Plasma surface modification of carbon fibers: a review

The properties of the fiber/matrix interface in carbon fiber-reinforced composites play a dominant role in governing the overall performance of the composite materials. Understanding the surface characteristics of carbon fibers is a requirement for optimizing the fiber-matrix interfacial bond and for modifying fiber surfaces properly. Therefore, a variety of techniques for the surface treatment of carbon fibers have been developed to improve fiber-matrix adhesion as well as to enhance the processability and handling of these fibers. Many research groups have studied the effects of plasma treatments, correlating changes in surface chemistry with the interfacial shear strength. This article reviews the recent developments relative to the plasma surface modification of carbon fibers.     

Effects of atmospheric pressure helium/air plasma treatment on adhesion and mechanical properties of aramid fibers

In order to investigate the effect of atmospheric pressure plasmas on adhesion between aramid fibers and epoxy, aramid fibers were treated with atmospheric pressure helium/air for 15, 30 and 60 s on a capacitively-coupled device at a frequency of 5.0 kHz and He outlet pressure of 3.43 kPa. SEM analysis at 10 000× magnification showed no significant surface morphological change resulted from the plasma treatments. XPS analysis showed a decrease in carbon content and an increase in oxygen content. Deconvolution analysis of C1s, N1s and O1s peaks showed an increase in surface hydroxyl groups that can interact with epoxy resin. The microbond test showed that the plasma treatment for 60 s increased interfacial shear strength by 109% over that of the control (untreated). The atmospheric pressure plasma increased single fiber tensile strength by 16-26%.     

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.     

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。     

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。     

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.     

The effect of atmospheric pressure helium plasma treatment on the surface and mechanical properties of ultrahigh-modulus polyethylene fibers

Ultrahigh-modulus polyethylene fibers were treated with atmospheric pressure He plasma on a capacitively coupled device at a frequency of 7.5 kHz and a He partial vapor pressure of 3.43 × 10³ Pa. The fibers were treated for 0, 1, and 2 min. Microscopic analysis showed that the surfaces of the fibers treated with He plasma were etched and that the 2-min He plasma-treated group had rougher surfaces than the 1-min He plasma-treated group. XPS analysis showed a 200% increase in the oxygen content and a 200% increase in the concentration of C—O bonds (from 11.4% to 31%) and the appearance of C=O bonds (from 0% to 7.6%) on the surface of plasma-treated fibers for the 2-min He plasma-treated group. In the microbond test, the 2-min He plasma-treated group had a 100% increase of interfacial shear strength over that of the control group, while the 1-min He plasma-treated group did not show a significant difference from the control group. The 2-min He plasma-treated group also showed a 14% higher single-fiber tensile strength than the control group.     

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     

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.     

水分对常压等离子体处理纤维结构与性能的影响

在空气相对湿度为5%,65%和95%的条件下,应用氦气/氧气常压等离子体处理芳纶和超高强度聚乙烯纤维,采用单纤维抽拔实验测定处理前后纤维与环氧树脂间的层间剪切强度,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:等离子体处理纤维随着处理环境湿度的增加,水分促进了芳纶表面的...     

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     

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.     

Chemical modification combined with corona treatment of UHMWPE fibers and their adhesion to vinylester resin

The influence of corona treatment on the near-surface structures of treated ultra-high-molecular-weight polyethylene (UHMWPE) fibers was studied first by atomic force microscopy (AFM). AFM pictures showed that the pits on the corona-treated PE fiber surfaces had different change characteristics in depth compared with in length and breadth with variations of corona power. Then the UHMWPE fibers were subjected to chemical modification following the corona treatment, named the two-stage treatment. Surface morphologies and chemical properties of the treated fibers were analyzed by scanning electron microscopy (SEM), FT-IR–ATR spectroscopy and Raman spectroscopy. The results obtained suggested that some carbon–carbon double bonds had been introduced on the surfaces of the PE fibers after the two-stage treatment. These unsaturated groups could participate in free-radical curing of vinylester resin (VER), and this resulted in improvement of interfacial adhesion strength in the PE fiber/VER composites. In addition, the mechanical properties of the UHMWPE fibers reduced after corona treatment did not reduce further after subsequent chemical treatment with increase of corona power. In short, the two-stage treatment proved to be effective in improving the interfacial adhesion of the composites and maintaining the high mechanical properties of the PE fibers, as this treatment method did not destroy the bulk structure of the UHMWPE fibers.     

Plasma surface treatments on carbon fibers. II. Mechanical property and interfacial shear strength

Carbon fiber are surface treated by oxygen, argon, and styrene plasma to study the effects on fiber strength and interfacial shear strength with PPS resin. Interfacial shear strength between carbon fiber and high melting temperature thermoplastic resins is successfully measured with the microbond pull-out test with the help of scanning CO₂ laser beam which solved the difficulties in preparing PPS microspheres. Tensile tests show that etching by oxygen plasma and deposition with plasma–PS increase strength of the fibers in some cases. ESCA spectra deconvolutions demonstrate that the improved interfacial strength is strongly related to the hydroxyl, ether, or aromatic groups on the surface. On the other hand, hydrocarbon segments are detrimental to the interface. Surface area and roughness have little influences on the interfacial strength of carbon fiber/PPS composites.     

常压等离子体处理芳砜纶的结构与性能研究

分别采用氦气和氦气/氧气对芳砜纶进行常压等离子体处理。采用滴水吸收实验测定处理前后纤维表面的润湿性,利用扫描电子显微镜和X射线光电子能谱仪分析处理前后纤维表面形态和化学成分的变化。结果表明:经常压等离子体处理后芳砜纶表面粗糙度增加,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,芳砜纶纱线的润湿性能提高,纱线强度没有明显变化,氦气/氧气等离子体处理比氦气等离子体处理效果更好。     

Atmospheric pressure helium + oxygen plasma treatment of ultrahigh modulus polyethylene fibers

Ultrahigh modulus polyethylene fibers were treated with atmospheric pressure helium + oxygen plasma in a capacitively coupled device at a frequency of 7.5 kHz. The fibers were treated for 0, 0.5, 1, 1.5, and 2 min. The surfaces of the fibers treated with He + O₂ plasma were etched and micro-cracks were formed. XPS analysis showed a 65ndash213% increase in oxygen content on the surfaces of all plasma-treated fibers, except for the 1.5 min group. An increase in the concentration of C—O and the appearance of C=O bonds on the surfaces of plasma-treated fibers were observed. In the micro-bond test, He + O2 plasma-treated groups had a 65–104% increase in interfacial shear strength over that of the control. The tensile strength of the fibers was either unchanged or decreased by 10–13% by the plasma treatments.     

The influence of surface modifications of glass on glass fiber/polyester interphase properties

Unsized glass fibers and planar glass substrates were subjected to low temperature plasma or wet-chemical process to modify the fiber or substrate surface and thus influence the interphase properties of the glass/polyester system. Plasma-polymerized thin films (interlayers) of organosilicon monomers (hexamethyldisiloxane and vinyltriethoxysilane) were deposited in an RF helical coupling plasma system on the glass surface. Commercial silane coupling agent (vinyltriethoxysilane) was coated onto an unmodified glass surface from an aqueous solution. Bonding at the glass/interlayer interface was analyzed by employing a micro-scratch tester together with an optical polarizing microscope for the planar samples. The results revealed that the adhesion bonding could be controlled by plasma process parameters. Scanning electron and atomic force microscopies enabled characterization of the film surface morphology. Chemical composition and chemical structure of prepared interlayers were characterized using X-ray photoelectron and infrared spectroscopies. Microcomposites (macrocomposites) were tested to evaluate the interfacial shear strength (short-beam strength) of the glass fiber/polyester interphase using the microbond test (short-beam shear). Our study indicated that the most efficient interphase could be prepared by plasma polymerization or wet-chemical process using the vinyltriethoxysilane monomer. The short-beam strength was 110% higher than that for untreated fibers in both cases.     

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.     

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.