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.

One of the main differences between low-pressure and atmospheric-pressure plasma treatments is that there is little moisture involved in the low-pressure plasma treatment, although moisture could exist at the wall of the vacuum chamber or react with the substrate after plasma treatment, while in the atmospheric-pressure plasma treatment moisture exists not only in the environment but also in any hygroscopic substrate. In order to investigate the influence of environmental moisture on the effect of atmospheric pressure plasma treatment, ultra-high-modulus polyethylene (UHMPE) fibers were treated using an atmospheric-pressure plasma jet (APPJ) with 10 l/min helium gas-flow rate, treatment nozzle temperature of 100°C and 5 W output power. The plasma treatments were carried out at three different relative humidity levels, namely 5, 59 and 100%. After the plasma treatments, the surface roughness increased while the water-contact angle decreased with increasing relative humidity. The number of oxygen containing groups increased as the environmental moisture content increased. The interfacial shear strength of the UHMPE fiber/epoxy system was significantly increased after the plasma treatments, but the moisture level in the APPJ environment did not have a significant influence on the adhesion properties. In addition, no significant difference in single fiber tensile strength was observed after the plasma treatments at all moisture levels. Therefore, it was concluded that the environmental moisture did not significantly influence the effect of atmospheric-pressure plasma treatment in improving interfacial bonding between the fiber and epoxy. The improvement of the interfacial shear strength for the plasma-treated samples at all moisture levels was mainly due to the increased surface roughness and increased surface oxygen and nitrogen contents due to the plasma etching and surface modification effect.

Multilayer films were prepared from poly(tetrafluoroethylene) (PTFE) and poly(ethylene terephthalate) (PET) films together with using an adhesion promoting layer (tie-layer) consisting of ethylene-methyl acrylate-glycidyl methacrylate (E-MA-GMA) terpolymer and low density polyethylene (LDPE) blend. Na/naphthalene treatment and subsequent acrylic acid grafting were applied on the surfaces of PTFE for chemical modification. FT-IR spectroscopy, XPS analysis and surface energy measurements were performed to characterize the modified PTFE films. The analyses showed defluorination and oxidation of PTFE surface, and supported the acrylic acid grafting. The surface energy of modified surfaces enhanced with respect to unmodified one, which promoted adhesion. The multilayers were subjected to T-peel tests to measure the adhesion strength between PET and modified PTFE. Peel strength between the films increased with increasing E-MA-GMA amount in the tie-layer. A proportional dependence of peel strength on Na/naphthalene treatment time was observed for multilayers containing acrylic acid grafted or ungrafted PTFE. From SEM analysis, it was observed that the texture of the PTFE surface after modifications became rougher when compared to untreated PTFE. The peeled surfaces were also analyzed by SEM. The micrographs evidence that the energy absorbing mechanism is the plastic deformation of the tie-layer, which is responsible for obtaining high peel strengths.

Wetting of hydrophobic polymer surfaces commonly employed in electronic coatings and their interaction with surfactant-laden liquids and aqueous polymer solutions are analyzed using a contact angle hysteresis (CAH) approach developed by Chibowski and co-workers. In addition, a number of low surface tension acrylic monomer liquids, as well as common probe liquids are used to estimate solid surface energy of the coatings in order to facilitate a thorough analysis of surfactant effects in adhesion. Extensive literature data on contact angle hysteresis of surfactant-laden liquids on polymeric surfaces are available and are used here to estimate solid surface energy for further understanding and comparisons with the present experimental data. In certain cases, adhesion tension plots are utilized to interpret wetting of surfaces by surfactant and polymer solutions. Wetting of an ultra-hydrophobic surface with surfactant-laden liquids is also analyzed using the contact angle hysteresis method. Finally, a detailed analysis of the effect of probe liquid molecular structure on contact angle hysteresis is given using the detailed experiments of Timmons and Zisman on a hydrophobic self-assembled monolayer (SAM) surface. Hydrophobic surfaces used in the present experiments include an acetal resin [poly(oxymethylene), POM] surface, and silane, siloxane and fluoro-acrylic coatings. Model surfaces relevant to the literature data include paraffin wax, poly(methyl methacrylate) and a nano-textured surface. Based on the results, it is suggested that for practical coating applications in which surfactant-laden and acrylic formulations are considered, a preliminary evaluation and analysis of solid surface energy can be made using surfactant-laden probe liquids to tailor and ascertain the quality of the final coating.

The occurrence of negative square roots of the Lifshitz–van der Waals (LW) component and acid and base (A and B) parameters calculated from the van Oss–Chaudhury–Good theory was checked for a small artificial set of the work of adhesion input data calculated for 9 solids and 7 liquids. Taking from the literature the data for the LW component and A and B parameters for 7 liquids and the values of such component and parameters for 9 solids (close to those in the literature), the work of adhesion was calculated and its value was assumed to be error-free (un-biased). Next, new values of the work of adhesion were obtained by adding a random error having normal distribution belonging to 8 distributions of a mean value equal to the error-free work of adhesion value and standard deviations of 1, 5, 7, 10, 20, 25, 30 and 40% of the mean value. The LW components and A and B parameters for the nine solids were back-calculated for each solid and the error (bias) level by solving the overdetermined system of equations (of matrix 7 × 3) for 7 liquids. These 9 solids were grouped in 3 sets of 3 solids in each. It was found that an experimental error caused the work of adhesion data for real systems to be biased. This bias caused the solution of the equation system also to be biased and both biases were linearly dependent. This paper confirms that the appearance of negative roots of A and B parameters is caused by a specific bias in the components of the work of adhesion matrix. If the work of adhesion matrix is negatively biased there is a greater possibility of obtaining a negative value of the square root of γ⁺, and the smaller the value of this parameter the greater is the possibility of obtaining a negative square root for it. Both the negative and positive biases in the work of adhesion matrix almost equally influence the bias in γ⁻. The smaller this parameter the greater is its bias and greater the possibility of obtaining its negative square root.

The van Oss–Chaudhury–Good theory (vOCGT) was checked for a small artificial set of the work of adhesion input data calculated for 9 solids and 7 liquids. Taking from the literature the data for Lifshitz–van der Waals (LW) component and acid and base (A and B) parameters for 7 liquids and the values of the component and the parameters for 9 solids (close to those in the literature), the work of adhesion was calculated and its value was assumed to be free of error. Next, new values of the work of adhesion were obtained by adding a random error of normal distribution belonging to 11 distributions of a mean value equal to the errorless work of adhesion value and standard deviations from 0.1 to 60% of the mean value. The LW components and A and B parameters for these solids were back-calculated for each solid and the error level by solving 20 3-equation systems. These 9 solids were grouped in 3 sets of 3 solids in each, and for each of the solid sets the over determined system of equations (of matrix 7 × 3) for these 7 liquids was solved. The root mean square errors (RMSEs) of the LW component and A and B parameters were linear functions of RMSE of the vector (matrix) of the work of adhesion in both solution methods of a set of equations. It was found that a solution of the 3-equation set of the vOCGT was always exact for all liquid triplets. Erroneous LW components and acid and base parameters are obtained because quite a different set of equations (caused by an existing error in the data) is solved than in the case of error-free data. There is a linear transformation from the input error in the work of adhesion vector (matrix) space into the output error in the solution vector (matrix) space, and the inverse (or pseudoinverse) of the matrix A is the transformation matrix. In the case of a 3-equation set there is a linear relationship between the total RMSE of the solution and the condition number of the matrix A. The higher the input error in the work of adhesion data the higher is the influence of the condition number on the error in the solution. The RMSE value of the solution of an over determined system of equations was about 10-times lower than the mean value of RMSE calculated for the same liquids used as separate triplets.

Numerous relationships have been proposed in the literature to interpret wettability in terms of solid and liquid surface free energies. In the classical approach based on surface free energy components, the energy of interactions between the liquid and the solid is obtained from the geometric mean of the dispersion and polar contributions of the liquid and solid surface free energies. In this work, it is shown that the surface polarity of polar liquids can be modeled by the interaction of aligned permanent dipoles. A good agreement is found between the surface polarity characterized by polar component of the surface free energy of polar liquids (water, formamide and ethylene glycol) and the dipolar energy of interactions calculated from their dipole moment. At the liquid/polymer interfaces, polar interactions are better described by a simple relationship of proportionality with the polar component of the liquid surface free energy. This observation leads us to evaluate the hypothesis of induced polar interactions at liquid/polymer interfaces, the surface polarity of the solid being induced by the polar liquid in contact with the solid surface. Thus, the variation of the contact angle of a series of polar and non-polar liquids on various polymer substrates appears to be in better agreement when compared to the classical description of permanent polar interactions, so that a surface polarizability is defined for polymers. Using the surface polarizability approach rather than the polar component for the solid surface, we find also that the dispersion (non-polar) component of the polymer surface free energy is obtained with a better confidence, especially by taking into account the contact angles of both non-polar and polar liquid probes, or even by considering only polar liquid probes.

The aging effects of atmospheric pressure plasma treated fiber surfaces are important for storage and processing of the fibers. One of the high-performance fibers, ultrahigh modulus polyethylene (UHMPE) fiber, was chosen as a model system to investigate the aging process of atmospheric pressure plasma jet (APPJ) treated fibers surfaces 0, 7, 15 and 30 days after initial plasma treatment. The fiber was first plasma-treated and then stored at temperatures varying from −80 to 80°C on the same relative humidity (RH, 0%) and on RH of 0%, 65% and 100% at the same temperature of 20°C. Immediately after the plasma treatment, scanning electron microscope (SEM) showed the roughened fiber surface. X-ray photoelectron spectroscopy analysis showed changed surface chemical compositions. Contact-angle measurement showed increased surface wettability and microbond test showed an increase in IFSS. With increasing relative humidity or decreasing temperature, the IFSS value decreased and the contact angle increased more slowly. However, after 30 days, the IFSS values and contact angles reached a similar level for all groups. Moisture showed no effect on the single fiber tensile strengths during aging. The reasons for the observed aging behavior could be that decreasing temperature or increasing relative humidity hindered the surface rearrangement of polymer chains after plasma treatment.

In this study the effect of low temperature plasma (LTP) treatment of cotton fabric for ink-jet printing was investigated. Owing to the specific printing and conductivity requirements for ink-jet printing, none of the conventional printing chemicals used for cotton fabric can be directly incorporated into the ink formulation. As a result, the cotton fabric requires treatment with the printing chemicals prior to the stage of ink-jet printing. The printing chemicals as a treatment to cotton fabric are applied by the coating method. The aim of this study was to investigate the possibility and effectiveness of applying LTP pre-treatment to enhance the performance of treatment paste containing sodium alginate, to improve the properties of the ink-jet printed cotton fabric. Experimental results revealed that the LTP pre-treatment in conjunction with the ink-jet printing technique could improve the final properties of printed cotton fabric.

The surface of polypropylene (PP) film was oxidized by exposure to a flame fueled by isotopically labeled methane (CD4). The isotopic sensitivity of static secondary ion mass spectrometry (SIMS) was then used to gain new insights into the mechanism of flame treatment. SIMS analysis indicated that much of the oxidation of PP occurring in fuel-lean flames is not deuterated, while for PP treated in fuel-rich flames, some of the affixed oxygen is deuterated. These observations imply that O₂ is the primary source of affixed surface oxygen in fuel-lean flame treatments, but that OH may be a significant source of affixed oxygen in fuel-rich flame treatments. Hydroxyl radicals are primarily responsible for hydrogen abstraction in fuel-lean flames, while H is the primary active gasphase species in fuel-rich flames. SIMS also detected trace quantities of oxidized nitrogen groups affixed to the flame-treated PP.

The influence of different surface treatments on the physical and chemical surface properties of poly(etheretherketone) (PEEK), poly(phenylenesulfide) (PPS) and a liquid crystal polymer (LCP) was studied. For all the three polymers, the adhesion strength of an adhesively-bonded copper foil could be increased significantly by a chemical etching process using chromic sulphuric acid or a low pressure air-plasma treatment. However, for LCP the enhancement of adhesion by the surface treatments was lower than for the other polymers. Peel tests were employed for determining the adhesion strength of the copper foil. The physical surface properties were investigated by laser scanning microscopy (LSM). Contact-angle measurements and X-ray photoelectron spectroscopy (XPS) provided detailed information on the chemical surface properties. The detailed XPS analyses revealed different chemical mechanisms of the surface treatments depending on the polymer investigated. In all cases an incorporation of oxygen containing groups by the surface treatments was found to be responsible for a better adhesion of the copper foil on the treated polymer films compared to the untreated.

Four ethylene vinyl acetate (EVA) co-polymers with different vinyl acetate (VA) contents (9–20 wt%) were treated with corona discharge to improve their adhesion to polychloroprene (PCP) adhesive. The thermal properties of the EVAs decreased as their VA content increased, caused by a decrease in crystallinity. The elastic and viscous moduli of the EVAs decreased and the temperature and modulus at the cross-over between these moduli decreased with increasing VA content. Contact-angle measurements (water), infrared spectroscopy (ATR-IR), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) were used to analyse the surface modifications produced in the corona-discharge-treated EVAs. The corona discharge treatment produced improved wettability and created roughness and oxygen moieties on the EVA surfaces. The higher the VA content and the higher the corona energy, the more significant modifications were produced on the EVA surface. The VA content also affected the T-peel strength values of treated EVA/polychloroprene + isocyanate adhesive joints, as the values increased with increasing VA content. Mixed failure modes (interfacial + cohesive failure in the EVA) were obtained in the adhesive joints produced with corona discharge treated EVAs containing more than 9 wt% VA. The accelerated ageing of the joints did not affect the T-peel strength values, but the locus of failure in most cases became fully cohesive in the EVA, likely due to the higher extent of curing of the adhesive.

The wetting behavior of a series of polymer-coated papers has been studied. Different ways of determining the acid–base properties of the polymers are presented. The well-known van Oss–Chaudhury–Good (vOCG) bi–bi polar model is compared with more simplified mono–bi polar and mono–mono polar models. The effect of surface roughness on the wetting was also studied with atomic force microscopy. The overall wetting of each probe liquid was evaluated by calculating the work of adhesion to the polymer surfaces. It is shown that ethylene glycol and water may be considered as mono polar liquids, which simplifies the original vOCG-model. It is also shown that in most cases the surface energy values are in the same range when using both the complex bi–bi polar approach and the simpler mono–mono polar approach. The different polymers used are found to be of a predominating basic character.

Low pressure glow discharge nitrogen plasma has been used to improve wettability in a low density polyethylene (LDPE) film for technical applications. The plasma treatment was carried out at a power of 300 W for different exposure times in the 1–20 min range. Wettability changes were analyzed using contact angle measurements. In addition to this, plasma-treated samples were subjected to an aging process to determine the durability of the plasma treatment. X-ray photoelectron spectroscopy, atomic force microscopy, and scanning electron microscopy were used for surface characterization. The nitrogen plasma treatment considerably reduced contact angle values thus indicating an increase in surface wettability. The spectroscopic study showed presence of oxygen-based species on the plasma-treated samples, which are mainly generated after the plasma treatment as a consequence of air exposure. These polar species contribute to improve surface functionalization, but this is almost lost during aging due to the hydrophobic recovery process. Microscopic studies revealed that also small changes in surface roughness occurred during the plasma treatment but these are very low compared to surface activation. The results confirmed that low pressure nitrogen can be considered as an environmentally efficient process to improve wettability in low density polyethylene films. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2390–2399, 2007

o optimize the effects of some discharge parameters on the surface wettability of polypropylene (PP) in atmospheric pressure dielectric barrier discharge, a surface modification model is created based on statistical theory and orthogonal experimental design method. Contact angle measurements, atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS) are used to study the changes in the surface wettability, surface topology and chemical compositions of the samples. The results show that surface wettability has been improved due to roughness increasing and the introduction of oxygen-containing functional groups. High-resolution XPS of C1s peak deconvolution indicates that the types and contents of oxidized functional groups are different in different discharge conditions or plasma energy. Moreover, the model analysis reveals that it has better predictive ability, and different discharge parameters has selective influence on water contact angle and surface O atom percentage.

The capability of the PDMS based antiadhesion surface treatment strategy for high resolution unconventional lithography using hard or soft molds as representatives of imprint lithography or soft lithography was investigated. A thin film of PDMs was used as an antiadhesion release layer as PDMS has a fairly low surface energy and allows for the easy release of the mold from the patterned polymer on the substrates. The surface of the Si wafer was coated with a thin film of PDMS and using this PDMS-coated Si wafer as a hard mold line/space patterns were printed on the SU-8-coated PET substrates. Using this photoresist replica mold as a template for a soft mold the same PDMS-based coating strategy was applied. The imprinting of nanostructure-patterned mold onto a polymer composed of the same chemical as the mold led to pattern collapse during the release of the assembly because of the extremely strong adhesion between the mold and the polymer.

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.

In the last few decades there has been an intense development in non-equilibrium (“cold”) plasma surface processing systems at atmospheric pressure. This new trend is stimulated mainly to decrease equipment costs by avoiding expensive pumping systems of conventional low-pressure plasma devices. This work summarizes physical and practical limitations where atmospheric plasmas cannot compete with low-pressure plasma and vice-versa. As the processing conditions for atmospheric plasma are rather different from reduced pressure systems in many cases these conditions may increase final equipment costs substantially. In this work we briefly review the main principles, advantages and drawbacks of atmospheric plasma for a better understanding of the capabilities and limitations of the atmospheric plasma processing technology compared with conventional low-pressure plasma processing.

In atmospheric pressure corona systems, the densities of electrons and ions determine the level of treatments. Here, the electron and ion densities in a corona plasma are evaluated for a DC positive-polarity wire discharge in dry air at atmospheric pressure, in the coaxial wire-cylinder geometry. We use a new numerical iterative approach to solve the coupled equations for the electric field and charge densities. The role of electron diffusivity is discussed and the influence of the charge distribution between electrodes on the electric field strength and on the plasma region is analyzed.

A review is presented of the adhesion between polymers with particular emphasis on the processes that occur during failure at the level of polymer chains and how these processes relate to the macroscopic interface toughness. The same processes at the chain level, pull-out and scission, occur in both glassy polymers and elastomers, but the two classes of material are considered separately because their deformation processes around a crack tip are so different. Emphasis is placed on the work in which the author has participated and so the review makes no attempt to be an unbiased survey of the field.