Enhancement of wettability in low density polyethylene films using low pressure glow discharge N2 plasma

Low pressure glow discharge nitrogen plasma has been used to improve wettability in a low density polyethylene (LDPE) film for technical applications. The plasma treatment was carried out at a power of 300 W for different exposure times in the 1–20 min range. Wettability changes were analyzed using contact angle measurements. In addition to this, plasma‐treated samples were subjected to an aging process to determine the durability of the plasma treatment. X‐ray photoelectron spectroscopy, atomic force microscopy, and scanning electron microscopy were used for surface characterization. The nitrogen plasma treatment considerably reduced contact angle values thus indicating an increase in surface wettability. The spectroscopic study showed presence of oxygen‐based species on the plasma‐treated samples, which are mainly generated after the plasma treatment as a consequence of air exposure. These polar species contribute to improve surface functionalization, but this is almost lost during aging due to the hydrophobic recovery process. Microscopic studies revealed that also small changes in surface roughness occurred during the plasma treatment but these are very low compared to surface activation. The results confirmed that low pressure nitrogen can be considered as an environmentally efficient process to improve wettability in low density polyethylene films. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2390–2399, 2007     

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…     

微波等离子体诱导聚乙烯表面接枝甲基丙烯酸甲酯

聚乙烯（ＰＥ）通常作为性能优良的薄膜材料被广泛使用,但由于其表面能低,导致表面亲水性差,粘结性弱,染色性能、印刷性能等很不理想［１,２］．在高分子材料的各种表面改性方法中,接枝共聚是一种很有效的途径［３～５］．本文探讨了用微波冷等离子体激活聚乙烯表面...     

Modification of Polyimide in Barrier Discharge Air-Plasmas: Chemical and Morphological Effects

Chemical and physical modifications of polyimide (PI) surfaces caused by an air plasma have been studied. The plasma-induced surface changes of PI were investigated by using a local dielectric barrier discharge (DBD) in air at atmospheric pressure and room temperature as a function of the plasma exposure time and plasma power, while the excitation frequency was kept constant at about 130 kHz. The first results obtained in this work suggest that DBDs operating in air at atmospheric pressure can be an efficient alternative plasma source for surface treatment of polymers: a short time air plasma treatment of few seconds leads to chemical and physical changes including the rise of wettability, surface oxidation, and enhancement of surface roughness. Therefore, this simple kind of dry surface treatment seems to be an effective, low cost method for production of well-adhering subsequent layers such as metal films, paints, glues, etc. on DBD pretreated polymers.     

Surface modification of low density polyethylene (LDPE) film by low pressure O2 plasma treatment

In this work, low pressure glow discharge O₂ plasma has been used to increase wettability in a LDPE film in order to improve adhesion properties and make it useful for technical applications. Surface energy values have been estimated using contact angle measurements for different exposure times and different test liquids. In addition, plasma-treated samples have been subjected to an aging process to determine the durability of the plasma treatment. Characterization of the surface changes due to the plasma treatment has been carried out by means of Fourier transformed infrared spectroscopy (FTIR) to determine the presence of polar species such as carbonyl, carboxyl and hydroxyl groups. In addition to this, atomic force microscopy (AFM) analysis has been used to evaluate changes in surface morphology and roughness. Furthermore, and considering the semicrystalline nature of the LDPE film, a calorimetric study using differential scanning calorimetry (DSC) has been carried out to determine changes in crystallinity and degradation temperatures induced by the plasma treatment. The results show that low pressure O₂ plasma improves wettability in LDPE films and no significant changes can be observed at longer exposure times. Nevertheless, we can observe that short exposure times to low pressure O₂ plasma promote the formation of some polar species on the exposed surface and longer exposure times cause slight abrasion on LDPE films as observed by the little increase in surface roughness.     

Surface roughness and hydrophilicity enhancement of polyolefin‐based membranes by three kinds of plasma methods

The introduction of antibacterial property, conductivity, wettability and antithrombogenicity into polyolefin‐based membranes has evoked much attention, which can be achieved by coating hydrophilic polymers. Therefore, it is necessary to modify the roughness and hydrophilicity of polyolefin‐based membranes to enhance the coating ability. In this paper, three kinds of plasma methods, including inductively coupled (ICP) plasma, radio frequency low pressure (RFP) plasma and atmospheric dielectric barrier discharge (DBD) plasma, were used to modify the surface of the polyethylene (PE), polypropylene (PP) and polyester‐polypropylene (PET–PP) membranes. The surface roughness of the plasma‐modified PE, PP and PET–PP films was investigated by scanning electron microscopy (SEM) and atomic force microscope (AFM). The polar functional groups of films were observed by energy dispersive spectrometer (EDX) and X‐ray photoelectron spectroscopy (XPS). Besides, the hydrophilicity of the plasma‐modified PE, PP and PET–PP films was evaluated by water contact angle measurement. It was found that the surface roughness and hydrophilicity of plasma‐modified PE, PP and PET–PP films increased with the generation of oxygen‐containing functional groups (i.e. C―O, and C?O). The PET–PP membranes were treated by RFP plasma at different processing powers and times. These results indicated that plasma is an effective way to modify films, and the treatment time and power of plasma had a certain accumulation effect on the membranes' hydrophilicity. As for the roughness and hydrophilicity, the DBD plasma modifies the PE film, which is the optimum way to get the ideal roughness and hydrophilicity. Copyright © 2015 John Wiley & Sons, Ltd.     

Effects on surface properties of natural bamboo fibers treated with atmospheric pressure argon plasma

Argon plasma at atmospheric pressure was used to improve the wettability and dyeability of natural bamboo fibers. Optical emission spectroscopy (OES) was employed to characterize the discharge. SEM and scanning probe microscopy (SPM) analyses show that the fiber surface becomes rougher after plasma treatment because of the effects of plasma bombardment and etching. The wettability and dyeability are significantly enhanced after plasma treatment. Longer treatment time, leading to rougher surface, results in better surface wettability and dyeability. These results reveal that atmospheric pressure argon plasma treatment is an effective method to improve the performance of bamboo fibers. Copyright © 2006 John Wiley & Sons, Ltd.     

Polymer matrix of polyethylene porous films functionalized by electrical discharge plasma

The polyethylene porous films were treated by dielectric surface barrier discharge (DSBD) plasma at atmospheric pressure in oxygen (O₂) or nitrogen (N₂), and by radio-frequency discharge (RFD) plasma in air at reduced pressure 46 Pa. The surface energy of films was carried out by direct measurements of contact angles of six testing liquids. The strength of adhesive joints in the system modified polyethylene porous films - polyacrylate was measured by peeling of the joints under the angle of 90°. The significant increase of the surface energy and its polar component of polyethylene porous films modified by all types of plasma were observed. The higher strengths of adhesive joints were found for modification of polyethylene porous films by radio-frequency discharge plasma in comparison with modification of the films by barrier discharge plasma.     

Treatment of a Polyethylene Powder Using a Remote Nitrogen Plasma Reactor Coupled with a Fluidized Bed: Influence on Wettability and Flowability

A Far Cold Remote Nitrogen Plasma is used both to fluidize and to treat a polyethylene powder in order to increase its hydrophilic character. The evolution of the wettability of the powder as well as the one of its physical (density, particles size distribution, average diameter, shape factor, and BET surface area) and flow properties (angle of repose, angle of slide, and Hausner index) are determined versus various experimental conditions. It is shown that the plasma treatment efficiency is strongly dependant on the oxygen content of the nitrogen flow and on the velocity of fluidizing gas. Best wettability is obtained by the addition of 0.75% of O₂ in the nitrogen plasma gas and with a high gas velocity. It is also evidenced that the flowability of the powder is slightly altered by the plasma treatment.     

The Effects of Cold Plasma Treatments on LDPE Wettability and Curing Kinetic of a Polyurethane Adhesive

A cold plasma feed with either oxygen or nitrogen was used to modify thin Low Density Polyethylene films. The treatment improved both the surface wettability and the curing kinetic of a polyurethane based adhesive spread on the surface. The chemical functionalities responsible of the observed behaviours were investigated and monitored over time by high resolution x-ray photoelectron spectroscopy. Atomic force microscopy were used to compare the effects of the two feeding gases on the surface morphology of films exposed (to the plasma) for equal times. The effect on the treated films of the atmosphere exposure and of the aging time were also considered.     

Surface modification of poly(tetrafluoroethylene) by a low-temperature cascade arc torch and radio-frequency plasmas

Poly(tetrafluoroethylene) (PTFE) films were treated with a low-temperature cascade arc torch (LTCAT) and radio-frequency (RF) plasmas of argon and hydrogen. The plasma-treatment effect on the PTFE surface was studied with contact-angle measurement and scanning electron spectroscopy (SEM). LTCAT argon plasma, which is recognized as a beam of excited argon neutrals, was very efficient at improving the surface hydrophilicity of PTFE. For both the LTCAT and RF operation, argon plasma was more effective at modifying the surface wettability of PTFE films than hydrogen plasma was. Furthermore, the sample positions (inside or beyond the glow region) had a strong impact on the efficiency of the plasma treatment. SEM surface images indicated that no significant morphology change was induced on the PTFE films exposed to a LTCAT and RF argon plasmas. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 4432–4441, 1999     

TiOx Films Deposited by Plasma Enhanced Chemical Vapour Deposition Method in Atmospheric Dielectric Barrier Discharge Plasma

The plasma enhanced chemical vapour deposition method applying atmospheric dielectric barrier discharge (ADBD) plasma was used for TiO_x thin films deposition employing titanium (IV) isopropoxide and oxygen as reactants, and argon as a working gas. ADBD was operated in the filamentary mode. The films were deposited on glass. The films?? chemical composition, surface topography, wettability and aging were analysed, particularly the dependence between precursor and reactant concentration in the discharge atmosphere and its impact on TiO_x films properties. Titanium in films near the surface area was oxidized, the dominating species being TiO₂ and substoichiometric titanium oxides. The films exhibited contamination with carbon, as a result of atmospheric oxygen and carbon dioxide reactions with radicals in films. No relevant difference of the film surface due to oxygen concentration inside the reactor was determined. The films were hydrophilic immediately after deposition, afterwards their wettability diminished, due to chemical reactions of the film surface and chemical groups involved in the atmosphere.     

On the correlation of surface charge and energy in non‐thermal plasma‐treated polyethylene

Non‐thermal non‐equilibrium oxidative air 40‐kHz frequency, 13.56‐MHz radiofrequency and 2.46‐GHz microwave discharge plasma treatment were used for modifying low‐density polyethylene foils. The untreated and treated samples were chemically characterised by X‐ray photoelectron spectroscopy. In order to estimate the extent of the plasma sources at distinct treatment times, surface charge and energy were determined by zeta potential (ζ) and surface tension measurements. In addition, the isoelectric points (IEPs) of the studied samples were ascertained, and surface property variations were appraised by ageing time. The overall outcome indicated that ζ‐potential and surface energy progressively changed after each treatment, as well as the influences of ageing on surface features, the IEP shifting to lower pH values and how all of these changes are associated with the new surface chemistry. This contribution seeks to shed light on topics related to polymer science and plasma‐based strategies for surface modification. Copyright © 2014 John Wiley & Sons, Ltd.     

Surface oxidation of polyethylene using an atmospheric pressure glow discharge with liquid electrolyte cathode

This study investigated the action of an atmospheric pressure air glow discharge (APGD) with aqueous electrolyte cathode onto the surface of polyethylene (PE) films. Distilled water and aqueous solutions of KCl and HCl were utilized as a cathode. The surface properties of PE were characterized by contact angle measurement followed by surface free energy calculation, Fourier transform infrared by attenuated total reflectance (FTIR-ATR), and XPS. After treating the PE surface, we observed OH groups, CO groups in ester, ketone, and carboxyl groups, and CO groups in unsaturated ketones and aldehydes. For a treatment time of 20 min and a discharge current of 40 mA, atomic concentrations of O and N were 12% and 2%, respectively, under distilled water application. Modification processes were able to improve the surface free energy of PE.     

The Role of Dielectric Barrier Discharge Atmosphere and Physics on Polypropylene Surface Treatment

Dielectric barrier discharge (DBD) is the discharge involved in corona treatment, widely used in industry to increase the wettability or the adhesion of polymer films or fibers. Usually DBD's are filamentary discharges but recently a homogeneous glow DBD has been obtained. The aim of this paper is to compare polypropylene surface transformations realized with filamentary and glow DBD in different atmospheres (He, N₂, N₂ + O₂ mixtures) and to determine the relative influence of both the discharge regime and the gas nature, on the polypropylene surface transformations. From wettability and XPS results it is shown that the discharge regime can have a significant effect on the surface transformations, because it changes both the ratio of electrons to gas metastables, and the space distribution of the plasma active species. This last parameter is important at atmospheric pressure because the mean free paths are short (m). These two points explain why in He, polypropylene wettability increase is greater by a glow DBD than by a filamentary DBD. In N₂, no significant effect of the discharge regime is observed because electrons and metastables lead to the same active species throughout the gas bulk. The specificity of a DBD in N₂ atmosphere compared to an atmosphere containing oxygen is that it allows very extensive surface transformations and a greater increase of the polypropylene surface wettability. Indeed, even in low concentration and independently of the discharge regime, when O₂ is present in the plasma gas, it controls the surface chemistry and degradation occurs.     

Comparison Between Air Filamentary and Helium Glow Dielectric Barrier Discharges for the Polypropylene Surface Treatment

Recently, a glow like dielectric controlled barrier discharge (GDBD) working at atmospheric pressure has been observed. Such a discharge could replace a filamentary dielectric controlled barrier discharge (FDBD) used in corona treatment systems to improve the wettability or the adhesion of polymers. So it is of interest to compare these two types of discharges and their respective effect on a polymer surface. This is the aim of an extensive study we have undertaken. The first step presented here is the comparison of a filamentary discharge in air with a glow discharge in helium. Helium is the most appropriate gas to realize a glow discharge at atmospheric pressure. Air is the usual atmosphere for a corona treatment. The plasma was characterized by emission spectroscopy and current measurements. The surface transformations were indicated by the water contact angle, the leakage current measurement and the X-ray photoelectron spectroscopy. Results show that the helium GDBD is better than air FDBD to increase polypropylene wettability without decreasing the bulk electrical properties below a certain level. Contact angle scattering as well as leakage current measurements confirm that the GDBD clearly results in more reproducible and homogeneous treatment than the FDBD.     

Surface Modification of Textile Fibers and Cords by Plasma Polymerization

In this paper we report on the treatment of industrial fibers and cords by means of plasma polymerization techniques. Coatings of plasma-polymerized pyrrole or acetylene were deposited on aramid fibers, aramid cords and polyester cords. The equipment was a custom-built semi-continuous reactor operated on a pulsed DC glow discharge. The fibers and cords were tested for adhesion to various polymers such as tire cord skim stock rubber compounds and epoxy adhesives. Standard industrial pull-out force adhesion measurement techniques were used. The deposition conditions of the plasma polymer films were varied within wide limits. It was found that, in general, films deposited under low-power and high-pressure conditions performed better than films prepared under high-power and low-pressure conditions. For some systems pulsing of the discharge power improved the performance further. For all systems studied, the optimized plasma polymer surface modification outperformed current industrial standards. The plasma-polymerized coatings were characterized by various techniques and the excellent performance results are explained in a tentative model based on the molecular structure of the films. This structure was found to be strongly dependent on the discharge conditions.     

A comparative study between inductively and capacitively coupled plasma deposited polystyrene films: chemical and morphological characterizations

Thin polystyrene films were deposited on stainless steel substrates by capacitively and inductively coupled radio frequency glow discharge plasma, in order to compare their chemical and morphological properties. The films were characterized by Fourier‐transform infrared spectroscopy (FTIR), X‐Ray photoelectron spectroscopy (XPS), time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS), atomic force microscopy (AFM) and scanning electron microscope (SEM). Wettability properties were also determined by contact angle measurements. Ageing effect was studied by analysing films aged for 15 min and for 1 week. Results from both capacitively and inductively plasma polymerized polystyrene (pPS) films aged for 15 min showed that the chemical structure of the bulk, chemical composition of the surface (depth < 10 nm) and wettability properties were rather similar. Only their microstructures were very different: the pPS_capa film's microstructure showed homogeneous distribution of spherical particles of about 100 nm in diameter but the pPS_ind film's microstructure seemed to be mainly influenced by the surface of the metallic substrate: orientated ‘lamellae‐like layers’ of polymers were observed on each metallic grain. Ageing for 1 week in ambient air induced low oxygen uptake in the surface of both pPS films. The pPS_ind topmost surface (depth < 3 nm) was more oxidized than that of pPS_capa but no modification of the chemical structure of the bulk or of the morphology was noticed after ageing. Copyright © 2006 John Wiley & Sons, Ltd.     

Surface modification of clay-coated paper by atmospheric-pressure plasma in air

The aim of this work was the wettability improvement of clay-coated paper by ambient air plasma exposure. Industrial corona with a volume dielectric barrier discharge in cylindrical configuration was used as a plasma source; the exposure times varied from 0.25 up to 5 s. Water contact angle (WCA) measurement and surface free energy (SFE) evaluation were carried out for the estimation of wettability changes. Plasma treatment in the duration of 0.25 s was sufficient to decrease the WCA almost to the half of the original value, which was 76°. SFE of paper has increased by 40%–50% after plasma treatment. Long-term ageing effect study of treated samples was carried out up to 3 months after the treatment. WCA did not reach the original value even after 3 months, and it was still 20%–30% lower. O/C ratio increased from 0.7 to 1.8 in case of 5-s plasma treatment, and the new chemical bonds (C=O, O–C=O) were created on the surface.     

Surface modification of PVC endotracheal tubes by oxygen glow discharge to reduce bacterial adhesion

A d.c. oxygen glow discharge was used to modify medical‐grade poly(vinyl chloride) (PVC) to study how surface chemistry and hydrophilicity influence Pseudomonas aeruginosa adhesion. The effects of plasma exposure time on the resulting surface, including chemical composition, wettability and roughness, were assessed using x‐ray photoelectron spectroscopy, contact angle measurements and atomic force microscopy analysis. A significant alteration in the hydrophilicity of the native PVC surface was observed after oxygen glow discharge treatment. The water contact angle decreased from ～80° to 8–20°, with a weak dependence of the exposure time used. The change in surface wettability resulted from the incorporation of oxygenated functional groups, including esters, ketones and acids, as indicated by XPS analysis. The amount of oxygen incorporation was shown to be essentially independent of plasma exposure time. However, prolonged plasma exposure resulted in increased surface roughness. Bacterial adhesion efficiency was evaluated for PVC modified by 120 s of plasma exposure, because this exposure time was determined to yield the maximum decrease in contact angle. Oxygen plasma treatment of native PVC was found to yield a 70% reduction in bacterial adhesion for the four strains of Pseudomonas aeruginosa tested. Copyright © 2003 John Wiley & Sons, Ltd.