The treatment of surfaces by corona discharges is a well-established method to improve surface properties. The surface to be treated is moved continuously and is exposed to transient gas discharges, known as microdischarges, in air at atmospheric pressure between electrodes, where at least one electrode is covered with a dielectric barrier. Because of the short duration, only some 10 ns, the current through the microdischarges is predominantly carried by electrons. The ion temperature remains close to room temperature. Owing to these properties such discharges are qualified to treat surfaces which are sensitive to higher temperatures. For a large number of applications this treatment is adequate, but the adhesion of aqueous glues and inks to some plastic materials is insufficient if the surfaces are treated in this way. Furthermore, it is difficult to meet the requirements of surface properties of, for instance, polyolefine film (e.g. surface tension, adhesion). This material is not based on monomers containing chlorine or fluorine and is preferred for ecological reasons. This paper presents the results of experiments which demonstrate that in comparison to a common corona treatment significant improvements in surface properties of plastic materials can be achieved if repetitively generated pulse trains and reactive gases are used instead of air. If, for instance, the microdischarges are established in acetylene, thin films with a thickness of several namometres are formed on surfaces, which increase and stabilize the surface tension up to a level of 72 mN m−1. The state of the art of this new technology is discussed.

The effects of corona discharge treatment on polyethylene and polypropylene homopolymers have been studied. X-ray photoelectron spectroscopy was used to determine surface compositions which were related to surface free energy estimates from contact angle measurements. Changes in composition and surface free energy were measured as a function of treatment level. The work of adhesion was seen to increase with oxygen incorporation. The increase was not linear and this is attributed to an increase in the degree of sub-surface to near-surface oxidation at intense treatment levels. Aging of samples followed by XPS and contact angle measurement showed that surface wettability is reduced whereas a slight increase in surface oxygen was found. This phenomenon was attributed to the reorientation/migration of functional groups. Morphological examination by scanning electron microscopy indicated no surface roughening at any power level.

The properties of an ac dielectric-barrier corona discharge in argon under atmospheric pressure were studied and the results of testing of this type of gas discharge in the low-temperature treatment of polymer films and fabrics for the purpose of enhancement of their wettability were reported.

The synthesis of ozone from oxygen in a cylindrical ozonizer operating under surface discharge conditions with a plasma electrode was studied. The conditions of ozone synthesis were optimized. The dependence of ozone concentration and specific energy consumption on gas pressure in the plasma electrode and on distance between the coils of a corona electrode was determined. The results were compared with data obtained with the use of classical surface barrier discharge.

The treatment of elastomer articles in a low-temperature glow-discharge plasma in fluorinated organics is an effective method for the enhancement of their wear resistance without changing the formulation of rubbers. As a result of plasma-assisted deposition on an elastomer of a fluorinated antifriction film chemically bound to the substrate, the elastomer friction coefficient is considerably decreased, sticking to a counterface is prevented, and the wear resistance of the elastomer is enhanced, retaining their bulk properties. Based on the study of the structure of the antifriction film at different modification stages and its transformation during friction, a conclusion on the mechanism of elastomer surface failure under dynamic friction conditions was made.

The process of modifying the surface of polytetrafluoroethylene in a glow discharge plasma in vapors of organic compounds of various classes was investigated. It was established that the greatest increase of wettability is seen when modification is done in acrylic acid vapor. Multiple attenuated total internal reflection infrared spectroscopy was used to study the spectra of the coatings that formed and to demonstrate their difference in the case of acrylic acid.

A new plasma-based micropatterning technique, here referred to as plasma printing, combines the well known advantages given by the nonequilibrium character of a dielectric barrier discharge (DBD) and its operation inside small gas volumes with dimension between tens and hundreds of micrometres. The discharge is run at atmospheric pressure and can be easily implemented for patterned surface treatment with applications in biotechnology and microtechnology. In this work the local modification of dielectric substrates, e.g. polymeric films, is addressed with respect to coating and chemical functionalisation, immobilisation of biomolecules and area-selective electroless plating.

Atmospheric pressure plasma treatment has unique advantages over vacuum treatment for such industrial applications as surface energy ehancement of materials, cleaning, decontamination, and sterilization of surfaces, surface etching, plasma chemical vapor deposition (PCVD), and related tasks. The MOD VIII plasma reactor system has been developed to provide roll-to-roll surface treatment of fabrics and films using a One Atmosphere Uniform Glow Discharge Plasma (OAUGDP®) operating in air. Webs can be continuously and uniformly treated by proper control of gas flow; electrode configuration; plasma voltage, current, and frequency; fabric speed; and fabric tension.

A novel plasma chemical process PPCP (pulse corona induced plasma chemical process) can produce copious active radicals in air under NTP (normal temperature and pressure) by using an extremely fast rising narrow high voltage pulse between corona electrodes and grounded counter electrodes so that intense streamer coronas are generated. This provides an effective means of surface treatment to a plastic material placed between the two electrodes through generation of free bonds on the surface directed to the corona electrodes. Special features of this method are that it can cope with a complex shape of the material to be treated, and that it does not spark even at the periphery near the grounded counter electrode. This method is suitable for the surface treatment of polypropylene bumpers so as to provide a strong adhesion of color paint to it. The adhesion strength of a paint film is raised from zero to ca. 1000 g/cm/sup 2/ by PPCP treatment for 60 seconds.

Surface charge decay on thick flat samples of high temperature vulcanized silicone rubber is studied prior and after ac and dc corona pre-treatments. It is found that the charge decay rate on the material exposed to ac corona becomes much higher and sensitive to moisture content in the surrounding air. These features are associated with an increased surface conductivity and formation of a silica-like layer on the polymeric surface, both resulting from ac corona treatment. In contrast, characteristics of the charge decay on the material exposed to dc corona are found to be similar to that measured on untreated samples.

Electrical characterization is based on a display of voltage and charge which appears as a simple parallelogram. The area is a measure of energy input per cycle and is independent of voltage waveform but very dependent on the maximum voltage. A useful model for such corona discharges employs a Zener diode to simulate the corona drop. The buffer dielectric plays a major roll in controlling the corona power, and the air gap importance depends on the electrode system employed. Proper interpretation of the voltage-charge traces provides insight as to the corona performance and serves as a diagnostic procedure for obtaining optimum performance.

Applications of corona discharge induced plasmas and unipolar ions are reviewed. Corona process applications emphasize one of two aspects of the discharge: the ions produced or the energetic electrons producing the plasma. The ion identities depend on the polarity of the discharge and the characteristics of the gas mixture, specifically on the electron attaching species. The electron energies depend on the gas characteristics and on the method of generating the corona. In general, in an application using ions, the corona induced plasma zone will occupy a small fraction of the total process volume, while a process using the electrons will fill most of the volume with the plasma. Current state-of-the knowledge of ionized environments and the function of corona discharge processes are discussed in detail.

A low-temperature, atmospheric pressure oxygen and helium plasma was used to treat the surfaces of polyetheretherketone, polyphenylsulfone, polyethersulfone, and polysulfone. These aromatic polymers were exposed to the afterglow of the plasma, which contained oxygen atoms, and to a lesser extent metastable oxygen (^1δ_g O₂) and ozone. After less than 2.5 seconds treatment, the polymers were converted from a hydrophobic state with a water contact angle of 85±5 to a hydrophilic state with a water contact angle of 13±5 . It was found that plasma activation increased the bond strength to adhesives by as much as 4 times. X-ray photoelectron spectroscopy revealed that between 7% and 27% of the aromatic carbon atoms on the polymer surfaces was oxidized and converted into aldehyde and carboxylic acid groups. Analysis of polyethersulfone by internal reflection infrared spectroscopy showed that a fraction of the aromatic carbon atoms were transformed into C=C double bonds, ketones, and carboxylic acids after plasma exposure. It was concluded that the oxygen atoms generated by the atmospheric pressure plasma insert into the double bonds on the aromatic rings, forming a 3-member epoxy ring, which subsequently undergoes ring opening and oxidation to yield an aldehyde and a carboxylic acid group.