigated for CFRP prepared from carbon fiber and epoxy resin. Flexural, tensile and impact strengths all went through maximum values when plotted against the surface treatment time of the carbon fiber. The flexural strength of CFRP as a function of the treatment time of the carbon fiber behaved similarly to the adhesive strength of the resin and carbon fiber. Also, the results indicated that the bahavior of tensile and impact strengths varied with the treatment time in much the same way as the interfacial shear strength did. The occurrence of these two types of macroscopic and microscopic property effects can be understood by taking into account the chemical activity and roughness of the carbon fiber surface.     

Effects of environmental exposure on fiber/epoxy interfacial shear strength

The TRI microbond technique for direct determination of fiber/resin interfacial shear strength in composites has been used for investigation the influence of environmental conditions on adhesive bonding in certain systems. The small dimensions involved in the method facilitate uniform exposure and short exposure times. We have observed significant changes in both average shear strength and in shear strength distributions on exposing aramid/epoxy and glass/epoxy microbond assemblies to steam or hot water. Shear strength dropped to a plateau value in both cases, the reduction being more drastic with the glass fiber. Vacuum drying restored shear strength completely in aramid/epoxy microassemblies, even when the surface of the aramid fiber had been chemically modified, but there was only partial regeneration of bond strength with the glass/epoxy system.     

Surface modification of nylon 6 films treated with an He/O2 atmospheric pressure plasma jet

To investigate the effect of the gas composition of the plasma treatment on the surface modification of an atmospheric pressure plasma jet (APPJ), nylon 6 films were treated with APPJ with pure helium (He), He + 1% oxygen (O₂), and He + 2% O₂, respectively. Atomic force microscopy showed increased surface roughness, whereas X‐ray photoelectron spectroscopy revealed increased oxygen contents after the plasma treatments. The plasma‐treated samples had lower water contact angles and higher T‐peel strengths than the control. The addition of a small amount of O₂ to the He plasma increased the effectiveness of the plasma treatment in the polymer surface modification in terms of surface roughness, surface oxygen content, etching rate, water contact angle, and bonding strength. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011