A plasma treatment that renders asymmetric polysulfone membranes permanently hydrophilic is reported. Our modification strategy entails treating these membranes downstream from an inductively coupled rf plasma source. Contact angle measurements confirm that the membranes are completely wettable with water as a result of H₂O plasma treatment. More importantly, the hydrophilic modification is permanent as plasma-treated membranes remain wettable for more than 16 months after plasma treatment. This treatment achieves the desired change in wettability for microporous as well as ultrafiltration polysulfone membranes, illustrating the universality of this method. XPS analysis of treated membranes demonstrates this dramatic change in wettability is a result of chemical changes in the membrane induced by plasma treatment. Moreover, the membrane modification is complete as the plasma penetrates the thickness of the membrane, thereby modifying the entire membrane cross-section.

The influence of the gas mixture of oxygen and nitrogen on the treatment efficiency distribution is investigated. The treatment efficiency is evaluated by contact angle measurement on polypropylene (PP) samples placed in varying distance from the coplanar barrier discharge electrode module. A planar electrode operated with 4 kHz signal and power of typically 10–21 W is used for treatment. A strong variation of contact angle as a function of distance from the CDB electrode surface is observed for samples treated 4 s in nitrogen discharge. Contact angle changes within 0.3 mm from 37.9 to 62.5° and it reaches 94.1° for 1.5-mm distance. It is already very close to the value of 103° measured on untreated PP. Much smaller treatment depth is obtained for mixture of nitrogen and oxygen. The experiments are performed without gas flow.fferent plasma treatments in a rf

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.

Growing demands on the functionality of technical textiles as well as on the environmental friendliness of finishing processes increase the interest in physically induced techniques for surface modification and coating of textiles. In general, after the application of water-based finishing systems, the textile needs to be dried. The removing of water is energy intensive and therefore expensive. In contrast to conventional wet finishing processes, a plasma treatment is a dry process. The textile stays dry and, accordingly, drying processes can be avoided and no waste water occurs. Plasma treatments represent, therefore, energy efficient and economic alternatives to classical textile finishing processes. Within plasma processes, a high reactive gaseous phase interacts with the surface of a substrate. In principle, all polymeric and natural fibres can be plasma treated. For many years, mainly low-pressure plasma processes have been developed for textile plasma treatment. However, the integration of these processes, which typically run at pressures between 0.1 and 1 mbar, into continuously and often fast-running textile production and finishing lines is complex or even impossible. In addition, due to the need for vacuum technology, low-pressure processes are expensive. The reasons why plasma processes at atmospheric pressure are advantageous for the textile industry are in detail: • The typical working width of textile machines is between 1.5 and 10 meters. Textile-suited plasma modules need to be scalable up to these dimensions, which is easier for atmospheric-pressure techniques.• Textiles have large specific surfaces compared to foils, piece goods or bulk solids. Even with strong pumps, the reduced pressure which is necessary for low pressure plasma will only be reached slowly due to the desorption of adsorbed gases.

Corona discharge treatment of isotactic polypropylene surfaces in N₂ and CO₂ was investigated by contact angle measurements and ESCA. The electrical characteristics of the discharges as well as the influence of indirect parameters (moment of air contact and ageing time) and direct parameters (applied charge, electrical field strength and film temperature) on the surface modification were determined. These investigations showed that electrons, emitted by photo effect are the dominant charge carriers and the main cause of surface activation. The active species in the surfaces (presumably radicals) can either perform crosslinking and H-abstraction or react with the discharge gas. In the N₂-discharge the polymer radicals can only react with atomic or excited nitrogen whereas in CO₂ they also react with ground state molecules. If the samples are brought into air contact after discharge leftover radicals are oxidized by atmospheric oxygen. In addition a UV-radiation causing activation in a surface layer was found. The bulk of the polymer is not influenced by corona discharge.

The paper investigates the effect of corona discharge (CD) treatment on the properties of surface layer (SL) of polylactide (PLA) film. The modification of PLAwas carried out in the air and helium atmosphere and the results were compared on the basis of the assessment ofwettability, surface free energy (SFE) calculated using Owens-Wendt method aswell as the degree of oxidation (O/C) of the modified SL, determined by photoelectron spectroscopy.

Surface layer of com. polylactide (PLA) was modified with corona discharges and studied for contact angle (H2O, CH2J2) and the geometric structure (at. force microscopy). The surface free energy was caled, by using Owens-Wendt equation. The treatment resulted in a decrease in the contact angle and an Increase in the surface free energy of the PLA film.

The autohesion of polyethylene sheets was markedly improved by corona discharge treatments in oxygen, nitrogen, argon and helium. Equal bond strength was produced by an equal number of discharge cycles regardless of the time or frequency of application. At a given operating voltage the power consumed in a discharge rather than the chemical nature of a gas proved to be a factor controlling the enhancement of autohesion. The detrimental effect of the oxidation upon autohesion was noted after a prolonged treatment in an oxygen corona.

Low density polyethylene sheet was subjected to treatment by corona discharge in oxygen, nitrogen, helium and argon; in addition some sheets were treated with ozone gas. The bond strength between two similarly treated sheets was then measured using a commercial flexographic ink as an adhesive. The results showed that although surface oxidation improved both the ink adhesion and the wetting properties of polyethylene it is not a necessary prerequisite for good bonding. When the sheet was subjected to electrical discharge in nitrogen, argon or helium, considerable enhancement of ink adhesion was obtained without any detectable change in the surface chemistry of the polymer. The results indicate that ink adhesion after treatment in various gases follows closely the trends established previously in corona-induced autohesion of polyethylene. This suggests that the mechanism of bonding is similar in the two cases.

With increase in sample density, corona treatment was found to be decreasingly effective in enhancing the autohesion of polyethylene sheets. The effect of higher density could be offset in part by an increase in temperature of lamination. This parallel behaviour suggests that similar molecular mechanisms govern the phenomena of thermally-induced and corona-induced autohesion.

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.

X-ray photoelectron spectroscopy (ESCA), wettability measurements, and an ink adhesion test were used to characterize changes in the surface properties of air-corona-treated polypropylene (PP) films upon aging under a variety of storage conditions. No changes in ESCA O/C atomic ratios as a function of aging were observed for corona-treated PP films. The wettability data indicated a slight decrease in wettability upon aging. Aging did not affect ink adhesion for the particular PP and ink studied. The responses obtained were independent of the various film storage conditions employed. The slight decrease in wettability observed upon aging was attributed to reorientation of oxidized functionalities within the surface region.

—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.

Contact-angle measurements in air and water environments and X-ray photoelectron spectroscopy (XPS) were used to characterize the surface properties of air-corona-treated polypropylene (PP) and poly(ethylene terephthalate) (PET) films. Surface properties were examined as a function of the storage time at various temperatures. Corona treatment forms water-soluble, low-molecular-weight oxidized materials on both polymer films. Corona-treated PP and corona-treated PET films have markedly different responses to aging. For corona-treated PP stored at ambient temperatures, only a slight decrease in wettability was observed. This decrease was attributed to the reorientation of oxidized functionalities within the surface region. At elevated storage temperatures, migration of oxidized species out of the surface region occurred under some conditions. For corona-treated PET, extensive migration and reorientation of oxidized groups occurred even at ambient temperatures, leading to significant decreases in wettability and a loss of surface oxidation. The contrasts in the responses of PP and PET to corona treatment are primarily due to differences in the properties of the base polymer resins.

A cross-web non-uniformity ('laning') in the flame surface modification of polypropylene (PP) film was investigated using flame temperature measurements and Wilhelmy plate force measurements. To associate the cross-web non-uniformity in the flame treatment with specific features of the flame supported on an industrial 4-port ribbon burner, the temperature and force measurements were registered to a specific burner port. The Wilhelmy force measurements show that the upstream pair of ribbon-burner ports causes a slightly greater treatment of the PP surface than the corresponding downstream pair of ports. The average temperature experienced by the PP as the film traverses through the flame is noticeably higher along the down-web line of the upstream burner ports as compared with a line passing through the downstream pair. This greater average temperature correlates to an exposure to a greater concentration of the active species, such as OH radicals, that cause the surface oxidation of the PP.

Contact-angle measurements, the ASTM standard wetting test for polyolefin films, and X-ray photoelectron spectroscopy (XPS or ESCA) were used to characterize flame-treated polypropylene (PP) films. Two combustion models, STANJAN and PREMIX, were then used to determine the chemical and physical properties of the flames used to treat the PP films. Both the flame equivalence ratio and the position of the PP film in the flame are important variables in determining the extent of oxidation and improvement in wettability obtained by flame treating. The optimal equivalence ratio for the flame treatment of PP is 0.93, while the optimal luminous flame-to-film distance is 0-2 mm. Modeling of the combustion processes occurring in the flame provides evidence that the extent of treatment correlates closely with the concentrations of H, O, and OH radicals present in the flame. The extent of surface modification of the flame-treated PP does not appear to correlate with either the flame temperature or the concentraion of oxygen molecules. The mechanism of surface oxidation by flame treatment probably involves polymer-radical formation by O and OH, followed by rapid reaction of the polymer radicals with O, OH, and O₂.

Contact-angle measurements and X-ray photoelectron spectroscopy (XPS or ESCA) were used to characterize polypropylene (PP) films that were exposed to laminar premixed air: natural gas flames containing small quantities of nitrous oxide. During combustion, the nitrous oxide generates gas-phase nitrogen oxides that lead to the affixation of nitrogen-containing functional groups to the PP surfaces. Treatment of PP in nitrous oxide-containing flames also leads to an increase in surface oxidation and markedly improves wettability when compared with standard flame treatments. The chemical form of the nitrogen affixed to the PP surface is strongly dependent on the flame equivalence ratio. Fuel-lean flames tend to affix highly oxidized forms of nitrogen such as nitrate and nitro groups, while fuel-rich flames tend to affix less-oxidized nitrogen groups such as nitroso, oxime, amide, and amine. A computational model, SPIN, was used to elucidate the chemistry of the flame as it impinges upon the cooled PP surface. The SPIN modeling indicates that the principal reactive gas-phase species at or near the PP surface are O₂, OH, H, NO, NO₂, HNO, and N₂O. A number of possible reactions between these species and the PP can account for the formation of the various nitrogen functional groups observed.

Contact-angle measurements, atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS or ESCA) were used to characterize flame-treated biaxially oriented polypropylene (PP) films. While the surface of PP treated in a fuel-lean flame is highly oxidized, no watersoluble low-molecular-weight oxidized material (LMWOM) is formed by the flame treatment. A new computational model, SPIN, was used to determine the chemical composition of the impinging flames used to modify the PP. The SPIN model indicates that the species primarily responsible for the surface oxidation of the PP are OH, HO₂, H₂O₂, and O₂. Because the concentration of atomic O in the flame is low, there is little scission of the PP chains and no formation of LMWOM. AFM indicates that a 'nodular' surface topography is generated during the flame oxidation of the PP. The surface topographical features generated by flame treatment are probably the result of the agglomeration of intermediate-molecular-weight materials.

ESCA and contact-angle measurements were used to characterize the surfaces of polystyrene films exposed to SF₆, CF₄, and C₂F₆ plasmas. SF₆ plasmas cause loss of aromaticity in the polystyrene surface region via saturation of the phenyl ring and/or carbon-bond breakage and subsequent fluorination. C₂F₆ plasmas graft CF_x radicals directly to the polystyrene surface without necessarily destroying the aromaticity of the polymer. CF₄ plasmas appear to be intermediate in character between SF₆ and C₂F₆ plasmas.

ESCA and contact angle measurements were used to characterize the surfaces of polypropylene and glass substrates exposed to CF₄, CF₃H, CF₃Cl, and CF₃Br plasmas. The use of both organic and inorganic substrates allowed clear distinction between treatments which led to plasma polymerization and treatments which caused grafting of functional groups directly to the substrate surfaces. CF₄ plasmas were the only treatments studied which fluorinated polypropylene surfaces directly, without the deposition of a thin, plasma-polymerized film. CF₃H polymerized in a plasma, while CF₃Cl and CF₃Br plasmas caused chlorination and bromination of polypropylene surfaces, respectively. Correlations were made between the active species present in the plasmas and the surface chemistry observed on the treated polypropylene substrates.

ESCA and contact angle measurements were used to characterize the surfaces of Polyethylene and polypropylene films exposed to SF₆, CF₄, and C₂F₆ plasmas. None of these gases polymerized in the plasma. However, all plasma treatments grafted fluorinated functionalities directly to the polymer surfaces. SF₆ plasmas graft fluorine atoms to a polyolefin surface. CF₄ plasmas also react by a mechanism dominated by fluorine atoms, but with some contribution from CF_x-radical reactions. Although C₂F₆ does not polymerize, the mechanism of grafting is still dominated by the reactions of CF_x radicals. For all gases studied, the lack of polymerization is attributed to competitive ablation and polymerization reactions occurring under conditions of ion bombardment.

Advancing and receding contact angle measurements on polymer surfaces can be performed using a number of different methods. Ballistic deposition is a new method for both rapidly and accurately measuring the receding contact angle of water. In the ballistic deposition method, a pulsed stream of 0.15-μL water droplets is impinged upon a surface. The water spreads across the surface and then coalesces into a single 1.8-μL drop. High-speed video imaging shows that, on most surfaces, the water retracts from previously wetted material, thereby forming receding contact angles that agree with the receding angles measured by the Wilhelmy plate technique. The ballistic deposition method measures the receding angle within one second after the water first contacts the surface. This rapid measurement enables the investigation of polymer surface properties that are not easily probed by other wettability measurement methods. For example, meaningful contact angles of water can be obtained on the water-soluble low-molecular-weight oxidized materials (LMWOM) formed by the corona and flame treatment of polypropylene (PP) films. Use of the ballistic deposition method allows for a characterization of the wetting properties and an estimation of the surface energy components of LMWOM itself. Both corona- and flame-generated LMWOM have significant contact angle hysteresis, almost all of which is accounted for by the non-dispersive (polar) component of the surface rather than by the dispersive component. Surface heterogeneity is thus associated primarily with the oxidized functionalities added to the PP by the corona and flame treatments.

The comparison of corona-treated and flame-treated polypropylene (PP) films provides insight into the mechanism of these surface-oxidation processes. Atomic force microscopy (AFM), contact-angle measurements, and X-ray photoelectron spectroscopy (XPS or ESCA) were used to characterize surface-treated biaxially oriented PP. While both processes oxidize the PP surface, corona treatment leads to the formation of water-soluble low-molecular-weight oxidized materials (LMWOM), while flame treatment does not. Computational modeling of the gas-phase chemistry in an air corona was performed using a zero-dimensional plasma-chemistry model. The modeling results indicate that the ratio of O to OH is much higher in a corona discharge than in a flame. Chain scission and the formation of LMWOM are associated with reactions involving O atoms. The higher ratios of O to OH in a corona are more conducive to LMWOM production. Surface-oxidized PP exhibits considerable thermodynamic contact-angle hysteresis that is primarily caused by microscopic chemical heterogeneity.

The effects of low-molecular-weight oxidized materials generated by corona treatment on the adhesion properties of polypropylene (PP) film were investigated by adhering four different materials to the modified PP: a polyamide printing ink, vapor-coated aluminum, a synthetic-rubber pressure-sensitive adhesive, and an acrylate-based pressure-sensitive adhesive. The low-molecularweight materials enhanced the adhesion of the ink and acrylate-based material, but hindered the adhesion of the metal and the rubber-based adhesive. This seemingly contradictory adhesion behavior can be readily explained using the principles outlined by Brewis and Briggs in the 1980s.

Oxidation is the most common surface modification of polymers. This paper presents a comparison of five gas-phase surface oxidation processes: corona discharge, flame, remote air plasma, ozone, and combined UV/ozone treatments. Well-characterized biaxially oriented films of polypropylene and poly(ethylene terephthalate) were treated by each of the five techniques. The surface-treated films were then analyzed by X-ray photoelectron spectroscopy (XPS or ESCA), contact-angle measurements, and Fourier-transform IR (FTIR) spectroscopy. Corona, flame, and remote-plasma processes rapidly oxidize polymer surfaces, attaining XPS O/C atomic ratios on polypropylene of greater than 0.10 in less than 0.5 s. In contrast, the various UV/ozone treatments require orders of magnitude greater exposure time to reach the same levels of surface oxidation. While corona treatment and flame treatment are well known as efficient means of oxidizing polymer surfaces, the ability of plasma treatments to rapidly oxidize polymers is not as widely appreciated. Of the treatments studied, flame treatment appears to be the ‘shallowest’; that is, the oxygen incorporated by the treatment is most concentrated near the outer surface of the film. Corona and plasma treatments appear to penetrate somewhat deeper into the polymers. At the other extreme, the UV/ozone treatments reach farther into the bulk of the polymers.