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.     

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.     

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.     

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.     

CO2 plasma modification of high-modulus carbon fibers and their adhesion to epoxy resins

Interfacial bond strength is often a performance-limiting factor of carbon-fiber-reinforced composites. This limitation is most prevalent when higher-modulus fibers or relatively unreactive matrix resins, such as engineering thermoplastics or high-temperature thermoset resin systems, are used. Radio-frequency (RF) glow discharge plasmas are an effective means of modifying carbon-fiber surface chemical characteristics to promote adhesion. It has been previously shown that oxidizing plasmas are especially effective compared with electro-oxidative treatments for treating carbon fiber surfaces as revealed by titrations, electron spectroscopy, wetting, and inverse gas chromatography measurements. This study evaluated the effectiveness of CO₂ plasmas on two experimental high-modulus carbon/graphite fibers and correlated the plasma surface modification with interfacial adhesion in an epoxy matrix composite system. The results show that CO₂ plasma treatment increased the surface oxygen content by nearly a factor of 2 over typical electro-oxidation treatments. The increased oxygen is mainly in the form of hydroxyl, ketone, and carboxyl-like moieties. Unidirectional composites were prepared from as-received and plasma-modified versions of each type of experimental fiber. The composites containing plasma-modified filaments exhibited 1.5-3.0 times the strength of composites fabricated with untreated or electro-oxidized filaments in transverse-flexural tests. Short-beam shear strength increased by two times over those with as-produced filaments and is equivalent to that of composites containing electro-oxidized filaments.     

Physico-Chemical and micromechanical analysis of the interface in a poly(phenylene sulfide)/glass fiber composite—a microbond study

The glass fiber/PPS composite has excellent thermal and chemical properties. The main disadvantage of the composite is its poor mechanical resistance to impact. To improve this property, the fibers were coated with a new type of sizing. The equired characteristics for this sizing is to create strong interactions between the PPS matrix and the glass fiber surface. The ability of the sizings to improve the glass/PPS adhesion has been assessed by the microbond technique. An inconvenience of this technique is the difficulty in defining a parameter that is characteristic of the interfacial adhesion. The objective of this publication is to demonstrate that a plastic flow of the PPS matrix around the fiber leads to a uniform shear strength. The adhesion between these two materials can therefore be obtained by the mean interfacial shear strength.     

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。     

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。     

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     

Foreword

The effect of surface treatments and fiber sizings on the stress transfer characteristics and composite properties of AS-4 carbon/epoxy materials has been determined. Fiber surface chemistry was systematically varied from acidic to basic with RF glow discharge plasmas of CO₂ and NH₃ and characterized with ESCA techniques. Sizings applied to some of the treated fibers consisted of diglycidyl ether of bisphenol-A(DGEBA). Single fiber tension tests were used to measure the interfacial shear strength of samples made with DGEBA/metaphenylene diamine resin. Short beam shear and transverse flexure tests were used to examine the composite properties of modified materials.

Results showed that the plasma treatments were effective in altering the surface chemistry of the fiber but that changes in surface chemistry had surprisingly little effect on the critical stress transfer length. Sizing had a more significant effect on the transfer length. The interlaminar shear strength of the composites were unaffected by the treatments. Transverse flexure tests were more sensitive to the changes in surface characteristics. The work indicates that the interface properties of AS-4 fibers are close to optimal but that improvements in composite performance are possible through interphase formation.     

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     

Plasma etching and plasma polymerization coating of carbon fibers. Part 1. Interfacial adhesion study

Unsized AS-4 carbon fibers were etched by RF plasma and then coated via plasma polymerization in order to enhance their adhesion to vinyl ester resin. Gases utilized for plasma etching were Ar, N₂ and O₂, while monomers used in plasma polymerization coating were acetylene, butadiene and acrylonitrile. Plasma etchings were carried out as a function of plasma power (30–70 W), treatment time (1–10 min) and gas pressure (20–40 mtorr). Plasma polymerizations were performed by varying the treatment time (15–60 s), plasma power (10–30 W) and gas pressure (20-40 mtorr). The conditions for plasma etching and plasma polymerization were optimized by measuring interfacial adhesion with vinyl ester resin via micro-droplet tests. Plasma etched and plasma polymer coated carbon fibers were characterized by SEM, XPS, FT-IR and α-Step, dynamic contact angle analyzer (DCA) and tensile strength measurements. In Part 1, interfacial adhesion of plasma etched and plasma polymer coated carbon fibers to vinyl ester resin is reported, while characterization results including tensile strength of carbon fibers are reported in Part 2. Among the treatment conditions, a combination of Ar plasma etching and acetylene plasma polymer coating provided greatly improved interfacial shear strength (IFSS) of 69 MPa, compared to 43 MPa obtained from as-received carbon fiber. Based on the SEM analysis of failure surfaces and load-displacement curves, the failure was found to occur at the interface between plasma polymer coating and vinyl ester resin.     

Adhesion characteristics of oxygen plasma-treated rayon fibers

The effect of oxygen plasma treatment of fiber on the adhesion between regenerated cellulose fiber and polyethylene (PE) was investigated using the single-fiber fragmentation test. In addition to allowing the determination of the interfacial shear strength, the fragmentation test provided a great deal of useful information on shear stress transfer and failure mechanisms in the systems. It was found that oxygen plasma treatment considerably enhanced the interfacial adhesion, as established by both the shear strength values that were measured and the birefringence patterns observed. The influence of the duration of treatment on adhesion was studied and found to be a very important parameter. The roles of surface chemistry, surface energetics, and surface topography of fiber in the interaction balance were investigated using electron spectroscopy for chemical analysis (ESCA), contact angle measurements, and scanning electron microscopy (SEM). It was seen that neither the plasma-induced changes in the surface energetics nor those in the surface topography could have exerted a positive effect on adhesion. Instead, the improved adhesion was ascribed to covalent bonds formed between the fiber and the matrix, as hydroperoxides, which were created on the fiber surface by the plasma treatment, decomposed during the fabrication of single-fiber specimens.     

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.     

Influence of environmental moisture on atmospheric pressure plasma jet treatment of ultrahigh-modulus polyethylene fibers

One of the main differences between low-pressure and atmospheric-pressure plasma treatments is that there is little moisture involved in the low-pressure plasma treatment, although moisture could exist at the wall of the vacuum chamber or react with the substrate after plasma treatment, while in the atmospheric-pressure plasma treatment moisture exists not only in the environment but also in any hygroscopic substrate. In order to investigate the influence of environmental moisture on the effect of atmospheric pressure plasma treatment, ultra-high-modulus polyethylene (UHMPE) fibers were treated using an atmospheric-pressure plasma jet (APPJ) with 10 l/min helium gas-flow rate, treatment nozzle temperature of 100°C and 5 W output power. The plasma treatments were carried out at three different relative humidity levels, namely 5, 59 and 100%. After the plasma treatments, the surface roughness increased while the water-contact angle decreased with increasing relative humidity. The number of oxygen containing groups increased as the environmental moisture content increased. The interfacial shear strength of the UHMPE fiber/epoxy system was significantly increased after the plasma treatments, but the moisture level in the APPJ environment did not have a significant influence on the adhesion properties. In addition, no significant difference in single fiber tensile strength was observed after the plasma treatments at all moisture levels. Therefore, it was concluded that the environmental moisture did not significantly influence the effect of atmospheric-pressure plasma treatment in improving interfacial bonding between the fiber and epoxy. The improvement of the interfacial shear strength for the plasma-treated samples at all moisture levels was mainly due to the increased surface roughness and increased surface oxygen and nitrogen contents due to the plasma etching and surface modification effect.     

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     

Effect of Halloysite Nanotube Incorporation in Epoxy Resin and Carbon Fiber Ethylene/Ammonia Plasma Treatment on Their Interfacial Property

Abstract

Effects of halloysite nanotube (HNT) loading of up to 2% in epoxy resin on its mechanical properties were characterized. The interfacial property of the resin with carbon fiber nanocomposite was also studied. Single fiber composite (SFC) technique was used to characterize the carbon fiber/epoxy resin interfacial shear stress. Carbon fibers were also coated with ammonia/ethylene plasma polymer to obtain a thin coating of the polymer with amine groups that could react with the epoxy and thus improve the interfacial property. The results indicated that the Young’s modulus of HNT containing nanocomposites increased slightly up to a loading of 0.25% after which it started to decrease. The tensile strength, however, steadily decreased with increasing of HNT loading although the fracture strain did not change significantly. This might be related to the nanotube shape, size and clustering. The interfacial shear strength (IFSS) was also increased slightly with HNT loading. The ethylene/ammonia plasma polymer coated fibers exhibited significantly higher IFSS by over 150%, independent of the HNT loading. The highest IFSS obtained was almost 79 MPa for plasma treated fibers. The results suggest that the carbon fiber/epoxy interface is not affected by the incorporation of up to 1.5% of HNT. Furthermore, the fiber surface modification through plasma polymerization is an effective method to improve and control the IFSS.     

New Coupling Agents as Adhesion Promoters at the Poly(Phenylene Sulfide)/Glass Interface-Studies with Micro and Macro Composites

Carboxy-functionalized poly(phenylene sulfide) having different molar masses and amount of the functional group were prepared in order to be used with γ-aminopropyltriethoxysilane as surface treatment of E-glass fibers. These grafted polymer chains act as connecting chains in order to improve the interfacial shear strength of the PPS-glass interface. According to their chemical nature, which is the same as the PPS matrix, and their ability to crystallize in the same crystalline form as the pure PPS, a continuum of bonding from the fiber surface to the bulk matrix is achieved. A chemical linkage is established at the glass surface by means of hydrolyzed ethoxysilane groups of the γ-APS and from the formation of amide units resulting from the reaction of amine functions of the silane and the carboxylic groups of the modified PPS. A “physical” linkage is expected between the grafted PPS and the PPS chains by means of entanglements and co-crystallization. A large improvement of the interfacial shear strength measured from the microdroplet test is observed when a modified-PPS having a medium molar mass and a low amount of functional groups is used in comparison with untreated or silane-treated glass fibers. This improvement is also observed for short glass fibers/PPS composite materials. In fact, a large improvement is obtained on mechanical properties such as the tensile, flexural, and impact strengths.     

Effect of sizing on interfacial adhesion of commercial high strength carbon fiber‐reinforced resin composites

The influence of sizing agent on interfacial shear strength (IFSS) of carbon fiber/epoxy (CF/EP) and carbon fiber/bismaleimide (CF/BMI) was investigated. Since sizing agent can alter physicochemical properties of CF surface, possible affecting factors, including sizing reactivity, chemical reactions between sizing and resin, wettability of fiber with resin, fiber surface roughness, and chemical composition of fiber surface, were discussed. It is found that contact angle of fiber with resin and sufficient chemical reactions between sizing and resin reveal strong correlation with the interfacial adhesion of CF/EP and CF/BMI, while the effect of surface roughness and the amount of oxygen on the fiber surface are relatively weak. Due to EP type of the composition, the sizing agent tends to improve the wettability of CF with EP, while goes against for the fiber with BMI. POLYM. COMPOS., 254–261, 2016. © 2014 Society of Plastics Engineers     

等离子体射流载气流量大小对玻璃纤维改性效果影响的研究

通过大气压等离子体射流在玻璃纤维（GF）表面沉积氧化硅（SiOx）纳米颗粒的方法改善玻璃纤维增强聚丙烯（GFRP）复合材料的界面结合性能,利用扫描电子显微镜、原子力显微镜和X射线光电子能谱等表征分析了改性纤维的表面形貌、化学成分、润湿性能和复合材料的界面结合性能,并考察了等离子体射流载气流量大小对GF改性效果的影响。结果表明,当载气流量为40 mL/min时,GF的改性效果最好,且此时GF的表面能相比对照组提高了43.18%,GFRP复合材料的层间剪切强度提高了30.79%;经过等离子体处理后,GF的表面粗糙度增大,极性官能团增多,复合材料的界面结合性能提升。