The most important function of a packaging material is to shield the product inside the package. Extrusion coated paperboard is generally used in food, medical and cosmetic packages. Extrusion coatings give a barrier against water, water vapour, aroma, grease, oxygen, etc. In addition to barrier properties, heat sealability and printability are important properties in packaging applications. From point of view of printing, the dense and impervious structure of extrusion coatings is challenging: printing inks and toners do not penetrate into the coatings. The durability of the printed image is significant, because the image must withstand various converting operations when the package is constructed. The most common method for obtaining good ink adhesion is to oxidize the surface. Surface treatments are used to change the chemical composition, increase the surface energy, modify the crystalline morphology and surface topography, or remove the contaminants and weak boundary layers. Two widely used methods are electrical corona discharge treatment and flame treatment. These processes generally cause physical or chemical changes in a thin surface layer without affecting the bulk properties. Treatments will increase surface energy and also provide polar molecular groups necessary for good bonds between ink and polymer molecules. In addition to printability, surface treatments also affect the heat sealing properties of extrusion coatings. In this study, the surface chemistry of the extrusion coatings has been modified with corona and flame treatments. The effect of corona and flame treatment on surface energy has been evaluated with contact angle measurements. Surface energy has the habit of decreasing with time after treatment. In this work, the decay of surface energy and surface oxidation is followed for six months. ESCA and FTIR-ATR have been used to analyze oxidation and the surface chemical composition. Furthermore, the heat sealing and hot tack properties of the extrusion coatings are evaluated. The aim of this study is also to evaluate printability of extrusion coatings and to map out the role of surface modification in print quality formation. This study has concentrated on digital printing, particularly on dry toner-based electrophotographic printing process.

Surface properties of polycarbonate (PC), polypropylene (PP), polyethylene terephthalate (PET) samples treated by microwave-induced argon plasma have been studied with contact angle measurement, X-ray photoelectron spectroscopy (XPS) and scanned electron microscopy (SEM). It is found that plasma treatment modified the surfaces both in composition and roughness. Modification of composition makes polymer surfaces tend to be highly hydrophilic, which mainly depended on the increase of ratio of oxygen-containing group as same as other papers reported. And this experiment further revealed that CO bond is the key factor to the improvement of the hydrophilicity of polymer surfaces. Our SEM observation on PET shown that the roughness of the surface has also been improved in micron scale and it has influence on the surface hydrophilicity.

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.

A basic and affordable experimental apparatus is described that measures the static contact angle of a liquid drop in contact with a solid. The image of the drop is made with a simple digital camera by taking a picture that is magnified by an optical lens. The profile of the drop is then processed with ImageJ free software. The ImageJ contact angle plugin detects the edge of the drop and fits its profile to a circle or an ellipse. The tangent to the triple line contact is calculated and drawn by the ImageJ software, thus, returning the value of the contact angle with acute precision on the measurement.

Corona discharge (CD) treated polyethylene films were examined using X-ray photoelectron spectroscopy (XPS) and a variety of chemical derivatization techniques. The composition of the CD-treated surfaces were found to be relatively unaffected by aging at temperatures between 70 and 80°F. Ink adhesion testing of films treated under progressively more serve conditions indicated the efficiency of adhesion varied directly with the severity of treatment. Derivatization of CDtreated polyethylene films with pentaflurophenylhydrazine (PFPH) resulted in the formation of a stable hydrazone complex. The PFPH complex extends the detection limit for enolizable carbonyl groups ca. eight-fold and provides relative quantitation of the number of these groups on variously treated polyethylenes. Formation of the hydrazone complex destroyed ink adhesion, indicating that the complex had blocked the site responsible for chemical bonding to the ink. Adhesion of water-soluble printing inks to CD-treated polyethylene is a direct consequence of hydrogen bonding between enolic hydroxyls on the polymer surface and carbonyl groups of the ink.

The adhesion between a polyurethane (PU) adhesive and four foams containing different low-density polyethylene (LDPE)/ethylene vinyl acetate (EVA) blends was improved by using different surface treatments. UV-ozone, corona discharge, and low-pressure oxygen plasma treatments for different times were used to increase the surface energy of the foams. The low-pressure oxygen plasma was the most successful surface treatment to promote the adhesion of the foams. A reduced length of treatment was needed to improve the adhesion of the foams containing higher EVA content. The surface treatments produced a noticeable decrease in contact angle values due mainly to the creation of different carbon–oxygen moieties and to the formation of cracks/heterogeneities on the foams surfaces. After oxygen plasma, removal of non-polar material from EVA surfaces allowed to expose acetate groups which are likely to be important for increasing the adhesion of the foams.

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

Plasma treatment and vacuum Al deposition on films from biaxially oriented polypropylene is a multistep large scale industrial process, mainly ending up in packaging film laminates. As atmospheric plasma treatment processes suffer from lack of reproducibility, low pressure plasma treatment processes that can be operated in-line with the metal deposition are being developed. Process development is difficult, because the final packaging film laminate has to deliver optimum properties of adhesion as well as of the barrier against oxygen and water vapor permeation. As a typical production run involves tens of thousands to up to one hundred thousand square meters of film, experiments on an industrial scale are expensive, so smaller scale experimental processes are needed, which so far do not match well enough with industrial process characteristics. Moreover, bonding mechanisms between the treated substrate film and the deposited Al layer are not sufficiently understood. This paper describes the sequence in development and optimization of substrate films and plasma treatment that has been performed on an experimental as well as on an industrial scale. A sufficient correlation between experimental and industrial scales was achieved, which helps to perform development and optimization on a small scale before scaling up to industrial processes. However, improvement is still needed both in fundamental understanding of the aluminum–polypropylene interface as well as in experimental equipment and methodology.

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.

Polycarbonate surfaces have been treated with radiofrequency plasmas of oxygen, air and argon to hydrophilise the surfaces and to provide good cell culture properties. Surfaces treated at high RF power/gas flow ratios were highly hydrophilic and stable towards washing in 70% ethanol, while those treated at lower ratios were not wash-stable. Cell growth properties as good as on commercial tissue-culture polystyrene could be obtained down to 20° water contact angle (measured after ethanol washing) on the treated surfaces for three different human cell lines (HeLa cervix carcinoma cells, MRC-5 lung fibroblasts and Chang hepatoma cells). The HeLa cells were most sensitive to the treatment conditions, while the Chang cells showed the most robust behaviour. Cells grown on surfaces with around 20° water contact angle were assessed by immunofluorescence staining methods and phase contrast microscopy. The cells showed normal behaviour with respect to morphology, spreading, cytoskeleton structure, cell-surface contacts and DNA synthesis.

The modifications induced by excimer laser irradiation of poly(ether ether ketone) (PEEK) surfaces have been investigated as a function of the laser process parameters for laser fluences below the material ablation threshold. In the case of 193 nm laser treatment, a significant increase in the adhesion properties of PEEK was obtained due to the formation of new polar and reactive groups on the surface. The extent of these reactive groups has to be controlled since their presence in high concentration may also have a negative effect on the mechanical properties of the treated surface. Laser treatments using 248 nm radiation did not result in a significant increase in the adhesion properties of PEEK. This probably results from thermal degradation of the surface at this laser wavelength.

The modifications induced by excimer laser radiation on different types of polymer surfaces (polyether-etherketone (PEEK), polycarbonate (PC) and epoxy resin) performed at laser fluences below the material ablation threshold have been investigated. Particular attention was given to the role of laser irradiation wavelength (193 or 248 nm) on the nature and properties of the treated surfaces. Results indicate that a much stronger reactivity was obtained after treatments at 193 nm for all the investigated polymers. At this wavelength, the original polymer surfaces are strongly modified by UV photons; surface reorganization occurs and polar groups induce an increase in the surface wettability.

The chemical modifications induced on PET by an excimer laser radiation or a lowpressure plasma were studied by XPS and Tof SIMS analyses. Both treatments induced surface oxidation but differences related to the type of oxidized groups and the level of degradation of the treated surface were evidenced. Both treatments can significantly enhance the adhesion but the surface change responsible for the improvement was different for each pretreatment.

The thermodynamic aspects of the evolution of surface free energy of acrylic acid grafted polyethylene films have been examined as a function of time of contact on water. The dispersive and polar components vary with time and the interfacial free energy reaches a minimal value. Two terms participate in these variations: adsorption of water molecules and reorientation of polar acrylic groups at the water-polymer interface. Irreversible process thermodynamics has been applied to these phenomena. The surface can be characterized by a phenomenological coefficient relating the orientation rate and the orientation affinity of the polar groups at the interface.

Characterization of poly(ethylene terephthalate) (PET) films surfaces through wettability measurements and inverse gas chromatography techniques leads to a better knowledge of the potential interactions with a coating. An important case is the one relative to gelatin coatings for photographic films. In order to favor adhesion on PET, it is of interest to examine the problem in terms of acid–base interactions. PET is found amphoteric and gelatin rather basic. Several surface treatments on PET like orientation on water and flame or plasma treatment in air lead to an increase in surface acidity. Adhesion with gelatin as determined by the peel test is increased through a flame treatment, because of the higher acidity of PET and subsequent chemical bonding at the interface. Determination of acid-base surface properties of PET and gelatin appears to be an excellent tool for adhesion prediction.

The reorganization of the surface of a polyethylene grafted with 1% acrylic acid during contact with water has been studied using contact-angle measurements, a color test, esterification, inverse gas chromatography and ESCA spectroscopy. The evolution of the surface properties of the polymer in contact with water is explained by movements of the macromolecular chains followed by the orientation at the surface of the acrylic grafts, initially buried in the bulk of the polymer. The concept of “potential” surface energy of a polymer is proposed.

The surface of the bio-material polymethyl methacrylate (PMMA) was treated with CO₂, Nd:YAG, excimer and high power diode laser (HPDL) radiation. The laser radiation was found to effect varying degrees of change to the wettability characteristics of the material depending upon the laser used. It was observed that interaction with CO₂, Nd:YAG and HPDL effected very little change to wettability characteristics of the PMMA. In contrast, interaction of the PMMA with excimer laser radiation resulted an increase in a marked improvement in the wettability characteristics. After excimer laser treatment the surface O₂ content was found to have increased and the material was seen to be more polar in nature. The work has shown that the wettability characteristics of the PMMA could be controlled and/or modified with laser surface treatment. However, a wavelength dependence of the change of the wetting properties could not be deduced from the findings of this work.

The manufacture of polyolefin films by an extrusion process will today almost certainly include as part of the processing line some form of adhesion promoter. For Cast and Blown extrusion this would mean corona as the adhesion promoter. Often overlooked as being an insignificant component on the manufacturing line, the Corona Treater is often purchased in haste and without adequate deliberation. Without this consideration a capital expenditure may arise that may meet current requirements but offers little or no flexibility for the future. When considering a Corona Treater, first and foremost a choice must be made between Bare Roll and Covered Roll. This paper deals with the decision making process leading up to this determination. We will stress that one should not allow any preconceived notions to cloud the issue on the type of treater station required. Both Bare Roll and Covered Roll treater stations serve a particular purpose and play an integral part in the manufacturing process.

The formation of the interface between aluminium and O₂ or CO₂ plasma-modified poly(ethylene terephthalate) (PET) has been investigated by X-ray photoelectron spectroscopy (XPS). As demonstrated by the changes in the C 1s, O 1s, and A1 2p core level spectra upon A1 deposition, the metal was found to react preferentially with the original ester, with the plasma-induced carboxyl and carbonyl groups to form interfacial complexes. The phenyl ring at the modified PET surface was seen to be involved in the formation of the interface, but to a lesser extent. This confirms the high reactivity of the oxygen-containing groups towards the deposited A1 atoms. The adhesion between A1 and the plasma-modified PET films was evaluated by means of a 180° peel test. A considerable (up to ten times) improvement in adhesion was achieved by plasma treatment of the PET substrate, but for either plasma gas the adhesion strength was found to depend strongly on the plasma power and treatment time. The results are discussed in terms of the concentration of oxygen-containing groups at the polymer surface, the surface topography, and the possible presence of low-molecular-weight materials at the metal-polymer interface.

PET (Polyethylene terephthalate) films were modified with two different plasmas, nitrogen and oxygen, as a function of treatment times and RF powers. Firstly, the chemical composition of the plasma-modified PET films was investigated by XPS. In the case of nitrogen plasma, the formation of amine, imine and amide groups is detected. A slight diffusion of nitrogen-containing species into the PET bulk is also observed by angle-resolved XPS measurements. The appearance of alcohol, carbonyl and carboxyl functions is observed in the case of oxygen plasma treatment. After thermal deposition of an aluminium film, peel tests reveal that the Al/PET adhesion increases as follows: untreated < nitrogen plasma < oxygen plasma treatment.

Secondly, after sevderal successive depositions of thermally evaporated Al on oxygen plasma treated PET film, XPS was used to study the chemistry at the interface. The XPS results reveal that the additional reactive sites created on the PET surface by the treatment explain the significant improvement in Al/PET adhesion observed for plasma-modified samples.

Chemical modification of the PET surface by carbon dioxide plasma treatment has been studied using X-ray photoelectron spectroscopy (XPS). The plasma process results mainly in the formation of carbonyl, carboxyl, and carbonate groups at the PET surface. Under rather mild treatment conditions (low plasma power combined with a short treatment time), the formation of CO bonds was found to be dominant, whereas the formation of highly oxidized carbon or double-bonded oxygen-containing groups required a high plasma power or a relatively long treatment time. The treatments performed under excessive conditions frequently led to degradation at the polymer surface. Angle-resolved XPS analyses performed on a freshly modified PET film showed a slight decrease in the O/C atomic ratio when the take-off angle (TOA) increased, indicating a relatively uniform distribution of oxygen within the sampling depth (estimated to be about 8 nm at 80° TOA). The chemical composition of the plasma-modified surface was found to be relatively stable on extended storage in air under ambient conditions. The decrease in oxygen-containing groups at the carbon dioxide-plasma-treated PET surface upon ageing is mainly ascribed to the surface rearrangement of macromolecular segments, the loss of oxygen-containing moieties introduced by the plasma treatment, and the possible migration of non-affected PET chains from the bulk to the surface region.

The surface tensions of a series of poly(isobutylenes) in the molecular weight range 400–3000 have been determined at 24°C. These results, together with surface tension values from the literature for poly(dimethyl siloxanes) and three series of different pure chain-molecule homologues, are found to exhibit a linear dependence on (molecular weight)^{$\text{−2}\text{2}$}. A simple free-volume argument seems to be consistent with this empirical observation.

Apparatus for treating the exterior surfaces of plastic objects to improve their adherency to and compatibility with inks and adhesives comprising a pair of electrodes spaced apart from each other, means including a source of electric current of sufficient intensity to produce a spark discharge across the gap between said electrodes, electrical conducting means connecting said electrodes and said source, and means for positioning the objects in the gap between said electrodes, and electrodes being arranged with regard to the size and configuration of the objects to provide a nearly direct electron path around the objects whereby desired portions of the object surfaces may be passed over by the spark discharges during the passage of the latter along said path from electrode to electrode.