The barrier solutions presently available on the market all have their drawbacks, e.g. cost, water-sensitivity, opacity or perceived environmental bad-will. At the same time there is a trend to use more plastic-based packaging materials for different applications, e.g. as replacements for metal and glass containers. This situation has stimulated the industry to provide new, more efficient barrier solutions. The innovations go along five major lines: (a) thin, transparent vacuum-deposited coatings; (b) new barrier polymers as discrete layers; (c) blends of barrier polymers and standard polymers; (d) organic barrier coatings; and (e) nanocomposite materials. This paper provides a comprehensive review of the different approaches, outlining the principle behind each barrier technology, its performance, its potential and the companies developing and producing the materials. Copyright © 2003 John Wiley & Sons, Ltd.
https://onlinelibrary.wiley.com/doi/abs/10.1002/pts.621

The means by which plasma treatment enhances the adhesion of polymer materials, remains obscure. Thus far, two possible mechanisms have been proposed: an increase in surface energy, and the anchor effects imparted by plasma etching. Independently from these mechanisms, reactions between free radicals, generated by plasma irradiation and adhesives are also likely to affect the adhesive properties of polymer materials. Free radicals generated on polyethylene (PE) by glow-discharge plasma were exposed to air and converted to peroxide. The peroxides were converted back to free radicals with the application of heat, and then graft polymerization was initiated, by adding a hydrophilic monomer such as acrylic acid. The peroxides formed by the reaction between free radicals and the oxygen in air was detected by chemiluminescence (CL). In this work, plasma-treated PE surfaces were bonded to aluminum boards, using epoxy resin as an intermediate adhesive and then subjected to a series of peeling tests. The sample with the highest peeling strength also had the highest level of CL-detected peroxides. These findings suggest that the free radicals generated by plasma treatment influence the adhesive properties of the polymer materials.

The rate of production and the spatial distribution of ozone in the negative DC corona discharge are predicted with a numerical model. The results are compared to prior experimental data and to results previously presented by the authors for the positive corona discharge. In agreement with experimental data, ozone production rate in the negative corona is an order of magnitude higher than in the positive corona. The model reveals that this significant difference is due to the effect of discharge polarity on the number of energetic electrons in the corona plasma. The number of electrons is one order of magnitude greater and the chemically reactive plasma region extends beyond the ionization region in the negative corona. The paper also extends our prior modeling effort to lower velocities where the Joule heating reduces ozone production. The magnitude of the reduction is characterized by a new dimensionless parameter referred to as the electric Damkohler's third number(Da_III–e).

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.

Different plasma treatments in a rf discharge of Ar, He, or N₂ are used to etch, cross-link, and activate polymers like PC, PP, EPDM, PE, PS, PET and PMMA. Due to the numerous ways a plasma interacts with the polymer surface, the gas type and the plasma conditions must be adjusted on the polymer type to minimize degradation and aging effects. Wetting and friction properties of polymers can be improved by a simple plasma treatment, demonstrated on PC and EPDM, respectively. However, the deposition of ultra-thin layers by plasma enables the adjustment of wetting properties, using siloxane-based or fluorocarbon films, and further reduction of the friction coefficient, applying siloxane or a-C:H coatings. Nevertheless, the adhesion of plasma-deposited coatings should be regarded, which can be enhanced by depositing a graded layer.

Effects of the exposure of ultraviolet (UV) excimer light on the physicochemical surface properties of polymer films were investigated by contact angle measurements and X-ray photoelectron spectroscopy (XPS). The UV light at wavelength of 172 nm was exposed to polyethylene (PE), polyimide (PI), and polytetrafluoroethylene (PTFE) films in ambient air. The advancing and receding contact angles of water on the unexposed and UV-exposed films were determined by the sessile drop and the Wilhelmy methods as a measure of the wettability. For the PE and PI films, remarkable decrease in the water contact angle was accomplished by the UV exposure of several or several 10 s. The XPS data showed that such increase in the wettability was attributed to the increased atomic oxygen concentration at the film surfaces. The wettability of the PTFE film did not change due to the UV exposure. When the UV-exposed PE and PI films were stored in ambient air, the increase in the water contact angle, i.e. the hydrophobic recovery, was observed over a time scale of several days. It was suggested that the gasification of the low-molecular weight oxidized materials as well as the reorientation and the migration of polymer chains in the oxidized surface layer was responsible for the hydrophobic recovery in air. The UV exposure was also attempted to the PI film being covered with a metal mesh to prepare the film having both non-exposed and UV-exposed surface regions. The differences in the advancing and receding contact angles between the both regions were observed on the continuous weight recording at constant interfacial moving velocity by the Wilhelmy method. The Wilhelmy method in combination with the UV lithography technique enabled the simultaneous evaluation of the wettabilities of the treated and untreated surfaces.

In this paper, the corona charge stability in electret polytetrafluoroethylene Teflon film is investigated after the film is treated by radio-frequency plasma. It is found that the charge stability depends strongly on the plasma composition and the film exposure to plasma, especially for negative charge. When a non-metalized film is held horizontally on the ground holder, i.e. with one side facing the plasma, oxygen plasma treatment achieves a superior negative charge retention on the front side, while its rear side retention decreases significantly. Under the same conditions in oxygen/helium and helium plasmas, the charge stability also increases but the potentials are lower compared with pure oxygen plasma after annealing. In a hydrogen plasma, the stability only slightly enhances. If the film is held vertically on the holder, so that both sides contact the plasma, the surface potential on both sides decreases dramatically and arrives at a few volts within 2 min, after annealing at 170°C. By Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS), we conclude that oxidation formed on the front side is responsible for increasing the stability of negative charge. The positive carriers, generated in the film during plasma treatment, recombine with charge from corona charging and causes the surface potential in the rear side of the horizontal non-metalized film, or in both sides of the vertical non-metalized film, to discharge after heating.

We examined the possibility of the surface modification of hydrophobic polystyrene (PS) and poly(methyl methacrylate) (PMMA) by ozone aeration, UV irradiation and combination of ozone aeration and UV irradiation (ozone/UV) in distilled water. The surface states of treated films and particles were investigated by means of contact angle, atomic force microscopy (AFM) and FT-IR measurements. According to the contact angle measurements, the values of the contact angle of ultrapure water on treated PS films decreased with an increase in the elapsed time of the treatments. The most remarkable decrease was seen in ozone/UV treatment. On the other hand, the contact angle on treated PMMA films slightly increased to an equal extent after three types of treatments. The film and the particle surfaces of PS with aromatic rings were found to be well modified with hydroxyl (OH) and carbonyl (CO) groups and to give the most remarkable effects in ozone/UV treatments, whereas those of PMMA with no aromatic ring were hardly modified, merely resulting in a slight disorder in their surface roughness. The experimental results on surface modification of PS and PMMA revealed that the ozone/UV treatment in distilled water is usable as one of the useful techniques for the surface modification of polymers with aromatic rings.

The adhesion strength of a perfluorinated dielectric adhesive to polyphenylene sulfide (PPS) was investigated. The effect of different fillers in the PPS as a function of plasma treatment conditions was evaluated. The change in adhesion as a result of thermal baking was also addressed. The surface composition and surface energy were monitored and systematically quantified by X-ray Photoelectron Spectroscopy (XPS) and contact angle measurements, respectively. The correlations between the presence of certain functional groups, change in surface energy and polarity, and variation in adhesion properties indicate that the adhesion mechanism is mainly due to van der Waals forces. Enhanced wetting at the adhesive/substrate interface and a deeper interfacial diffusion zone are found to be necessary conditions to achieve the optimal adhesion.

Oxygen mixed with nitrogen trifluoride (NF3) was used as the gas source for the plasma etching to increase the etching rate of the polyimide (PI) film. In order to investigate the effects of NF3 addition, surfaces of the etched PI films were analyzed with various methods. From the results of x-ray photoelectron spectroscopy (XPS), the chemical bonding state of the etched PI surface with 30% NF3/70% 02 plasma was similar to that of the surface prepared using 100% 02 plasma. The results of FT-IR analyses showed that a part of materials deposited on the etched PI film was soluble in chloroform and it contained carbonyl and ether compounds. Furthermore, the etching products were analyzed using quadrupole mass spectrometry (QMS) and gas chromatography. The main products were found to be H20, HF, CO and C02. In addition, CO/C02 ratio was found to be related to the etching rate which depended on the NF3 concentration.

The retention of chemical structure and functional groups during plasma polymerisation was investigated. Usually plasma polymer layers, prepared by continuous wave radio-frequency plasma, are often chemically irregular in their structures and chemical compositions. To minimise these irregularities, low wattages and the pulsed plasma technique were applied to avoid fragmentations. The polymerisation of vinyl and acryl-type monomers was strongly enhanced in the dark phase (plasma-off) of a pulsed rf plasma caused by the reactivity of the vinyl or acryl-type double bonds. Bifunctional monomers with acryl or allyl double bonds and also polar groups such as OH, NH2, and COOH were used to produce plasma polymers with defined (regular) structures and a high density of a single type of functional groups. The maximum yields were 30 OH, 18 NH2, 24 COOH groups per 100 C atoms. To vary the density of functional groups a chemical copolymerisation with “chain-extending” comonomers such as butadiene and ethylene was initiated in the pulsed plasma. The composition of these copolymers was investigated by XPS and IR spectroscopy. Homopolymers and copolymer layers were deposited on polypropylene (PP) foils and then aluminium was thermally evaporated. The peel force increased considerably and showed a dependence on the density of functional groups. The plasma polymer deposition was also monitored in situ by the Self-Exciting Electron Resonance Spectroscopy (SEERS) to show correlations between plasma parameters and properties of the deposited plasma polymer layers measured “quasi-in situ” by coupling the plasma chamber with an XPS spectrometer.

Barrier discharges (BDs) produce highly non-equilibrium plasmas in a controllable way at atmospheric pressure, and at moderate gas temperature. They provide the effective generation of atoms, radicals and excited species by energetic electrons. In the case of operation in noble gases (or noble gas/halogen gas mixtures), they are sources of an intensive UV and VUV excimer radiation. There are two different modes of BDs. Generally they are operated in the filamentary one. Under special conditions, a diffuse mode can be generated. Their physical properties are discussed, and the main electric parameters, necessary for the controlled BD operation, are listed. Recent results on spatially and temporally resolved spectroscopic investigations by cross-correlation technique are presented. BDs are applied for a long time in the wide field of plasma treatment and layer deposition. An overview on these applications is given. Selected representative examples are outlined in more detail. In particular, the surface treatment by filamentary and diffuse BDs, and the VUV catalyzed deposition of metallic layers are discussed. BDs have a great flexibility with respect to their geometrical shape, working gas mixture and operation parameters. Generally, the scaling-up to large dimensions is of no problem. The possibility to treat or coat surfaces at low gas temperature and pressures close to atmospheric once is an important advantage for their application.

The surface modification of poly(vinylidene fluoride) (PVDF) film induced by remote Ar, H₂, and O₂ plasmas have been investigated using contact angle measurement, X-ray photoelectron spectroscopy, and scanning probe microscope. The contact angle of water shows an improvement in the PVDF surface wettability during short plasma exposure time. Three remote plasmas treated PVDF sheet surfaces occurred dehydrofluorination and oxidation reactions simultaneously. Remote hydrogen plasma was the most effective in defluorination reactions and remote oxygen plasma was unfavorable to abstract fluorine atoms.

The capacity of a cold atmospheric-pressure air plasma (CAAP) device for advanced first aid is presented. Using swine as an animal model, two trials: 1) a large, curved cut in hindquarters area and 2) amputation of a front leg, were performed. Cold atmospheric-pressure air plasma effluent, which carries reactive oxygen species (ROS) atomic oxygen (OI), is applied for wound treatments. Swift hemostasis of the wounds by the CAAP treatment was demonstrated. The pressure applied by a finger on the cut arteries in trial 1 and the tourniquet applied in trial 2 could be removed immediately after the treatment and there was no re-bleed in both cases. CAAP hemostasis mechanism was explored via in-vitro tests. The tests on sodium citrate mixed blood-droplet samples show that 1) the heat delivered by the CAAP has no impact on the observed clot formation, 2) plasma effluent activates platelets to promote coagulation state and cascade, and 3) the degree of clotting increases with the total amount of applied OI by means of the CAAP effluent. It took only 16 s of the CAAP treatment to reach full clotting, which was considerably shortened from the natural clotting time of about 25 minutes. The tests on smeared blood samples show that the reduction of the platelet count and the increase of RBC count are proportional to the amount of applied OI. A plausible CAAP hemostasis mechanism is concluded from the in vitro test results and the animal model trials.

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.

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.

A corona discharge treatment of low-density polyethylene film (LDPE) was carried out in preparation for flexographic printing. Such treatment of the PE film is necessary if maximum adhesion of ink is to be achieved. This project involved three different treating machines for which the current had to be manipulated in all the machines so that a standard treatment could be accomplished. Using a mathematical relation, current requirements for each machine were calculated and used to standardize treatment level of PE films. Standardization was achieved by controlling input current in all the three machines so as to attain a treatment level of 38 dynes/cm. This level of treatment showed the best results in adhesion of ink to the PE film during printing. The exercise also confirmed that printing must be carried out within 24 h of treatment since the level of treatment deteriorates with time.

Surface potential decay after negative corona charge deposition has been studied for polypropylene films 50μm thick, over a wide range of decay times and charging voltage (500–2800V). At low initial potential (500–800V), the surface potentials were stable and did not decay. At high initial potential (1200–2800V), the surface potential decay has been clearly observed with differences in the decay rate. The observed decay behavior has been computer simulated to elucidate the transport mechanism in polypropylene films. A good agreement between measured and calculated decay curves was obtained with a model in which charges are transported by hopping of injected carriers between localized trapping centers. The model is characterized by parameters such as the free carrier mobility, the mean free time of carrier between traps and the mean capture time in trap. The transport parameters have been determined by a fitting procedure.

A series of low-density polyethylene (LDPE) surfaces, chemically modified using a number of oxidative techniques employed for adhesion enhancement (pretreatments), have been studied by time-of-flight (ToF) SIMS and XPS. The methods consisted of corona discharge, flame, electrochemical, chromic acid, acid dichromate and acid permanganate treatment. All except flame treatment were performed under mild and fairly severe conditions to yield a range of surface chemistries. The XPS analysis, using high energy resolution and a refined approach to C 1s curve-fitting, provided some new insights into the quantitative assessment of the type and concentration of functional groups. Both positive and negative ion ToF-SIMS spectra were obtained at high mass resolution. The oxygen-containing fragments were identified by accurate mass analysis and subjected to a detailed comparison with the XPS results. No convincing relative intensity correlations could be identified that would allow particular secondary ion fragments to be associated strongly with particular functional groups (in this multi-functional surface situation). Inorganic residues resulting from wet chemical treatments were also investigated and here the two techniques were found to be more complementary. Copyright © 2003 John Wiley & Sons, Ltd.
https://analyticalsciencejournals.onlinelibrary.wiley.com/doi/10.1002/sia.1515