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.     

Development and evaluation of surface treatments to enhance the fiber-matrix adhesion in PAN-based carbon fiber/liquid crystal polymer composites. Part I: Coupling agent and amine surface treatments

Several surface treatments, using both commercially available coupling agents and reagents containing multiple amines, were applied to commingled continuous as-received AS4 carbon reinforcing fiber/liquid crystal polymer (LCP) matrix fibers. Unidirectional composites (normally 60 vol% carbon fiber) were prepared from as-received and treated commingled fibers and characterized. To estimate the effect the effect of the treatments on fiber-matrix adhesion, short beam shear (SBS) tests were conducted, the failure surfaces were examined, and spectroscopic studies wee performed. The mean SBS strength of the as-received unidirectional AS4 carbon fiber/LCP matrix composite system was 49 MPa. The best coupling agent and amine treatments yielded increases in composite shear strength of ∼ 10 to 20%, relative to the as-received AS4/LCP system. For the amine treatments, ESCA and FTIR analyses suggested of both the carbon and LCP fibers may have caused the increased adhesion. Moreover, SEM analysis of the failure surfaces of SBS specimens from composites prepared with the treated fibers may have caused the increased adhesion. Moreover, SEM analysis of the failure surfaces of SBS specimens from composites prepared with the treated fibers (both with coupling agents and amines) showed that strong fiber-matrix adhesion was present. That is, failure occurred in the LCP matrix material.     

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.     

Surface Characterization of Plasma Treated Carbon Fibers and Adhesion to a Thermoplastic Polymer

The surface chemistry of IM7 carbon fibers was characterized by x-ray photoelectron spectroscopy (XPS). The fiber surface energetics were determined from a two-liquid tensiometric method. The adhesion between as-received and plasma-treated carbon fibers and polyethersulfone (PES) was measured by the microbond pull-out test.

The surface characterization techniques showed that the effect of any plasma treatment is attained within less than 15 seconds. It was found that both argon and air plasmas increased the oxidation state of the fiber surface and that they reduced the dispersive component (γ_s ^d) of the fiber surface free energy considerably. The ammonia plasma treatment resulted in a cleaning of the surface. This plasma treatment was also effective in improving the fiber/matrix adhesion of quenched samples. A similar adhesion enhancement between as-received fibers and PES is obtained by annealing the samples above the Tg of the polymer. The air plasma treatment did not have any significant effect on the fiber/matrix adhesion.     

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.     

Influence of surface treatment of carbon fibers on interfacial adhesion strength and mechanical properties of PLA‐based composites

In the present study C/PLA composites with different fiber surface conditions (untreated and with nitric acid oxidation for 4 h and 8 h) were prepared to determine the influence of surface treatment on the interfacial adhesion strength and mechanical properties of the composites. A chemical reaction at the fiber–matrix interfaces was confirmed by XPS studies. Nitric acid treatment was found to improve the amount of oxygen‐containing functional groups (particularly the carboxylic group, —COOH) on carbon fiber surfaces and to increase the surface roughness because of the formation of longitudinal crevices. The treated composites exhibited stronger interface adhesion and better mechanical properties in comparison to their untreated counterparts. There was a greater percentage of improvement in interfacial adhesion strength than in the mechanical properties. The strengthened interfaces and improved mechanical performance have been mainly attributed to the greater extent of the chemical reaction between the PLA matrix and the carbon fibers. The increased surface roughness also has had a slight contribution. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 367–376, 2001     

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.     

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.     

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.     

Three‐dimensionally braided carbon fiber–epoxy composites,a new type of materials for osteosynthesis devices. II. Influence of fiber surface treatment

Interfacial adhesion between carbon fiber and epoxy resin plays an important role in determining performance of carbon–epoxy composites. The objective of this research is to determine the effect of fiber surface treatment (oxidization in air) on the mechanical properties (flexural strength and modulus, shear and impact strengths) of three‐dimensionally (3D) braided carbon‐fiber‐reinforced epoxy (C_3D/EP) composites. Carbon fibers were air‐treated under various conditions to improve fiber–matrix adhesion. It is found that excessive oxidation will cause formation of micropits. These micropits are preferably formed in crevices of fiber surfaces. The micropits formed on fiber surfaces produce strengthened fiber–matrix bond, but cause great loss of fiber strength and is probably harmful to the overall performance of the corresponding composites. A trade‐off between the fiber–matrix bond and fiber strength loss should be considered. The effectiveness of fiber surface treatment on performance improvement of the C_3D/EP composites was compared with that of the unidirectional carbon fiber–epoxy composites. In addition, the effects of fiber volume fraction (V_f) and braiding angle on relative performance improvements were determined. Results reveal obvious effects of V_f and braiding angle. A mechanism was proposed to explain the experimental phenomena. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1040–1046, 2002     

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     

Mechanical properties of surface‐modified ultra‐high molecular weight polyethylene fiber reinforced natural rubber composites

The mechanical properties of ultra‐high molecular weight polyethylene (UHMWPE) fibers reinforced natural rubber (NR) composites were determined, and the effects of fiber surface treatment and fiber mass fraction on the mechanical properties of the composites were investigated. Chromic acid was used to modify the UHMWPE fibers, and the results showed that the surface roughness and the oxygen‐containing groups on the surface of the fibers could be effectively increased. The NR matrix composites were prepared with as‐received and chromic acid treated UHMWPE fibers added 0–6 wt%. The treated UHMWPE fibers increased the elongation at break, tear strength, and hardness of the NR composites, especially the tensile stress at a given elongation, but reduced the tensile strength. The elongation at break increased markedly with increasing fiber mass fraction, attained maximum values at 3.0 wt%, and then decreased. The tear strength and hardness exhibited continuous increase with increasing the fiber content. Several microfibrillations between the fiber and NR matrix were observed from SEM images of the fractured surfaces of the treated UHMWPE fibers/NR composites, which meant that the interfacial adhesion strength was improved. POLYM. COMPOS., 38:1215–1220, 2017. © 2015 Society of Plastics Engineers     

Wettability and Adhesion Characteristics of Plasma-Treated Carbon Fibers

The surface free energy (γ_s) of modified carbon fibers was determined by tensiometry and effects of CF₄-O₂ plasma treatment were evaluated. The treatment with the gas mixture in which oxygen was above 40% accelerated preferentially the oxidation of fiber surfaces and the nondispersive component of the surface free energy, γ^P_S, increased to about three times that of the untreated fiber. On the other hand, the treatment with the gas containing CF₄ above 80% induced fluorination and surface species such as - CF, - CF₂, or - CF₃ were formed. The γ^P_S values decreased to almost zero and the dispersive component became about 18 mJ/m². The calculated work of adhesion between various fibers and the epoxy resin was well correlated with the interfacial shear strength of the composites formed with these materials.     

Carbon fiber‐reinforced gelatin composites. I. Preparation and mechanical properties

Composites were made from carbon fibers and gelatin using a solvent‐casting or solution‐impregnation technique. Relationships between the fiber volume fraction (Vf), glycerol (plasticizer) content, gelatin content, fiber form, and mechanical properties (tensile strength and modulus, elongation at break, and shear strength) of the composites were investigated. In long carbon fiber gelatin composite (C_L/Gel), tensile strength, modulus, and shear strength increased steadily with the Vf. In the case of a short carbon fiber gelatin composite (C_S/Gel), an initial improvement in tensile strength and modulus was followed by a reduction, whereas the shear strength improved with the Vf and then reached a constant value. The elongation decreased with the Vf for both composites. It is shown that C_L/Gel had higher values of strength, modulus, and elongation than did C_S/Gel at any Vf level. The effects of glycerol and gelatin contents on the mechanical properties of the composites were found to be much less significant as compared to the Vf. According to scanning electron microscopic observation of the fracture surfaces, the fibers were uniformly distributed in the gelatin matrix, but the interfacial adhesion between the gelatin matrix and the carbon fibers was not very good for both composites. Fiber surface modification would be necessary to further improve the mechanical properties of the two composites. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 987–993, 2000     

Effect of plasma modification on the mechanical properties of carbon fiber/phenolphthalein polyaryletherketone composites

A study was carried out to investigate the effect of plasma modification on the mechanical properties of carbon fiber/phenolphthalein polyaryletherketone composites. The influence of oxygen plasma treatment on the surface properties of carbon fibers was investigated by X‐ray photoelectron spectroscopy and atomic force microscopy. The results indicated that oxygen plasma treatment was capable of increasing the concentrations of the oxygen‐containing groups of the carbon fiber surface as well as enhancing surface roughness. Both the chemical bonding and mechanical interlocking gave rise to an increase of the interlaminar shear strength of composite. Scanning electron microscope photographs showed that the destruction mode of composites was changed after the carbon fibers were treated by oxygen plasma. The results also indicated that the flexural properties of plasma‐treated carbon fiber composites were improved. POLYM. COMPOS., 2013. © 2013 Society of Plastics Engineers     

Effect of Plasma Treatment on the Adhesion of Carbon Fibers to Thermoplastic Polymers

A study has been made of the effect of RF plasmas on the adhesion of carbon fibers to polycarbonate and polysulfone. Treatment in oxygen plasma significantly increased the adhesion to both polymers. The effect is lost if the treated fiber is stored in air for a week. Surface analysis using XPS indicated an increase in atom percent oxygen but the spectra were unchanged for the stored fibers even though there had been a significant loss in adhesion. It is suggested that oxygen surface functionality is responsible for the improved adhesion but that this surface activation is lost on storage. Due to a sampling depth of 5-10 nm, XPS would not be expected to detect this small change in surface functionality.     

Surface Characterization of Plasma Treated Carbon Fibers and Adhesion to a Thermoplastic Polymer

The surface chemistry of IM7 carbon fibers was characterized by x-ray photoelectron spectroscopy (XPS). The fiber surface energetics were determined from a two-liquid tensiometric method. The adhesion between as-received and plasma-treated carbon fibers and polyethersulfone (PES) was measured by the microbond pull-out test.

The surface characterization techniques showed that the effect of any plasma treatment is attained within less than 15 seconds. It was found that both argon and air plasmas increased the oxidation state of the fiber surface and that they reduced the dispersive component (γ_s^d) of the fiber surface free energy considerably. The ammonia plasma treatment resulted in a cleaning of the surface. This plasma treatment was also effective in improving the fiber/matrix adhesion of quenched samples. A similar adhesion enhancement between as-received fibers and PES is obtained by annealing the samples above the Tg of the polymer. The air plasma treatment did not have any significant effect on the fiber/matrix adhesion.     

Effect of Plasma Treatment on the Adhesion of Carbon Fibers to Thermoplastic Polymers

A study has been made of the effect of RF plasmas on the adhesion of carbon fibers to polycarbonate and polysulfone. Treatment in oxygen plasma significantly increased the adhesion to both polymers. The effect is lost if the treated fiber is stored in air for a week. Surface analysis using XPS indicated an increase in atom percent oxygen but the spectra were unchanged for the stored fibers even though there had been a significant loss in adhesion. It is suggested that oxygen surface functionality is responsible for the improved adhesion but that this surface activation is lost on storage. Due to a sampling depth of 5-10 nm, XPS would not be expected to detect this small change in surface functionality.     

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。     

Effect of Organic Gas Plasmas on the Adhesion of Matrix Resins to Carbon Fibers

IM7 carbon fibers were surface treated in methane, ethylene, trifluoromethane and tetrafluoromethane plasmas. The surface chemical composition of the fibers was determined by X-ray photoelectron spectroscopy (XPS). The adhesion between as-received and plasma-treated carbon fibers and polyethersulfone (PES) and an epoxy resin was measured by the microbond pull-out test. XPS showed that the methane and ethylene plasmas deposited a thin layer of hydrocarbon on the fiber surface. The trifluoromethane plasma deposited a layer of fluorocarbon on the surface of the fibers. The tetrafluoromethane plasma etched the fibers and introduced a significant amount of fluorine on the surface. The microbond pull-out test results indicated that an etching plasma, such as the tetrafluoromethane plasma, improved the adhesion between carbon fibers and PES. These results are consistent with earlier work performed with ammonia plasma. The adhesion is believed to be due primarily to the differential thermal shrinkage between the fiber and the matrix. It was shown that in the case of a reactive matrix such as an epoxy resin, the fiber chemical composition plays a role in the fiber-matrix adhesion. However, this chemical effect is secondary to the cleaning effect of the surface treatment.