低温等离子体处理对高强聚乙烯纤维表面影响的研究

采用空气低温等离子体处理高强聚乙烯纤维,测试处理前后纤维表面摩擦系数的变化,并采用电子扫描显微镜（SEM）和原子力显微镜（AFM）对纤维表面形貌进行观察分析。结果发现,空气低温等离子体处理的刻蚀作用会在纤维表面形成致密的＂小坑群＂,使得纤维表面产生剥落、联结,造成纤维表面的粗糙程度有所增加,其处理后的纤维表面静、动摩擦系数有所提高。     

Flame versus air atmospheric gliding arc plasma treatment of polypropylene-based automotive bumpers: Physicochemical characterization and investigation of coating properties

In this research, the polypropylene (PP) sheets used for automotive bumper surface were treated using two methods: air atmospheric gliding arc plasma and flame modifications. Atomic force microscopy was applied to study the morphology of surfaces before and after treatment processes. While calculating the surface free energy (SFE), contact angle of the surfaces was measured, and the chemical composition of the PP surface was analyzed using X-ray photoelectron spectroscopy. Surface modifications by gliding arc plasma increased the ratio of the oxygen and nitrogen atoms on the surface by 100%, indicating that polar chemical functionalities form on the surface. The surface morphology was highly affected by gliding arc plasma treatments, which triggered an impact on roughness and etching. It was also found that the SFE was drastically increased by certain modifications. Noticeable improvement was also observed in wettability by the gliding arc plasma technique. In the next stage, polyurethane paints were coated on the treated and untreated PP surfaces. Then, we examined the flame and gliding arc plasma treatments' effect on coating properties of PP bumper, adhesion analysis, water immersion resistance, and sulfuric acid resistance. Finally, high-pressure carwash test and gloss analysis were conducted on the treated and untreated coated sheets, respectively.     

Effects of argon plasma treatment on surface characteristic of photopolymerization PEGDA–HEMA hydrogels

The aim of this research was to determine the influence of argon plasma treatment condition on the surface properties of poly(ethylene glycol) diacrylate (PEGDA)–hydroxyethly methacrylate hydrogel films, a kind of scaffold materials for tissue engineering. The changes of surface properties have been evaluated by contact angles, X‐ray photoelectron spectra (XPS), and scanning electron microscopy (SEM). From the contact angle measurements of different liquids, the surface free energy of the hydrogel was calculated according to approaches by Owens–Wendt–Kaelble. Results showed that the contact angle of the hydrogel to water decreased remarkably after argon plasma treatment, which was caused by the changes in morphology (SEM images) and chemical composition (XPS results) of the argon plasma‐treated surface. The surface free energy increased with the increase of the argon plasma treated time and power, and these increasing was mainly due to the increase of polar component. The XPS results confirmed that plasma oxidation reaction produced oxygen‐containing functional groups onto the surface. This functional group played an important role in increasing the hydrophilic properties of the hydrogel. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of Activated Gas Plasma on Surface Characteristics and Bondability of RTV Silicone and Polyethylene

An RTV silicone and high density polyethylene are exposed in an activated gas plasma for varying times and varying conditions. Both oxygen and argon are used. Changes in critical surface tension of wetting as determined by contact angle measurements are reported. Bondability of the treated surfaces is evaluated with both the aged bonds and aged surfaces prior to bonding being evaluated. In contradiction to some of the recent work reported in the literature on the effect of activated inert gas on surface characteristics, contact angles always decreased on the materials studied indicating an increase in surface energy. The significance of the results on present adhesion theories is discussed.     

Adhesion Improvement of Glass-Fibre-Reinforced Polyester Composites by Gliding Arc Discharge Treatment

A gliding arc is a plasma that can be operated at atmospheric pressure and applied for plasma surface treatment for adhesion improvement. In the present work, glass-fibre-reinforced polyester plates were treated using an atmospheric pressure gliding arc discharge with an air flow to improve adhesion with a vinylester adhesive. The treatment improved wettability and increased the polar component of the surface energy and the density of oxygen-containing polar functional groups at the surfaces. Double cantilever beam specimens were prepared for fracture mechanics characterisation (fracture resistance as a function of nominal mode mixity) of the laminate adhesive interface. It was found that gliding arc treatment significantly increases the interfacial fracture energy and fracture resistance in comparison with a standard peel ply treatment, although the mixed mode fracture energy of the gliding arc treated specimen was not as high as that of the laminate itself.     

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 low‐temperature plasma conditions on wicking properties of PA/PU knitted fabric

Plasma surface treatment has been extensively applied in the textile industry for the modification of polymer materials. In this study low‐temperature plasma (LTP) is used for surface treatment of polyamide/polyurethane (PA/PU) knitted fabric. The envisaged plasma effect is an increase in the surface energy of the treated textile, leading toward improved hydrophilic properties. The knitted fabric was treated by LTP using three non polymerizing gases: oxygen, air, and carbon dioxide. After plasma treatment, wettability of samples was tested through their wicking properties measuring capillary rise after water bath contact. The PA/PU knitted fabric samples treated with different plasma gases exhibited different hydrophilic performances. The influence of plasma variables (discharge power, time, pressure) was investigated. Although the chemical characteristics of elastan (PU) and nylon (PA) threads are different, the study has demonstrated that plasma treatment can in the same time alter the surface‐wetting behavior of both the components of the knitted fabric. It was also shown how these treatments can be regulated to produce the desired level of hydrophilicity dependently on the request application. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Role of PLLA plasma surface modification in the interaction with human marrow stromal cells

The effects of oxygen‐based radio frequency plasma enhanced chemical vapor deposition (rf PECVD) on the surface of poly(L ‐lactide) (PLLA) polymers and the influence thereof on protein adsorption and on bone–cell behavior have been studied. Thin films and porous scaffolds based on PLLA polymer were developed, and the role of surface modifications were investigated extensively. PECVD surface treatments were used to alter surface functionality and modulate protein adsorption on the PLLA polymer matrix. In particular, Bovine Serum Albumine fluorescein isothiocyanate (fitc‐BSA) conjugate adsorption on patterned surfaces of treated PLLA was analyzed by fluorescence microscopy. Human marrow stromal cells (MSCs) were cultured on scaffolds and cell adhesion and morphology were assessed using fluorescence microscopy. The results indicated that the PLLA surface became hydrophilic and its roughness increased with the treatment time and it had a dominant influence on the adsorption process of the protein. The outcome of the plasma treatment of various PLLA surfaces has been shown to be the up‐regulator of the cell‐adhesive proteins expression and consequently the improvement of cell adhesion and growth. Oxygen‐treated PLLA promoted higher adhesion and proliferation of the MSCs in comparison to the untreated samples. It can be concluded that following plasma treatment, PLLA samples show enhanced affinity for osteoprogenitor cells. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

A Study of the Effects of Low Power Plasma Treatment on Graphite and Highly Orientated Pyrolytic Graphite (HOPG) Surfaces

We have studied both the chemical and topographical changes induced on graphitic surfaces by low power plasmas using surface-sensitive X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), and atomic force microscopy (AFM). Evidence is presented for two totally different reaction mechanisms for air plasma and nitrogen plasma interactions with these surfaces. Both plasmas chemically alter the first few atomic layers of the surface; however, air plasma treatment results in the formation of an oxidised layer, whereas nitrogen plasma treatment generates a much more open structure of loosely adhered material.     

Surface modification of ultrahigh molecular weight polyethylene fibers by plasma treatment. I. Improving surface adhesion

The fiber/epoxy resin adhesion increases after plasma treatment on ultrahigh molecular weight polyethylene (UHMW-PE) fibers. The surface modification of UHMW-PE monofilaments was studied using a combination of techniques: contact-angle measurements, SEM, and pullout tests. The results may be summarized as follows: Infiuenced by different plasma parameters and draw ratios of the monofilaments, the adhesion increases by at least four times by plasma treatment. Failure in the pullout tests involve rupture within a treated monofilament and the skin of it was peeled off; the degree of peeling-off is affected by different plasma treatment conditions and draw ratios of the monofilaments. There is only a slight decrease in the surface energy of the treated monofilaments with aging time. Ways of combining plasma etching with other chemical treatments to further improve the fiber/resin adhesion have also been studied. © 1993 John Wiley & Sons, Inc.     

Wettability,ageing and recovery process of plasma-treated polyamide 6

The wetting properties of polyamide 6 rods treated with radiofrequency (RF) low-temperature plasma (LTP) using three different non-polymerizing gases (air, nitrogen and water vapour) were determined using the Wilhelmy contact-angle technique. Information on the acidic or basic nature of the ionizable groups generated on the rod surface was obtained using contact-angle titration. The wettability obtained depends on the plasma gas used, and it tends to decrease with time elapsed after the treatment when the samples are kept in an air environment. However, the wettability can be recovered by immersion of the aged samples in water. The degree of recovery depends on the plasma gas used and the highest recovery was obtained with water vapour plasma treated samples. Both ageing and recovery behaviour can be attributed to the reorganisation of hydrophilic groups which tend to reversibly migrate or orient towards the bulk phase depending on the storage conditions, although other factors can also have influence.     

Enhanced adhesion of epoxy-bonded steel surfaces using O2/Ar microwave plasma treatment

Steel surfaces have been modified using low pressure microwave plasma to enhance its adhesion with an epoxy adhesive. Optimization of the wettability of the surface was done using contact angle measurements for varying plasma parameters. Maximum wettability (19.9°) was obtained at 1000 W microwave power with 20 min of treatment time, −50 V sample bias and 1.67% O₂/Ar gas flow rate ratio. Enhanced wettability of the steel surface was attributed to increased surface roughness and oxide deposition. Using atomic force microscopy, surface roughness was observed to increase from 64.4 nm for the untreated surface to 76.7 nm for the O₂/Ar plasma treated surface. Deposition of oxides on the steel surface was also confirmed by the energy dispersive x-ray spectroscopy. Moreover, the increase in the total surface energy to 53.2 mN/m for the O₂ plasma treated steel surface supported the enhancement of its wettability, and hence, the adhesion with epoxy. Based on tensile test results, the adhesion strength of epoxy-bonded O₂/Ar plasma treated surfaces at optimum settings was increased to 3816.0 N, which is significantly higher compared to 3038.3 N for the epoxy-bonded untreated surfaces.     

Plasma Treatment of Polyacetal-Copolymer, Polycarbonate, Polybutylene terephthalate and Nylon 6, 6 Surfaces to Improve the Adhesion of Ink

Polyacetal-copolymer (POMB), polycarbonate (PC), polybutylene terephthalate (PBT), and nylon 6, 6 (PA6, 6) have been treated in an electron cyclotron resonance (ECR) plasma chamber to improve their adhesion properties towards ink. The chemical composition, the surface free energy, and the macroscopic adhesion have been studied by X-ray photoelectron spectroscopy (XPS), contact angle measurements, cross-cut tests, and the Scotch Tape test. Their dependence on the neutral gas, the treatment time, the pressure, and the ageing in air have been investigated. The XPS results reveal that the plasma treatment allows one to clean the surface and, if reactive gases are used, to incorporate new chemical species. The static and dynamic contact angles decrease with the plasma treatment and continue to decrease after contact with air. Very slow hydrophobic recovery is visible in the advancing contact angle, whereas the receding contact angle remains non-measurable even after more than a week of air exposure. Lower pressures and longer treatment times (120 s) lead to better macroscopic adhesion and reproducibility. For optimal treatment conditions (0.5 Pa, 120s N₂ plasma treatment time), the improvement of the adhesion remains excellent after seven days exposure of the sample in air.     

Surface free energy changes of stainless steel after one atmospheric pressure plasma treatment

Stainless steel plates (AISI 304L) were treated by an atmospheric pressure plasma treatment at room temperature in order to modify the surface properties. After plasma treatment, the surface wettability and the surface free energy were both improved. The wettability and the surface free energy of stainless steel plates before and after plasma treatment were measured from the results of contact angle test. Through the results of contact angle and surface free energy, optimum plasma treatment conditions were obtained, such as the treatment time of 60 sec and the treatment power of 120 W. In addition to this, the optimum aging time was 3 to 5 min in air.     

Atmospheric pressure plasma surface modification of titanium for high temperature adhesive bonding

In this investigation surface treatment of titanium is carried out by plasma ion implantation under atmospheric pressure plasma in order to increase the adhesive bond strength. Prior to the plasma treatment, titanium surfaces were mechanically treated by sand blasting. It is observed that the contact angle of de-ionized water decreases with the grit blast treatment time. Optical microscopy and scanning electron microscopic (SEM) analysis of untreated and atmospheric plasma treated titanium are carried out to examine the surface characteristics. A substantial improvement in the surface energy of titanium is observed after the atmospheric pressure plasma treatment. The surface energy increases with increasing exposure time of atmospheric pressure plasma. The optimized time of plasma treatment suggested in this investigation results in maximum adhesive bond strength of the titanium. Unmodified and surface modified titanium sheets by atmospheric pressure plasma were adhesively bonded by high temperature resistant polyimide adhesive. The glass transition temperature of this adhesive is 310 °C and these adhesively bonded joints were cured at high temperature. A substantial improvement in adhesive bond strength was observed after atmospheric pressure plasma treatment.     

Improved adhesion of low-density polyethylene/EVA foams using different surface treatments

The adhesion between a polyurethane (PU) adhesive and four foams containing different low-density polyethylene (LDPE)/ethylene vinyl acetate (EVA) blends was improved by using different surface treatments. UV-ozone, corona discharge, and low-pressure oxygen plasma treatments for different times were used to increase the surface energy of the foams. The low-pressure oxygen plasma was the most successful surface treatment to promote the adhesion of the foams. A reduced length of treatment was needed to improve the adhesion of the foams containing higher EVA content. The surface treatments produced a noticeable decrease in contact angle values due mainly to the creation of different carbon–oxygen moieties and to the formation of cracks/heterogeneities on the foams surfaces. After oxygen plasma, removal of non-polar material from EVA surfaces allowed to expose acetate groups which are likely to be important for increasing the adhesion of the foams.     

射流等离子体放电气氛对木塑复合材料表面性质的影响

利用空气、氮气、氧气3种不同气氛的射流等离子体放电对聚乙烯木塑复合材料（PE-WPC）表面进行处理以改善其胶接性能，其中空气、氮气、氧气气氛处理后的试样分别记为PE-WPC-A、PE-WPC-N和PE-WPC-O。通过对剪切强度、表面接触角、表面形貌、表面官能团以及表面元素含量的测试与表征，研究了不同气氛射流等离子体处理对PE-WPC表面物理化学性质的影响。研究结果表明：射流等离子体处理可以通过改变PE-WPC的表面性质，进而大幅度提高材料的胶接剪切强度，由未处理样品的0.62 MPa提高到处理后试样的11.32~13.79 MPa。对于胶接性能来说，不同气氛的射流等离子体处理效果差别不大；而对于处理后材料表面的微观结构，不同气氛射流等离子体的处理效果存在差别，氮气气氛处理以表面化学改性为主，在材料表面引入更多的含氮基团；氧气气氛处理以表面氧化刻蚀为主，在材料表面引入更多含氧基团；空气气氛处理则是以上2种作用的综合体现。     

Plasma Treatment of Wood–Plastic Composites to Enhance Their Adhesion Properties

In this study, the adhesion properties of adhesives and paints on wood–plastic composites (WPCs) after plasma treatment at atmospheric pressure and ambient air were investigated. Surface energy determination by means of contact angle measurements according to the Owens–Wendt approach and atomic force microscopy to detect changes in surface topography were carried out. An increase in the polar component of surface energy and an increase in surface roughness after plasma treatment were detected, indicating enhanced bond strength. To confirm these results, bond strength tests were conducted. By tensile bond strength tests, increased adhesion of waterborne, solventborne and oil-based paints on plasma treated surfaces was found. Furthermore, by shear bond strength tests, an increase in bond strength of plasma treated WPCs bonded with poly(vinyl acetate) and polyurethane adhesives was ascertained.     

Plasma surface modification of polyethylene: short-term vs. long-term plasma treatment

A remote plasma reactor, with air as the plasma gas, has been used for in-line surface modification of linear low-density polyethylene tape (LLDPE) passing 10 cm below the main plasma zone. Line speeds of up to 0.70 m/s were tested, allowing the study of 0.014 s exposure times to the plasma. Oxygen to carbon (O/C) ratios averaging 0.11 were observed on a reproducible basis. The reactor was also used for static plasma treatment under similar experiment onditions. This allowed a comparative study of short-term (milliseconds) vs. long-term (several seconds) plasma treatment. High-resolution X-ray photoelectron spectroscopy (XPS) analysis of the treated polymer surface suggested the formation of hydroxyl (C-OH), carbonyl (C=O) and carboxyl (O-C=O) groups, even after short plasma treatment. The intensities of these components were seen to increase in approximately equal quantities with increasing O/C ratio. Water washing of polyethylene surfaces with high O/C ratios showed a loss of oxygen, apparent as a decrease in O-C=O groups in the C 1s spectra. A smaller loss in oxygen was observed when washing samples that had been plasma-treated for milliseconds. A surface ageing study revealed that polyethylene surfaces that had been plasma-treated for short time periods showed only a negligible loss of oxygen on prolonged exposure to air. Surfaces treated for longer time periods showed a loss of up to 50% of the total oxygen on the surface within a few days of treatment. Static secondary ion mass spectrometry has provided some supporting evidence for surface damage of the treated films.