Macroscopic wetting behavior is investigated theoretically from a thermodynamic viewpoint. The axisymmetric liquid meniscus formed under a conical solid surface is chosen as the subject of the theoretical analysis. Using the meniscus configuration obtained by the Laplace equation, the total free energy of the system is calculated. In the case of the half vertical angle of the cone φ = 90 deg (horizontal plate), the system shows thermodynamic instability when the meniscus attaches to the solid surface at the contact angle. This result, unlike the conventional view, agrees well with the practical wetting behavior observed in this study. On the other hand, when 0 deg < φ < 90 deg, the system shows thermodynamic stability at the contact angle. However, when the solid cone is held at a position higher than the critical height from a stationary liquid surface, the system becomes unstable. It is possible to measure the contact angle easily using this unstable phenomenon.

By fluorinating the surface of a polymer, the hydrogen bonding energy of a polar surface has been defined. The contact angles for three solvent classes; nonpolar, polar and hydrogen bonding, on a polar surface results in the separation of dispersion, polar, and hydrogen bonding energies. Both critical surface tension plots and theoretical calculations were used to define the surface energy for fluorinated polyethylene.

In adhesion applications, the rapid ageing of corona discharge pretreated surfaces is a well-known problem. Very often the corona treatment has to be renewed just before the application. Oxyfluorination process presents an interesting alternative to the corona discharge treatment. In this work, the outstanding ageing properties of the oxyfluorinated polyolefin surfaces are described on the basis of acid–base surface characteristics.

Polypropylene (PP) was exposed to various fluorine-gas mixtures and the fluorinated PP surfaces were characterised by means of X-ray photoelectron spectroscopy, Rutherford backscattering, attenuated total reflectance infrared spectroscopy, solid–liquid contact angles and thermogravimetric analysis. The surface wettability and surface tensions of PP, as functions of fluorination and oxyfluorination times, were also determined and discussed.

Surface fluorination is an interesting method of rendering surfaces more acceptable to adhesion. The adhesive properties of fluorinated and oxyfluorinated propylene surfaces, using epoxy, polyester and epoxy vinyl ester adhesives, are described. Lap shear tests were carried out to determine the strength of the adhesive joints.

In this work a DC plasma reactor was used for deposition of plasma polymerized coating from hexamethyldisiloxane-Ar (35/65%) mixture on polypropylene films. Surface energy parameter have been calculated using Owens-Wendt approaches with the sessile drop method are used to obtain the dispersive γ^D and polar γ^P component of surface free energy. The surface morphology of samples were investigated using scanning electron microscope. Also the chemical properties and wetability of prepared samples were tested using Fourier transform infrared spectroscopy and contact angle measurement, respectively.

Atmospheric low-temperature plasma was produced using dielectric barrier discharge (DBD) plate-type plasma reactor and high frequency of 13.56 Hz. The surfaces of polyimide films for insulating and packaging materials were treated by the atmospheric low-temperature plasma. The contact angle of 67 was observed before the plasma treatment. The contact angle was decreased with deceasing the velocity of plasma treatment. In case of oxygen content of 0.2 %, electrode gap of 2 mm, the velocity of plasma treatment of 20 mm/sec, and input power of 400 W, the minimum contact angle of 13 was observed. The chemical characteristics of polyimide film after the plama treatment were investigated using X-ray photoelectron spectroscopy (XPS), and new carboxyl group bond was observed. The surfaces of polyimide films were changed into hydrophilic by the atmospheric low-temperature plasma. The polyimide films having hydrophilic surface will be very useful as a packaging and insulating materials in electronic devices.

The modification of polymer surfaces by gas plasma treatment is reviewed. The two regimes of major interest are radio-frequency at low pressure (about 1 torr) and corona discharge at atmospheric pressure. The reactions produced by plasmas at polymer surfaces are due to both radiation and chemically active species created by electron bombardment. The major changes produced are in wettability, molecular weight, chemical composition, and surface morphology. The mechanisms of plasma polymerization and the properties of polymers produced by this technique are described. Finally, a brief outline is given of the industrial applications of plasma techniques.

The surface structures of low-density polyethylene (LDPE) film exposed to plasma or γ-ray in air were characterized by ESCA, IR, and EMS. The formation of trans C[dbnd]C bond on the LDPE film surface was observed by the exposure to ac air plasma (2 × 10⁻² torr, 19 W plasma power). Large amounts of O and N atoms as an amide structure were incorporated into the polymer surface by the plasma treatment. These plasma reactions occurred mainly in the amorphous region, and the polymer surface became rough enough to have a microdomain structure upon increasing the plasma treatment time up to 3 h. γ-Irradiation of LDPE in air only brought about O-atom incorporation as ketone and ether linkages. The polymer surface did not undergo etching under γ-irradiation as it did in plasma treatment.

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

Interfacial and surface tensions of polymers are important in the technology of plastics, coatings, textiles, films, and adhesives through their roles in the processes of wetting, adsorption, and adhesion. Because of experimental difficulty due to high viscosity, however, reliable measurements of these quantities were not reported until 1965 for surface tensions [l, 2] and 1969 for interfacial tensions [3, 4]. A body of scattered data has been accumulated in the literature. This review will evaluate, compile, and interpret these results.

The effect of nonpolymer-forming plasma (e.g., plasma of hydrogen, helium, argon, nitrogen) can be viewed as the following two reactions: 1) reaction of active species with polymer, and 2) formation of free radicals in polymer which is mainly due to the UV emitted by the plasma. The incorporation of nitrogen into the polymer surface by N₂ plasma and the surface oxidation by O₂ plasma are typical examples of the first effect. The latter effect generally leads to incorporation of oxygen in the form of carbonyl and hydroxyl and to some degree of cross-linking depending on the type of substrate; however, the degradation of polymer at the surface manifested by weight loss occurs in nearly all cases when polymers are exposed to plasma for a prolonged period of time. The effects of polymer-forming plasma is predominated by the deposition of polymer (plasma polymer); however, with some plasma-susceptible polymer substrates the effect of UV emission from polymer-forming plasma cannot be neglected. The mechanism of polymer formation can be explained by the stepwise reaction of active species and/or of an active specie with a molecule, and the chain addition polymerization of some organic compounds (e.g., vinyl monomers) is not the main route of polymer formation.

Plasma polymers contain appreciable amount of trapped free radicals; however, the concentration is highly dependent on the chemical structure of the monomer. In plasma polymerization, 1) triple bond and/or aromatic structure, 2) double bond and/or cyclic structure, and 3) saturated structure are three major functions which determine the rate of polymer formation and the properties of plasma polymers. The changes of some properties of plasma polymers with time are directly related to the concentration of trapped free radicals in plasma polymers. The amount of trapped free radicals in a plasma polymer is also influenced by the conditions of discharge; however, the UV irradiation from the polymer-forming plasma is not the main cause of these free radicals. Excess amount of free radicals are trapped during the process of polymer formation (rather than forming free radicals in the deposited polymer by UV irradiation). The properties of a plasma polymer is generally different from what one might expect from the chemical structure of the monomer, due to the fragmentation of atoms and/or functions during the polymerization process. This is another important factor to be considered for the modification of polymer surfaces by plasma polymerization.

A technique is described for performing temperature scanning measurements of the surface tension of polymer solutions. Measurements on solutions of a high molecular weight and a low molecular weight monodisperse polystyrene in tetralin, decalin, and n-hexadecane are reported. Whereas previous investigations of other physical properties of polystyrene solutions had revealed only one anomaly, at about 50°C in some cases and at about 70–80°C in others, the curves presented here show two anomalies, near 45°C and 70°C, respectively. These anomalies are tentatively attributed to conformational changes of the polymer chains.

Surface tension data can be used for estimating the solubility of polymers in liquids. By determining the apolar and the polar components of the surface tension of polymers and of solvents, the attractive free energy, δG₁₂₁, of a polymer (1) in a given solvent (2) can be established. By also taking into account the contactable surface area of two polymer molecules, immersed in a liquid, δG₁₂₁ can be expressed in units of kT. Solubility then is favored when -1.5 kT < δG₁₂₁ < 0 for apolar systems, and when -1.5 kT < δG₁₂₁ for polar systems. In polar solvents, hydrogen bonding can often increase δG₁₂₁ from <-1.5 kT to > + 1.5 kT. Positive values are frequently attained and this strongly shifts the behavior from insolubility to solubility. A number of proteins exemplify this behavior.

Unprinted, unsized, and sized security papers (SP) were treated under SiCl₄−, O₂−, and CF₄-cold plasma conditions. The plasma treatments were carried out in a stainless steel, parallel plate RF (30 kHz) reactor. The influence of plasma parameters, such as RF power, pressure, and treatment time, on the surface properties of plasma-modified security paper was examined. The newly gained surface characteristics were evaluated by Wilhelmy wettability measurements, x-ray photoelectron spectroscopy (ESCA), and scanning electron microscopy (SEM). Statistical experimental designs were used to understand the interactive effects of the plasma parameters. It was found that short treatment times and low RF power values produced the highest wettability with both SiCl₄ and O₂ plasmas regardless of the sizing. Printing and durability characteristics of the plasma-treated substrates were equivalent or superior to the standard samples. Mechanisms of plasma-induced surface modifications are discussed for the paper substrates.

The increasing use of polymeric materials in high technological fields, such as automotive, has forced the need to overcome some of their limitations by means of innovative processing. In the automobile industry a complex and critical process is used in order to enhance both wettability and adhesive properties of polypropylene bumper surfaces. Cold plasma treatment represents an efficient, clean and economic alternative to activate polymeric surfaces.

The present work deals with air cold plasma treatment of polypropylene surfaces. Particularly, the influence of AC electrical discharge cold plasma parameters on wettability and adhesion of polymeric surfaces was studied. Also, the nature of the relationship between wettability and adhesion was investigated. Owing to the complexity of plasma–workpiece interaction, an experimental approach was followed. A set of process variables (voltage, time and air flow rate) was identified and used to conduct some experimental tests on the basis of design of experiment techniques. The experimental results show that the proposed plasma process may considerably increase polypropylene wettability and adhesion properties. These outcomes represent the first step in trying to optimise the polymeric adhesion by means of this non-conventional manufacturing process.

Results from x-ray photoelectron spectroscopy (XPS or ESCA), low-energy ion scattering spectrometry (LEIS or ISS); and Fourier transform infrared spectroscopy (FTIR) analyses are presented for unmodified and modified poly (methylmethacrylate) (PMMA) polymer films. Analysis of the unmodified PMMA polymers (isotactic, syndiotactic, and atactic) via ESCA, ISS, and FTIR, established the surface composition, bonding, and functionality before the modification was employed. An rf-plasma glow discharge created from an Ar/H₂gas mixture at different exposure times and power levels was used to treat the polymer surface. Subsequent ESCA, ISS, and FTIR analyses of these modified PMMA's show the effects of surface modification in terms of a model of structural differences, over a limited depth (50–100 Å). The composition and functionality changes of the resulting surfaces are discussed with respect to proposed mechanisms of the plasma reaction and differences in tacticity of the reactant. A two-step reaction mechanism involving reactive decarboxylation/reduction followed by H₂O adsorption is proposed to understand the spectroscopic results.

Results from the x-ray photoelectron spectroscopy (XPS or ESCA), ion scattering spectroscopy (ISS or LEIS), and Fourier transform infrared spectrometry (FTIR) analyses are presented for unmodified and modified poly (methylmethacrylate)/poly (methacrylic acid) (PMMA/PMAA) copolymer films. Analyses of the unmodified PMMA/PMAA copolymer series, via ESCA, ISS, and FTIR, established the surface composition and functionality of the PMMA/PMAA copolymers before the H₂O/Ar rf-plasma treatment was employed. The ESCA, ISS, and FTIR analysis of these modified PMMA/PMAA copolymers show that surface modification over a limited depth (50–200 Å) has occurred. The composition, bonding, and functionality changes of the surfaces are discussed. A two-step modification mechanism (surface reduction of the PMMA/PMAA copolymer followed by H₂O adsorption) is proposed to interpret the spectroscopic results.

Ar⁺1 ion irradiation on a polycarbonate (PC) surface was carried out in an oxygen environment in order to investigate the effects of surface chemical reaction, surface morphology, and surface energy on wettability of PC. Doses of Ar⁺ ion were changed from 5 × 10¹⁴ to 5 × 10¹⁶ at 1 keV ion beam energy by a broad ion beam source. Contact angle of PC was not reduced much by Ar⁺ ion irradiation without flowing oxygen gas, but decreased significantly as Ar⁺ ion was irradiated with flowing 4 sccm (ml/min) oxygen gas and showed a minimum of 12° to water and 5° to formamide. A newly formed polar group was observed on the modified PC surface by Ar⁺ ion irradiation with flowing oxygen gas, and it increased the PC surface energy. On the basis of x-ray photoelectron spectroscopy analysis, the formed polar group was identified as a hydrophilic CO bond (carbonyl group). In atomic force microscopy (AFM) study, the root mean square of surface roughness was changed from 14 Å to 22–27 Å by Ar⁺ ion irradiation without flowing oxygen gas and 26–30 Å by Ar⁺ ion irradiation with flowing 4 sccm oxygen gas. It was found that wettability of the modified PC surface was not greatly dependent on the surface morphology, but on an amount of hydrophilic group formed on the surface in the ion beam process.

Ion irradiation with various oxygen flow rates has been carried out to improve the wettability of polymethylmethacrylate (PMMA) to water and to enhance the adhesion between Al and the polymer. Ar+ ion and oxygen ion were irradiated on the polymer, and amounts of ions were changed from 5 × 1014 Ar+/cm2 to 5 × 1016 Ar+/cm2 by a broad ion beam source. Oxygen gas from 0 ml/min to 7 ml/min was flowed near the polymer surface during the ion irradiation, and the energy of ions was changed from 500 eV to 1500 eV. The wetting angle was reduced from 68° to 49° with the Ar+ ion irradiation only at 1 keV energy, to 43° with the oxygen ion irradiation, and dropped to 8° with Ar+ ion irradiation with flowing 4 ml/min oxygen gas near the polymer surface. Changes of wetting angle with oxygen gas and Ar+ ion irradiation were explained by a two-step chemical reaction among polymer matrix, energetic ions, and oxygen gas. The effects of Ar+ ion and oxygen ion irradiation were explained by considering formation of hydrophilic groups due to a reaction between irradiated polymer chain by energetic ion irradiation and blown oxygen gas, and enhanced adhesion between Al and PMMA was explained by the formation of electron acceptor groups in polymer and electron donors in metal, and by the chemical reaction in the interface between irradiated polymer surface and deposited metal.

Aramid and extended-chain polyethylene fibres have been treated in ammonia and oxygen plasmas in order to enhance adhesion to vinylester resins and thereby improve fibre/resin interfacial properties in composites made from these materials. For both aramid/vinylester and extended-chain polyethylene/vinylester composites, the plasma treatments result in significant improvements in interlaminar shear strength and flexural strength. Extended-chain polyethylene/vinylester composites also exhibit increased flexural modulus. Scanning electron and optical microscopic observations have been used to examine the microscopic basis for these results, which are compared with results previously obtained for aramid/epoxy and extended-chain polyethylene/epoxy composites. It is concluded that the increased interlaminar shear and flexural properties of vinylester matrix composites are due to improved wetting of the surface-treated fibres by the vinylester resin, rather than covalent chemical bonding.

A study of the effects of flame treatments on a high-impact polypropylene has been performed. Both physico-chemical and mechanical properties have been investigated. The surface chemical composition has been determined by XPS, while the surface tension and the polarity were obtained through contact angle measurements. A remarkable agreement in the behaviour of chemical composition and polarity has been found, emphasizing the role of carbonyl and carboxyl groups. The adhesion of treated and untreated samples to paint coatings hua been mechanically tested. The force of adhesion remains quite constant after the first flame treatment. This suggests the importance of chemical interactions of the coating with the first layers of the polymer.

Static secondary ion mass spectroscopy (fast atom bombardment mass spectroscopy), (SIMS (FABMS)) and Fourier transform infrared-photo-acoustic spectroscopy (FTIR-PAS) studies have been performed on samples of polypropylene subjected to different numbers of flame treatments. SIMS spectra allowed us to identify unambiguously the site of oxidation in the methyl pendant groups, because of the striking decrease in the intensity of the methyl fragment in positive-ion spectra. The behaviour of the surface concentrations of hydroxyl, formyl and carboxyl groups as a function of the number of flame treatments has also been observed, leading us to an hypothesis supporting the effectiveness of hydroxyl groups in promoting paint adhesion. FTIR-PAS spectra did not show evident changes on passing from untreated to flame-treated samples. This negative evidence is also important: it implies a limited depth of oxidation. In the light of previous XPS results and FTIR-PAS characteristics (thickness of the observed layer and sensitivity) we suggest a depth of oxidation of some 10 to 20 nm.

Previously published pull-out adhesion results have been substantiated by more extensive studies of chemical and plasma treatment. Particular attention has been paid to the affect of geometrical variables on the values of adhesion obtained. The effect of strain rate has also been examined. Most of the results can be understood on a semi-quantitative basis by a simple extension of lap joint theory.

X-ray photoelectron spectroscopy showed that a normal flame treatment caused a high level of oxidation in low-density polyethylene. 0.02% of the antioxidant 2,6-ditertbuty-p-cresol did not reduce the degree of oxidation or the level of adhesion in contrast to the extrusion of low-density polyethylene. It is estimated that the depth of oxidation is between 40 and 90 Å which is much less than for a moderate chromic acid treatment or with extrusion. There were no significant changes in the XP-spectra or adhesion levels of flame treated samples after 12 months.

The interfacial adhesion of ultrahigh-modulus polyethylene (UHMPE) fibre–vinylester composites was improved by the oxygen plasma treatment of the UHMPE fibre. The chemical functional group formations on the UHMPE fibre surface by oxygen plasma treatment were analysed using diffuse reflectance Fourier transform infrared spectroscopy and the morphological changes of the UHMPE fibre surface by plasma etching were observed by scanning electron microscopy. The wettability enhancement by the chemical functional group formation and the mechanical interlocking due to the micropits were important factors in improving the interfacial adhesion of the UHMPE fibre–vinylester composites by oxygen plasma treatment. In order to investigate the relative importance of the two factors, wettability enhancement and mechanical interlocking, in the improved interfacial adhesion of the UHMPE fibre–vinylester composites, nitrogen plasma treatment was also performed. Nitrogen plasma treatment of the UHMPE fibre was proved to be effective in the formation of the micropittings and ineffective in the chemical functional group formation in comparison with the oxygen plasma treatment. The interlaminar shear strengths of the nitrogen-plasma-treated UHMPE fibre–vinylester composites showed almost the same value as those of the oxygen-plasma-treated UHMPE fibre–vinylester composites. The wettability enhancement and mechanical interlocking are important in the improvement of interfacial adhesion of UHMPE fibre–vinylester composites by plasma treatment and mechanical interlocking seems to be more important.

The influence of substrate roughness on wettability has been investigated at room and high temperatures using sixteen material combinations, mostly liquid metals and solid ceramics but also water, glycerol and solid nickel. The contact angles assumed by both wetting and non-wetting drops of all but two material combinations increased linearly with the relative steepness of the surface features, the effect being less for experiments conducted at high temperatures. In contrast, the contact angles of good wetting drops of glycerol and exceptionally good wetting drops of Easy-flo decreased when their silica and nickel substrates were roughened. Similarly, contact angles of both wetting and non-wetting drops were decreased by ultrasonic vibration. The experimental data can best be interpreted in terms of the metastable equilibrium configuration models in which an advancing liquid front has to overcome energy barriers associated with surface features. This occurs more readily if these barriers are small relative to the energy of the liquid which our data suggest can be equated with the enthalpy of the liquid. This interpretation enables the effects of substrate roughness at one temperature or with one liquid to be used to predict behaviour at other temperatures and with other liquids.

In the present paper, the following topics are reviewed in detail: (a) the available adhesives, as well as their recent advances, (b) thermodynamic factors affecting the surface pretreatments including adhesion theories, wettability, surface energy, (c) bonding mechanisms in the adhesive joints, (d) surface pretreatment methods for the adhesively bonded joints, and as well as their recent advances, and (e) combined effects of surface pretreatments and environmental conditions on the joint durability and performance. Surface pretreatment is, perhaps, the most important process step governing the quality of an adhesively bonded joint. An adhesive is defined as a polymeric substance with viscoelastic behavior, capable of holding adherends together by surface attachment to produce a joint with a high shear strength. Adhesive bonding is the most suitable method of joining both for metallic and non-metallic structures where strength, stiffness and fatigue life must be maximized at a minimum weight. Polymeric adhesives may be used to join a large variety of materials combinations including metal-metal, metal-plastic, metal-composite, composite-composite, plastic-plastic, metal-ceramic systems. Wetting and adhesion are also studied in some detail in the present paper since the successful surface pretreatments of the adherends for the short- and long-term durability and performance of the adhesive joints mostly depend on these factors. Wetting of the adherends by the adhesive is critical to the formation of secondary bonds in the adsorption theory. It has been theoretically verified that for complete wetting (i.e., for a contact angle equal to zero), the surface energy of the adhesive must be lower than the surface energy of the adherend. Therefore, the primary objective of a surface pretreatment is to increase the surface energy of the adherend as much as possible. The influence of surface pretreatment and aging conditions on the short- and long-term strength of adhesive bonds should be taken into account for durability design. Some form of substrate pretreatment is always necessary to achieve a satisfactory level of long-term bond strength. In order to improve the performance of adhesive bonds, the adherends surfaces (i.e., metallic or non-metallic) are generally pretretead using the (a) physical, (b) mechanical, (c) chemical, (d) photochemical, (e) thermal, or (e) plasma method. Almost all pretreatment methods do bring some degree of change in surface roughness but mechanical surface pretreatment such as grit-blasting is usually considered as one of the most effective methods to control the desired level of surface roughness and joint strength. Moreover, the overall effect of mechanical surface treatment is not limited to the removal of contamination or to an increase in surface area. This also relates to changes in the surface chemistry of adherends and to inherent drawbacks of surface roughness, such as void formations and reduced wetting. Suitable surface pretreatment increases the bond strength by altering the substrate surface in a number of ways including (a) increasing surface tension by producing a surface free from contaminants (i.e., surface contamination may cause insufficient wetting by the adhesive in the liquid state for the creating of a durable bond) or removal of the weak cohesion layer or of the pollution present at the surface, (b) increasing surface roughness on changing surface chemistry and producing of a macro/microscopically rough surface, (c) production of a fresh stable oxide layer, and (d) introducing suitable chemical composition of the oxide, and (e) introduction of new or an increased number of chemical functions. All these parameters can contribute to an improvement of the wettability and/or of the adhesive properties of the surface.

This study concerns the surface and adhesive properties of isotactic polypropylene (iPP) modified by an electric discharge plasma and affected by long-term hydrophobic recovery of the polymer surface after modification. The investigations were focused on the change in polarity of the modified polymer expressed by the polar fraction as well as on the decrease in the surface free energy, its polar component and mechanical work of adhesion (A _m) to polyvinyl acetate. A _m of modified iPP to polyvinyl acetate as a function of polar fraction can be described by a mathematical formula. It has been confirmed that the most intensive decrease in the surface and adhesive properties investigated is produced by the long-term hydrophobic recovery of the polymer appears in the course of the first 30 days after its modification. During subsequent aging the process of polymer hydrophobic recovery proceeds more slowly. It has been found that the value of surface and adhesive properties of iPP as well as the dynamics of the decrease in these properties during hydrophobic recovery of the surface after modification is, in the main, dependent on the iPP crystallinity.

A study of the durability of corona discharge plasma effects on a polymer surface was investigated in this work. We used the corona discharge plasma technique to modify the wettability properties of low density polyethylene (LDPE) film and evaluated the influence of relative humidity and temperature on the aging process with three different storage conditions. The effects of the aging process on the plasma-treated surface of LDPE film were quantified by contact angle measurements, Fourier-transformed infrared spectroscopy, and X-ray photoelectron spectroscopy. The results obtained with these techniques have allowed us to determine how the aging process promotes changes in the plasma-treated surface by decreasing its wettability and taking place a remarkable hydrophobic recovery process.

Hydrophilicity of polyethylene modified by electric discharge in the course of aging was investigated. The experiments were carried out with the foils of low-density polyethylene (PE) containing additives as well as with additive-free foils. Antiblocking or sliding agents, antioxidants and antistatic agents were used as additives. The results showed that the absence of additives in PE was responsible for the higher degree of modification of PE foils by corona discharge when compared with the polymer containing additives. The value of surface free energy (SFE) found after 30 days of aging of the modified PE foils was lower than the value recommended for inking the printing foils.

The change in adhesive properties of discharge plasma-modified biaxially oriented polypropylene was not very strong. Very low changes were detected in free surface energy (FSE) values; more intensive was the decrease in the polar contribution to FSE, polar fraction and the mechanical work of adhesion to polyvinyl acetate. After 30 days of aging of the biaxially oriented polypropylene foils, the measured value of FSE was suitable for printing. It has been determined that the correlation between mechanical adhesion work to polyvinyl acetate and polar fraction of polypropylene modified by discharge plasma is linear.

Ultrahigh molecular weight polyethylene fibres have been treated in nitrogen plasma at atmospheric pressure. The plasma was generated by a pulsed electric discharge on the fibre surface. Fibre/rubber matrix interfacial adhesion was improved substantially by the plasma treatment. Zeta-potential measurements indicate an increase in hydrophilicity and basic groups density on the treated fibre surface. EPR spectrometry study reveals creation of peroxy type radicals by the plasma treatment.

Polypropylene electrets 20-μm thick obtained in a corona discharge were studied. After the electrets were charged, they were put into a vacuum chamber at various pressures and the electret surface potential was measured over a 1-h period. A desorption from the electrets is suggested to explain the results obtained.

Oxygen plasma treatment was used to change the hydrophobic polysulfone ultrafiltration membrane to the hydrophilic membrane. The contact angle of water decreased with increasing the oxygen plasma treated time of polysulfone membrane and was saturated with 20 s of oxygen plasma treated time. Functional groups introduced by oxygen plasma treatment were examined using X-ray photoelectron spectroscopy (XPS) and zeta potential of oxygen plasma treated polysulfone membrane was measured using electrophoretic light scattering (ELS) spectrometer. O/C ratio increased from 33 to 50% and isoelectric point (IEP) of membrane surface increased from pH 3 to 4.5. For oxygen plasma treated polysulfone membrane, the flow rates of pure water and gelatin solution increased at all pH range and plasma treated membranes showed less fouling at membrane surface. The mechanisms of reduced fouling and improved cleaning efficiency of oxygen plasma treated polysulfone membrane were also studied.

Nitrogen-based plasma systems such as N₂, NH₃, Ar/NH₃, and O₂/NH₃ were used to modify microporous polyethersulfone membranes. Treatments were designed to alter the surface chemistry of the membranes to create permanently hydrophilic surfaces. Contact angle measurements taken initially, as well as 1 year post-treatment confirmed that treatments using O₂/NH₃ plasmas (with a 5:3 gas flow ratio) were successful in achieving our designed goals. Analyses by FT-IR and XPS established the incorporation of NH_x and OH species in the PES membranes. Moreover, the plasma penetrates the thickness of the membrane, thereby modifying the entire membrane cross-section. Optical emission spectroscopy studies of excited state species present in the modifying gases revealed the presence of OH^*, which was not present in a 100% ammonia plasma, suggesting OH^* must play a critical role in the membrane modification process. Investigations using bubble point analysis, differential scanning calorimetry, and scanning electron microscopy demonstrate there is no damage occurring under these specific treatment conditions. The usefulness of this treatment is revealed by increased water flux, reduced protein fouling, and greater flux recovery after gentle cleaning when compared to an untreated membrane.