Promoting the adhesion of high‐performance polymer fibers using functional plasma polymer coatings

Plasma‐copolymerized functional coatings of acrylic acid and 1,7‐octadiene were deposited onto high strength, high modulus, poly‐p‐phenylene benzobisoxazole (PBO) fibers. X‐ray photoelectron spectroscopy (XPS) with trifluoroethanol derivatization confirmed that the PBO fibers were covered completely with the plasma copolymer and that the coating contained a quantitative concentration of carboxylic acid groups. Microdebond single filament adhesion and interlaminar shear strength (ILSS) tests were used to evaluate the interfacial strength of epoxy resin composites containing these functionalized PBO fibers. Both the interfacial shear strength (IFSS) obtained from single filament tests, and the ILSS of high volume fraction composites were a function of the surface functionality of the fibers so that there was a good correlation between ILSS and IFSS data. The tensile strengths of single fibers with or without coating were comparable, demonstrating that the fiber surface was not damaged in the plasma‐coating procedure. Indeed, the statistical analysis showed that Weibull modulus was increased. Therefore, plasma‐polymerized coatings can be used to control the interfacial bond between PBO fibers and matrix resins and act as a protective size for preserving the mechanical properties of the fibers. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

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.     

Enhancing hygrothermal resistance of aeronautical carbon fabric/epoxy composites via air plasma processing

Air plasma processing is introduced as a surface modification technique for carbon fibers to enhance the hygrothermal resistance of carbon fabric/epoxy composites. On carbon fiber surface subjected to 4-min plasma processing, there are 37.6% of carbon species present as –C–O–C groups and 9.3% of carbon species as –COOH groups. The moisture adsorption behavior of composites can be described by Fick’s law. Increase in temperature accelerates the initial moisture adsorption rate and results in a higher diffusion coefficient. The decreasing interlaminar shear strength (ILSS) of composites is mainly ascribed to the loss of adhesion at the fiber/matrix interface. A lower equilibrium moisture content of composites is caused by air plasma processing, which leads to the improved interfacial bonding strength and the higher retention rate of ILSS of carbon fabric/epoxy composites. The interface sensitivity and temperature dependence of moisture adsorption for carbon fabric/epoxy composites are discussed. The results presented herein demonstrate an effective strategy for enhancing hygrothermal resistance of carbon fiber-reinforced composites.     

Mechanical properties of carbon fiber composites modified with nano-SiO2 in the interphase

The performance of carbon fibers-reinforced composites is dependent to a great extent on the properties of fiber–matrix interface. To improve the interfacial properties in carbon fibers/epoxy composites, nano-SiO₂ particles were introduced to the surface of carbon fibers by sizing treatment. Atomic force microscope (AFM) results showed that nano-SiO₂ particles had been introduced on the surface of carbon fibers and increase the surface roughness of carbon fibers. X-ray photoelectron spectroscopy (XPS) showed that nano-SiO₂ particles increased the content of oxygen-containing groups on carbon fibers surface. Single fiber pull-out test (IFSS) and short-beam bending test (ILSS) results showed that the IFSS and ILSS of carbon fibers/epoxy composites could obtain 30.8 and 10.6% improvement compared with the composites without nano-SiO₂, respectively, when the nano-SiO₂ content was 1 wt % in sizing agents. Impact test of carbon fibers/epoxy composites treated by nano-SiO₂ containing sizing showed higher absorption energy than that of carbon fibers/epoxy composites treated by sizing agent without nano-SiO₂. Scanning electron microscopy (SEM) of impact fracture surface showed that the interfacial adhesion between fibers and matrix was improved after nano-SiO₂-modified sizing treatment. Dynamic mechanical thermal analysis (DMTA) showed that the introduction of nano-SiO₂ to carbon fibers surface effectively improved the storage modulus of carbon fibers/epoxy.     

Influence of silane coupling agents on the surface energetics of glass fibers and mechanical interfacial properties of glass fiber-reinforced composites

The effect of various silane coupling agents on glass fiber surfaces has been studied in terms of the surface energetics of fibers and the mechanical interfacial properties of composites. γ-Methacryloxypropyltrimethoxysilane (MPS), γ-aminopropyltriethoxysilane (APS), and γ-glycidoxypropyltrimethoxysilane (GPS) were used for the surface treatment of glass fibers. From contact angle measurements based on the wicking rate of a test liquid, it was observed that silane treatment of glass fiber led to an increase in the surface free energy, mainly due to the increase of its specific (or polar) component. Also, for the glass fiber-reinforced unsaturated polyester matrix system, a constant linear relationship was observed in both the interlaminar shear strength (ILSS) and the critical stress intensity factor (K_IC) with the specific component, γ_S ^SP, of the surface free energy. This shows that the hydrogen bonding, which is one of the specific components of the surface free energy, between the glass fibers and coupling agents plays an important role in improving the degree of adhesion at the interfaces of composites.     

A Novel Route to Modify the Interface of Glass Fiber-Reinforced Epoxy Resin Composite via Bacterial Cellulose

A simple and novel method to modify the surface of glass material with Acetobacter xylinum bacteria to deposit bacterial cellulose (BC) around glass material during the process of fermentation was described. The modified glass material with more hydrophobic and rougher surface was characterized by FTIR, SEM, XPS, peeling experiments, and water/air contact angle. It was found that heat treatment at 140 ～ 150°C was able to improve the interaction between BC and glass material owing to the increase in chemical bonds between them. The biological modified glass fibers were compounded with epoxy resin. The influence of incubation time and high temperature on the interfacial shear strength (IFSS) between glass fibers and epoxy resin was identified by Microbond Test. The strongest IFSS could be obtained with incubation time of 1 hour and temperature of 140°C, which then offers a biological approach to improve the interface of silicates materials and resin matrix.     

炭纤维表面处理对CF／PMR—15复合材料力学性能的影响

研究了炭纤维表面不同处理方法对复合材料力学性能的影响,采用等离子体和等离子体接枝技术对炭纤维表面进行处理后,CF／PMR－15复合材料的界面剪切强度与层间剪切强度均有所提高,随着界面状态的改善,界面剪切强度提高的幅度比层间剪切强度提高的大,本文为指导炭纤维的表面处理,评价处理效果,进一步预报复合材料的宏观性能打下了基础。     

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 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.     

Temperature effect on graphene‐filled interface between glass–carbon hybrid fibers and epoxy resin characterized by fiber‐bundle pull‐out test

The overall mechanical performance of glass–carbon hybrid fibers reinforced epoxy composites depends heavily upon fiber–matrix interfacial properties and the service temperatures. Fiber‐bundle pull‐out tests of glass (GF) and/or carbon fiber (CF) reinforced epoxy composites were carried out at room and elevated temperatures. Graphene nanoplatelets were added in the interfacial region to investigate their influence on the interfacial shear strength (IFSS). Results show that IFSS of specimens with fiber‐bundle number ratio of GF:CF = 1:2 is the largest among the hybrid composites, and a positive hybridization effect is found at elevated temperatures. IFSS of all the specimens decreases with the increasing of test temperatures, while the toughness shows a contrary tendency. As verified by scanning electron microscopy observations, graphene nanoplatelets on fiber surface could enhance the IFSS of pure glass/carbon and hybrid fibers reinforced epoxy composites at higher temperatures significantly. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46263.     

The influence of the interphase on composite properties: Poly(ethylene-co-acrylic acid) and poly(methyl vinyl ether-co-maleic anhydride) electrodeposited on graphite fibers

The electrodeposition of saturated copolymers onto carbon fibers is investigated, focusing particular attention on improvement of shear and impact properties of the corresponding composites. Carbon fibers are electrocoated with poly(ethylene-co-acrylic acid) and poly(methyl vinyl ether-co-maleic anhydride) from aqueous media, and fabricated into epoxy composites. The results of interlaminar shear strength (ILSS) tests, initially employed to assess fibermatrix adhesion, are vitiated by the occurrence of mixed-mode failure. Interfacial shear strength (IFSS) is hence evaluated by stressing single-fiber composite specimens to obtain ultimate aspect ratios of the fiber fragments. The data are combined with fiber strengths by a recently developed statistical theory (1) to yield a distribution for IFSS. Both copolymer interphases improve fiber-matrix bonding to an extent greater even than that obtained with commercial fiber surface treatment. Good fiber-matrix adhesion is further apparent from SEM studies of fractured ILSS test specimens. A key to this improved adhesion is the interpenetration of matrix resin and interphase polymer, revealed by electron microprobe analysis (2). Notched Izod impact strength is also increased over uncoated-fiber composites. These copolymer interphases behave as deformable interlayers, absorbing impact energy and blunting the growing crack tip. Further energy is absorbed in deflecting the crack through a more tortuous path. Simultaneous improvements in impact and shear strengths are thus obtained, which may be further enhanced by optimizing the electrodeposition parameters and the coating thickness. The influence of the interphase on composite properties is better understood from this study, paving the way for refinement in interphase design.     

氨气处理碳纤维 第II报 碳纤维表面和复合材料的性能

常压下,使碳纤维通过以氨气为气体介质的600℃热反应炉,反应停留时间为30s。采用三点短梁法和界面评价装置研究处理前后复合材料的层间剪切强度(ILSS)和界面剪切强度(IFSS),经氨气处理后二者分别提高了13.2%和32.1%。接触角测试结果表明:处理后碳纤维与水和环氧树脂的浸润性得到很大改善。采用扫描电子显微镜(SEM)研究处理前后碳纤维表面和复合材料断裂面形貌的变化,发现氨气处理对碳纤维表面形貌没有影响。力学性能测试数据表明,氨气处理不影响碳纤维的强度。     

Evaluation of interfacial properties and microfailure mechanisms in single fiber‐reinforced epoxy composites at low temperature

In this preliminary study, micromechanical techniques were used to compare the interfacial properties of both carbon and glass fiber composites with two structurally different epoxy matrices (YD‐114 and YDF‐175) at ambient and relatively low temperatures (25°C and −10°C). Tensile modulus of elasticity for both epoxies was higher at lower temperature. Although both fibers exhibited more bimodality at lower temperature than at ambient temperature, glass fiber composites exhibited a statistically greater improvement in tensile strength. This may be attributed to differences in inherent flaws and rigidity. A decrement in stress was observed for YDF‐175 epoxy composites under cyclic loadings at both temperatures, which was attributed to lower interfacial shear strength (IFSS). In contrast to the IFSS of conventional YD‐114 epoxy composites, the IFSS of both the carbon and glass fibers/YDF‐175 epoxy composites studied was higher at the lower temperature. The microfailure pattern observed in microdroplet pullout tests was consistent with the other IFSS results. POLYM. COMPOS., 2012. © 2011 Society of Plastics Engineers     

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 effect of silica (SiO2) nanoparticles and ammonia/ethylene plasma treatment on the interfacial and mechanical properties of carbon-fiber-reinforced epoxy composites

A nanoparticle dispersion is known to enhance the mechanical properties of a variety of polymers and resins. In this work, the effects of silica (SiO₂) nanoparticle loading (0–2 wt%) and ammonia/ethylene plasma-treated fibers on the interfacial and mechanical properties of carbon fiber–epoxy composites were characterized. Single fiber composite (SFC) tests were performed to determine the fiber/resin interfacial shear strength (IFSS). Tensile tests on pure epoxy resin specimens were also performed to quantify mechanical property changes with silica content. The results indicated that up to 2% SiO₂ nanoparticle loading had only a little effect on the mechanical properties. For untreated fibers, the IFSS was comparable for all epoxy resins. With ethylene/ammonia plasma treated fibers, specimens exhibited a substantial increase in IFSS by 2 to 3 times, independent of SiO₂ loading. The highest IFSS value obtained was 146 MPa for plasma-treated fibers. Interaction between the fiber sizing and plasma treatment may be a critical factor in this IFSS increase. The results suggest that the fiber/epoxy interface is not affected by the incorporation of up to 2% SiO₂ nanoparticles. Furthermore, the fiber surface modification through plasma treatment is an effective method to improve and control adhesion between fiber and resin.     

Plasma surface treatment of poly(p-phenylene benzobisthiozol) fibers

Poly(p-phenylene benzobisthiozol) (PBZT) fibers were subjected to radio-frequency (RF)-induced, glow-discharge plasma treatments using argon and carbon dioxide gases in order to modify the adhesion of the fibers to bisphenol-A epoxy. The interfacial shear strength (IFSS) was used as a measure of the adhesion and was determined using the microbond technique. Scanning electron photomicrographs revealed no visible surface etching at magnifications of up to 10 000 x . Slight, but statistically significant, improvements in IFSS were noted with the CO₂ plasma-treated fibers as compared with control fibers, but Ar plasma-treated fibers showed no improvement.     

淀粉纳米晶对玻璃纤维的表面改性研究

采用自制的淀粉纳米晶(SNC)对玻璃纤维进行表面处理,增加其与环氧树脂基体的界面剪切强度(IFSS)。研究了处理方式、处理时间、SNC乙醇分散液浓度、热处理温度等工艺参数对SNC在玻璃纤维表面沉积情况的影响,以及对改性玻璃纤维与环氧树脂的界面性能的影响规律。采用扫描电子显微镜、单纤维强力仪对处理前后玻璃纤维进行表征,并采用微脱粘法测试玻璃纤维与环氧树脂的界面粘结情况。结果表明,当重力静置处理时间24 h,SNC乙醇分散液浓度为1 g/100 m L时,SNC在玻璃纤维表面均匀沉积,且能显著提高玻璃纤维与环氧树脂的IFSS,为27.29 MPa,较未处理的纤维增加29.3%。150℃热处理4 h后,X射线光电子能谱结果显示SNC与玻璃纤维形成化学键合,进一步增加纤维与环氧树脂的界面粘结,IFSS值达到32.30 MPa,较未处理的纤维增加53%,且纤维的拉伸强度得到较好的维持。     

Covalent functionalization of carbon fiber with poly(acrylamide) by reversible addition–fragmentation chain transfer polymerization for improving carbon fiber/epoxy interface

A novel method was developed for grafting poly(acrylamide) (PAAM) on to the carbon fiber (CF) surface via reversible addition–fragmentation chain transfer (RAFT) polymerization to improve the interaction between carbon fibers and epoxy matrix in the composites system. The carbon fibers were first treated with nitric acid and γ‐methacryloxypropyltrimethoxy silane (KH570). Then, the PAAM was grafting onto the carbon fiber surface via RAFT polymerization. The resulted carbon fibers functionalized with PAAM (CF‐PAAM) were characterized by FTIR, XPS, and TGA, and the results revealed that CF‐PAAM were synthesized successfully. The introduction of PAAM chains could make the fiber surface rougher and introduce a large numbers of –NH₂ groups, which can improve the interfacial adhesion in the composites. The microbond test results showed that the interfacial shear strength (IFSS) of the composites reinforced by CF‐PAAM has been enhanced about 107%. POLYM. COMPOS., 38:27–31, 2017. © 2015 Society of Plastics Engineers     

Electrostatic deposition of silica nanoparticles between E‐glass fibers and an epoxy resin

The achievement of optimum adhesion between a thermoset and an inorganic material is an important goal for the composites and coatings industries. There is a growing interest in the use of structural surface modifiers, such as nanotubes, nanoparticles, and whiskers, to improve this adhesion. Here, a method for electrostatically depositing poly(ethylene imine)‐functionalized silica nanoparticles onto E‐glass fibers was developed. The deposition of 26‐nm functionalized particles onto glycidyloxypropyltrimethoxysilane (GPS)‐functionalized E‐glass fibers and then their embedding in a resin of diglycidyl ether of bisphenol A and m‐phenylene diamine increased the interfacial shear strength (IFSS) 35% over that of bare fibers and 8% over that of GPS‐functionalized fibers. IFSS was highly dependent on the particle size; the 16‐nm functionalized particles had little effect on the IFSS. When the particles size was increased to 71 and 100 nm, this led to increasingly poor IFSS values, whereas the 26‐nm particles produced the best results. Similar results were seen with the transverse flexural strength of the unidirectional composites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41516.     

Kevlar fiber–epoxy adhesion and its effect on composite mechanical and fracture properties by plasma and chemical treatment

Kevlar 49 fibers were surface-modified by NH₃-, O₂-, and H₂O-plasma etching and chlo-rosulfonation and subsequent reaction with some reagents (glycine, deionized water, eth-ylendeiamine, and 1-butanol) to improve the adhesion to epoxy resin. After these treatments, the changes in fiber topography, chemical compositions of the fiber surfaces, and the surface functional groups introduced to the surface of fibers were identified by SEM, XPS, and static SIMS. Interlaminar shear strength (ILSS) and T-peel strenght between the fiber and opoxy resin, as measured by the short-beam test and T-peel test, were remarkedly improved by gas plasma and chlorosulfonation (0.1% and 0.25% CISO₃H at 30 s). However, from the results of similar G_IC values of the treated and untreated fiber composites, it is clear that the fiber/matrix interfacial bond strength is only a minor contributor to G_IC. SEM was also used to study the surface topography of the fracture surfaces of composites in T-peel test. It could be seen from SEM observations that the improvement of fiber/matrix interfacial bond strength often accompanied a change in fracture mode from the interface of fiber/epoxy resins to the fiber fibrillation and the resins. © 1996 John Wiley & Sons, Inc.