—ESCA, wettability measurements, SEM, weight-loss determinations, and an ink adhesion test were used to characterize low-molecular-weight oxidized materials (LMWOM) formed during the corona-discharge treatment of polypropylene film. Water-soluble LMWOM is readily formed by scission processes occurring during corona treatment. The presence of water-soluble LMWOM complicates the interpretation of wettability-based measurements of corona effectiveness. Surface roughening on corona-treated polypropylene is caused by the interaction of LMWOM and water in a high-relative-humidity environment. LMWOM does not necessarily form a weak boundary layer that hinders subsequent adhesion of ink to the corona-treated film.

ETFE film surfaces were modified by CO₂, O₂ and Ar plasmas in order to form carboxylic groups on their surfaces, and the possibility that carboxylic groups could be predominantly introduced into the CH₂–CH₂ component rather than the CF₂–CF₂ component in the ETFE polymer chains was investigated from the viewpoint of chemical composition analyzed by XPS. The CO₂ plasma modification was more effective in the selectivity of the CH₂CH₂ component for the introduction of carboxylic groups, as well as in the concentration of the carboxylic groups formed on the film surfaces than O₂ plasma modification. The concentration of carboxylic groups formed on the ETFE film surfaces by the CO₂ plasma modification was 1.40–1.50 groups per 100 carbons. Topographical changes on the ETFE film surfaces by the plasma modification were also investigated by scanning probe microscopy.

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.

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 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.

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.

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 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.

The effect of the addition of clay and TiO₂ pigments on the surface energy and surface chemistry of films made from polymers used in paper coating formulations was evaluated. The polymers were carboxymethyl cellulose, polyvinyl alcohol and a protein-based polymer - all water-soluble - and two styrene-butadiene latexes of different carboxylation levels. The morphology of the surfaces was characterized by SEM examination, gloss measurement and stylus profilometry. Chemical composition was determined by EDS and XPS techniques. Surface energy and its Lifshitz-van der Waals and acid-base components were obtained from contact angle measurements using the van Oss et al. approach. Even though the addition of pigment increasingly upset the planar surface of the films, their surface chemistry and surface energy were only slightly affected over the pigmentation range studied (up to 40% by volume) and were dominated by the characteristics of the binder polymer.

The apolar and the polar (electron-acceptor and electron-donor, or Lewis acid-base) surface tension components and parameters of solid surfaces can be determined by contact angle measurements using at least three different liquids, of which two must be polar. With swelling clay minerals (e.g. smectite clay minerals), smooth contiguous membranes can be fabricated, upon which contact angles can be measured directly. With non-swelling clay minerals (e.g. talc), contact angles can be determined by wicking, i.e. by the measurement of the rate of capillary rise of the liquids in question through thin layers of clay powder adhering to glass plates. The apolar and polar (acid-base) surface tension components and parameters thus found for various untreated and quaternary ammonium base-treated clays allowed the determination of the net interfacial free energy of adhesion of human serum albumin onto the various clay particle surfaces immersed in water. The free energies of adhesion, thus found, correlate well with the experimentally observed degree of adsorption of human serum albumin.

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.

Webs of Kapton 200-H and Upilex-S polyimide films were treated using oxygen plasma prior to sequential sputter deposition of chromium and copper in a roll metallization system. Two plasma system configurations were employed for treatment. In one configuration, the sample traveled downstream from a microwave plasma; in the other, the web moved through a DC-generated glow discharge. For the DC-glow treatment, the potential difference between the plasma and the web, Φ_f, and relative ion densities, n+, were measured at various values of chamber pressure and DC power using a Langmuir probe. Although samples treated downstream from the microwave plasma were not subjected to bombardment by energetic ions, Φ_f for the DC-glow operating conditions was between 5 and 13 eV. For both films, advancing DI water contact angles of less than 20° were achieved using both modes of treatment. Contact angles for untreated films were greater than 60°. However, 90° peel tests yielded values of 15 to 20 g/mm for microwave plasma treatments and 40 to 60 g/mm for DC-glow treatment. Peel values for untreated Kapton and Upilex films were about 25 g/mm. High-resolution X-ray photoelectron spectroscopy in the C1s region for Kapton film surfaces treated downstream from the microwave plasma showed increases in carbonyl groups, with concentrations inversely proportional to web speed. In contrast, DC-glow modification was due mainly to formation of carboxylates with a small increase in carbonyl component. It is proposed that treatment downstream from the microwave plasma results in formation of a weak boundary layer at the polyimide surface. Ion bombardment occurring in the DC-plasma configuration results in relatively more crosslinking at the polymer surface. Furthermore, adhesion between the sputter-deposited chromium and the DC-glow modified polyimide improved with increasing values of Φ_fn+.

X-Ray photoelectron spectroscopy (XPS) was used to determine plasma induced chemical species on the surface of polyethylene (PE). Argon plasmas were found to have no detectable chemical effect on the PE surface, whereas oxygen and nitrogen plasmas created new chemical species which altered the chemical reactivity of the PE surface. Oxygen plasmas were found to react more rapidly with the PE surface than nitrogen plasmas. The degree of incorporation of new chemical species in the near surface region is approximately 20 at. % at the saturation level for both oxygen and nitrogen plasmas. Core level spectra for oxygen and nitrogen plasma treated PE suggest the formation of primarily C-O-C species in the former and C-N species in the latter. Angle-resolved XPS measurements indicate that the depth of incorporation of new chemical species is confined to the top 25 A.

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.

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.

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.

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.

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.

In this paper, we present a simple, yet novel, method, utilizing scraping to obtain continuous rough microstructures over large areas, leading to a tunable wettability conversion from hydrophilicity to superhydrophobicity on polymer surfaces. A series of polymers ranging from hydrophobic to hydrophilic were used, and we found that the wettability of these polymer surfaces could be modified by the scraping process, irrespective of their hydrophobicity or hydrophilicity. More importantly, those polymers with contact angle ranging from 65° to 90° on their smooth surfaces also exhibit enhanced hydrophobicity after scraping. Our results indicate that 65° is the critical value which is more suitable to define hydrophobicity and hydrophilicity for polymer materials.

Measurements of the surface tension (γ_LV) and advancing contact angle () on poly(tetrafluoroethylene) (PTFE) were carried out for aqueous solutions of cetyltrimethylammonium bromide (CTAB), cetylpyridynium bromide (CPyB), sodium decylsulfate (SDS), sodium dodecylsulfate (SDDS), p-(1,1,3,3-tetramethylbutyl) phenoxypoly(ethylene glycol)s, Triton X-100 (TX100) and Triton X-165 (TX165) and their mixtures. The results obtained indicate that the values of the surface tension and wettability of PTFE depend on the concentration and composition of the surfactants mixture. In contrast to Zisman finding, there was no linear dependence between cos and the surface tension of aqueous solutions of surfactants and their mixtures for all studied systems, but a linear dependence existed between the adhesional tension and solution surface tension for PTFE in the whole concentration range, the slope of which was –1, indicating that the surface excess concentration of surfactant at the PTFE–solution interface was the same as that at the solution–air interface for a given bulk concentration. It was also found that the work of adhesion of aqueous solutions of surfactants and their mixtures to PTFE surface did not depend on the type of surfactant, its concentration and composition of the mixture. This means that for the studied systems the interaction across PTFE–solution interface was constant, and it was largely of Lifshitz–van der Waals type. On the basis of the surface tension of PTFE and the Young equation and thermodynamic analysis of the work of adhesion of aqueous solutions of surfactants to the polymer surface it was found that in the case of PTFE the changes of the contact angle as a function of the total mixture concentration in the bulk phase resulted only from changes of the polar component of the solution surface tension.

Surface modification by corona discharge plasma is one of the most interesting industrial applications for surface modification compared with other techniques which require vacuum conditions. In this work, we have used the corona discharge plasma technique to modify the wettability properties of low density polyethylene (LDPE) film. The effects of this treatment on the surface of LDPE film have been quantified by contact angle measurements, Fourier-transform Infrared Spectroscopy, X-ray photoelectron spectroscopy and atomic force microscopy. With these methods, we have determined how the treatment modifies, activates and functionalizes the surface of LDPE film, increasing its hydrophilic behavior, and how the process parameters influence the uniformity and homogeneity of the treated surface. The results obtained show good treatment homogeneity and an improvement of adhesion properties by the functionalization and etching of the film surface.

A superhydrophobic polyurethane-based film is described, on which the water advancing and receding contact angles are 150° and 82°, respectively. The film was prepared from surface-fluorinated polyurethane (PU), obtained from a well-defined fluorinated isocyanate, with silica particles incorporated within the film. In the absence of the silica particles, smooth fluorinated PU films with about 2 wt% fluorine demonstrate water advancing and receding contact angles of 110° and 63°, respectively. A major cause for the large contact angle hysteresis, similar to the so-called 'sticky' superhydrophobic behavior, on the roughened PU films is believed to originate from the surface reorganization of the fluorinated PU upon contact with water, which is characteristic for the partially fluorinated PU film. When a similar poly(dimethylsiloxane) (PDMS)-based roughened film was made, the water contact angle hysteresis could be reduced significantly, since the long PDMS chain can effectively suppress the surface reorganization upon contact with water.

The effects of acid oxidation on the surface properties of gel-spun ultra-high modulus and molecular weight polyethylene (UHMWPE) fibers were investigated. Three acid-assisted reactions with CrO₃ (I), K₂Cr₂O, (II), and one base-catalyzed reaction with K₂Cr₂O₇ (III) were studied. In reaction II, two levels of sulfuric acid were used for IIa and IIb, with reaction IIa containing the higher concentration. Under the reaction conditions chosen, i.e. 1 min at 23°C, the effects of these oxidations were restricted to the fiber surfaces. All oxidation reactions either significantly reduced or eliminated the axially oriented macrofibril striations and changed the lamellae perpendicular to the fiber axis to irregular hairline surface structures. The oxidative attacks on the fiber surfaces appeared to have occurred in the fibrillar structure and likely at the disorder regions along the fibrils. The epoxy resin wettability and the interfacial adhesion to the epoxy resin were both improved with reactions I and IIa, whereas reaction III did not affect either of these properties. A positive relationship between surface wettability and interfacial adhesion on single fibers was observed on the untreated and acid oxidized gel-spun UHMWPE fibers.

The solid surface tension γsv of hydrophobic polymer powders has been determined using the capillary penetration technique. By plotting Kγlv cos ζ, where K is a geometric factor, versus the liquid surface tension γlv, the following values of γsv were directly derived from the curves: poly(tetrafluoroethylene) γsv = 20.4 mJ/m², polypropylene γsv = 30.2 mJ/m², polyethylene γsv = 34.4 mJ/m², and polystyrene γsv = 27.5 mJ/m². These values are in good agreement with the γsv values obtained from contact angle measurements on flat and smooth solid surfaces of the same materials. If the contact angles were first calculated from the capillary penetration experiments, which is the usual procedure applied in the literature, distinctly higher contact angles were obtained. Obviously these angles are affected by the powder morphology and are therefore meaningless contact angles in terms of a surface energetic interpretation.

The strength of an adhesive bond depends on the thermodynamic work of adhesion, among other properties. In this paper, we report the direct measurement of the thermodynamic work of cohesion and adhesion between poly(ethylene terephthalate) (PET) and polyethylene (PE) films. The pull-off force between polymer surfaces was measured using the surface forces apparatus (SFA). Thermodynamic work of adhesion was determined from pull-off force measurements using the theory of contact mechanics developed by Johnson, Kendall, and Roberts (JKR theory). The values of the surface energies of PET and PE, and the interfacial energy between PET and PE were obtained from these measurements. The dependence of the measured values of the work of adhesion on the rate of separation, time in contact, and other variables that could reflect an irreversible contribution to the measured adhesion was found to be negligible. The critical surface tensions of PET and PE were determined from contact angle measurements. The critical surface tension of wetting depends on the characteristics of the probe liquids. The surface energy of PET determined by the direct force measurements is higher than the critical surface tension of wetting. These values are 61.2 mJ/m² and about 43 mJ/m , respectively. However, in the case of PE the surface energy determined using the SFA and the critical surface tension of wetting are about the same, 33 mJ/m². The interfacial energy between PET and PE, obtained from direct measurements, is about 17.1 mJ/m².

SBS rubbers containing different loadings of calcium carbonate and/or silica fillers were surface treated with UV-ozone to improve their adhesion to polyurethane adhesive. The surface modifications produced on the treated filled SBS rubbers have been analyzed by contact angle measurements, ATR-IR spectroscopy, XPS and SEM. The adhesion properties have been evaluated by T-peel strength tests on treated filled SBS rubber/polyurethane adhesive/leather joints. The UV-ozone treatment improved the wettability of all rubber surfaces, and chemical (oxidation) and morphological modifications (roughness, ablation, surface melting) were produced. The increase in the time of UV-ozone treatment to 30 min led to surface cleaning (removal of silicon-based moieties) due to ablation and/or melting of rubber layers and also incorporation of more oxidized moieties was produced. Although chemical modifications were produced earlier in an unfilled rubber for short time of treatment with UV-ozone, they were more noticeable in filled rubbers for extended length of treatment, mainly for S6S and S6T rubbers containing silica filler. The oxidation process seemed to be inhibited for S6C and S6T rubbers (containing calcium carbonate filler). On the other hand, the S6S rubber containing silica filler and the lowest filler loading showed the higher extent of modification as a consequence of the UV-ozone treatment. The UV-ozone increased the joint strength in all joints, more noticeably in the rubbers containing silica filler, in agreement with the greater extents of chemical and morphological modifications produced by the treatment in these rubbers. Finally, the nature and content of fillers determined the extent of surface modification and adhesion of SBS rubber treated with UV-ozone.

Ink–cellulose interactions were evaluated using a new technique in which the adhesion properties between ink and cellulose were directly measured using a Micro-Adhesion Measurement Apparatus (MAMA). The adhesion properties determined with MAMA were used to estimate the total energy release upon separating ink from cellulose in water. The total energy release was calculated from interfacial energies determined via contact angle measurements and the Lifshitz–van der Waals/acid–base approach. Both methods indicated spontaneous ink release from model cellulose surfaces, although the absolute values differed because of differences in measuring techniques and different ways of evaluation. MAMA measured the dry adhesion between ink and cellulose, whereas the interfacial energies were determined for wet surfaces. The total energy release was linked to ink detachment from model cellulose surfaces, determined using the impinging jet cell. The influences of surface energy and surface roughness were also investigated. Increasing the surface roughness or decreasing the surface energy decreased the ink detachment due to differences in the molecular contact area and differences in the adhesiom properties.

The acid-base theory as developed by van Oss, Chaudury and Good is a powerful tool to analyze the surface free energy of polymeric materials; however, some problems are encountered in its application and some authors have shown that these problems can be theoretically solved considering this theory as an example of the so-called LFER theories. From this point of view, the definition of a well-defined scale of acid-base strength and the use of a wide and well-equilibrated, appropriate set of liquids is very important. In the present paper some recent results are presented which are based on the mathematical approach discussed by Della Volpe and Siboni in previous papers. The treatment is developed as a list of questions, Frequently Asked Questions (FAQs), whose theoretical implications are discussed using numerical examples chosen from the literature. Some literature data, collected by the opponents of the acid-base theory and recently published, are re-analysed using these methods, showing that they constitute a well-defined set to calculate, with a good precision, the acidbase components of the considered materials and the interfacial energies of liquids used. The present paper is the premise of a second one, in which a set of contact angles data collected by the authors and by other researchers will be analysed following the principles discussed here.

Ethylene-co-tetrafluoroethylene copolymer (ETFE) films were modified by four plasmas: direct and remote H2 plasmas and direct and remote O2 plasmas; and the hydrophobic recovery process of these plasma-modified surfaces was investigated using water contact angle measurements and angular XPS. The water contact angle measurements showed important aspects for the hydrophobic recovery process. (1) All plasma-modified ETFE surfaces, regardless of the kind and mode of plasmas, showed increases in the contact angle with increasing aging time. The increase continued for 5 days after finishing the plasma modification, and stopped after 5 days. (2) The plasmamodified surfaces after the aging process never reverted back to the same level of the contact angle as for the unmodified (original ETFE) surfaces. (3) The contact angle after the aging process was strongly dependent on to what plasma the ETFE surfaces were exposed in the modification. (4) The aging temperature influenced the contact angle value after the aging process. The angular XPS measurements also provided a detailed description of the chemical composition of the topmost layer. (1) The chemical composition at the topmost layer of the surfaces altered during the aging process. (2) CH₂-CH₂-CHF, and CH₂-CHF-CH₂ and CH₂-CH(OH)-CF₂ groups disappeared from the topmost layer during the aging process; and CH₂-CH₂-CH₂, and CH₂-CH₂-CF2 and CH₂-CH(OH)-CHF groups appeared at the topmost layer. (3) Such disappearance and appearance occurred on all plasma-modified surfaces regardless of the kind (H₂ or O₂ plasma) or mode (direct or remote plasma) of plasmas used for the modification. This may be due to segmental mobility of CH₂-CH₂-CH₂ sequences rather than of CF₂-CF₂-CF₂ sequences.

One of technologically imminent problems related to the use of pressure sensitive adhesives (PSAs) in the LCD industry is how to properly control the surface properties of various polymeric films used in devices to obtain sufficient bond strength with PSAs. To provide practical solutions to this issue, we used two types of surface treatments, NaOH and corona, to control the surface properties of polymeric films that are widely used in the LCD industry. Here we report a significant increase in surface tension in triacetyl cellulose (TAC) and discotic liquid crystal (D-LC) films along with a remarkable enhancement of bond strength in TAC/PSA and D-LC/PSA systems. The major portion of surface tension increase, in both types of films, was found to be due to an increase of polar component. The continuous increase of OH functionality in TAC with NaOH treatment time supported this observation. Furthermore, we established a map of surface treatment by studying the sequential effects of the two treatments, and based on this, we clearly demonstrated that each treatment had its own limiting value that could not be altered regardless of the sequence of surface treatment.

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.

The effects of intense pulsed high power ion beam (HPIB) treatment of ultra-high strength polyethylene (UHSPE) fibers on the fiber/epoxy resin interface strength were studied. For this study, argon ions were used to treat Spectra^™ 1000 (UHSPE) fibers in vacuum. Chemical and topographical changes of the fiber surfaces were characterized using Fourier transform infrared spectroscopy in attenuated total reflectance mode (FTIR-ATR), X-ray photoelectron spectroscopy (XPS), dynamic wettability measurements, and scanning electron microscopy (SEM). The fiber/epoxy resin interfacial shear strength (IFSS) was evaluated by the single fiber pull-out test. The FTIR-ATR and XPS data indicate that oxygen was incorporated onto the fiber surface as a result of the HPIB treatment. The wettability data indicate that the fibers became more polar after HPIB treatment and also more wettable. Although the total surface energy increased only slightly after treatment, the dispersive component decreased significantly while the acid-base component increased by a similar amount. SEM photomicrographs revealed that the surface roughness of the fibers increased following the HPIB treatment. The single fiber pull-out test results indicate that HPIB treatment significantly improved the IFSS of UHSPE fibers with epoxy resin. This enhancement in IFSS is attributed to increased roughness of the fiber surface resulting in mechanical bonding and in increased interface area, increased polar nature and wettability, and an improvement in the acid-base component of the surface energy after the HPIB treatment.

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.

To analyze various approaches for the determination of surface free energies of solids from liquid-solid contact angles, comb-like polymers with controlled grafting rates and macromolecular structures have been synthesized. The surface free energy parameters were calculated from the contact angles of standard liquids on the solid surfaces. A mathematical approach of the so-called acid-base theory of adhesion was used to characterize the nucleophilic and/or electrophilic behavior of the polymeric solid surfaces. Thus, correlations were established between the macromolecular structures and the dispersive component of the surface free energy, on the one hand, and the acid and base components, on the other. The main conclusion is that the surface free energy components are relevant for the characterization of functional comb-like polymeric materials: the dispersive and base components increase with the number of grafted electron-donating groups, whereas the acid component decreases.

The deposition of plasma polymers on poly(acrylonitrile) (PAN) fibers has been investigated by X-ray photoelectron spectroscopy and dynamic contact angle measurements. Four polymerizable monomers were examined: tetrafluoromethane (TFM), perfluoropropene (PFP), tetramethyldisiloxane (TMS), and hexamethyldisiloxane (HMS). The deposition rate of TFM was undetectable and the treated fibers exhibited some fluorination and an increase of hydrophilicity, due to posttreatment oxidation after exposure to air. The deposition rate of PFP was quite slow and the formation of an incomplete fluorinated layer was observed, with a remarkable increase of the water advancing contact angles. TMS and more so HMS quickly formed continuous and reproducible polysiloxane layers having pronounced hydrophobic properties. The influence of the position of the fibers in the plasma reactor chamber was also investigated. A good uniformity of deposition was found when the fibers were placed at different points between the electrodes.

FEP sheets were modified with a remote hydrogen plasma and the effects of the modification on the adhesion between copper metal and FEP sheets were investigated. The remote hydrogen plasma treatment is able to make FEP surfaces hydrophilic. In the remote hydrogen plasma treatment process, both defluorination and oxidation occur on the FEP surface. The oxidation reactions on the FEP surface form oxygen functional groups such as CO and CO groups. Modification of the FEP surface by the remote hydrogen plasma is effective in improving the adhesion of copper metal. The peel strength of the Cu/FEP system increased form 0 to 195 mN/5 mm, and the failure mode changed from the Cu metal/FEP polymer interface to within the FEP polymer layer. Remote hydrogen plasma treatment may be a preferable pretreatment of the FEP surface for adhesion with copper metal.

The thin-layer wicking technique was used to determine the surface free energy components and the surface character of three celluloses (Sigmaccll 101, Sigmacell 20, and Avicel 101), using an appropriate form of the Washburn equation. For this purpose, the penetration rates of probe liquids into thin porous layers of the celluloses deposited onto horizontal glass plates were measured. It was found that the wicking was a reproducible process and that the thin-layer wicking technique could be used for the determination of the celluloses' surface free energy components. The size of the cellulose particles was characterized with the Galai CIS-100 system and their crystallinity was measured by X-ray diffraction. The three celluloses have high apolar (y^LWS = 50-56 mJ/m²) and electron donor (γs = 42-45 mJ/m²) components, while the electron acceptor component (γS⁺ ) is practically zero. The free energy interactions of cellulose/water/cellulose calculated from the components are positive, regardless of the cellulose crystallinity. This would mean that the cellulose surfaces have a hydrophilic character. However, the work of spreading of water has a small negative value (3-9 mJ/m²), indicating that the surfaces are slightly hydrophobic. It is believed that the work of spreading characterizes better the hydrophobicity of the surface than the free energy of particle/water/particle interaction, because in the latter case, no electrostatic repulsion is taken into account in the calculations.