Nitrogen plasmas at atmospheric pressure produced by 2.45 GHz microwaves at a power density of approximately 10 MW m^-3 have a degree of ionization less than about 10^-7. Nevertheless they have interesting and potentially important effects on polymer and metal surfaces exposed to them. An experimental programme is underway to identify the active species in the plasma and its afterglow. This paper describes a simplified model of the chemical kinetics in the plasma that allows species concentrations to be estimated in a range of conditions, for comparison with experimental data. It predicts a high degree of dissociation combined with low gas temperature in microwave-generated plasmas.

The surface of oxygen-plasma-treated polystyrene (PSox) was investigated using X-ray photoelectron spectroscopy (XPS), streaming potential measurements and a dynamic study of the wetting properties at different pH (Wilhelmy plate method). The PSox surface is functionalized with various oxygen-containing groups, including carboxyl functions, and must be viewed as covered by a polyelectrolyte which swells depending on pH. The wetting hysteresis, its evolution upon repeated cycles and the influence of pH are controlled by the dissolution of functionalized fragments and the retention of water upon emersion; the retained water may evaporate progressively and allow macromolecule compaction and/or reorientation. Modification of the PSox surface upon aging in dry atmosphere, humid atmosphere, and water was studied using XPS and dynamic wetting measurements. Aging in water provoked the dissolution of PSox macromolecular chains, as indicated by adsorption of released fragments on a check PS sample placed nearby. However, the concentration of functionalized molecules at the surface of water-aged PSox was still sufficient to allow swelling at pH 5.6 and 11.0. Hydrophobicity recovery was faster in humid air (R. H. 95%) compared to dry air (R. H. 5%), due to the plasticizing effect of water. Hydrophobicity recovery upon aging in air was reversed quickly by immersion at pH 5.6 or 11.0, due to deprotonation and swelling.

The surface modification and adhesive bonding of a unidirectional GFRP Nylon-6,6 thermoplastic composite has been investigated. Wettability studies of plasma-treated specimens showed a significant reduction in the advancing and receding contact angles in water, relative to untreated material. The most effective treatment used oxygen plasma. The increases in wettability observed were determined to be the result of (a) an increase in the concentration of oxygen- and nitrogen-containing functional groups on the surface of the polymer and, (b) removal of fluoropolymer contamination, the source of which was identified as the PTFE mould release agent. This was established by SSIMS analysis. The surface modification resulted in significantly improved adhesion between the composite and an applied toughened epoxy adhesive; a considerable increase in the Mode II critical strain energy release rate, G_IIc, was observed following plasma treatment. Specimens treated in an oxygen plasma showed the greatest improvement in G_IIc, failing cohesively at a value of 1.6 kJ·m⁻² after only 15 seconds exposure. Without plasma treatment the specimens failed in an adhesive mode at very low values of G_IIc. Adhesion was further optimised by moulding the GFRP Nylon-6,6 against steel plates instead of PTFE.

In this work, melt-spun polypropylene (PP) fibers were treated in an electric field of a corona discharge. The fibers were then characterized using the thermally stimulated current (TSC) spectroscopy. It has been shown that the electret state of corona-treated PP fibers is a result of the combination of Maxwell–Wagner polarization and charge trapping. Activation energies and relaxation times for these processes have been determined, and characteristics of trapping sites have been calculated. The electret state induced in PP fibers by the corona discharge treatment holds for a long time (several months). Our analysis of the effect of processing temperature and electric field intensity on the characteristics of the electret state in melt-spun PP fibers allows one to specify optimum technological regimes for industrial production of PP-based electret filter materials. © 2000 John Wiley & Sons, Inc. Adv Polym Techn 19: 312–316, 2000
https://onlinelibrary.wiley.com/doi/abs/10.1002/1098-2329%28200024%2919%3A4%3C312%3A%3AAID-ADV7%3E3.0.CO%3B2-X

We examined the influence of the geometric parameters of the system on the modification power as determined by the contact angle on the surface of the treated low-density polyethylene (LDPE). We have found that (1) with a constant electric energy to generate a corona discharge, the modification power decreases as the distance from the center of surface (the point on the film immediately below the point electrode) increases and that the corona discharge in a point-to-grid system can modify the film surface over a wider area than in a point-to-LDPE system without grid; (2) with a constant discharge current, the modification power on the center of surface decreases when the point-to-grid gap in negative corona treatment increases, but increases in positive corona treatment; (3) the modification power compared to the electric energy used to generate a corona discharge (the yield) is inversely proportional to the point-to-grid gap. However, in a positive corona discharge, the yield did not reach zero when the point-to-grid gap was extrapolated to infinity, possibly because the streamer reduces the effective point-to-grid gap and produces neutral activated species along the streamer; and (4) in a negative corona, the modification power as measured by the temperature increases at the plain electrode (anode) and varies with the energy dissipated by neutral activated species.

Plasma treatment of PET films was carried out under argon, followed by exposure to an oxygen atmosphere. The films underwent considerable changes in surface composition and morphology, as demonstrated by contact angle measurements, FTIR-ATR, AFM, and XPS. It was found that the surface acquired oxygen containing polar functional groups such as CO, OH, and OOH, which increased in number as the plasma treatment time increased. During storage, the treated films underwent significant surface reorganization, and both the time and temperature contributed to the increase in the contact angle. As revealed by AFM measurements, these changes were accompanied by an increase in roughness in the form of ridges. The ridges were observed to grow in height with increasing treatment time, although their spacing showed little evolution. A correlation among the observations obtained from various techniques was established, giving a comprehensive picture of the structure and dynamics of plasma-treated PET surfaces. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1083–1091, 2000
https://onlinelibrary.wiley.com/doi/abs/10.1002/1097-4628%2820001031%2978%3A5%3C1083%3A%3AAID-APP170%3E3.0.CO%3B2-5

Chemical etching, plasma, and ion beam treatments were used to modify the surface of Polytetrafluoroethylene (PTFE). Each surface treatment method developed different surface characteristics. In addition to morphological observation, contact angle, atomic chemical composition, and adhesion strength were measured after treatment with various methods. The different adhesion strengths were explained based on the morphology and atomic chemical composition of the treated PTFE surfaces. The chemical etching showed substantial defluorination, and the adhesion strength was fairly high. The argon plasma treatment introduced very large amounts of oxygen into the surface, and the surface was very smooth with a crater-like structure. Ion beam treatment induced a form of spires whose dimensions were of several micrometers, depending on the ion dose, whereas the oxygen plasma-treated samples showed short spires with spherical particles on the top. The spire-like surface morphology and increased surface area during bonding by ion beam treatment appear to be the reason for a higher adhesion strength than that of the oxygen plasma-treated PTFE. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1913–1920, 2000
https://onlinelibrary.wiley.com/doi/abs/10.1002/1097-4628%2820000829%2977%3A9%3C1913%3A%3AAID-APP7%3E3.0.CO%3B2-%23

The spreading of surfactant solutions over hydrophobic surfaces is considered from both theoretical and experimental points of view. Water droplets do not wet a virgin solid hydrophobic substrate. It is shown that the transfer of surfactant molecules from the water droplet onto the hydrophobic surface changes the wetting characteristics in front of the drop on the three-phase contact line. The surfactant molecules increase the solid–vapor interfacial tension and hydrophilize the initially hydrophobic solid substrate just in front of the spreading drop. This process causes water drops to spread over time. The time of evolution of the spreading of a water droplet is predicted and compared with experimental observations. The assumption that surfactant transfer from the drop surface onto the solid hydrophobic substrate controls the rate of spreading is confirmed by our experimental observations.

In adhesion applications, the rapid ageing of corona discharge pretreated surfaces is a well-known problem. Very often the corona treatment has to be renewed just before the application. Oxyfluorination process presents an interesting alternative to the corona discharge treatment. In this work, the outstanding ageing properties of the oxyfluorinated polyolefin surfaces are described on the basis of acid–base surface characteristics.

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.

Synchronous, real-time optical and electrical diagnostics have been carried out on dielectric barrier discharges in flowing gases (air, He, N₂) at atmospheric pressure. A true “Atmospheric Pressure Glow Discharge” (APGD) is observed in N₂ when O₂ and H₂ concentrations are below ≈500 ppm and 2500 ppm,respectively, and the APGD regime can be beneficially modified by suitably chosen dielectric coatings. X-ray photoelectron spectroscopy (XPS) analyses of some APGD-treated polymer surfaces are presented.

Morphological and chemical changes of the surface of low-density polyethylene (LDPE), linear middle-density polyethylene (L-MDPE), and their 80/20 blend were studied by different techniques after corona-discharge treatment in air and subsequent annealing. The surface tension was determined by wetting; the roughness was measured by atomic force microscope (AFM), and the surface chemical composition was analyzed by X-ray photoelectron spectroscopy (XPS), whereas the low-molecular-mass fraction washed off by chloroform by FTIR. The surface tension of the films increases with the electrode current. The surface roughness depends primarily on the polymer type and is less affected by the corona treatment. At the initial stage of annealing, posttreatment-type oxidation and hydrophobic recovery are competing. The former is more pronounced in L-MDPE, the latter in LDPE. After annealing at 50°C for 160 days, hydrophobic recovery becomes predominant in each film studied, which is accompanied by significant smoothening of the surface. According to XPS and FTIR results, this is due to the migration of low-molecular-mass components (oligomers, oxidized polymer fractions, and additives) to the surface. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1529–1541, 2000
https://onlinelibrary.wiley.com/doi/abs/10.1002/%28SICI%291097-4628%2820000606%2976%3A10%3C1529%3A%3AAID-APP6%3E3.0.CO%3B2-J

The adhesive interaction between oxygen-plasma-treated, polyacrylonitrile-based, high-tensile-strength carbon fibers and a polycarbonate matrix has been studied. Several models have been used to predict the impact of the plasma treatment process on the strength of adhesion between both jointing partners. These approaches have been the thermodynamic work of adhesion which was calculated from the solid surface tensions, based on the results of contact angle measurements versus test liquids, the contact angle which was directly obtained via polycarbonate melt droplets on single carbon fibers and the zeta (ς)-potential data provided by streaming potential measurements. The results have been compared with the interfacial shear strength determined from the single-fiber fragmentation test. Additionally, the single-fiber tensile strength of the oxygen-plasma-treated carbon fibers was determined.

We confirmed that any physico-chemical method on its own fails to describe exactly the measured adhesion. However, for the investigated system, the conscientious interpretation of the data obtained from wetting measurements, in conjunction with the thermodynamic approach, is sufficient to predict the success of a modification technique which has been applied to one component in order to improve adhesion.

Electroless plating of non-conducting materials needs, prior to the metal deposition itself, to make the sample surface catalytically active. The route involving the chemical reduction of a thin solid metal–organic coating has, for this purpose, a significant potential in reducing the number of steps which are required today in conventional wet chemical metallization processes. In this work, a novel activation process using a dielectric barrier discharge (DBD) is described for the first time. This process is based on the plasma-induced chemical reduction at atmospheric pressure in air of palladium acetate (PdAc) layers resulting in the formation of palladium (Pd) on non-active surfaces. Fast surface activation of polymers like polyimide (PI) was found to occur in only a few seconds using a simple DBD device instead of expensive excimer UV lamps or complicated laser systems. The DBD-induced Pd layers on PI exhibit high activity with regard to initiation of the electroless copper plating. Indeed, copper deposition starts immediately after dipping the activated PI samples in the electroless solution without any inhibition time. Homogeneous copper coatings on PI were achieved under optimal plasma treatment conditions. The results are compared to those achieved with excimer UV lamps and excimer UV lasers.

Radio frequency plasma treatment of polydimethylsiloxane (PDMS) is a useful way of increasing wettability to improve adhesion. Its main defect is the subsequent rapid recovery of hydrophobicity. The fluorosilicone polymethyltrifluoropropylsiloxane (PMTFPS) is another low surface energy silicone where improved wettability is often desired. We have directly compared the behavior of PMTFPS and PDMS using air, oxygen, helium and argon plasma gases. The effect of the plasma has been investigated by water contact angle changes and by x-ray photoelectron spectroscopy (XPS) surface characterization. Both an unfilled PMTFPS gum and a filled elastomer were examined. PMTFPS is affected in much the same way as PDMS, an oxidized silica-like surface region is produced. This is shown by the shift in the high resolution Si 2p spectra to higher binding energy which is most marked in the case of helium treatment. Significant improvements in water wettability occur with helium treatment having the greatest effect but the hydrophobic recovery is mostly complete within 24 hours in all cases. Multiple treatments followed by water storage are effective in maintaining wettability for at least a week.

Most printing inks used in major printing processes such as lithography, gravure, and flexography contain organic solvents. Some of these solvents, e.g., toluene, are toxic and can be harmful to humans. Both environmental and workplace safety considerations exert growing pressure on the printing industry to limit the use of toxic organic solvents. Due to this pressure, the share of water-based liquid printing inks in packaging printing (including corrugated) has achieved a respectable level of about 50%. In newspaper printing the share is estimated at about 10 to 15% of the total. To prepare for a possible ban on the use of toxic organic solvents, the printing industry is exploring the viability of water-based technology.