The measurements of the contact angle of the aqueous solutions of TX-100 and TX-165 mixture with propanol on polytetrafluoroethylene (PTFE) and polymethyl methacrylate (PMMA) were carried out. On the basis of the obtained results, the dependence between the cosine of contact angle and surface tension as well as between the adhesion and surface tension of the solutions in the light of the work of adhesion of the solutions to the PTFE and PMMA surface was discussed. The dependence between the adhesion and surface tension for PMMA was correlated to the surface concentration of propanol as well as TX-100 and TX-165 mixture concentration determined from the Frumkin equation at the PMMA-air, PMMA-solution and solution–air interfaces. For this purpose, the surface tension of PMMA covered by a surface active agent film was determined using the Neumann et al. equation and next the PMMA–solution interface tension was evaluated from the Young equation. The values of the surface tension of PMMA covered by propanol and surfactants mixture layer were applied to describe the changes of the adhesion work of solutions to PMMA surface as a function of propanol and surfactants mixture concentration. The adhesion work of the aqueous solutions of TX-100 and TX-165 mixture with propanol to the PTFE and PMMA surfaces was discussed in the light of the adhesion work of particular components of the solutions. On the basis of the results obtained from the contact angle measurements, the standard Gibbs free energy of adsorption of particular components of solution was also considered.

A wide variety of plasma treatments was performed on polyethylene surfaces, resulting in a wide range of total surface energies. The linear correlation of with cos θ was discussed in light of the Young–Dupré equation. Hundred percent of the surface energy variation was accounted for by the polar component of surface energy; the dispersive component was not affected by surface treatment. These data show that for this polymer the contact angle of a single polar liquid can be used as a robust quantitative indicator of treatment level, and because of its excellent linear correlation with total surface energy for this system, can be used as a quantitative measure of total surface energy.

In this study, a surface modification of the poly (ethylene terephthalate) (PET) film using TiO₂ photocatalytic treatment was investigated. In order to enhance the adhesion strength between the PET film and the electroless copper film, the effects of TiO₂ crystal forms, TiO₂ particle sizes, and TiO₂ content, as well as treatment condition, upon the surface contact angle, surface characterization, and adhesion strength were investigated. Anatase TiO₂ with a particle size of 5 nm had a high catalytic activity and dispersibility in aqueous solution. After the optimal photocatalytic treatment, the surface contact angle of the PET film decreased from 84.4° to 19.8°, and the surface roughness of the PET film increased from 36 to 117 nm. The adhesion strength between the PET film and the electroless copper film reached 0.89 KN m⁻¹. X-ray photoelectron spectroscopy analyses indicated the carbonyl group was formed on the PET surface after photocatalytic treatment, and the surface hydrophilicity was improved. Consequently, TiO₂ photocatalytic treatment is an environmentally friendly and effective method for the surface modification of the PET film.

Polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) films were treated with an atmospheric-pressure plasma (APP) jet and a 172-nm ultraviolet (UV) excimer light in air. The advancing and receding water contact angles on both films decreased after the treatments, especially after APP treatment. After the treatments, the hydrophobic recovery was observed and almost diminished within a week. The dispersive component of the surface free energy of the two polyester films did not change due to the APP and UV exposure, whereas the acid–base component drastically increased after the treatments. The X-ray photoelectron spectroscopy results showed that the polyester film surfaces were oxidized by the treatments. From the AFM images, the topographical change on the film surfaces due to the treatments was clearly observed. It was found that the APP treatment of the PET film prevented the deposition of particulate soils in air due to the decrease in the contact area between the film and the soil particle. Furthermore, the soil release in the aqueous solutions was promoted as a result of the hydrophilization of the polyester films due to the APP treatment.

This paper reports on a special pilot coating and industrial printing trial designed to gain fundamental knowledge on ink adhesion failure on coated papers. We found that ink adhesion failure resulted in white spots without ink on the paper, referred to as uncovered areas and these spots gave print mottle problems. The white spots were due to two fundamentally different types of ink adhesion failure. One is the well-known ink rejection, which simply means that ink is not transferred to the surface. The other is a new type of ink adhesion failure, confirming a previous hypothesis suggested from laboratory observations. We refer to this as ink-lift-off adhesion failure, meaning that ink initially deposited on the paper surface becomes lifted off from the surface in a subsequent print unit. Adhesion failure by this mechanism was seen to occur more frequently than failure due to the well-known ink rejection.

This paper studies the effects on valid domain of contact angles and error limits of solid surface tension components and parameters (SSTCPs)/square roots of SSTCPs (SQSSTCPs) from the changes in liquid surface tension components and parameters (LSTCPs) when applying the van Oss–Chaudhury–Good (vOCG) approach. The results of maximum absolute errors and maximum relative errors (MREs) in SQSSTCPs/SSTCPs, induced by errors in LSTCPs or contact angles, show that most SQSSTCPs/SSTCPs can be evaluated at moderate accuracy from the lowest condition number liquid triplets, assuming that |Δθ_i| = 1° and  = 0.1 mN/m (i = 1, 2, 3, k = LW, +, −). This confirms the validity of the vOCG approach. The accuracy of each SQSSTSCP/SSTCP declines with increasing θ_i or decreasing parameter when θ_i > 0 or a critical value, provided the other two contact angles are kept fixed. This explains the underlying reasons for negative SQSSTCPs. At the scale proposed by vOCG, dimethyl sulphoxide is not suggested for use. Comparing with the MREs obtained at vOCG scale, considering the acidity of diiodomethane improves the accuracy of ; using the scales proposed by Lee and Shen do not affect the accuracy of SSTCPs, but using the scale proposed by Della Volpe et al. improves the accuracy of SSTCPs at low θ₂ and θ₃ while declines that at high ones. For a low , low surface tension apolar liquid is preferred for high accuracy. The dependence of the accuracy of SQSSTCPs/SSTCPs on contact angles suggests the importance of considering contact angle in accuracy evaluation.

The optimization of heat-sealing process parameters, including time, temperature, and pressure, was performed on a monolayer linear low-density polyethylene (LLDPE) film. The seal properties examined for each process condition were: seal initiation temperature (T_si), plateau initiation temperature (T_pi), final plateau temperature (T_pf), plateau seal strength (SS_p), and failure mode. Increasing dwell time enhanced seal strength. However, it was found that the rate of this enhancement is different for each interval of dwell time. A narrow temperature plateau was observed for dwell times lower than 0.4 s and higher than 2 s, while in between a broad temperature window was observed. The pressure shows its influence up to the stage of wetting. And after providing the intimate contact between two film layers, additional increase in pressure does not enhance seal strength significantly. A 3D mapping of process safety zone was introduced for seal strength in the range of heat seal process variables for the very first time. The analysis of this 3D representation revealed that seal strength has a linear correlation with the square root of dwell time. In addition, the interfacial bond strength was shown to be proportional to the fraction of melted crystals. It was found that this fraction is determined by dwell time and temperature. Topography and morphology of surfaces after peeling revealed enlargement of fibrillar morphology to taller failure fracture complex shapes. Extensive roughness analysis on film surfaces after peeling found the much rougher surfaces after breakage of strong bonding.

Polydimethylsiloxane (PDMS) and glass are among the most widely used materials in biomedical and microfluidic applications. In this paper, oxygen plasma exposure was used to improve the adhesion properties of PDMS and glass. The effect of bonding quality parameters such as RF power, time of activation and oxygen flow was investigated. Bonding area and strength, two main indicators of bonding quality, were detected using manual peel and mechanical shear tests, respectively, to optimize the bonding parameters. It was observed that increase in activation time and RF power increased the bonding strength considerably. The oxygen flow had a slight influence in increasing the bonding strength. The application of this bond has also been demonstrated in PDMS–glass micropump, so this technique can be potentially applied for fabrication of PDMS–glass-based microfluidic and biomedical devices.

In this paper, a polymeric coating based on the modified chlorinated polypropylene (CPP) emulsion was synthesized, methyl methacrylate (MMA), butyl acrylate (BA) and acrylic acid (AA) were grafted onto CPP backbone and phase inversion was conducted to obtain waterborne emulsion. Results showed that the concentration of initiator (BPO) had the greatest effect on graft copolymerization. The concentration of emulsifier and temperature influenced the results of phase inversion. Besides, the thermal performances of modified CPP were better than untreated one. In addition, the coating obtained in optimum condition had excellent adhesion to BOPP film, and apparently improved the printing quality of the film. The printability promotion should be attributed to the different movement trend of coating’s polar and un-polar chains during the baking step, as well as the subsequent formations of new coating/substrate and coating/ink interface layer.

The surface characteristics of a two-part polyurethane adhesive formulation, based on controlled amounts of polyol, isocyanate, and catalyst, have been studied by methods including contact angle analysis, 1R spectroscopy, and inverse gas chromatography (IGC). The response of surface properties to various cure regimes and to exposure to water has been established. IGC analyses show that the adhesive surface is mildly basic, and as first evaluated by contact angle methods, has a surface energy close to 40 mJ/m². This is largely accounted for by dispersion forces. Following immersion in water at 60°C, however, the surface energies change, the most important effect being an increase in the non-dispersive component. FTIR spectra show that immersion in water also produces chemical changes in the surface region, likely related to enolization effects. On subsequent immersion of the adhesive surface in non-polar n-heptane, the non-dispersive component of the surface energy is again reduced, showing that surface restructuring of polyurethane chains contributes significantly to the observed surface dynamics. The magnitude of the restructuring effects was shown to vary with, but to persist for, all cure regimes applied to the formulation. The documented surface dynamics of the polymer are fully analogous to earlier results obtained for a series of two-part (soft-segment) polyurethanes. As expected, the surface dynamics in this family of polymers affect the bond strength of joints using the polyurethanes as adhesives.

The surface energy parameters of polycaprolactone (PCL) were determined at 160 and 180°C from its interfacial tensions with probe polymers. The probe polymers were polystyrene (PS) and poly(methyl methacrylate) (PMMA). This method is based on the well-known relationship between blend interfacial tension and polymer surface energy parameters, and requires the use of at least two probe polymers, whose surface energy parameters at the temperature of interest have been independently determined. It also requires direct measurement of blend interfacial tension at the high temperatures of interest. The interfacial tensions were obtained from direct measurements by the imbedded fiber retraction method. The following results were obtained: (a) γ^P (polar component) values for PCL was within the range reported using other methods, (b) γ^D (dispersion component) values for PCL decreased with increasing temperature, consistent with expectations and (c) γ^D values for PCL were on the high end, but still within the rather broad range of reported values.

Untreated aluminium and aluminium hydrated for 60 s in boiling water have been extrusion-coated with low-density polyethylene (LDPE). The hydration transforms the oxide surface into a porous oxyhydroxide, known as pseudoboehmite. LDPE samples with different melt indices (4.5, 7.5, and 15) were used, which influence the ability to penetrate into the pores. Compared with untreated aluminium, a superior peel strength was obtained for the laminates with hydrated aluminium. In almost all cases, the peel strength for the laminates with hydrated aluminium could not be measured, due to rupture in the polymer film. This improvement is suggested to be due to stronger acid-base interactions, increased contact surface, and mechanical keying into the porous surface. The obtained peel strength and analysis by means of scanning electron microscopy indicated that the polymer with the highest melt index or lowest melt viscosity had the greatest ability to penetrate into the formed pores. After ageing up to 12 weeks in solutions with 1% and 3% acetic acid, the peel strength dropped rapidly for the untreated Al laminates, but remained constant for the hydrated Al laminates. This is explained by the fact that, besides the improved adhesion, the hydrated oxide prevents corrosive attack.

The primary goal of surface modification of fluoropolymers is to improve adhesion to these low surface energy materials. Both classical methods and newer processes have been used as a means to this end. Various methods of modifying fluoropolymer surfaces include wet chemical etching, electrochemical reduction, grafting, application and removal of metals, ion and electron beam techniques, and plasma modification. In addition to the modification procedure, it is necessary to evaluate the effectiveness of the chosen method by subsequent analysis of the modified surface. Physical analytical methods include contact angle and wettability measurements, lap shear and composite tensile shear strengths, peel strengths, and surface topographical determinations. Chemical analyses used include infrared, Raman, Rutherford backscattering, ultraviolet-visible, wide angle X-ray scattering, X-ray fluorescence, and X-ray photoelectron spectroscopies as well as thermal desorption mass spectrometry. Each of the modification methods, with results of the subsequent chemical or physical analysis, will be discussed.

Although many thousands of measurements have been made to determine the pull necessary to detach a ring from the surface of a liquid, it is a surprising fact that until three years ago there was no “ring method” for the measurement of surface tension. Thus in “International Critical Tables,” nine experimental methods for surface tension are listed but a ring method is not included, since the procedure which had been designated by this term did not supply even one single measured value of surface tension of these tables.

The failure of the ring procedure was due to the fact that the theory had not been sufficiently developed to permit its use as a method of measurement, although an incomplete theory had been developed by Cantor,¹ Lohnstein,² Lenard,³ Tichanowsky⁴ and MacDougall.⁵

In 1926 Harkins, Young and Cheng,⁶ on the basis of the well-justified assumption that the capillary height method, properly applied, gives correct values for the surface tensions of suitable liquids, showed how the ring procedure could be used as a moderately accurate method for such measurements. In the present paper the method is given a still higher degree of accuracy (about 0.25%).

Wenzel’s modification of Young’s equation for contact angles, equation (1), may be derived from considerations of free surface energy, though not from the assumption that surface “tensions” may be represented by vectors. A theory is presented for the hysteresis of contact angles. The “driving force” toward the attainment of an equilibrium contact angle is found to be equal to the surface tension of the liquid times the deviation of the cosine of the contact angle from its equilibrium value. It is shown that this may be equated to the “contortional energy” Fc that the drop must have in order for its edge to surmount a ridge. The result is in the same form as the equation of Adam and Jessop: í-(-yi— 72)= 72 cos 6,, r± Fc, but with a new and physically meaningful interpretation of Fc.

Contact angle behavior of four relatively high surface tension ionic liquids (1,3-dimethylimidazolium methyl sulfate, 1-ethyl-3-methylimidazolium ethyl sulfate, 1-ethyl-3-methylimidazolium fluoroborate, and bis(hydroxyethyl)dimethylammonium methane sulfonate) was studied on seven hydrophobic surfaces and compared with water contact angle behavior. Smooth surfaces of various chemical compositions exhibit contact angles with ionic liquids that are lower than values obtained with water and that scale with liquid surface tension values. Contact angles of ionic liquids on rough perfluoroalkyl surfaces exhibit the highest contact angles reported for liquids other than water and are indistinguishable from those of water and not dependent on liquid surface tension. Superhydrophobic methylsilicone surfaces that exhibit high water contact angles and low hysteresis exhibit very low receding contact angles with ionic liquid probe fluids and high hysteresis. The potential for ionic liquids as probe fluids is argued because of their variable and controllable surface tension, interface charge density, interface dipole density, as well as their variable and controllable cation/anion structure and molecular volume.

An investigation of the surface by XPS photoelectron spectroscopy has shown that the process of production of cast contact lenses based on poly(2-hydroxyethyl methacrylateco-diethyleneglycol methacrylate) is accompanied by mass transfer at the lens-mold boundary. This phenomenon, which impairs the compatibility of the lens during its application, can be considerably suppressed by employing a suitable surface modification of polypropylene molds. The surface treatment consisting in the oxidation of the mold surface by an AC corona discharge in the oxygen atmosphere increased hydrophilicity of the material, thus facilitating separation of the lens from the mold. The results of the XPS study were also confirmed microscopically by employing the SEM method. © 1992 John Wiley & Sons, Inc.
https://onlinelibrary.wiley.com/doi/abs/10.1002/jab.770030406

During the past decade polylactide acid (PLA) polymer has been the subject of numerous researches aimed at comparing it with traditional petroleum based polymers for many packaging applications. PLA is biodegradable and derived from agricultural by-products such as corn starch or other starch-rich substances like maize, sugar or wheat.While PLA is currently being used in many packaging applications with well documented performance, little work has been done comparing printing processes and performance. This study presents PLA printing performance and sustainability findings using the common flexography printing process. Various analytical methods were used to evaluate performance and provide recommendations for optimized printing on PLA as compared to PET, oriented PP and oriented PS. Results of this study found that PLA films were comparable in printability and runnability to standard petroleum based flexible packaging films.

This paper, as the title underlines, will be focused on flame treatment technology applications, mainly on BOPP substrates.

After an introduction regarding flame chemistry and BOPP surface activation mechanisms, this paper will be focused on unique flame treatment oxidation performances, in comparison with other treatment methods actually used in the market.

Focus will then be moved to the characteristics and advantages of using flame treatment for film surface treatment. In particular, a comparison will be run with other surface treatment technologies (corona surface treatment and atmospheric plasma treatment) in terms of:

• q surface energy after treatment;
• surface oxidation mechanisms and chemical species involved;
• quantity of oxygen on treated surface (oxidation level);
• quality of oxygen on treated surface;
• adhesion;
• printability/print quality.

Typical and new applications of flame treatment will be presented, underlining benefits coming from flame usage for pretreating different types of skins. Finally, the paper will try to make rid of prejudices and misinformation concerning flame treatment process applications, especially to certain kind of webs and substrates.

The uncoated side of dispersion-barrier-coated paperboards was exposed to positive and negative direct current corona treatments in order to confirm the occurrence of backside treatment and clarify its effects on the usability of the paperboard. The main component of the coating dispersions was hydroxypropylated potato starch and the effects of talc and styrene-butadiene latex additions on backside treatment were evaluated. Coatings with a high talc proportion showed excellent initial grease resistance, but corona-induced strikethroughs caused a drastic decrease in grease penetration time. The root-mean-square roughness measurements revealed moderate surface roughening at the backside, indicating thus backside treatment. The alterations in surface free energies and rapeseed oil contact angles confirmed the occurrence of backside treatment. The high polarization potential of latex played a key role in these observations. At the same time, the inertity of talc had a stabilizing effect but it did not prevent backside treatment completely. X-ray photoelectron spectroscopy results verified that backside treatment occurs also when the barrier-coated side of the substrate is treated with corona, indicating that a dispersion coating layer does not prevent this undesired phenomenon. Bearing in mind that expressing customized information or including personalized elements in food packages or disposable cups and plates is under great interest, it can be assumed the exposure of packaging materials to corona will become more common in the near future, and the need for optimizing bio-based packaging materials for such purposes is obvious.

Ti films were deposited onto high‐density polyethylene (HDPE) samples by electron‐beam evaporation. Prior to film deposition the samples were in situ pretreated by Ar ion bombardment using a sputter ion gun. The adhesion of the films, determined as the pull strength required for film failure, was measured as a function of ion dose. HDPE substrates processed at two different temperatures were examined. The adhesion of the Ti films to HDPE samples processed at ≊150 °C increased with the ion dose to a steady‐state value corresponding to the cohesive strength of the HDPE substrate. The adhesion to the samples processed at ≊200°C increased to a maximum and then decreased for further ion bombardment to a level of the same order as that for films deposited onto as‐prepared samples. The effects of the ion bombardment upon the HDPE surface chemistry were examined by means of x‐ray photoelectron spectroscopy (XPS). The ion bombardment resulted in dehydrogenation and cross linking of the surface region and for prolonged ion bombardment, a graphitelike surface was obtained. The film/substrate interface as well as the initial Ti film growth were examined by XPS analysis. A chemical interaction which resulted in Ti–C bonds was observed at the interface. The Ti film growth followed a pronounced three‐dimensional growth mode on as‐prepared surfaces whereas the ion bombardment resulted in a change toward a more two‐dimensional growth mode. The difference in adhesion behavior for the two types of HDPE substrates was found to be due to a difference in the amounts of low molecular weight products present within the substrates. The HDPE substrates processed at ≊200°C contained larger amounts of low molecular weight products and also had a lower degree of crystallinity and a less closely packed structure compared to those substrates processed at ≊150°C. This resulted in a segregation of low molecular weight products towards the surface of substrates processed at ∼200 °C. This segregation in turn is suggested to lead to a weak boundary layer, reducing the adhesion to as‐prepared samples and to substrates exposed to a high ion dose.

The wetting of cylindrical monofilaments by liquid polymers is a problem of much scientific and technological importance. In particular, the characterization of the physicochemical nature of interfaces is a key problem in the field of advanced fibrous composites. The macroscopic regime contact angle, which reflects the energetics of wetting at the solid-liquid interface, is difficult to measure by usual methods in the case of very thin cylindrical fibers.

In the present article a numerical method is proposed for the calculation of macroscopic regime contact angles from the shape of a liquid droplet spread onto a cylindrical monofilament. This method, which builds on earlier theoretical treatments by Yamaki and Katayama [1], and Carroll [2], very much improve the accuracy of the contact angle obtained. Experimental results with high-strength carbon, para-aramid, and glass fibers, are presented to demonstrate the high degree of accuracy of the method proposed.

The interfaces formed by evaporating copper, nickel, and chromium layers on polystyrene, polyvinyl alcohol, polyethylene oxide, polyvinyl methyl ether, polyvinyl acetate, and polymethyl methacrylate have been studied with x‐ray photoemission spectroscopy (XPS). The adhesion strengths of the metal films to the polymers were measured by a tensile‐pull test. At submonolayer coverages of the metals, the peak positions and widths of the metallic electron core levels measured with XPS vary significantly from one polymer substrate to another. Most of these variations can be accounted for in terms of changes in the atomic and extra‐atomic relaxation energies during the photoemission process. Much of this change is brought about when the metal atom deposited on an oxygen‐containing polymer interacts with the substrate oxygen and forms a metal‐oxygen‐polymer complex. The presence of this complex is verified by changes in the photoemission lineshapes of the substrate carbon and oxygen atoms. The XPS signatures of these various complexes are quite similar and suggest that they are chelate‐like complexes. The adhesion strength of any metal on an oxygen‐containing polymer is greater than on the oxygen‐free polystyrene. In general, the increased adhesion strength correlates with the presence of the metal‐oxygen chelate complexes.

The wettability of crystals, glasses, and even of water itself can be temporarily decreased by bringing ions of high polarizability into their surfaces. Base exchange experiments are described where the hydrogen ions present in the surface layers of bentonite (a clay mineral of high exchange capacity) and of a soda‐lime glass are replaced by different cations. This substitution seems to have no particular effect on the hydrophilic and rheological properties of the carriers as long as their surfaces are kept in contact with water. After drying, however, the surfaces which contain ions of high polarizability become hydrophobic, at least temporarily. A porous clay film will no longer absorb water instantaneously after having been treated with Ni²⁺, Mn²⁺, Hg²⁺, or similar ions with incomplete outer electron shells. Contact angles with water up to 70° could be observed for a short period for Hg²⁺ and Pb²⁺ clays.

Glass capillary tubes which have been treated with non‐noble gas‐type ions show a capillary rise which is much smaller than that observed with the tubes which have been treated with HCl and water only. This depression of the capillary rise, too, is temporary and can be observed only if the glass wall has been thoroughly dried previous to the experiment and if the capillary rise is measured in the upward direction.

An explanation is presented for these and allied phenomena on the basis of the polarization of ions in the strongly asymmetrical forcefields of interfaces. The experiments are correlated with the hysteresis of the contact angle and with observations concerning adhesion phenomena and catalytic activities of heavy metal ions at interfaces.

The effect of ion implantation including ion species (N₂ and C₃H₈⁺) and the fluences (1x10¹⁴-5x10¹⁵ ions/cm²) on the surface energy of ultrahigh molecular weight polyethylene (UHMWPE) were investigated. The total surface energy increases significantly after implanting with the fluence of 1x10¹⁴ ions/cm² regardless of ion species, then, the total surface energy slightly increases for N₂⁺ implanted UHMWPE and decreases slightly for C₃H₈⁺ implanted UHMWPE with a further increase of fluence. The structural changes of UHMWPE with different fluence for different ion species are very similar. The linear chains of UHMWPE are damaged and cross linking is generated after implantation. As the fluence increases, the polymer surface becomes more disordered, and the surface becomes hydrogenated amorphous carbon when the fluence exceeds 1x10¹⁵ ions/cm². The surface roughness increases with the increase of the fluence regardless of ion implantation species.

This paper presents and discusses particle behavior at solidification fronts from a thermodynamic point of view. Engulfing or rejection of particles embedded in a melt by solidification fronts depends on whether such quantities as the free energy of adhesion or of engulfing are positive or negative. As the relevant energy balances contain solid‐liquid interfacial tensions which are difficult to determine, these studies may also be viewed as tests for the validity of such data and the underlying theories used to determine them. In this paper, solid‐liquid interfacial tensions are derived from contact angle data and the equation of state approach for interfacial tensions [Neumann et al., J. Colloid Interface Sci. 49, 291 (1974)]. The thermodynamic predictions obtained in this way for approximately 60 systems agree very well with microscopic observations with particles in the range of 10–200 mm in diameter.

A triode glow discharge system was used for the plasma treatment of polytetrafluoroethylene (PTFE) films and the formation of plasma polymerized hexamethyldisiloxane (PPHMDS) films on PTFE films. The nitrogen plasma increased the surface tension of the PTFE films to about 40 dyn/cm by applying an rf voltage to the substrate electrode. The contact angle of water on the PPHMDS films with the rf voltage was changed to 40°∼90° by corona discharge exposure for 30 s at 6 kV. This reduction is due to the decarbonization and the oxidation of PPHMDS films.

Experimental results on plasma treatments of polysulfone and polyetherimide to improve the wettability of these polymers are presented. The plasma is characterized by optical emission spectroscopy. The wettability of the polymer surfaces were checked by contact angle measurements and ESCA is used to compare the surfaces before and after plasma treatment. Correlations between contact angle, concentration of oxygen at the surface, and optical emission intensity of the OH radical have been established. Optimization of operational plasma parameters leading to the best wettability of the treated samples is reported.

Polypropylene–nylon 6 10 composites were prepared by the in situ polymerization of the nylon monomers on polypropylene films. The adhesion between the nylon and the polypropylene was markedly improved by a brief corona discharge treatment of the films in nitrogen prior to coating. This improvement was demonstrated by an increase in the peel strength of the nylon coating and a decrease in brittleness of photo-oxidized compesites when corona treatment was used. Adhesive bonding between the nylon and substrate was sufficiently strong to cause cohesive failure in the corona-treated polypropylene. Only interfacial failure was observed at untreated surfaces. These effects were demonstrated by electron microscopy of the surfaces produced in peel tests. The effects of corona treatment on adhesive bonding characteristics of surfaces are discussed in terms of the chemical and physical changes observed in treated surfaces.

The effect of a remote nitrogen plasma on polyethylene and polystyrene was studied. The gas flow rate, the dilution of reactant gas, exposure times, and reactor base pressure were all found to have a large impact on the efficiency of nitrogen incorporation. Optimum conditions caused 18 atom % nitrogen to be incorporated within 20 seconds for polyethylene and 10 seconds for polystyrene. Studying a remote nitrogen plasma treated polyethylene sample over a period of 1 month indicated that except for a drop in the % N on initial exposure to air the concentration of nitrogen on the surface remained steady within the experimental limits. Angle resolved photoelectron spectroscopy indicated that nitrogen is incorporated to a depth below the analysis depth of XPS.

The use of plasma deposition to introduce sulfonate groups to the surface of a polyurethane was attempted. In previous work, the bulk incorporation of sulfonate groups was found to improve the blood contacting properties of the base polyurethane but physical properties in the hydrated state were adversely affected. Plasma deposition schemes involving ammonia and sulfur dioxide were utilized in an attempt to incorporate sulfonate groups. Surface characterization by X-ray photoelectron spectroscopy (XPS) and contact angle measurements was used to follow polymer surface rearrangement dynamics and to address the issue of plasma chemistry specificity. Concerns of reaction specificity were alleviated by using the plasma as a pretreatment which is followed by a chemical surface derivatization.

The efficiency of different techniques of obtain improved adhesion in polyethylene-aluminum laminates have been studied. Both surface treatments, such as thermal oxidation and corona discharge, and the use of copolymers with polar comonomers, i.e., vinyl acetate (EVA) and butyl acrylate (EBA), have been included. Thermal oxidation performed by high temperature extrusion including an ozone shower seems to be more effective than corona discharge. In a model experiment thermal oxidation was studied in more detail. The adhesion, as measured by a T-peel test, increased with the content of carbonyl measured by reflexion IR, except for relatively long thermal treatments. In the latter case molecular scission gave a large fraction of low molecular weight material with low cohesive strength. For EBA and EVA the peel strength increased linearly with the bulk concentration of comonomer from about 100 N/m for untreated polyethylene to 450 and 300 N/m, respectively, at 5 mol % comonomer. Corona discharge treatment of these copolymers had, however, a most remarkable effect on the adhesion properties. The increases, relative to untreated EBA and EVA, were much more dramatic compared to polyethylene, e.g., three to four and less than two times, respectively. The higher values obtained with EBA are suggested to be due to the conversion of acrylate groups into carboxylic acid. In the case of EVA, loss of acetic acid might instead decrease the content of polar groups.

Polymers formed from plasma-polymerized methane were employed to modify the surface properties of silicone rubber membrane. Polymers were evaluated based on the energy input parameter W/FM, where W is the discharge power, F is the monomer flow rate, and M is the molecular weight of the monomer. Dealing with the characteristics of plasma polymerization and the deposited polymer film, the effect of pumping rate on deposition rate and the coating thickness, surface energy, and gas permeabilities of methane-plasma-polymer-coated silicone rubber membrane were investigated in three plasma regions. Because more reactive species are expelled at high pumping rates, the monomer-deficient region is reached at lower W/FM in the high pumping rate system than that in the low pumping rate system. The composite parameter W/FM had a strong influence on coating thickness, gas permeability, surface energy, and the polar component of the surface energy but little effect on its dispersion component. Examination of gas permeabilities indicated that coating thickness was another important controlling factor on the properties of plasma polymer.

Surface graft polymerization of a hydrophobic monomer, 2,2,3,3,3-pentafluoropropyl methacrylate (5FMA), onto hydrophilic poly(vinyl alcohol) (PVA) and cellulose films was studied after corona discharge of the films. It was found that grafting strongly depended on the reaction medium; especially, addition of alcohol to the monomer greatly accelerated graft polymerization. For instance, when an ethanol/ water /5FMA mixture (65/25/10, by volume) was used as the polymerization medium. the PVA and cellulose films corona-discharged for a few minutes exhibited a high contact angle up to 100° after 30 min polymerization, the graft density being approximately 170 μg/cm² for cellulose and 80 μg/cm² for PVA. © 1993 John Wiley & Sons, Inc.
https://onlinelibrary.wiley.com/doi/abs/10.1002/app.1993.070481016

To draw a relationship between surface concentration of the siloxane segment and adhesion performance, surface properties of the polydimethylsiloxane—poly(methyl methacrylate) block copolymers(PDMS-b-PMMA) prepared via poly(azo-containing siloxaneamide)s and their PMMA blends have been studied by measurements of FT-IR spectra, water contact angle, ESCA spectra and 180° peel strength toward pressure-sensitive adhesive tape. The water contact angles of the chloroform-cast blend films increased abruptly with siloxane bulk concentrations, or siloxane contents, particularly, on the air-side surfaces to reach almost 100° in low siloxane content. A marked increase of the contact angle was observed in the blends containing siloxane chain length (SCL) of longer than 2000. ESCA data evidently confirmed for these blend systems that the siloxane segments with low surface energy were accumulated or enriched mainly on the air-side surface, and that, on the other hand, polar PMMA segments with high surface energy were oriented to the glass-side surface and the inside of the films. This surface accumulation behavior of the siloxane segments reflected the 180° peel strength, as a measure of adhesion performance. The water contact angle and 180° peel strength were unequivocally correlated to the siloxane surface concentration estimated from ESCA data. Conversely, in the compression-molded blend films made by a hydraulic press between a Teflon and a stainless steel plate, the extent of surface accumulation of the PDMS segment was lower than that of the chloroform-cast films, suggesting lower degree of segment migration in hot-press films, probably due to substrate surface energy and lower relaxation in the blend melts.

Polypropylene films were treated with chromic acid mixture. The change in the treated films was investigated by comparing change in amount of 2,4-dinitrophenylhydrazones formed in the treated films with their change in wettability with water. Oxidation of the film surface zone, partial breakdown of polymer in the film surface zone, and oxidation of surface zone bared from the film inner zone seemed to occur with increase in treatment time or with increase in treatment temperature.

Corona treatment of low-density polyethylene in oxygen or oxygen-containing gases produced bumps on the surface, while treatment in nitrogen, hydrogen, argon, or helium caused no detectable surface change. Bumps made by an oxygen corona increased in size with time and temperature of the treatment. The bumps were removed when a treated polymer sheet was dipped into solvents such as CCl₄, ethanol, or 0.2% aqueous NaOH. Infrared analysis indicated that most of the oxidized layer was eliminated from the polymer surface by solvent dipping and that the degraded products contained a substantial proportion of CH₂ groups. It is suggested that the bumps are caused by the migration of low molecular weight degradation products to charged areas of the polymer surface.