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.     

Improvement of adhesion between polyethylene and regenerated cellulose fibers by surface fibrillation

Regenerated cellulose fibers spun from straw pulp using the N-methylmorpholine N-oxide (NMMO) process were evaluated as a reinforcement for low-density polyethylene (LDPE). Surface fibrillation was carried out by a mechanical treatment to improve interfacial adhesion. Surface fibrillation resulted in a gradual change in surface topography, as detected by SEM. Long and numerous twisted fibrils were observed on the surface of the treated fibers. The fiber perimeters, determined by the Wilhelmy plate method, increased with an extended degree of fibrillation, while the strength of the fiber was not affected by the surface treatment. Model composites were prepared by embedding untreated and surface-fibrillated single fibers into an LDPE matrix, and the single fiber fragmentation (SEF) test was carried out to determine the critical fiber length. The interfacial shear strength (τ) was then calculated by applying a modified form of the Kelly-Tyson equation. It was found that the interfacial shear strength increased significantly as a result of surface fibrillation. The proposed mechanism for the improvement of interfacial adhesion is a mechanical anchoring between the matrix and the fiber.     

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.     

Surface modification of armos fibers with oxygen plasma treatment for improving interfacial adhesion with poly(phthalazinone ether sulfone ketone) resin

We introduce in this article oxygen plasma treatment as a convenient and effective method for the surface modification of Armos fibers. The effects of oxygen‐plasma‐treatment power on both the Armos fiber surface properties and Armos‐fiber‐reinforced poly(phthalazinone ether sulfone ketone) composite interfacial adhesion were investigated. The Armos fiber surface chemical composition, surface morphology and roughness, and surface wettability as a function of oxygen‐plasma‐treatment power were measured by X‐ray photoelectron spectroscopy, scanning electronic microscopy, atomic force microscopy, and dynamic contact angle analysis. The results show that oxygen plasma treatment introduced a lot of reactive functional groups onto the fiber surface, changed the surface morphology, increased the surface roughness, and enhanced the surface wettability. Additionally, the effect of the oxygen‐plasma‐treatment power on the composite interfacial adhesion was measured by interlaminar shear strength with a short‐beam bending test. Oxygen plasma treatment was an effective method for improving the composite interfacial properties by both chemical bonding and physical effects. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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     

Influence of plasma treatment on properties of ramie fiber and the reinforced composites

In this research, 9 series of ramie fibers were treated under low-temperature plasma with diverse output powers and treatment times. By analysis of the surface energy and adhesion power with epoxy resin, 3 groups as well as control group were chosen as reinforced fibers of composites. The influences of these parameters on the ramie fiber and its composites such as topography and mechanical properties were tested by scanning electron microscopy (SEM), atomic force microscopy (AFM), tensile property and fragmentation test of single-fiber composites. Contact angle and surface free energy results indicated that with the increased treatment times and output powers, surface energy and adhesion work with epoxy resin improved. Compared with the untreated fibers, surface energy and adhesion work with epoxy resin grew 124.5 and 59.1% after 3 min-200 w treatment. SEM and AFM showed low temperature plasma treatment etched the surface of ramie fiber to enhance the coherence between fiber and resin, consequently fiber was not easy to pull-out. After 3 min-200 w treatment, tensile strength of ramie fiber was 253.8 MPa, it had about 30.5% more than that of untreated fiber reinforced composite. Interface shear stress was complicated which was affected by properties of fiber, resin and interface. Fragmentation test showed biggest interface shear stress achieved 17.2 MPa, which represented a 54.0% increase over untreated fiber reinforced composites.     

Adhesion: Comparison Between Physico-chemical Expected and Measured Adhesion of Oxygen-plasma-treated Carbon Fibers and Polycarbonate

The adhesive interaction between oxygen-plasma-treated, polyacrylonitrile-based, high-tensile-strength carbon fibers and a polycarbonate matrix has been studied. Several models have been used to predict the impact of the plasma treatment process on the strength of adhesion between both jointing partners. These approaches have been the thermodynamic work of adhesion which was calculated from the solid surface tensions, based on the results of contact angle measurements versus test liquids, the contact angle which was directly obtained via polycarbonate melt droplets on single carbon fibers and the zeta (?)-potential data provided by streaming potential measurements. The results have been compared with the interfacial shear strength determined from the single-fiber fragmentation test. Additionally, the single-fiber tensile strength of the oxygen-plasma-treated carbon fibers was determined.

We confirmed that any physico-chemical method on its own fails to describe exactly the measured adhesion. However, for the investigated system, the conscientious interpretation of the data obtained from wetting measurements, in conjunction with the thermodynamic approach, is sufficient to predict the success of a modification technique which has been applied to one component in order to improve adhesion.     

Adhesion: Comparison Between Physico-chemical Expected and Measured Adhesion of Oxygen-plasma-treated Carbon Fibers and Polycarbonate

The adhesive interaction between oxygen-plasma-treated, polyacrylonitrile-based, high-tensile-strength carbon fibers and a polycarbonate matrix has been studied. Several models have been used to predict the impact of the plasma treatment process on the strength of adhesion between both jointing partners. These approaches have been the thermodynamic work of adhesion which was calculated from the solid surface tensions, based on the results of contact angle measurements versus test liquids, the contact angle which was directly obtained via polycarbonate melt droplets on single carbon fibers and the zeta (ς)-potential data provided by streaming potential measurements. The results have been compared with the interfacial shear strength determined from the single-fiber fragmentation test. Additionally, the single-fiber tensile strength of the oxygen-plasma-treated carbon fibers was determined.

We confirmed that any physico-chemical method on its own fails to describe exactly the measured adhesion. However, for the investigated system, the conscientious interpretation of the data obtained from wetting measurements, in conjunction with the thermodynamic approach, is sufficient to predict the success of a modification technique which has been applied to one component in order to improve adhesion.     

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.     

Study on the interfacial properties of two‐dimensionally arranged glass fiber/epoxy resin model composites

The effect of interfiber distance on the interfacial properties in two dimensional multi‐E‐glass fiber/epoxy resin composites has been investigated using fragmentation test. In addition, the effect of the fiber surface treatment on the interfacial properties has been studied. We found that the interfacial shear strength decreased with the decreasing interfiber distance at the range of <50 μm and the extent of the decreasing was more serious as the increasing of the number of adjacent fiber. This is probably that the interface between the fiber and the resin was damaged by the breaking of adjacent fibers and the damage increased with minimizing the interfiber spacing and the number of adjacent fibers. We can guess that interfacial shear strength in real composites is much smaller than that of multifiber fragmentation sample with touched fiber. When the interfiber distance was >50 μm, the interfacial shear strengths were saturated regardless of fiber surface treatment and were in close agreement with those of the single fiber fragmentation test. Finally, the interfacial shear strength evaluated using two dimensional fragmentation tests are shown as real values in‐site regardless of fiber surface treatment, interfiber distance, and existing matrix cracks. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1541–1551, 2006     

Study on the interfacial properties of three‐dimensionally arranged glass fiber/epoxy resin model composites

The effect of interfiber distance on the interfacial properties in three‐dimensional multi‐E‐glass fiber/epoxy resin composites has been investigated using fragmentation test. In additions, the effect of the fiber surface treatment on the interfacial properties has been studied. The interfacial shear strength decreased with the decreasing the interfiber distance at the range of under 50 μm and the extent of the decreasing was more serious as the increasing of the number of adjacent fiber. This is probably due to the fact that the interface between the fiber and the resin was damaged by the adjacent fiber breaks and the damage increased with closing the interfiber spacing and the number of adjacent fiber. It was found that the interfacial shear strengths saturated when the interfiber distance was over 50 μm, the ones were saturated regardless of fiber surface treatment and the ones were in close agreement with those of the single fiber fragmentation test. Finally, the interfacial shear strength evaluated using three‐dimensional fragmentation tests are shown as real values in‐site regardless of fiber surface treatment, interfiber distance and existing of matrix cracks. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Modification of the Carbon Fiber Surface by Oxygen Plasma and its Influence on Adhesion Strength in Acrylate-Based Composites Cured by Electron Beam and Ultra Violet Light

Oxygen plasma was used to modify the surface properties of carbon fibers and their adhesion strength with an acrylate resin cured by electron beam. A characterization of the surface topography and the surface chemistry was carried out (topography at a micrometric and nanometric scale, specific surface area, temperature programmed desorption, and X-ray photoelectron spectroscopy). The topography remained unchanged. Regarding the surface chemistry, carboxylic acids, alcohols, lactones, and ethers were created and their location was at the outer surface of the fibers. A pull-out test was used to measure the adhesion strength with the acrylate resin cured by electron beam. For comparison, an isothermal UV curing was also investigated. The value of the interfacial shear strength was increased only in the case of UV curing. No improvement was observed with electron beam curing, which highlighted the generation of an interphase, the mechanical properties of which are dependent on the processing conditions.     

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。     

Characterization of ramie fiber/soy protein concentrate (SPC) resin interface

Ramie fiber/soy protein concentrate (SPC) polymer (resin) interfacial shear strength (IFSS) was measured using the microbond technique. To characterize the effect of plasticization, SPC resin was mixed with glycerin. Fibers were also treated with ethylene plasma polymer to reduce fiber surface roughness and polar nature to control the IFSS. Fiber surfaces after ethylene plasma polymerization, and fracture surfaces of specimens before and after the microbond tests were characterized using a scanning electron microscope (SEM). Some specimens were also characterized using electron microprobe analyzer (EMPA) to map the residual resin on the fiber surface after the microbond test. Effects of glycerin concentration in SPC and ethylene plasma fiber surface treatment time on the IFSS were investigated. Preparation of SPC resin requires a large amount of water. As expected, during drying of SPC resin, the microdrops shrank significantly. The high IFSS values indicate strong interfacial interaction in the ramie fiber/SPC resin system. This strong interfacial interaction is a result of a highly polar nature of both the ramie fiber and the SPC resin and rough fiber surface. Ethylene plasma polymerization was used to control the IFSS. The plasma polymer imparted a polyethylene-like, non-polar polymer coating on the fiber surface. As a result, the fiber surface became smoother compared to the untreated fiber. Both fiber smoothness and non-polar nature of the coating reduced the ramie fiber/SPC resin IFSS. Plasticization of the SPC resin by glycerin also decreased the adhesion strength of the ramie fibers with the SPC resin. The load-displacement plots for IFSS tests obtained for different resin and fiber combinations indicate different interfacial failure modes.     

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.     

Residual Stresses in Microcomposites and Macrocomposites

Existing models for built-in residual stresses in composite materials are reviewed and discussed. In particular, the thermal longitudinal stress present in the fiber prior to a single-fiber fragmentation experiment is studied using various model composite data. It is found that this stress is typically compressive in nature and that, quantitatively, it depends on the fiber content, the degree of undercooling, and the thermoelastic constants of the fiber and the matrix. In the case of single-fiber composites (or microcomposites), the thermal longitudinal stress present in the fiber is high enough to either induce fiber sinewave buckling (such as in E-glass/epoxy), or extensive fiber fragmentation (such as in graphite HM/polypropylene) that may then be used to measure the dependence of compressive fiber strength upon length. This has to be accounted for in quantitative models that calculate interfacial adhesion parameters using single-fiber tests, such as the fragmentation test or the microbond test. Implications for high fiber content composites (or macrocomposites) are discussed.     

The effects of surface treatments of fibers on the interfacial properties in single-fiber composites

The interfacial properties between fibers and the matrix contribute to the overall properties in high performance composites. Plasma treatments (Ar, O₂, CF₄/O₂, N₂/H₂) have been performed on carbon fibers to improve the fiber-matrix interaction. The treatment efficiency was checked by the single-fiber technique, while the surface chemistry and morphology were characterized by X-ray photoelectron spectroscopy (XPS), static secondary ion mass spectroscopy (SSIMS), and scanning electron microscopy (SEM). The O₂- and N₂/H₂-plasma treatments proved most effective both for introducing oxygen-containing functionalities at the fiber surface and for improving the interfacial shear strength of carbon fiber/epoxy composites. A relationship between the oxygen concentration at the fiber surface and the interfacial shear strength is demonstrated.     

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     

低温氨气等离子体对芳纶表面的改性

采用氨气等离子体对芳纶表面进行改性,用X-射线光电子能谱、场发射扫描电子显微镜、力学性能测试等手段对改性前后纤维表面的元素组成、形貌及其拉伸强度进行表征,并进一步通过微脱黏方法分析了等离子体处理条件对芳纶/环氧树脂复合材料界面黏结强度的影响。结果表明:芳纶经表面改性后,其表面极性官能团、表面粗糙度均有所增加,同时与环氧树脂基体的界面黏结强度明显增加。