The surface free-energies of the polyethers, polyethylene glycol, polypropylene glycol, polyepichlorohydrin, and polybutylene glycol, their mixtures and their random and block copolymers were determined by means of the pendant drop method. In all cases, except that of random copolymers, surface excesses of the low surface-energy component have been found. In the mixtures of homopolymers the behavior of surface excess isotherms depends on the molecular weight of the two components, while in block copolymers it depends on the degree of polymerization of the base unit. The Belton and Evans Equation for perfect solutions and the Prigogine equation for r-mer solutions have been applied to the experimental data.

The surface tension and surface entropies of different molecular weight polyethylene glycols and polypropylene glycols have been measured. The surface entropy of a mixture of polyethylene glycol and polypropylene glycol and that of block copolymers have also been determined. In the case of homopolymers, there is no effect of molecular weight on surface free energy and the increase in free energy on passing from the interior to the surface is due mainly to the heat content with the entropic contribution being very small.

In the case of a mixture of homopolymers and block copolymers, a minimum is observed when surface entropy is plotted against composition. At any particular composition, the surface entropy of a mixture is higher than that of a block copolymer of the same composition.

Presently, it is desirable that one type of ink be suitable for printing on various substrates with different properties. Hence, the emphasis on new models and methods of printability prediction is necessary. The main objective of this work was to study and find correlation between physical properties of printing ink and substrate and finally how these properties can affect printability. For this purpose, contact angle measurement, surface tension measurement, rheology, and various methods for surface characterization of substrates were used.

The effect and interrelationship between primary (segmental backbone) and secondary (side chain) molecular motions on thrombogenesis, independent of morphological order/disorder, crystallinity, and/or associated water is elucidated using an amorphous hydrophobic polymer of poly-[(trifluoroethoxy) (fluoroalkoxy)phosphazene], PNF. The results indicate that thrombogenesis for an amorphous hydrophobic polymer is sensitive and dependent on the degrees and types of primary and secondary molecular motions at the polymer interface.

In this paper, surface modification of polyethylene (PE) films is studied by dielectric barrier discharge plasma treatment in air. The treated samples were examined by water contact angle measurement, calculation of surface free energy, Fourier transform infrared attenuated total reflection spectroscopy (FTIR-ATR), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). The water contact angle changes from the original value of 93.2° to the minimum value of 53.3° and surface free energy increases from 27.3 to 51.89 J/m2 after treatment time of 50 s. Both ATR and XPS show some oxidized species are introduced into the sample surface by the plasma treatment and that the change tendencies of the water contact angle and surface free energy with the treatment time are the same as that of the oxygen concentration on the treated sample surface. Cu films were deposited on the treated and untreated PE surfaces. The peel adhesive strength between the Cu film and the treated sample is 1.5 MPa, whereas the value is only 0.8 MPa between the Cu film and the untreated PE. SEM pictures show that the Cu film deposited on the plasma treated PE surface is smooth and the crystal grain is smaller, contrarily the Cu film on the untreated PE surface is rough and the crystal grain is larger.

The chemical species created in a low-pressure electrical discharge in oxygen attack the polymer at the surface, converting it to gaseous products. This process is interesting because: 1) the chemical changes on the resulting surface facilitate the formation of strong adhesive bonds and provide sites for the chemical attachment of other molecules, 2) significant morphological features lying below the surface may be revealed, 3) polymer can be cleanly removed from surfaces which are resistant to oxidation, and 4) dielectric breakdown frequently is preceded by the attack on the polymer of chemical species created in a corona discharge. Atomic oxygen is an important chemical species created in such a discharge. It reacts with organic substances rapidly at room temperature, but lives long enough in the low-pressure gas that it can be separated from many other reactive species created in the discharge. “Titration” with NO₂ provides a straightforward chemiluminescent means for determining the concentration of atomic oxygen to which the sample is exposed. This paper characterizes the attack of atomic oxygen, perhaps in the presence of long lived but less reactive species such as excited O₂molecules, on polymer surfaces, using electron microscopic observations of known morphological features of polyethylene to observe the changes produced by atomic oxygen. Lamellar polyethylene crystals were attacked both at the edges and the fold surfaces. Layers many microns thick were removed from spherulitic samples and replicas obtained from the surfaces thus exposed. Thick samples were thinned to the point at which they were transparent to an electron beam and interior morphological features were directly observed.

This study systematically characterises a matrix of water-based flexographic inks with respect to their rheology, surface tension and wetting of liquid packaging board, to provide a basis for interpretation and prediction of their printing performance. For all pigment and acrylate polymer vehicles and mixing proportions the inks were shown to be shear thinning and thixotropic, with plastic viscosity, yield stress and storage and loss moduli increasing strongly with content of solution polymer (at comparable solids contents). The solution polymer decreases the static surface tension of the inks, but generally leads to an increase in their equilibrium drop contact angle on the polyethylene- (PE-) coated board due to increase in the ink-board interfacial energy. The solution polymer also decreases the drop spreading rate, and a simple model is tested to express the spreading dynamics in terms of equilibrium contact angle and a rate parameter given by the effective ratio of surface tension to viscosity.

The performance of water-based acrylic flexographic inks laboratory printed on three different polymer-coated boards, namely coated with LDPE, OPP and PP, have been analysed and interpreted. The print quality and resistance properties obtained were related to varying ink formulation, in particular choice of emulsion polymer and presence of silicone additive in the vehicle, as well as varying levels of corona pretreatment. Print mottle and adhesion were worst on PP, while wet (water) rub and scratch resistance were worst on OPP and PE, respectively. However, these properties could be greatly influenced by the ink formulation, more so than corona level. In general addition of silicone improved scratch resistance, due to reduction in polar energy component of the print surface, but at the expense of worsened wet rub resistance. The emulsion polymer giving best resistance performance was generally found to give poorest optical properties, presumably due to more limited resolubility on press.

The effect of corona treatment of Polyethylene-(PE-) coated liquid packaging board on its surface chemistry was quantified using surface energy determination by drop spreading and dyne-liquids, x-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). The increase in total surface energy, due to its polar component, with increasing corona dosage, and its decrease on aging and washing, was strongly correlated to surface oxidation fraction from XPS. A fine structure of nano-mounds formed by oxidised material was revealed by AFM, with size and substrate coverage increasing with corona dosage, but no longer visible after washing. Resistance properties of water-based flexographic prints on these treated PE substrates were tested, with only wet rub resistance exhibiting a significant dependence on corona dosage. This property first increased at lower dosages before decreasing at higher levels, presumably due to worsened water resistance from soluble oxidised material dissolved in the ink film.

The growth of Cu and Al films thermally evaporated onto polyethylene (PE) and polyethyleneterephthalate (PET) surfaces is followed in situ by XPS (X-ray Photoelectron Spectroscopy) and XAES (X-ray Auger Electron Spectroscopy) from the early submonolayer stages up to the completion of a metallic film. PE and PET surfaces were metallized first without any preliminary treatment. A second series of metallization experiments were run on the polymer surfaces but pretreated by a remote O₂ microwave plasma (2.45 GHz). These metal films have also been investigated by AFM (Atomic Force Microscopy) in air. Both metals are shown not to undergo chemical interaction with low surface energy polyolefin such as PE. While an abrupt interface is seen with A1, a diffusion of Cu into the bulk of the polymer is demonstrated. Large size clusters are evidenced by AFM in the initial steps of deposition. Cu and A1 are both shown to react with PET, but not in the same way. In the case of A1, the chemical interaction across the metal/polymer interface proceeds through an electron transfer from the metal toward the ester group O=C-O. With Cu, the chemical interaction is not so clearly evidenced and the Cu is found to diffuse into the PET. Oxygenated functionalities grafted by O₂ plasma on PE and PET are C-O, C=O, O-C-O, O-C=O, and O₂C=O. The roughness of the PE and PET surfaces is observed by AFM to increase with the plasma treatment. A metal-CO type complex is clearly observed with Al/treated PE and Cu/treated PET. No chemical interaction was observed at the Cu/treated PE interface.

In this study, polyimide was treated by atmospheric pressure dielectric barrier discharge plasma using a helium and/or helium-oxygen mixture gasses. The polyimide was placed between copper electrodes with dielectric material installed on the cathode electrode. To investigate the surface treatment, the plasmas as a function of power, treatment time, and plasma gasses were introduced on the polyimide substrate. The experimental results show that the polyimide treated by dielectric barrier discharge plasma increases the wetting property. This property can be attributed to the surface roughness and the water compatible functional groups. The roughness increases by helium plasma treatment and can be further improved by increasing plasma power or the presence of oxygen in the helium-oxygen mixture plasma. On the other hand, the plasma surface treatment led to formation of oxygen related functional groups of -C=O and -OH.

Different types of PLA films treated by corona are currently available in the market for coating or printing applications. However, data relative to its impact on PLA film properties are scarce and do not generally consider industrial scale production. The objective of this study was to assess the impact of corona treatment on the surface, structure and barrier properties of bi-oriented PLA films produced at industrial scale. Thus, a comparative study between corona treated (CT) and non-corona treated (NCT) PLA films was conducted. The surface of films was studied using Attenuated Total Reflectance Fourier Infrared Spectroscopy (ATR-FTIR), X-ray Photoelectron Spectroscopy (XPS), Atomic Force Microscopy (AFM) and goniometry measurements. The structure of films was analyzed with thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and uniaxial tensile analysis. The barrier properties of films to three gases (He, O2, CO2) were also determined. This study unambiguously revealed that corona treatment led to modifications in both surface and bulk of PLA films. In particular, surface analysis displayed the well-known capability of corona treatment to chemically and physically modify the surface of PLA films at the nanometer scale by increasing polarity and roughness. The structural analysis displayed a slight increase in the crystallinity degree and slight modifications in mechanical properties of films. This probably originated from temperature increase associated to corona treatment, which favored physical changes (e.g. relaxation, crystallization) of a part of the bi-orientated PLA chains, and therefore highlights the importance of such an industrial step on the film properties for packaging applications. As a result of these modifications, the barrier properties of films to three gases (He, O2, CO2) are also slightly improved.

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.

The interfacial tension along the boundary formed between two immiscible polymer liquids has been measured by the pendant drop method. The polymers employed for the study are polyethylene, polydimethylsiloxane, poly(ethylene oxide), polytetrahydrofuran, poly(vinyl acetate) and an ethylene-vinyl acetate copolymer. Surface tensions of these polymers (against air) were also determined by the same technique. The values of interfacial tension between polyethylene and each of the five polar polymers, together with the surface tension data, were utilized to calculate the separate contributions to the surface tension by dispersion and dipole interaction forces, in accordance with the procedure proposed by Fowkes. The interfacial tension between two polar polymers was then analyzed in terms of these separate components of forces. An empirical relation has been shown to correlate the dipole interaction term in interfacial tension with the individual dipole force components of the two polar polymers involved.

Metallized polymer or polymer-based materials are used in a large range of electronics applications including the fabrication of ohmic contacts, chip-level interconnects, printed circuit boards and shielded materials.^1–7 For such technological applications, electroless deposition is the most widely used method in practice today.⁸ Basically, electroless plating is an autocatalytic redox process occurring in aqueous solution between ions of the metal to be deposited (generally Ni or Cu) and a strong reducer. Typical procedures involve a variety of multi-step sequences for the preparation of the surfaces to be coated. Conventionally, substrates are cleaned with solvents to remove surface contaminants, chemically etched to obtain a micro-roughened oxidized surface, and then seeded with a catalyst such as palladium. Chronologically, the seeding process was first accomplished by using a two-step procedure involving substrate treatment successively in dilute SnC1₂ (sensitization step) and PdC1₂ (activation step) acidic solutions. Further, a one-step procedure using a colloidal suspension containing both Sn and Pd species (a SnC1₂/PdC1₂ acidic solution) has been developed and is presently in common use in industrial environments. In this last case, the Pd/Sn colloidal particles adsorbed on the polymer surface must be exposed (acceleration step) to a solubilizer (a HCl or NaOH solution) to remove the excess of Sn⁺² species surrounding the catalytic Pd-based core of the colloidal particles. As can easily be inferred from the details of such multi-step procedures, it is today highly desirable to develop alternative approaches for making the insulating surfaces catalytically active. These approaches should require no chemical surface etching, reduce the number of process steps, and provide a highly selective, well-defined interaction between the catalytic species and the surface to be coated.⁹

The effectiveness of the treatment with ultraviolet light (UV) on several polymeric surfaces has previously been established. In this study, a low pressure mercury vapour lamp was used as a source of UV radiation for the surface treatment of a difficult-to-bond block styrenebutadiene-styrene rubber (S6), the treatment time ranging from 10 s to 30 min. The UV-treated S6 rubber surfaces were characterized by contact angle measurements (ethylene glycol, 25°C), ATR-IR spectroscopy, XPS, Scanning Electron Microscopy (SEM), and Atomic Force Microscopy (AFM). T-peel tests on UV-treated S6 rubber/polyurethane (PU) adhesive/ leather joints (before and after ageing) were carried out to quantify adhesion strengths. The UV treatment of S6 rubber produced improved wettability, the formation of CO, CO and COO moieties, and ablation (removal of a thin rubber layer from the surface). The extent of these modifications increased with increasing treatment time. The extended UV treatment produced greater surface modifications, as well as the incorporation of nitrogen moieties at the surface. Furthermore, noticeable ablation of S6 rubber surface occurred. Peel strength values increased with increased treatment time of UV treatment of S6 rubber. Also, with increasing treatment time, the adhesive joints showed different loci of failure: adhesional failure for the as-received and 2 min-UV treated S6 rubber/polyurethane adhesive/leather joints changed to mixed failure (cohesive in the treated S6 rubber + adhesional failure) for the 30 min-UV treated S6 rubber/polyurethane adhesive/leather joint.

A styrene-butadiene-styrene (S6) rubber was treated with corona discharge to increase its surface energy and adhesion to polyurethane (PU) adhesive. The influence of the length of treatment (the speed of the upper plate was varied from 80 to 900cm/min) during corona discharge was analyzed. The corona energy applied to S6 rubber surface ranged from 0.4 to 4.6J/cm ² . The surface modifications produced as a consequence of the corona discharge were characterized immediately after treatment was carried out and were monitored by means of different surface analysis techniques, mainly contact angle measurements (ethylene glycol, 25 ^o C), ATR-IR spectroscopy, XPS and Scanning Electron Microscopy (SEM). T-peel tests of corona-discharge-treated S6-rubber/polyurethane (PU) adhesive/leather joints (72h after joint formation) were carried out to evaluate the influence of the surface modifications produced by the corona discharge on the adhesion properties of the treated S6 rubber.The corona discharge improved the wettability of the S6 rubber due to the formation of polar moieties, mainly C-O, C=O and COO ^- groups. These chemical modifications were not detected by ATR-IR spectroscopy (depth of analysis about 5μm), indicating that a nanometer-range oxidized layer was created on the S6 rubber surface by treatment with corona discharge. Besides, surface cleaning and removal of rubber contaminants (mainly silicon moieties) were produced but roughness was not created as a consequence of the treatment. These modifications were enhanced when a low speed treatment (long treatment and high corona energy) was carried out. Peel strength values of corona-discharge-treated S6 rubber/PU adhesive/leather joints only moderately increased (mainly for long length of the corona discharge). Although corona treatment chemically modified the surface of the S6 rubber, the absence of surface roughness might likely be responsible for the slight improvement in its adhesion properties.