Influence of oxygen plasma treatment on hydrogen chloride removal of activated carbon fibers

The oxygen plasma treatment of activated carbon fibers (ACFs) was carried out to introduce oxygen-containing groups onto carbon surfaces. Surface properties of the ACFs were determined by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). N2/77 K adsorption isotherms were investigated by BET and D-R plot methods to characterize specific surface area, pore volume, and pore size distribution. The efficiency of hydrochloride removal was confirmed by two kinds of methods; one is detecting tubes (range: 1-40 ppm), and the other is a gas chromatography technique. As experimental results, the hydrochloride removal efficiency of the ACFs was increased with the number of plasma treatment times up to around 300%, resulting from newly formed oxygen-containing functional groups (especially phenolic and carboxylic) on carbon surfaces, in the decreased specific surface areas or pore volumes. These results indicate that the plasma treatment leads to the increase of hydrochloride removal due to the improvement of surface functional groups containing oxygen on the carbon surfaces.     

Influence of atmospheric plasma on physicochemical properties of vapor-grown graphite nanofibers

Vapor-grown graphite nanofibers (GNFs) were modified by plasma treatments using low-pressure plasmas with different gases (Ar gas only and/or Ar/O2 gases), flow rates, pressures, and powers. Surface characterizations and morphologies of the GNFs after plasma treatment were investigated by X-ray photoelectron spectroscopy (XPS), contact angle, titration, and transmission electron microscopy (TEM) measurements. Also, the investigation of thermomechanical behavior and impact strengths of the GNFs/epoxy composites was performed by dynamic-mechanical thermal analysis (DMTA) and Izod impact testing, respectively. The plasma treatment of the fibers changed the surface morphologies by forming a layer with a thickness on the order of 1 nm, mainly consisting of oxygen functional groups such as hydroxyl, carbonyl, and carboxyl groups. After functionalization of the complete surfaces, further plasma treatment did not enhance the superficial oxygen content but slightly changed the portions of the functional groups. Also, the composites with plasma-treated GNFs showed an increase in T(g) and impact strength compared to the composites containing the same amount of plasma-untreated GNFs.     

Influence of Plasma Treatment on the Electroless Deposition of Copper on Carbon Fibers

Air and nitrogen glow discharge were used to replace chromic acid pretreatment to deposit copper film on carbon fiber surfaces from an CuSO₄‐HCHO electroless system. A greater copper uptake and a more uniformly coated copper film were obtained for plasma‐treated carbon fibers. The adhesion between the copper film and the carbon fibers was also improved. An orthogonal table L₉(3⁴) was used to study the effects of discharge pressure, discharge power, time and gas type on the copper uptake. Scanning electron microscopy (SEM), reflection absorption infrared spectroscopy (RAIR) and X‐ray photoelectron spectroscopy (XPS) at different depths were applied to characterize the physical and chemical changes of the surface of the carbon fibers. The results showed that after plasma treatment, the carbon fiber surface became rough and several types of polar oxygen groups, such as carboxylic acid COOH, esters COOC, quinones Ph?O, etc., were introduced into the carbon fiber surface. A mechanism of plasma treatment effects on copper electroless deposition on the carbon fiber surface is also suggested.     

Surface modification of high-performance polymeric fibers by an oxygen plasma. A comparative study of poly(p-phenylene terephthalamide) and poly(p-phenylene benzobisoxazole)

Poly(p-phenylene terephthalamide) (PPTA) and poly(p-phenylene benzobisoxazole) (PBO) fibers were exposed to an oxygen plasma under equivalent conditions. The resulting changes in the surface properties of PPTA and PBO were comparatively investigated using inverse gas chromatography (IGC) and atomic force microscopy (AFM). Both non-polar (n-alkanes) and polar probes of different acid-base characteristics were used in IGC adsorption experiments. Following plasma exposure, size-exclusion phenomena, probably associated to the formation of pores (nanoroughness), were detected with the largest n-alkanes (C(9) and C(10)). From the adsorption of polar probes, an increase in the number or strength of the acidic and basic sites present at the fiber surfaces following plasma treatment was detected. The effects of the oxygen plasma treatments were similar for PPTA and PBO. In both cases, oxygen plasma introduces polar groups onto the surfaces, involving an increase in the degree of surface nanoroughness. AFM measurements evidenced substantial changes in the surface morphology at the nanometer scale, especially after plasma exposure for a long time. For the PBO fibers, the outermost layer - contaminant substances - was removed thanks to the plasma treatment, which indicates that this agent had a surface cleaning effect.     

Analytical investigation of plasma-treated carbon fibres

As-grown and heat-treated vapour grown carbon fibres (VGCF) in the as-prepared state, washed in HCl/H(2)O, and treated in O(2) plasma for different periods have been investigated by means of XPS and scanning electron microscopy (SEM). The surface energy of the carbon fibres before and after plasma treatment was determined from the wetting contact angle. Washing introduced hydroxyl, carbonyl and carboxyl groups onto the fibre surfaces and oxygen plasma treatment increases the total atomic concentration of oxygen up to 17%. This is in good agreement with the value of the polar component of the surface energy. Plasma treatment also enhanced the fibre surface porosity (by etching).     

Surface characteristic of poly(p‐phenylene terephthalamide) fibers with oxygen plasma treatment

Oxygen plasma is widely employed for modification of polymer surfaces. Plasma treatment process is a convenient procedure that is also environmentally friendly. This study reports the effects of oxygen plasma treatment on the surface properties of poly(p‐phenylene terephthalamide) (PPTA) fibers. The surface characteristics before and after oxygen plasma treatment were analyzed by XPS, atomic force microscopy (AFM) and dynamic contact angle analysis (DCAA). It was found that oxygen plasma treatment introduced some new polar groups (O? C?O) on the fiber surface, increased the fiber surface roughness and changed the surface morphologies obviously by plasma etching and oxidative reactions. It is also shown that the fiber surface wettability was improved significantly by oxygen plasma treatment. Copyright © 2008 John Wiley & Sons, Ltd.     

Surface Energy and Wettability of Plasma-treated Polyacrylonitrile Fibers

Polyacrylonitrile fibers were treated with a nitrogen glow-discharge plasma. The surfaces of untreated and treated fibers were examined with contact angle measurements, atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). Surface energy calculations of the fibers were carried out from contact angle measurements using the relationships developed by Fowkes. It is found that plasma treatment causes a reduction in water contact angle on the fiber surfaces. The dispersion component of surface energy changes slightly, while the polar component is increased significantly from 14.6 mN/m to 58.7 mN/m and the total surface energy increase is 139%. The increase of surface energy is mainly caused by the introduction of hydrophilic groups on the fiber surfaces after plasma treatment.     

Mechanical properties of interlayer hybrid textile composite materials based on modified aramid and UHMWPE fabrics

Aramid fibers and ultra-high molecular weight polyethylene (UHMWPE) fibers lack active surface functional groups, and the surface is smooth, limiting their practical application in textile composite materials. In this study, zinc oxide nanorods were used to grow on aramid fibers surfaces, and oxygen plasma followed by treatment with a silane coupling agent was used to modify UHMWPE fibers. The effects of surface modification on the surface morphology and composition, and mechanical properties of fibers and composites were investigated. The mechanical response of interlayer hybrid textile composite materials based on modified aramid and UHMWPE fabrics was examined. The results reveal that surface roughness, active surface functional groups, and wettability that can be controlled by treatment conditions and parameters are important for improving interface adhesion. In addition, the interlayer hybridization pattern as a result of using dissimilar layer materials and altering stacking sequence has a great impact on the mechanical behavior of hybrid textile composite materials.     

Comparison of the effect of excimer laser irradiation and RF plasma treatment on polystyrene surface

Polystyrene (PS) samples were treated with excimer laser, argon and oxygen plasmas. The surface of PS was irradiated using ArF excimer pulsed laser (λ=193 nm). Radio frequency glow discharge (RF) was used to generate the argon and oxygen plasmas. The samples were processed at different number of pulses and treatment times. The changes were characterized by atomic force microscopy (AFM), attenuated total reflectance Fourier transform infrared (ATR-FTIR), scanning electron microscopy (SEM) and contact angle measurements. The data from ATR-FTIR spectra showed the induction process of oxygen-based functional group in both PS samples treated with RF plasma and laser. AFM and SEM observations demonstrated that a specific nanostructure was created on the laser-treated PS surface. Contact angle measurement indicated higher wettability of the treated PS with both argon and oxygen plasmas and lesser wettability of laser-treated samples. The data from in vitro assays showed the significant cell attachment and growth onto plasma-treated surfaces in comparison with laser treated samples.     

Improved interfacial properties of carbon fiber/UHMWPE composites through surface coating on carbon fiber surface

Carbon fibers were coated in an attempt to improve the interfacial properties between carbon fibers and ultra‐high molecular weight polyethylene resin matrix. Atomic force microscopy, scanning electron microscopy, and X‐ray photoelectron spectroscopy were performed to characterize the changes of carbon fiber surface. Atomic force microscopy results show that the coating of carbon fiber significantly increased the carbon fiber surface roughness. X‐ray photoelectron spectroscopy indicates that silicon containing functional groups obviously increased after modification. Interlaminar shear strength was used to characterize the interfacial properties of the composites.     

Synthesis and characterization of chemically modified polystyrene as processable carbon fiber precursors

In this study, the chemically modified polystyrene was studied for improvement of polystyrene which had low carbon yield, as a carbon fiber precursor. The polystyrene was synthesized with divinylbenzene which was used as a cross-linking agent by the solution polymerization method. Then the synthesized polystyrene was nitrated with sulfuric and nitric acids solution (H₂SO₄/HNO₃) followed by reduction to form nitrogen-functional groups. The surface properties of the modified polystyrene were investigated by Fourier transfer infrared spectroscopy to confirm the introduction of functional groups on the modified polystyrene surfaces. The thermal properties of the modified polystyrene were measured by thermogravimetric analysis and differential scanning calorimetry. The morphologies of the electrospun polystyrene fibers by a chemical modification were observed by scanning electron microscopy. From the results, the nitrogen-functional groups were introduced on the modified polystyrene surfaces which affected the quantity of functional groups. Also, the chemical treatment affected the carbon yield of the polystyrene owing to the introduction of nitrogen-functional groups on polystyrene surfaces. Consequently, it was concluded that the chemical treatment of polystyrene fibers enables it to be used as a possible carbon fiber precursor.     

Chemical modifications of inert organic monolayers with oxygen plasma for biosensor applications

In this paper we present a study of using oxygen plasma for chemically modifying inert hydrocarbon self-assembled monolayers of octadecyltrichlorosilane (OTS-SAMs) and rendering active surfaces for protein immobilization. Detailed surface modification and protein immobilization were characterized by using ellipsometry, X-ray photoelectron spectroscopy (XPS), Fourier transform infrared-attenuated total reflectance spectroscopy, and fluorescence microscopy. Our XPS results showed that the surface reaction between OTS-SAMs and oxygen plasma can generate new surface functional groups such as alcohol (C-O), aldehyde (C=O), and carboxylic acid (O-C=O), and their compositions can be controlled by using different treatment times and powers. A short treatment time ( approximately 1 s) and high power (10 W) can lead to a higher density of aldehyde groups, which can serve as linker groups for protein immobilization through the formation of Schiff bases with the amine groups of proteins. By using the fluorescence immunostaining method, we confirmed that human immunoglobulin (IgG) can be immobilized on a glass slide, only if the surface was decorated with OTS-SAMs and if the OTS-SAMs were pretreated with oxygen plasma. The protein immobilized on the oxygen-plasma-treated surface can only be recognized by using a highly specific antibody, FITC-anti-IgG, but not FITC-anti-biotin.     

Effect of oxygen plasma treatment and gold sputtering on morphological and local mechanical properties of copolyimide/gold micropatterned structures

Atomic force microscopy (AFM) was used to analyze rectangular 3‐dimensional patterned microstructures with different functionalities induced on copolyimide containing alicyclic sequences film surfaces by means of oxygen plasma treatment. The plasma power was ranged to be big enough to accelerate the plasma species towards the copolyimide surface, and the exposure time was not very small to generate a roughness that still can be monitored by AFM. To create the rectangular pattern, transmission electron microscopy grid masks were placed on the samples before treatment. Plasma‐induced micropatterning with alternating hydrophilic and hydrophobic surface chemistries was evaluated by measuring the adhesion forces between the gold‐covered AFM tip and the copolyimide surfaces. To fabricate 3‐dimensional metallic microstructures arranged in well‐defined areas, thin metal layers were sputtered on these pretreated copolyimide films. The AFM morphological aspects of the obtained metallic structures were correlated with the surface modifications induced by plasma treatment conditions. Functional indexes and functional volume parameters were also calculate to characterize the functional behavior of the surface, such as wear, lubrication, and contact. The AFM data were compared with those obtained using the small‐angle X‐ray scattering measurements.     

气相生长碳纤维的表面改性及表征

用浓硝酸(65%~68%)对气相生长碳纤维(VGCF)进行了不同时间的表面化学改性。X射线衍射(XRD)分析表明：改性使得VGCF的石墨晶型结构改变，其改变的程度随改性时间的延长而加深；BET比表面积(S_BET)测试表明：改性后的VGCF的S_BET有一定的变化，经120 min长时间的改性处理后，S_BET明显降低；傅立叶变换红外光谱(FTIR)测定得出：改性后VGCF表面上生长了不同类型的含氧基团，其总含量随改性时间的增大而增加；程序升温还原(TPR)得出：改性后VGCF表面上生成有2类以上的热稳定性不同的含氧基团，计算求得含氧基团的氧总含量为2 mmol·g^-1以上；NH₃吸附微量量热测定得出：表面酸性基团的强度和含量随改性时间增加而增大；透射电子显微镜(TEM)结果表明：改性没有明显破坏VGCF的外观结构；吸油值(AOV)实验给出：改性后VGCF的AOV显著降低而亲水性增强；双液法接触角测试给出：改性后VGCF的表面能(SE)明显增大；偶联剂与VGCF作用的FTIR研究表明：改性后VGCF表面含氧基团和偶联剂发生反应，增强了偶联剂在VGCF表面上的结合强度。     

Atomic-scale scanning tunneling microscopy study of plasma-oxidized ultrahigh-modulus carbon fiber surfaces

In the present work, scanning tunneling microscopy (STM) was employed to study the surface modification of ultrahigh modulus carbon fibers at the atomic level by oxygen plasma. As detected by STM, the distinctive feature of the fresh, untreated surface was the general presence of atomic-scale arrangements in different degrees of order (from atomic-sized spots without a clearly ordered disposition to triangular patterns identical to those typical of perfect graphite). Following fiber exposure to the plasma, the STM images showed evidence of the abstraction of carbon atoms from random locations on the fiber surface, giving rise to the development of defects (i.e., structural disorder), which in turn were the places where oxygen could be introduced during and after the plasma etching. It was observed that the most effective treatments in terms of extent of surface structural modification (disordering) and uniform introduction of oxygen were those carried out for just a few ( approximately 3) minutes. Considerably shorter exposures failed to provide a homogeneous modification and many locations on the fiber surface remained unaltered, retaining their original atomic-scale order, whereas longer treatments did not bring about further structural changes to the surface and only led to fiber consumption. These results are consistent with previous X-ray photoelectron spectroscopy measurements on these fibers and provide an atomic-level understanding of the saturation effect observed in the surface oxygen concentration of this and other types of carbon fibers with plasma oxidation. Such understanding may also prove helpful for the accurate control and optimization of fiber-matrix interaction in composite materials.     

含二氮杂萘酮结构聚醚砜酮膜的微波等离子体处理研究

含二氮杂萘酮结构型聚醚砜酮(ＰＰＥＳＫ)是近年来本研究组开发成功的新型耐高温聚合物[1].该聚合物具有优异的力学性能和突出的耐热性,玻璃化转变温度(Ｔｇ)为265～305℃(随砜酮比不同而变化),其结构式如下:ＯＮＮＯＳＯＯＯＮＮＯＣＯ　　研究表明,用ＰＰＥＳＫ制成的气体分离膜对Ｏ2/Ｎ2、ＣＯ2/Ｎ2有良好的气体渗透性和透过选择性[2,3],但由于其亲水性不高进而限制了它在纳滤膜和反渗透膜等方面的应用,因此有必要对其进行改性.目前,常用的膜及膜材料改性的方法有磺化、氯甲基化季胺化、接枝等化学改性和低温等离子体与辐射等物理改性.其…     

Fabrication and study of supercapacitor electrodes based on oxygen plasma functionalized carbon nanotube fibers

Dry-spun Carbon Nanotube(CNT) fibers were surface-modified by atmospheric pressure oxygen plasma functionalization using a well controlled and continuous process. The fibers were characterized by scanning electron microscopy(SEM), Raman spectroscopy, and X-ray Photoelectron Spectroscopy(XPS). It was found from the conducted electrochemical measurements that the functionalized fibers showed a 132.8%increase in specific capacitance compared to non-functionalized fibers. Dye-adsorption test and the obtained Randles-Sevcik plot demonstrated that the oxygen plasma functionalized fibers exhibited increased surface area. It was further established by Brunauer-Emmett-Teller(BET) measurements that the surface area of the CNT fibers was increased from 168.22 m~2/g to 208.01 m~2/g after plasma functionalization. The pore size distribution of the fibers was also altered by this processing. The improved electrochemical data was attributed to enhanced wettability, increased surface area, and the presence of oxygen functional groups, which promoted the capacitance of the fibers. Fiber supercapacitors were fabricated from the oxygen plasma functionalized CNT fiber electrodes using different electrolyte systems. The devices with functionalized electrodes exhibited excellent cyclic stability(93.2% after 4000 cycles), flexibility, bendability, and good energy densities. At 0.5 m A/cm~2, the EMIMBF4 device revealed a specific capacitance, which is 27% and 65% greater than the specific capacitances of devices using EMIMTFSI and H_2 SO_4 electrolytes,respectively. The practiced in this work plasma surface processing can be employed in other applications where fibers, yarns, ribbons, and sheets need to be chemically modified.     

Effect of reactive oxygen species generated with ultraviolet lamp and plasma on polyimide surface modification

Understanding the effect of reactive oxygen species (ROS), such as singlet oxygen molecule and atomic oxygen, on polyimide (PI) film properties, such as wettability, morphology, and chemical bonding state, is essential for further development of PI‐based surfaces. We investigated the effect of different ROS generated during ultraviolet (UV) and plasma treatment in oxygen gas on surface modification of Kapton PI. Different surface modification techniques, UV and plasma treatment, are known to generate different ROS. In this work, we demonstrate the effect of different ROS on PI surface modification. From the diagnostics of ROS by means of electron spin resonance and optical emission spectroscopy, we confirmed that during UV treatment, excited singlet oxygen molecules are the main ROS, while plasma treatment mainly generated atomic oxygen. The wettability of PI surface treated by UV and plasma resulted in hydrophilic PI surfaces. XPS results show that the wettability of PI samples is mainly determined by their surface O/C ratio. However, chemical bonding states were different: while UV treatment tended to generate C=O bonds, while plasma treatment tended to generate both C―O and C=O bonds. Singlet oxygen molecules are concluded to be the main oxidant during UV treatment, and their main reaction with PI was concluded to be of the addition type, leading to an increase of C=O groups on the surface of PI film. Meanwhile, atomic oxygen species were the main oxidant during plasma treatment, reacting with the PI surface through both etching and addition reaction, resulting in a wider variety of bonds, including both C―O and C=O groups.     

Effects of plasma treatment of carbon fibers on interfacial properties of BMI resin composites

High performance continuous fiber surface modification by inductively coupled RF plasma (ICP) and dielectric barrier discharge (DBD) low temperature plasma were conducted. X-ray photoelectron spectroscopy (XPS) and other analytical testing methods systematically studied plasma treatment time, discharge power, discharge pressure, etc, on fiber surface state, surface composition, and surface shape changes in the appearance and wetting properties. The results show that after plasma treatment the surface of the fiber is grafted with a large number of polar functional groups such as carboxyl groups and hydroxyl groups. The surface roughness increases, the surface free energy increases, and the fiber wetting property is significantly improved, resulting in improvement in interlaminar shear strength (ILSS) between the fiber and the resin matrix. Finally, the surfaces of the fibers and its relationship with interfacial properties of fiber reinforced bismaleimide composites are also discussed.     

Investigation of glow discharge plasma for surface modification of polypropylene

Material surface properties of polymers, plastics, ceramics and textiles can be modified by atmospheric or low‐pressure glow discharge plasma. The aim of the present work is to study the surface modification of biaxially oriented polypropylene (BOPP) film in order to improve its hydrophilic and wetting properties. In this article we used low‐pressure, low‐temperature oxygen plasma for the surface treatment of BOPP. Scanning electron microscopy indicates that plasma treatment causes mainly physical changes by creating microcraters and roughness on the surface and increasing surface friction. Attenuated total reflectance infrared spectra show oxygen‐containing groups such as ? OH at 3513 cm^?1 and C?O at 1695 cm^?1. Microscopic investigations of water droplets on BOPP (treated, untreated) show that the interfacial adhesion of treated surfaces is increased. Copyright © 2003 John Wiley & Sons, Ltd.