A summary of recent studies on the corona treatment of films is presented. Chemical functional groups generated by the corona discharge on these films are identified and their effect on ink film wettability and adhesion discussed.

The surface modification of isotactic polypropylene (PP) in a microwave plasma of CO2 is described. The modified PP is characterized in bulk and also at its surface. The mechanism of plasma modification is discussed in terms of degradation and oxidation. The degradation leads to volatile products and to the formation of a layer of oxidized oligomers of PP. The oxidation leads to ketone, acid or ester groups. The degradation and oxidation rates depend on plasma parameters (duration, discharge power, gas flow, pressure, discharge or post-discharge treatment). The oxidation rates vs the various plasma parameters show a maximum. The crosslinking of PP (Crosslinking Activated Species of INert Gases) seems to be negligible.

Cold plasma treatments of polymers, dry processes, allow either the elaboration of hydrophilic or hydrophobic surfaces. For example, a poly(propylene) film treated in nitrogen plasma shows a surface having a hydrophilic and basic character since amino groups are attached onto the surface during the treatment. The treatment induces an increase of the surface tension of the polymeric material, which may be sometimes destroyed by an aging effect. For the treatment of poly(propylene) in nitrogen plasma, the aging is mostly due to a motion of attached groups from the surface to the bulk of the material and some oxidation of radicals formed during plasma treatment. The surface radicals formed and used for a post-reaction such as grafting are characterized in terms of chemical nature, density and reactivity.

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 surface energies of poly (methyl methacrylate), polycarbonate and poly (tetrafluoroethylene) which have been exposed to UV radiation in an ambient ozone-air atmosphere have been elucidated from surface tension and contact angle data using these test liquids: ethylene glycol, formamide, glycerol, methylene iodide and water. Comparisons of surface energy values obtained using Kaelble’s two-liquid method, Good’s three-liquid method and Neumann’s macroscopic apнproach are reported. It is tentatively suggested that atmospheric moisture may play a role in producнing discordant values since the test liquids ethylene glycol, formamide and glycerol are highly hyнgroscopic in nature. It has been demonstrated that UV/ozone irradiation produces changes in surface roughness. Poly (tetrafluoroethylene) shows three distinct regions: first, where at low irradiation times the surface roughness is enhanced and following this, the roughness decreases before increasнing finally to a terminal value. The behavior is somewhat similar for polycarbonate although the dramatic increase in roughness exhibited by poly (tetrafluoroethylene) is absent. The roughness characteristics are quite different for poly (methyl methacrylate) where a large change in roughness is observed at only one specific irradiation time. Thus presently it is not possible to predict surface roughness changes for a particular polymer and more studies on the morphological changes occurнring at different surfaces are being carried out.

It is demonstrated that extraneous electric charge can produce a large variation in contact angle for water drops on polytetrafluoroethylene surfaces.

Polyethylene (PE) is often used in several industrial applications including the building, packaging and transport industries. Aluminum (Al) is widely used in different applications in the automotive, railway, aeronautic, and naval industries because of its excellent mechanical and chemical properties. Laminates prepared from Al and PE lead to an enhancement in physical and mechanical properties. These materials play a main role in the packaging and building sectors, such as in TetraPak containers and aluminum composite panels. The main problem observed is associated with the adhesion between polymers and metals. This research focused on investigating the enhancement in the adhesion of the PE/Al laminate using the corona discharge. The corona treatment of the surfaces led to a significant increase in the adhesion of the PE/Al laminate as a result of improved surface properties confirmed by peel test measurements. Moreover, the positive effect of the corona treatment in combination with a primer on the improvement of adhesion characteristics was observed too. Different analytical techniques were employed to characterize the effect of the corona treatment on the improvement in adhesion of PE/Al. A significant increase in wettability was confirmed by the measurement of contact angles. Changes in the surface morphology of the PE and Al surface, after the corona treatments at different operating conditions, were observed using atomic force microscopy (AFM) and scanning electron microscopy (SEM). In addition, x-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR) were used to analyze changes in chemical composition after the corona discharge effect on PE and Al surfaces.

Polymers/metal laminates are often used to improve physical and mechanical properties, especially those required in building applications. A flat aluminum composite panel (ACP) consisted mainly of two thin metal sheets usually made of aluminum (Al) and a non-metal core, such as polyethylene (PE). The lack of adhesion associated with the low wettability of PE is a serious problem. An eco-friendly, dry, non-destructive corona treatment technique can be applied to solve this problem. In this work, the use of a corona treatment to enhance the adhesion properties of linear low-density polyethylene (LLDPE) was studied. The changes in surface and adhesion properties were thoroughly analyzed using various analytical techniques and methods to obtain the optimal parameters for corona discharge using contact angle measurements, Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and atomic force microscopy (AFM). AFM force adhesion measurements were used to analyze the effect of the corona treatment on the adhesion enhancement of LLDPE, and the peel tests confirmed a significant increase in peel resistance in the LLDPE/Al laminate. A synergy effect from using the corona treatment in combination with an ethylene acrylic acid dispersion primer was observed.

Physical and chemical surface modifications of polyethyleneterephthalate (PET) films due to treatment with excimer UV lamps (222 nm) have been studied. Interpretations of the reactions and products were made in comparison to known PET irradiations with excimer UV lasers and broad-band UV sources. In this context the advantages of the excimer UV lamps as a light source, i.e., a quasi monochromatic radiation source with a power density which is sufficient for initiating surface reactions without changing the topography of the substrate, have been shown. Analytical data on treated PET to characterize the surface modifications were obtained by contact-angle measurements, dyeing with cationic dyestuff, scanning electron microscopy (SEM), photoacoustic Fourier transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS) studies. With regard to possible industrial applications, the relevance for textile finishing and some perspectives for future developments are pointed out.

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 relationships of the optical characteristics of monomers (refractive index and specific refraction) and the cohesion parameters of polymers (effective cohesional energy and molar volume of the repeating unit) have been analyzed. New relationships are proposed that allow the calculation of the surface energies of homo- and copolymers using refractometric data of monomers. The relationships were tested with good consistency for a number of polymers of various chemical nature.

Pigment-coated, surface-sized, and surface-sized copy papers were treated with conventional corona, experimental pilot-scale plasma and laboratory-scale plasma. All the treatments increased the surface energy and oxidized the surface. The changes in the surface chemistry depended on treatment time and composition of the substrate surface. It seems that plasma especially oxidizes the long polymer chains, such as surfactants and other paper chemicals, on the surface of the paper. The ToF-SIMS distribution maps indicated that the pilot-scale treatment led to an uneven CO⁺ group distribution, whereas laboratory scale treatment gave a more even distribution of CO⁺ groups. In addition to chemical changes, topographical changes due to plasma treatment were detected. The RMS roughness increased for pigment-coated paper, whereas plasma treatment induced small nodules between the paper pigment particles with pigmented and surface-sized paper. The increase in roughness was also found to increase the wettability. This serves as a demonstration of roughness-induced increase of surface energy of the samples.

The objective of this paper was to understand the effects of plasma activation, and thus influence of the surface energy and chemistry changes on offset print quality. Pigment coated and surface sized papers were treated with corona and atmospheric plasma in pilot and laboratory scales. The surface energy and surface chemistry changes were evaluated by contact angle and X-ray photoelectron spectroscopy (XPS). Offset printing was performed in laboratory scale with an IGT unit with predampening and in a pilot scale sheet-fed offset printing press. In addition, the ink setting rate was measured using an ink on paper tack tester. Plasma activation increased the surface energy of the papers. Furthermore, the polarity of the paper surface increased due to formed polar oxygen containing molecular groups. Due to differences in treatment times laboratory scale plasma treatment formed mainly carboxyl and ester groups, whereas pilot scale treatment induced mainly alcohol, ethers, aldehydes and/or ketones on paper surfaces. Printing evaluation showed that plasma activation influences both ink and water absorption properties. According to print tack results plasma activation led to faster ink-setting. With hydrophobic surface-sized paper plasma activation influenced the ink transfer, print gloss and density by changing dampening water absorption properties. The difference in surface chemistry with laboratory scale plasma treated samples was also reflected in the print quality properties. SEM imaging showed that too intense plasma activation can cause topography changes in addition to of the surface chemistry changes.

This work concerns the ageing effect of the atmospheric plasma and corona treatments when used to treat paper substrates. Pigment coated and surface sized papers were modified using two types of atmospheric plasma equipment; one at the pilot scale and one at the laboratory scale. In addition, the plasma treatments were compared to conventional corona treatment. Surface energy was estimated by contact angle measurements and surface chemistry by X-ray photoelectron spectroscopy (XPS) as a function of the time during three months. The treatments increased surface energy and oxidation level of surface for both papers. The ageing effect could be detected only in the surface energy, whereas the oxidation level remained stable during the twelve weeks. The decay in surface energy was faster during the first weeks of storage and subsequently leveled off leading to a permanent change. The permanent change was explained as a contribution of oxygen containing polar molecular groups, which were detected by XPS. The ageing effect was suggested to originate from already existing polar molecular groups, which have rotated on the surface by plasma-related process and then rotate back into the material in time. A part of the decay was also explained by the plasma cleaning model, in which the ageing effect occurred through re-contamination. Paper is a multicomponent system, where the constituents that have the lowest surface energy were suggested to migrate to paper surfaces.

The objective of this paper was to understand the effects of plasma activation, and thus influence of the surface energy and chemistry changes on offset print quality. Pigment coated and surface sized papers were treated with corona and atmospheric plasma in pilot and laboratory scales. The surface energy and surface chemistry changes were evaluated by contact angle and X-ray photoelectron spectroscopy (XPS). Offset printing was performed in laboratory scale with an IGT unit with predampening and in a pilot scale sheet-fed offset printing press. In addition, the ink setting rate was measured using an ink on paper tack tester. Plasma activation increased the surface energy of the papers. Furthermore, the polarity of the paper surface increased due to formed polar oxygen containing molecular groups. Due to differences in treatment times laboratory scale plasma treatment formed mainly carboxyl and ester groups, whereas pilot scale treatment induced mainly alcohol, ethers, aldehydes and/or ketones on paper surfaces. Printing evaluation showed that plasma activation influences both ink and water absorption properties. According to print tack results plasma activation led to faster ink-setting. With hydrophobic surface-sized paper plasma activation influenced the ink transfer, print gloss and density by changing dampening water absorption properties. The difference in surface chemistry with laboratory scale plasma treated samples was also reflected in the print quality properties. SEM imaging showed that too intense plasma

It is recognized that the non-dispersive components, γ^ab, of the surface free energies, γ, play an important role in the interactions of a polymer with other substrates. Because of the difficulty in measuring the surface free energy of a solid polymer surface, many methods to estimate γ have been developed. The purpose here is to examine how to characterize a high energy polymer surface using our recently proposed model and the modified two-liquid contact angle technique. First, the dispersion component, γ^d, of surface free energy of polystyrene (PS) is obtained by measuring the contact angles of water on PS surface in a series of n-alkanes. Its γ^ab is then calculated by our three-parameter semi-empirical model using the contact angle data of several key non-alkane liquids on the surface. Given the surface thermodynamic parameters, our model also enables us to calculate the interfacial free energies, γ_SL, between PS and other liquids. An attempt to relate γ_SL to the equilibrium concentrations of crazing solvents in PS is presented.

Ultrahigh-modulus polyethylene fibers were treated with atmospheric pressure He plasma on a capacitively coupled device at a frequency of 7.5 kHz and a He partial vapor pressure of 3.43 × 10³ Pa. The fibers were treated for 0, 1, and 2 min. Microscopic analysis showed that the surfaces of the fibers treated with He plasma were etched and that the 2-min He plasma-treated group had rougher surfaces than the 1-min He plasma-treated group. XPS analysis showed a 200% increase in the oxygen content and a 200% increase in the concentration of CO bonds (from 11.4% to 31%) and the appearance of CO bonds (from 0% to 7.6%) on the surface of plasma-treated fibers for the 2-min He plasma-treated group. In the microbond test, the 2-min He plasma-treated group had a 100% increase of interfacial shear strength over that of the control group, while the 1-min He plasma-treated group did not show a significant difference from the control group. The 2-min He plasma-treated group also showed a 14% higher single-fiber tensile strength than the control group.

Ultrahigh modulus polyethylene fibers were treated with atmospheric pressure helium + oxygen plasma in a capacitively coupled device at a frequency of 7.5 kHz. The fibers were treated for 0, 0.5, 1, 1.5, and 2 min. The surfaces of the fibers treated with He + O₂ plasma were etched and micro-cracks were formed. XPS analysis showed a 65—213% increase in oxygen content on the surfaces of all plasma-treated fibers, except for the 1.5 min group. An increase in the concentration of CO and the appearance of CO bonds on the surfaces of plasma-treated fibers were observed. In the micro-bond test, He + O2 plasma-treated groups had a 65–104% increase in interfacial shear strength over that of the control. The tensile strength of the fibers was either unchanged or decreased by 10–13% by the plasma treatments.

We discuss in this review how the roughness of a solid impacts its wettability. We see in particular that both the apparent contact angle and the contact angle hysteresis can be dramatically affected by the presence of roughness. Owing to the development of refined methods for setting very well-controlled micro- or nanotextures on a solid, these effects are being exploited to induce novel wetting properties, such as spontaneous filmification, superhydrophobicity, superoleophobicity, and interfacial slip, that could not be achieved without roughness.

Total surface free energy, γ_S ^TOT, for several solids (glass, PMMA, duralumin, steel and cadmium) was calculated from the surface free energy components: apolar Lifshitz–van der Waals, γ_S ^LW, and acid–base electron–donor, γ_S ^-, and electron–acceptor, γ_S ⁺. Using van Oss and coworkers' approach (Lifshitz–van der Waals/acid–base (LWAB) approach), the components were determined from advancing contact angles of the following probe liquids: water, glycerol, formamide, diiodomethane, ethylene glycol, 1-bromonaphthalene and dimethyl sulfoxide. Moreover, receding contact angles were also measured for the probe liquids, and then applying the contact angle hysteresis (CAH) approach very recently proposed by Chibowski, the total surface free energy for these solids was calculated. Although the thus determined total surface free energy for a particular solid was expected to depend on the combination of three probe liquids used (LWAB approach), as well as on the kind of the liquid used (CAH approach), surprisingly the average values of the surface free energy from the two approaches agreed very well. The results obtained indicate that both approaches can deliver some useful information about the surface free energy of a solid.

The idea of the treatment of textiles with plasma is a few decennia old. There is no consensus about who was “the first,” but it is clear that the treatment of textiles is historically linked to the plasma treatment of polymers in general. As one of the most promising alternatives in many fields, the importance of plasma treatments results from the exceptional advantages it offers. It does have specific action only at the surface, keeping the bulk properties unaffected. The future of plasma is closely linked to the fact that this technique gives the treated surface some properties that cannot be obtained by conventional techniques, and this is without the need to use water as a reaction medium. At the level of textiles, this means changing an almost inert surface into a reactive one, and in this way, it becomes a surface engineering tool. The transfer of research results into the technological field would lead to nonpolluting and very promising operating conditions. In the prospect of chemical finishing using plasma, two main methods can be considered: grafting of a compound on the fiber or surface modification by means of discharges.