An environmentally friendly plasma amination process for the activation of polymers prior to electroless metallization using dielectric barrier discharges (DBD) at atmospheric pressure was investigated. One focus of the work was on the correlation between plasma parameters and palladium coverage on the polymer on the one hand and the palladium coverage and adhesion of a galvanic copper metallization on the other hand. Using XPS spectroscopy it was found that a DBD treatment of polyimide (PI) films with mixtures of N₂ and H₂ leads to considerably higher Pd surface concentrations than on untreated reference samples or foils treated in air-DBD. The Pd coverages achieved result in peel strengths of a copper metallization of up to 1.4 N · mm⁻¹.

Polyethylene (PE) samples were activated by an atmospheric pressure plasma jet. The improvement in adhesive bond strength is attributed to the incorporation of oxygen-containing functional groups into the PE surface. Optical emission spectroscopy in combination with XPS analysis shows differences in the surface reactions for a plasma jet operated with air or pure nitrogen. The results indicate that the surface modifications take place in two different environments with respect to location and time: (a) reactions while the substrate is hit by the plasma jet, and (b) reactions outside the plasma jet after the treatment.

The polyethylene (PE) coatings could be very promising for various branches of industry due to their chemical stability and impact resistance. Plasma modification of powder has recently attracted much interest because of new prospects to control the interfacial properties. Plasma modification also significantly enhanced the adhesion of the polymer to the substrate. Powders find wide application in various branches of industry like paintings, biotechnology, filling for composite materials etc., but the plasma modification of powder surface has not found such application as plasma modification of flat solid materials. This is due to problems connected with the three dimensional geometry, necessity of solid mixing (due to the aggregation phenomenon) and the large surface area of powders which should be treated. We investigated plasma modification of PE powder, its adhesion properties on steel surface and mechanism influencing this adhesion. PE powder was modified using various working gases and chemicals. It was found that adhesion properties were strongly influenced by concentration of oxygen containing groups and also by PE crosslinking after modification. The value of crosslinking depends on used working gas and chemicals. The ternary mixture of O₂/H₂O/methanol was found to be an appropriate working gas for plasma treatment of PE for adhesion purposes. The treated PE had good wettability, low crosslinking and very high adhesion to the steel substrate.

After the impact of the great review of M. Strobel and C. S. Lyons on contact angle measurements, we discuss some claims of the authors. The Wilhelmy method is not generally “the best technique for measuring the contact angle hysteresis” as the authors claimed. Otherwise, we think that, even though equilibrium contact angle is an “unattainable” angle, the most-stable contact angle obtained from the system relaxation is experimentally accessible. The most-stable contact angle is energetically significant for evaluating quantitatively the surface energy value of rough, chemically homogeneous surfaces from the Wenzel equation, and the average surface energy of smooth, chemically heterogeneous surfaces from the Cassie equation. The most-stable contact angle, the advancing contact angle and the receding contact angles enable the thermodynamic description of the range of contact angle hysteresis and the distribution of metastable system configurations.

The potential of contact angle measurements (CAM) as an analytical tool to characterize surface treatments or modifications is often not fully exploited. Agreeing with Strobel and Lyons, comparing contact angles is often much more reasonable than comparing deduced data like surface energies, because the latter are based on models, in turn involving the influence and knowledge of intermolecular forces at the respective interfaces. For a comprehensive picture, the measurement of contact angles itself has to be considered together with the appropriate model and the available techniques to carry out CAM. An appropriate measurement procedure will be given and a brief discussion of some models to derive free surface energy from CAM.

In this commentary we discuss the assay by M. Strobel and C. S. Lyons on contact angle measurements, critical and popular topic in surface/plasma science community. We agree with stressing the importance of dynamic contact angle measurements (i.e. the evaluation of both advancing and receding). However, we make some remarks about the meaning of angle hysteresis with particular regard to the concepts of roughness and chemical heterogeneity, on the basis of our experience in hydrophobic and super-hydrophobic surfaces. Further, we describe our different point of view in the dispute between Wilhelmy balance and sessile drop methods.

Contact angles are used to solve research and manufacturing problems in an industrial environment. Contact angle measurements are scientific, readily acquired using relatively low-cost instruments and simple procedures, are agreeable for use in environments from academic research laboratories to industrial manufacturing facilities, and are an extremely powerful method for characterizing surfaces. The measurement of dynamic contact angles is rate-dependent at high capillary numbers. Water is a preferred probe liquid for contact angle measurements not only because of the importance of aqueous systems in science and industry, but also because water has the highest surface tension of any commonly available probe liquid and therefore has measurable contact angles on most polymeric materials. Most theories of solid surface energy have a basis in Young's equation, which employs the equilibrium contact angle. If surface energy or surface energy component calculations are made, both the advancing and the receding contact angle data should be used in those calculations.

An atmospheric pressure oxygen and helium plasma was used to activate the surface of poly(methyl methacrylate) (PMMA). The plasma physics and chemistry was investigated by numerical modeling. It was shown that as the electron density of the plasma increased from 3 × 10¹⁰ to 1 × 10¹² cm⁻³, the concentration of O atoms and metastable oxygen molecules (¹Δ_g) in the afterglow increased from 6 × 10¹⁵ to 1 × 10¹⁷ cm⁻³. Exposing PMMA to the afterglow for times between 0 and 30 s led to a 35° ± 3° decrease in water contact angle, and a ten-fold increase in bond strength to several adhesives. X-ray photoelectron spectroscopy of the polymer revealed that after treatment, the surface carbon attributable to the methyl pendant groups decreased 5%, while that due to carboxyl acid groups increased 7%. The numerical modeling of the afterglow and experimental results indicate that oxygen atoms generated in the plasma oxidize the polymer chains.

In this work, an experimental investigation of fluorine gas (F₂) plasma treatment of polypropylene (PP) film reveals the evolution of PP fluorination. Surface analysis of fluorinated PP surfaces describes a surface modification process that is initially quite rapid but slows sharply as the fluorination progresses. The fluorination reaction occurs more rapidly at the PP film surface and evidence of a treatment gradient is seen in the ESCA sampling depth of 10 nm. The increasingly fluorinated surface becomes less reactive to the plasma chemistry and develops a fully fluorinated, cross-linked surface layer that eventually extends the full ESCA sampling depth.

The surface modification of polyethylene powder using a plasma reactor based on a dielectric barrier discharge in air at atmospheric pressure and ambient temperature is investigated. The process is inexpensive, and the necessity of any vacuum equipment and technical gases is alleviated. The efficiency of the modification process was successfully demonstrated by ESCA measurements that proved formation of new functional groups at the modified powder surface. The modification effect was also evaluated by means of dynamic capillarity rising measurements. Powder capillarity tests proved significant powder capillarity changes. The reduction of the modification effect was also limited (max. reduction of about 20% during 1 100 d after the modification date).

Underwater plasma and glow discharge electrolysis are interesting new methods for polymer surface functionalization. The achievable content of O-containing functional groups exceeds that of oxygen glow discharge gas plasmas by a factor of two (up to ca. 56 O/100 C). The percentage of OH groups among all O-containing groups can reach 25 to 40%, whereas it is about 10% in the gas plasmas. Addition of hydrogen peroxide increases the fraction of OH groups to at most 70% (27 OH/100 C). The liquid plasma systems are also able to polymerize acrylic acid and deposit the polymer as very thin film on substrate surfaces or membranes, thereby retaining about 80% of all COOH functional groups (27 COOH/100 C).

Non-thermal atmospheric pressure plasma jets/plumes are playing an increasingly important role in various plasma processing applications. This is because of their practical capability to provide plasmas that are not spatially bound or confined by electrodes. This capability is very desirable in many situations such as in biomedical applications. Various types of ‘cold’ plasma jets have, therefore, been developed to better suit specific uses. In this paper a review of the different cold plasma jets developed to date is presented. The jets are classified according to their power sources, which cover a wide frequency spectrum from DC to microwaves. Each jet is characterized by providing its operational parameters such as its electrodes system, plasma temperature, jet/plume geometrical size (length, radius), power consumption, and gas mixtures used. Applications of each jet are also briefly covered.

Combined surface treatments using plasma fluorination and surface roughening were applied to investigate whether they could increase the peel property of PET beyond the value needed for use as a release coating of pressure-sensitive adhesive tapes. The peel strength of PET treated with CF₄/He APG plasmas decreased to approximately 100 N · m⁻¹, but not quite to the ideal value of PTFE, 20 N · m⁻¹. We also prepared PET with a rough surface (matte PET) to examine the effect of surface roughening. The matte PET peel strengths were decreased by plasma fluorination; the roughest matte PET showed even lower peel strength than PTFE. We conclude that the combined treatments could be effective in the formation of a surface with high peel property on PET.

PTFE surface modifications have been realized using low-pressure RFGD, DBD and APGD in different atmospheres. Compared to the RFGD NH₃ plasma, the DBDs operating in H₂/N₂ lead to similar surface concentrations of amino groups and similar surface damage, but with a much higher specificity. Both APGDs in H₂/N₂ and NH₃/N₂ lead to lower concentrations of amino groups, but with similar specificity, and with lower surface damage than the RFGD treatment. A method is proposed to evaluate the efficiency of the different discharges for amine surface functionalization of PTFE, and it is concluded that the NH₃/N₂ APGD discharge is the one that give the best results for an effective surface treatment.

Polyolefin surfaces, namely isotactic poly(propylene) (iPP) and low-density polyethylene (LDPE), were modified by corona discharge plasma. The chemical changes on the modified surfaces were observed, deeply affecting the surface and the adhesive properties of the studied materials. The hydrophobic recovery in the case of iPP is considerably dependent on the polymer crystallinity. The presence of the processing agents in the LDPE has a significant influence on the surface hydrophobization dynamics.

Surface modification induced on poly(ethylene terephthalate) (PET) fibers by cold SF6 plasma treatment has been investigated systematically as a function of plasma device parameters. The observed wettability modifications of fibers plasma-treated under different operating conditions were correlated to their dyeability modifications and to the changes in surface chemical composition, determined by X-ray Photoelectron Spectroscopy (XPS), and topography, investigated by atomic force microscopy (AFM). Optical emission spectra from the SF₆ plasma at different pressures gave information on its content of fluorine atoms. A striking transition was observed between the increased hydrophilicity and high dyeability, imparted by plasma treatment at low pressure (<0.2 mbar), mainly as a consequence of surface etching and surface activation, and the increased hydrophobicity, imparted by plasma treatment in the higher pressure regime (0.2–0.4 mbar), consequent to extended surface fluorination.

Atomic force microscopy (AFM), contact-angle measurements, and X-ray photoelectron spectroscopy (XPS or ESCA) were used to characterize biaxially oriented poly(propylene) (PP) films modified by exposure to a corona discharge. Surface analysis was performed on PP films modified at various corona energies to explore the changes in surface topography, wettability, and oxidation state resulting from the corona treatment. Even at low corona energies, water-soluble low-molecular-weight oxidized materials (LMWOM) are formed. These LMWOM products agglomerate into small topographical mounds that are visible in the AFM images. For the detection of LMWOM on corona-treated surfaces, AFM appears to be at least as sensitive as contact-angle measurements or ESCA. A major advantage of AFM relative to the other surface analytical techniques used to confirm the presence of the LMWOM is that no washing of the surface with water is required in conjunction with the AFM analysis.

Three polyethylene (PE) types with different branching structures were subjected to air, water and ethanol aerosol-assisted dielectric barrier discharges (DBD) for surface modification. Using the air DBD the incorporated oxygen concentration was found to be independent on the branching of PE in contrast to the introduction of OH groups, which was PE-2 > PE-1 > PE-3. For water-aerosol DBD the succession of OH concentration was in the order of PE-1 > PE-2 > PE-3. Ethanol aerosol-assisted DBD produced the lowest concentration of OH groups also independent on the branching of PE. The chemical nature of introduced oxygen functional groups was inspected by X-ray photoelectron spectroscopy (XPS) and assigned as CO, >CO/CHO/OCO and OCO.

The effect of different nebulized liquids directly introduced into the dielectric barrier discharge (DBD) was compared with simple air DBD treatment of polyethylene foils. Water, alcohols and aqueous solutions of different organic substances (environmentally compatible) and water soluble polymers were applied as aerosols and injected into the DBD zone. The DBD residence time (number of treatment cycles) and the power were varied. The durability of the surface modification effect was studied after removing of Low-Molecular Weight Oxidized Material (LMWOM) by washing the samples with water and ethanol. The modified foils were characterized by XPS and contact angle measurements as a function of the applied plasma conditions. The concentration of functional groups at modified surfaces was estimated by derivatization and subsequent XPS measurement.

In this study, the surfaces of ultrahigh molecular weight polyethylene (UHMWPE), poly(ethylene terephthalate) (PET), and polytetrafluoroethylene (PTFE) films were treated with a helium-water vapor plasma at atmospheric pressure and room temperature. Surface changes related to hydrophilicity, chemical funtionalization, surface energy, and adhesive strength after plasma treatment were investigated using water contact angle (WCA) measurements, X-ray photoelectron spectroscopy (XPS), and mechanical T-peel tests. Results indicate increased surface energy accompanied with enhanced hydrophilicity. WCA decreased by 36, 50, and 16% for UHMWPE, PET, and PTFE, respectively, after only 0.4 s treatment. For UHMWPE, it is shown that the surface functionalization can be tailored depending on the plasma exposure time. Aging studies performed for these three polymers show the stability of the surface groups as indicated by a small increase in WCA values of plasma treated samples which can be attributed to cross-linking of surface and subsurface polymer chains. XPS analysis of the surfaces show increased oxygen content via the formation of polar, hydroxyl-based functional groups. Furthermore, major changes in the polymer structure of PET are observed, possibly due to the opening of the aromatic rings caused by the plasma energetic species. T-peel test results show an 8, 7.5, and 400-fold increase in peel strength for UHMWPE, PET, and PTFE, respectively. Most importantly, it is shown that water-vapor based plasmas can be a promising, “green,” inexpensive route to promote the surface activation of polymers.

Film samples of low-density polyethylene (LDPE) and biaxially oriented poly(propylene) (BOPP) were surface modified by vacuum ultraviolet (VUV) irradiation using a Kr resonant lamp at λ = 123.6 nm in low-pressure ammonia gas, and were then stored in air. The time-dependence of the surface properties was monitored using several complementary surface-sensitive techniques such as contact angle goniometry (CAG), X-ray photoelectron spectroscopy (XPS), and time-of-flight secondary ion mass spectroscopy (ToF-SIMS), which allows one to determine the surface energy, and chemical composition at different depths. The relative importance of four possible mechanisms involved in surface hydrophobic recovery is discussed, and we show that in our particular case the main mechanism is rotational and/or translational motion of polymer chains and chain segments. This restructuring determines the observed “loss” of functional groups, which occurs within the first few monolayers of the surface (∼1 nm), as shown by the ToF-SIMS results, and which leads to the observed decrease in the surface energy. In the deeper surface regions (∼10 nm) long-lived radicals react with oxygen and water vapor upon exposure to the atmosphere, leading to an increase in the concentration of bound oxygen, as observed by XPS. Finally, CAG measurements show that the hydrophobic recovery is reversible and can be significantly reduced by cross-linking near the surface, as illustrated by depth sensing nano-indentation measurements on BOPP surfaces.

Recently, there has been increased interest in using atmospheric pressure plasmas for materials processing, since these plasmas do not require expensive vacuum systems. However, APGDs face instabilities. Therefore, special plasma sources have been developed to overcome this obstacle, which make use of DC, pulsed DC and AC ranging from mains frequency to RF. Recently, the APPJ was introduced, which features an α-mode of an RF discharge between two bare metallic electrodes. Basically, three different geometric configurations have been developed. A characterization of the APPJs and their applications is presented.

Non-thermal plasmas under atmospheric pressure are of great interest in polymer surface processing because of their convenience, effectiveness and low cost. In this paper, the treatment of Polyethylene terephthalate (PET) film surface for improving hydrophilicity using the non-thermal plasma generated by atmospheric pressure glow discharge (APGD) in air is conducted. The discharge characteristics of APGD are shown by measurement of their electrical discharge parameters and observation of light-emission phenomena, and the surface properties of PET before and after the APGD treatment are studied using contact angle measurement, x-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEh4). It is found that the APGD is homogeneous and stable in the whole gas gap, which differs from the commonly filamentary dielectric barrier discharge (DBD). -4 short time (several seconds) APGD treatment can modify the surface characteristics of PET film markedly and uniformly. After 10 s APGD treatment, the surface oxygen content of PET surface increases to 39%, and the water contact angle decreases to 19°, respectively.

In this paper, we report and discuss a surface treatment method, using a dielectric barrier discharge (DBD) of random filamentary type. This offers a convenient, reliable and economic alternative for the controlled modification (so far, largely dependent on surface oxidation) of various categories of material surfaces. Remarkably uniform treatment and markedly stable modified surface properties result over the entire area of the test surfaces exposed to the discharge even at transit speeds simulating those associated with continuous on-line processing. The effects of air-DBD treatment on the surfaces of various polymer films and polymer-based fabrics were studied. The dielectric barrier concerned has been characterized in terms of the energy deposited by the discharge at the processing electrodes and the resultant modifications of the surface properties of the treated samples were investigated using x-ray photoelectron spectroscopy, contact angle/wickability measurement and scanning electron microscopy. The influence of the surface treatment parameters, such as the energy deposited by the discharge, the inter-electrode gap and the treatment time were examined and related to the post-treatment surface characteristics of the materials processed. Relationships between the processing parameters and the properties of the DBD treated samples were thus established. Of the three process variables investigated, the duration of the treatment was found to have a more significant effect on the surface modifications found than did the discharge energy or the inter-electrode gap. Very short air-DBD treatments (fractions of a second in duration) markedly and uniformly modified the surface characteristics for all the materials treated, to the effect that wettability, wickability and the level of oxidation of the surface appear to be increased strongly within the first 0.1–0.2 s of treatment. Any subsequent surface modification following longer treatment (>1.0 s) was less important. The modification of the surface properties also appears to be stable with time, as minimal recovery of the surface properties is shown on ageing post-treatment. The behaviour of the woven textile polymers examined was found to be very similar, under DBD treatment, to that of thin-film variants based on the same polymers. For the porous textile fabrics examined, rapid and efficient treatment (fractions of a second) on both sides of the treated samples was found to be ensured. Thereby the system regime used offers the attractive prospect of controlling the modification of non-compact materials of various texture, porosity, etc. The DBD described system thus provides a chemically mild and mechanically non-destructive means of altering surface properties targeting improved surface characteristics and potentially better application performance.

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 experimental work reported here is devoted to the electrical study of two atmospheric pressure dielectric barrier discharge (DBD) reactors operating at high gas flow, conceived for surface treatment applications in spatial afterglow conditions. Both reactors are of coaxial geometry with the dielectric covering the active electrode, and are driven by a power generator delivering quasi-sinusoidal voltage waveforms in the 100–160 kHz range. The influence of the gas flow value and of the input power on the electrical operation of these systems is investigated. The comparative study performed here, by means of electrical measurements, reveals the influence of parameters such as geometrical dimensions and dielectric material used on the operation of the DBD. Power factor measurements are used to quantify the reactors' electrical performance. Optical diagnostics and kinetic modelling reveal a high chemical activity of the systems appropriate for the treatment of surfaces at atmospheric pressure.

In this paper, continuing previous work, we report on the installation and the testing of an experimental dielectric barrier discharge (DBD) reactor run in a controlled atmospheric pressure gaseous environment other than air. Here, the effects of a N₂-DBD treatment on the surface of a test polymer material (UHMW polyethylene) are examined, reported, discussed and compared to results obtained previously following air-DBD treatment. Surface analysis and characterization were performed using x-ray photoelectron spectroscopy, contact angle measurement and scanning electron microscopy before and following the DBD processing described. The discharge parameters used were correlated with the changes in the surface characteristics found following DBD treatments of various durations in a nitrogen atmosphere. The work focuses on the control of the gaseous environment supporting the discharge and on the possibility of overcoming the potentially dominant effect of reactive oxygen-related species, derived from any residual air present. The results obtained underline the very high reactivity of such species in the discharge, but are encouraging in respect of the possibility of the implantation or generation of functional groups other than oxygen-related ones at the surface of interest. The processing conditions concerned simulate 'real' continuous high speed processing, allowing the planning of further experiments, where various gaseous mixtures of the type X + N₂ will be used for controlled surface functionalization.

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.

Novel types of non-thermal plasma sources at atmospheric pressure based on multi-pin DC (direct current) diffusive glow discharge and AC (alternative current) streamer barrier corona have been elaborated and tested successfully for cold surface treatment of polymer films [polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET),] and polyester fabric. Results on physical properties ofdischarges mentioned and output energy characteristics of new plasma sources as well as data on after-treatment changes in wettability of films and fabrics are presented. The main goal of this study was to find out the experimental conditions for gas discharge and surface processing to achieve a remarkable wettability change for a short treatment time.

We compare two surface treatments of biaxially-oriented polypropylene (BOPP), which are carried out in the same dielectric barrier discharge (DBD) apparatus, namely air corona, and N₂ atmospheric pressure glow discharge (APGD). Changes in the surface energy and chemistry are investigated by contact angle measurements, by X-ray photoelectron spectroscopy (XPS) and by attenuated total reflectance infrared spectroscopy (ATR-FTIR). It is shown that N₂ APGD treatment leads to a higher surface energy than air corona treatment, and to the formation of mostly amine, amide, and hydroxyl functional groups at the polypropylene surface. Finally, hydrophobic recovery of the treated film is studied; for both treatment types, the increased surface energy is found to decay in a similar manner with increasing storage time after treatment.

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.

The comparison of corona-treated and flame-treated polypropylene (PP) films provides insight into the mechanism of these surface-oxidation processes. Atomic force microscopy (AFM), contact-angle measurements, and X-ray photoelectron spectroscopy (XPS or ESCA) were used to characterize surface-treated biaxially oriented PP. While both processes oxidize the PP surface, corona treatment leads to the formation of water-soluble low-molecular-weight oxidized materials (LMWOM), while flame treatment does not. Computational modeling of the gas-phase chemistry in an air corona was performed using a zero-dimensional plasma-chemistry model. The modeling results indicate that the ratio of O to OH is much higher in a corona discharge than in a flame. Chain scission and the formation of LMWOM are associated with reactions involving O atoms. The higher ratios of O to OH in a corona are more conducive to LMWOM production. Surface-oxidized PP exhibits considerable thermodynamic contact-angle hysteresis that is primarily caused by microscopic chemical heterogeneity.

Commercial polyvinylchloride (PVC) sheets were treated by plasma immersion ion implantation, PIII. Samples were immersed in argon glow discharges and biased with 25 kV negative pulses. Exposure time to the bombardment plasma changed from 900 to 10,800 s. Through contact angle measurements, the effect of the exposure time on the PVC wettability was investigated. Independent of t, all samples presented contact angles, θ, equal to zero after the treatment. However, in some cases, surface hydrophilization was not stable, as revealed by the temporal evolution of θ. Samples bombarded for shorter periods recovered partially or totally the hydrophobic character while the one exposed for the longest time stayed highly hydrophilic. These modifications are ascribed to the Cl loss and O incorporation as shown by XPS measurements. Furthermore, the mobility of surface polar groups and the variation in the cross-linking degree can also affect the PVC wettability.

Polyester monofilaments were treated by a pulsed surface electrical discharge in nitrogen at atmospheric pressure, to increase their adhesion to an epoxy resin matrix. The treatment resulted in an eight-fold increase in adhesive strength, without any change in mechanical properties of the monofilaments. It is concluded that polar group interactions, rather than increased surface area, are responsible for the improved adhesive strength.

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.

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 (∼μm). 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.

We have used Time of Flight Secondary Ion Mass Spectroscopy (TOF-SIMS) in combination with X-ray photoelectron spectroscopy (XPS) to study chemical changes taking place at the surface of pure cellulose paper samples treated in N2 plasma for periods of time up to 60 seconds. High resolution TOF-SIMS spectra permit the detection of various functionalities containing nitrogen, even following very brief (∼2s) plasma exposure. Correlations between chemistry and surface properties, such as water wettability, are presented and discussed.

Recently, much attention has been paid to gas discharges producing nonthermal plasma because of many potential benefits in industrial applications. Historically, past work focused on Dielectric Barrier (silent) Discharges (DBD) and pulse-periodical corona discharges. Recently, a number of new different discharge techniques succeeded in producing stable gas discharge at atmospheric pressure. Among these are repetitively pulsed glow discharge; continuous glow discharge in a gas flow; hollow-cathode atmospheric pressure discharge; RF and microwave (MW) discharges. Several new variants of the DBD have been demonstrated over a rather wide range of frequencies. All these forms of gas discharge are characterized by a strong nonequilibrium plasma state. We attempt to classify these discharges with respect to their properties, and an overview of possible applications is made. Conditions for the existence of homogenous and filamentary forms of each of the discharge types are discussed.

The interactions between CO₂ plasma, less degrading than O₂ plasma, and polymeric surfaces are studied. CO₂ discharge and the relationships between the density of plasma reactive species are analyzed by optical emission spectroscopy and mass spectrometry. The optical emission spectrum was identified and five principal systems of carbon monoxide were assigned: the 4th and 3rd positive systems, Angstrom and 3A systems. Other systems dealing with ionized species CO⁺ ₂ and CO⁺ were also found. Mass spectrometry showed that the carbon monoxide and atomic oxygen were created through CO₂ dissociation by electronic impact. The detected molecular oxygen coming from the atomic oxygen recombination was associated with the power. The study of plasma/polymer interface showed the consumption of ionized species, the appearance of atomic hydrogen due to methyl groups transformation into exomethylene groups onto the polypropylene surface, and a degradation mechanism dependent on atomic oxygen density in the plasma phase.

The polypropylene modification in CO₂ plasma mainly contributes to degradation, functionalization, and cross-linking. The degradation, whose rate is depending on CO₂ dissociation and oxygen atom formation, is a quite slow reaction and it is associated with surface topography alteration, especially of the amorphous phase of the polypropylene. The surface roughness increases with the treatment duration and the amorphous phase is more degraded than the crystallized part. The functionalization, corresponding to an increase of the surface energy (57.3 mJċ m ^{− 2} in 30 s), and to an oxidation (23 oxygen at.%) with the appearance of alcohol, ketone, and acid functions is a much faster phenomenon. Cross-linking takes also place during this type of treatment and will reinforce the stability of the modified surface.