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

Based on the Corona process and a substitution of air with specific gaseous mixtures into the discharge area, the newly developed surface treatment ALDYNE™ offers both high level improvement and high flexibility to film converters. By grafting nitrogen-based chemical functions, it confers to the treated surface excellent properties such as high surface energy and high adhesion of coatings.

Without any preprocessing, polyester fabric has a lower ability to hold on water and inks due to the smooth morphology and chemistry property of polyester fibers. Therefore, patterns directly printed with pigment inks have poor color yields and bleed easily. Plasma surface treatment of polyester fabrics was carried out in composite atmosphere with air and 10% Ar under different experimental conditions. After plasma treatment the samples were printed with pigment inks. The results show that surface-modified polyester fabrics exhibited enhanced color yields and excellent pattern sharpness. SEM and XPS analyses indicated that this improved color performance was mainly contributed by not only the etching effect but also oxygen-containing polar groups induced onto fiber surfaces through plasma treatment. Thereby the surface modification of polyester fabrics using air/Ar plasma offers a potential way to fabric pretreatment for pigment inkjet printing with the advantages of environmental friendly and energy saving over traditional pretreatment methods.

In this work, polyamide (Nylon 6) fibers and films were treated under atmospheric pressure glow discharges (APGD) and the effects on the morphology and chemistry of the material were studied. The fibers were plasma treated with N ₂ , C ₂ H ₂ in He for (0.6–9.6) s at a frequency of 90 kHz, leading to the functionalization of the surface through the addition of new reactive chemical groups such as –COOH and –OH and changing the energy, chemical composition and wettability of the surface.Surface characteristics were examined via contact angle measurements, XPS, and SEM. Wettability tests revealed the improvement of the hydrophilic character of the surface as the water contact angle measured after the plasma treatments significantly decreased. The corresponding changes of the total surface energy were evaluated with a dynamic contact angle analysis system revealing a significant increase due to the exposure that can be mainly attributed to the increase of its polar component. Preliminary XPS results show a significant increase in oxygen content with the addition of carboxylic and hydroxylic groups and a decrease in the carbon content of the surface. Most importantly, the plasma modified nylon fibers and films exhibit a stable wetting behavior, even for weeks after being treated, suggesting that it is a promising technique to minimize aging phenomena.

In this work, the acrylic acid (AAc)-corona discharge was carried out on biaxially oriented polypropylene (BOPP) films by introducing AAc vapor into the corona region of a normal corona treater. Three different corona energies of 15.3, 38.2 and 76.4 kJ/m² were studied. Surface properties of treated films were compared with those of air-corona treated films prepared with the same corona energies. The change in chemical composition on the film surface was characterized by curve-fitting of the ATR-FTIR spectra. The wettability of treated films, before and after aging in different environments, was observed by water contact angle and surface free energy. The surface morphology of air- and AAc-corona treated films was investigated using SEM and AFM techniques. Adhesion of the treated films to some other substrate was determined with the T-peeling test. It was found that the hydrophilicity of all treated films increased with increasing corona energy. AAc-corona treated films showed greater wettability than did the air-corona treated films and could retain the surface hydrophilicity for more than 90 days of aging under ambient conditions. The surface morphology of BOPP films changed after corona treatment into a globular structure. The AAc-corona treated films showed rougher surfaces due to surface oxidation and polymer formation, whereas, air-corona treated films displayed a similar structure but of smaller size due to the formation of low molecular weight oxidized materials (LMWOM) arising from the degradation of BOPP films. AAc-corona treated films showed greater peel strength than did the air-corona treated films.

Plasma treatment is often used to modify the surface properties of polymer films, since it offers numerous advantages over the conventional surface modification techniques. However, plasma-treated polymer films have a tendency to revert back to the untreated state (aging process). Therefore, the stability of plasma-induced changes on polymer surfaces over a desired period of time is a very important issue. The objective of this study is to examine the effect of storage conditions (relative humidity and temperature) on the aging behavior in air of plasma-treated low density polyethylene (LDPE) films. Plasma treatment is performed using a dielectric barrier discharge (DBD) operating in different argon/water vapor mixtures at medium pressure (5.0 kPa). Results show that the aging process can be suppressed by storing the plasma-modified LDPE films at low temperature and by decreasing the relative humidity of the surrounding air. Adding water vapor in the plasma discharge has a positive influence on the aging process: lower plateau WCA values are found for plasmas containing a higher water vapor concentration and it takes a longer time to reach these plateau values. In this paper, it is also shown that storage first at a lower temperature and then aging at a higher temperature is not able to slow down the aging effect.

Polymers/metal laminates are often used to improve physical and mechanical properties, especially those required in building applications. A flat aluminum composite panel (ACP) consisted mainly of two thin metal sheets usually made of aluminum (Al) and a non-metal core, such as polyethylene (PE). The lack of adhesion associated with the low wettability of PE is a serious problem. An eco-friendly, dry, non-destructive corona treatment technique can be applied to solve this problem. In this work, the use of a corona treatment to enhance the adhesion properties of linear low-density polyethylene (LLDPE) was studied. The changes in surface and adhesion properties were thoroughly analyzed using various analytical techniques and methods to obtain the optimal parameters for corona discharge using contact angle measurements, Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and atomic force microscopy (AFM). AFM force adhesion measurements were used to analyze the effect of the corona treatment on the adhesion enhancement of LLDPE, and the peel tests confirmed a significant increase in peel resistance in the LLDPE/Al laminate. A synergy effect from using the corona treatment in combination with an ethylene acrylic acid dispersion primer was observed.

A Nylon-6,6 film has been treated using an atmospheric pressure air dielectric barrier discharge (DBD). The resultant surface modifications were studied using X-ray photoelectron spectroscopy (XPS), contact angle measurement and secondary ion mass spectrometry (SIMS). The surface oxidation arising in the DBD discharge was found to arise in two stages: in the first stage, the creation of the carbon sites singly bonded to oxygen is dominant, the second stage leads to further conversion of such lightly oxidised carbons to those more heavily oxidised. The marked increase found in the hydrophilicity of the surface post-treatment is in the main believed to be associated with the earlier outcome. Partial recovery of the surface contact angle values is found for the treated samples following extended storage in ambient air. The final contact angle obtained for the treated samples was ∼50°, still reduced significantly from that of 83.5° for the untreated material.

A uniform and smooth transfer of stresses across the polymer matrix/fiber interface is enhanced when adhesion between the matrix and fiber surface is optimized. In the absence of covalent bonds matching the Hansen solubility (cohesion) parameters (HSP) of the fiber surface with the HSP of a matrix polymer assures maximum physical adhesion to transfer loads uniformly. Plasma treatment of ultra-high-molecular-weight (UHMWPE) fibers is shown to significantly increase the amount of oxygen in the surface. There are two distinct types of surfaces in both the plasma treated and the untreated UHMWPE fibers. One type is typical of polyethylene (PE) polymers while the other is characteristic of the oxygenated surface at much higher values of HSP. The oxygenated surface of the plasma treated fibers has the HSP δ_D, δ_P, and δ_H equal to 16.5, 15.3, and 8.2, compared to the pure PE surface with HSP at 18.0, 1.2, and 1.4, all in MPa^½. The dispersion parameter has been lowered somewhat by the plasma treatment, while the polar and parameters are much higher. The HSP methodology predicts enhanced adhesion is possible by skillful use of anhydride and nitrile functional groups in matrix or tie polymers to promote compatibility in the system.

The wettability of materials depends strongly on their surfaces, and endowing them with expected wetting properties promotes their applications in various fields. In this work, the biodegradable and superhydrophilic poly(butylene succinate) (PBS) nanofibrous membranes were fabricated using a combination of electrospinning and oxygen plasma treatment for the first time. The surface morphologies, chemical composition and wettability of the PBS membrane were investigated. It was found that the plasma etched the fiber surface and the etching depth increased with the plasma treatment time. The membrane became superhydrophilic from hydrophobic upon treated with oxygen plasma and the water droplet could completely spread out within 0.5 s, which was mainly attributed to the introduction of oxygen-containing groups by plasma treatment rather than the enlarged surface roughness. Meanwhile, the speed of water spread out on the modified membrane was closely and reversely related to the density of membrane. The wettability differences between nanofibrous membrane and dense films were also pointed out, and the structure had great influence in the performance. Furthermore, the wetting stability of treated membrane was explored by monitoring the evolution of contact angle. The contact angle gradually increased with days due to the decreasing functional groups, and the ageing rate was dependent on the plasma exposure time. Even though the wettability of membranes changed fast in the first 10 days, surfaces were still remained moderately hydrophilic (contact angle ~50°) after a month. The investigation concentrated on the wettability of PBS nanofibrous membrane treated with oxygen plasma is beneficial to the creation of materials with desirable properties for various applications.

Polymers are commonly used in industry for packaging applications and as protective coatings but are sometimes unsuitable to use due to their low surface energies. For these latter applications, surface modification is usually necessary to improve wettability, printability and adhesive properties. In the past decades, plasma surface treatment of polymers has been extensively studied and different treatment conditions have been investigated. However, the influence of polymer crystallinity on plasma treatment effects is not well-known and therefore this study focuses on plasma treatment of PET foils with different degrees of crystallinity. The different PET foils are treated with a DBD discharge operating in air at medium pressure and the effect of polymer crystallinity on the treatment efficiency is studied in detail using contact angle measurements and atomic force microscopy (AFM). Also the ageing behavior of the different types of plasma-treated samples is investigated in this work. Results clearly show that the crystallinity of the PET foil influences both the plasma treatment effect as well as the ageing process of the samples. AFM analysis indicated that the DBD plasma homogeneously etches the surface of the amorphous PET foil resulting in smoother surfaces after plasma treatment, while for the more crystalline PET foil the etching effect is more randomly leading to rougher surfaces. As a result, amorphous polymer regions are most likely more prone to plasma etching than crystalline regions.

The food packaging industry demands cheap polymer films possessing a high barrier against permeation of gases, moisture and flavor. Candidates for the most successful materials fulfilling these requirements are newly developed laminates of biaxial oriented polypropylene (BOPP) films containing a thin inorganic barrier layer and possessing an oxygen permeability lower than 3 cm3/(m2 dbar) and a moisture permeability lower than 0.05 g/(m2 day). The thin barrier layers are produced by vacuum web coating of BOPP films. In order to achieve high barrier laminates, one key issue along the whole production chain — from film extrusion to lamination — is given by the surface properties of the non-coated films. Non-coated BOPP film surfaces were modified by different kinds of plasma pretreatment and characterized before the vacuum coating process. The functionality — as adhesion and permeation — of coated barrier films and final high barrier laminates was studied as a function of pretreatment parameters. The BOPP homopolymer or copolymer films were either pretreated subsequent to the film production by a standard corona atmosphere plasma or in situ before the vacuum web coating by an oxygen low-pressure plasma. The topography of non-treated and pretreated films was analyzed by atomic force microscopy (AFM) and the chemical surface properties by contact angle measurements as well as X-ray photoelectron spectroscopy (XPS). These BOPP films were vacuum web coated with aluminum (Al), aluminum oxide (AlOx) or silicon oxide (SiOx) and laminated with a two-component adhesive system. Typical pretreatment parameters of BOPP films necessary for high barrier laminates after coating and lamination could be identified.

A study has been undertaken in which both x-ray photoelectron spectroscopy (XPS) and Fast atom bombardment static secondary ion mass spectrometry (FAB-SSIMS) have been used to study the effects of remote nitrogen plasma treatment on polymers such as linear low-density polyethylene (LLDPE), poly(ethylene vinyl alcohol) (EVOH) and poly(ethylene terephthalate) (PET). For comparison, remote oxygen plasma treatment was also performed on LLDPE. A very rapid uptake of nitrogen was observed for all polymers. Negative FAB-SSIMS indicated CN⁻, CNO⁻ and C₂N fragments on each of the nitrogen plasma-treated polmers. Positive FAB-SSIMS spectra of plasma-treated LLDPE showed relatively high intensity, high mass fragments, thought to originate from additives. These were not observed for the other two polymers. Significant amounts of aromatic-type fragments were observed in the positive FAB-SSIMS spectra of all treated polymers. Surface stability studies have shown that for both nitrogen and oxygen plasma-treaed LLDPE there is a substantial decrease in the surface functionality on exposure to air. This effect was much less prevalent for EVOH and PET.

PTFE was treated with oxygen and argon plasmas and the effects of treatment were evaluated by actinometry, SEM, XPS, static SIMS and contact angle measurements. At short treatment times for both plasmas and at long treatment times for argon plasmas, chemical modification of the surface was dominant, while at longer oxygen plasma treatment times, surfaces are deeply etched but chemically equivalent to untreated PTFE. Interestingly, the change in surface chemistry is paralleled by a simultaneous variation in plasma chemistry, suggesting that the two vary accordingly. The wetting behaviour of treated surfaces is interopreted on the basis of current theories on surface dynamics and contact angle hysteresis.

The effects of flame treatment on the surfaces of a propylene-ethylene copolymer have been studied using XPS, contact angle measurement, vapour-phase derivatization and an adhesion test. The results obtained were compared to those from the homopolymer. An optimum air-to-gas ratios of ∼11:1 has been found. Close correspondence between water contact angle and oxygen concentration was found, with the exception of high oxygen concentrations. The orientation or migration of functional groups away from the surface has been proposed to cause the non-correspondence between water contact angle and oxygen concentration. Diiodomethane advancing contact angle was found to remain constant, independent of flame conditions. XPS analysis in conjunction with vapourphase derivatization with trifluroacetic anhydride (TFAA) suggests that up to 20% and 30% of the oxygen introduced in the surfaces is present as hydroxyl groups for propylene homopolymer and the copolymer, respectively. High adhesion levels of the flame-treated copolymer with a polyurethane-based paint were found. In most cases, the adhesion failure was complex, but involved the cohesive failure of the copolymer.

The changes induced on the surface of polypropylene homopolymer following flame treatment have been studied. Surface compositions were determined using x-ray photoelectron spectroscopy and compared to surface free energies estimated from contact angle measurements. The effect of air-to-gas ratio, total flow rate, contact time with the flame and the distance between the inner cone tip of the flame and the polymer have been investigated. Mild flame treatments were found to be effective in promoting the adhesion of polyurethane paints to the polypropylene. The adhesion between flame-treated polypropylene and the paint film was assessed using a composite butt test and the measured bond strengths were found to be well in excess of those obtained using solvent wiping or chlorinated polyolefin primers.

Corona discharge treatment (CDT) is a surface modification technique commonly used to treat plastic films prior to adhesive bonding, printing with inks, lamination to other films and other coating applications. In this study, the treatment conditions are, in energy terms, representative of those used in industrial and laboratory coating applications.

The physicochemistry of the surface of untreated and corona-discharge-treated biaxially oriented polypropylene (BOPP) film was investigated using a number of complementary surface analytical techniques: contact angle analysis; x-ray photoelectron spectroscopy (XPS); atomic force microscopy (AFM). This report describes the surface energetics, chemical functionality and morphology of polypropylene film before and after CDT. Both AFM and XPS were utilized, along with washing experiments, to investigate the presence of a weak boundary layer.

The surface energy was found, as expected, to increase with increasing energy of the corona. The functional groups incorporated onto the surface have been identified as hydroxyl [COH], peroxy [COO], carbonyl [CO], ester [COCO], carboxylic acid [HOCO] and carbonate [OC(O)O]. These groups are present in varying relative concentrations, depending on the energy of the corona utilized.

The morphology of the film changed after CDT. Initially, a fibrillar crystalline structure was observed, whereas after CDT a globular morphology became apparent. These globular features were attributed to low-molecular-weight oxidized material (LMWOM) created by CDT. The roughness of the film was not found to increase under the corona conditions employed.

Formation of LMWOM was found to be independent of treatment energy. However, two mechanisms have been suggested for its formation, dependent on the energy of treatment: below a threshold energy of ∼4 kJ m⁻², oxidation and scission of the inherent low-molecular-weight boundary layer present on polyolefin films is the dominant means for the formation of LMWOM; above 4 kJ m⁻², oxidation and scission of the polymer backbone is the main process.

This work provides a comprehensive reference around CDT of polypropylene film for industrial applications, while also informing how the optimal level of treatment can be determined. In the case of adhesion of silicones, it would be expected that optimal adhesion would be obtained where the maximum amount of oxygen incorporated was in a water-insoluble form. Copyright © 2002 John Wiley & Sons, Ltd.
https://analyticalsciencejournals.onlinelibrary.wiley.com/doi/abs/10.1002/sia.1217

XPS and contact angle measurement have been used to study oxygen–plasma-treated polypropylene (PP) surfaces aged at variable temperatures. Surface rearrangement leading to low wettabillity has been observed, without alteration of the surface composition, as determined by XPS. Experimental results have been interpreted in terms of internal rearrangements of a modified layer, <5 nm thick, formed on top of the PP and immiscible with it.

We also modelled the composition of the surface layer and calculated the relative mobility of modified and non-modified polymer chains. On this basis, the experimentally observed behaviour can be interpreted in terms of surface rearrangement driven by a compromise between striving for lower surface tension and maximizing inter-and intramolecular interactions, mainly hydrogen bonds.

The surface composition observed after treatment with plasma, corona, flame or other for enhancing surface tension is then time dependent. For this reason, the procedure used for surface analysis, namely the time allowed for surface equilibration, should be specified in reports.

A series of low-density polyethylene (LDPE) surfaces, chemically modified using a number of oxidative techniques employed for adhesion enhancement (pretreatments), have been studied by time-of-flight (ToF) SIMS and XPS. The methods consisted of corona discharge, flame, electrochemical, chromic acid, acid dichromate and acid permanganate treatment. All except flame treatment were performed under mild and fairly severe conditions to yield a range of surface chemistries. The XPS analysis, using high energy resolution and a refined approach to C 1s curve-fitting, provided some new insights into the quantitative assessment of the type and concentration of functional groups. Both positive and negative ion ToF-SIMS spectra were obtained at high mass resolution. The oxygen-containing fragments were identified by accurate mass analysis and subjected to a detailed comparison with the XPS results. No convincing relative intensity correlations could be identified that would allow particular secondary ion fragments to be associated strongly with particular functional groups (in this multi-functional surface situation). Inorganic residues resulting from wet chemical treatments were also investigated and here the two techniques were found to be more complementary. Copyright © 2003 John Wiley & Sons, Ltd.
https://analyticalsciencejournals.onlinelibrary.wiley.com/doi/10.1002/sia.1515

Extended chain polyethylene fibres have been treated in ammonia and oxygen lo-pressure gas discharges (plasmas) in order to enhance adhesion to epoxy and unsaturated polyester resins, respectively, and thus significantly improve fibre/resin interfacial properties in fibre-reinforced polymer composites. Ammonia plasma treatment results in the incorporation of amine functional groups onto the fibre suface. The treated fibre surface has been analysed using XPS and spectrophotometric techniques. Extended chain polyethylene/epoxy composites made from ammonia, plasma-treated fibres show a marked increase in interlaminar shear strength over composites made from untreated, corona-treated or oxygen plasma-treated fibres. The increase in fibre/resin adhesion after ammonia plasma treatment is confirmed by SEM observations of fracture surfaces, which show clean interfacial fracture surfaces in composites made from treated fibres. Fibres modified by oxygen plasma treatment contain a significant concentration of carbon-oxygen functionalities, which contribute to the polarity of the surface and hence increase wet-out by unsaturated polyester resins. The concentration and nature of carbon-oxygen species on the fibre surface have been determined by XPS. Pull-out tests on multifilament yarns embedded in a polyester resin confirm the high fibre/matrix adhesion achieved with the oxygen plasma-treated fibres compared to corona-treated or untreated fibres. Tensile properties of the fibres are reduced significantly after prolonged treatment in an oxygen plasma, while in an ammonia plasma the fibre strength is unaffected.

The effect of a cold remote N₂ plasma (CRNP) or N₂ + O₂ plasma (CRNOP) on poly(ether ether ketone) (PEEK) is studied. The amount of nitrogen or oxygen uptake and functionalities are determined by x-ray photoelectron spectroscopy (XPS). After CRNP treatment, the N/C and O/C atomic ratios are 0.301 and 0.333, respectively. Nitrogen functional groups are not detected by CRNOP treatment, and the O/C atomic ratio is then 0.785. The ageing process of the treated PEEK surface in the open air is investigated in both cases. For CRNOP treatment the O/C atomic ratio decreases by carbonate function departure, whereas for CRNP treatment the total amount of nitrogen and oxygen graft atoms goes through a maximum after 1 h of air exposure.

The effect of energy of corona discharge treatment (CDT) on the physico-chemistry of the surface of a polyester film was investigated systematically using a number of complementary surface analytical techniques: contact angle analysis, x-ray photoelectron spectroscopy, time-of-flight secondary ion mass spectrometry and atomic force microscopy. The energy of treatment can be controlled by either varying the speed of the treatment with constant power input or by varying the power of the treatment with constant speed. The changes in surface energy, surface chemistry and surface morphology of poly(ethylene terephthalate) (PET) induced by these two modes of CDT have been investigated.

The surface energy and the polar contribution of the film increased with increasing energy of corona. Phenolic-OH, carbonyl and carboxylic acid (HOC=O) have been identified as the functional groups incorporated onto the surface. Low-molecular-weight oxidized materials were observed in the form of a globular morphology on the surface of the film. By washing the film in methanol–water prior to surface analysis, it was shown that the oxygen content at the surface of the film decreased and the globular morphology was removed.

Differences in the surface energy of corona-treated PET films have been observed under similar corona energy conditions, depending on whether the sample was treated with constant speed or constant power. However, the total surface oxygen content was found to be similar at low-energy treatments. When the high-resolution C 1s XPS spectrum was peak fitted, the relative concentrations of functional groups introduced and other changes to the original polymer structure were shown to be independent of the mode of treatment.

These observations may be explained because although the total energy transferred from the power source to the PET under the conditions of ‘constant power, variable speed’ and ‘variable power, constant speed’ is theoretically the same, these experimental conditions are not interchangeable. At constant power, the concentration of active species, radiation and dielectric breakdowns in the discharge are independent of speed. However, in the case of constant speed, the concentration of active species, radiation and dielectric breakdown increase with increasing power, resulting in a different surface energy between the two sets of samples. However, because the composition of the active species will not change, the functional groups on the surface of the film will be the same across comparable energy levels, independent of mode of treatment. Copyright © 2002 John Wiley & Sons, Ltd.
https://analyticalsciencejournals.onlinelibrary.wiley.com/doi/abs/10.1002/sia.1429

A new approach to qualitatively predicting adhesion at a solid/solid interface is described. It is based on thermodynamic compatibility of the two adhering surfaces, but it overcomes the weaknesses of existing methods by using a full set of contact angle data and by assembling the data to reveal the main features of the set without loss of information. Adhesive performance data to support this approach are presented.

PET (Polyethylene terephthalate) films were modified with two different plasmas, nitrogen and oxygen, as a function of treatment times and RF powers. Firstly, the chemical composition of the plasma-modified PET films was investigated by XPS. In the case of nitrogen plasma, the formation of amine, imine and amide groups is detected. A slight diffusion of nitrogen-containing species into the PET bulk is also observed by angle-resolved XPS measurements. The appearance of alcohol, carbonyl and carboxyl functions is observed in the case of oxygen plasma treatment. After thermal deposition of an aluminium film, peel tests reveal that the Al/PET adhesion increases as follows: untreated < nitrogen plasma < oxygen plasma treatment.

Secondly, after sevderal successive depositions of thermally evaporated Al on oxygen plasma treated PET film, XPS was used to study the chemistry at the interface. The XPS results reveal that the additional reactive sites created on the PET surface by the treatment explain the significant improvement in Al/PET adhesion observed for plasma-modified samples.

Polystyrene and polyethyleneterephthalate surfaces were exposed to helium, oxygen/helium and nitrogen/hydrogen plasmas singly and in combination. The treated surfaces were evaluated by water contact-angle measurements and by x-ray photoelectron spectroscopy. It was found that the oxygen and nitrogen tend to graft to common carbon atoms, to form amide groups. The water wettability was found to correlate with the fraction of electronegative atoms incorporated into the surface. © 1998 John Wiley & Sons, Ltd.
https://analyticalsciencejournals.onlinelibrary.wiley.com/doi/abs/10.1002/%28SICI%291096-9918%28199808%2926%3A9%3C674%3A%3AAID-SIA414%3E3.0.CO%3B2-5

The virtues of chemical inertness and low surface energy which make polytetrafluoroethylene (PTFE) a valuable engineering polymer also account for the difficulty in achieving structural adhesive bonds. While plasma surface treatment has proven to be the most effective means of maximizing strength and permanence of adhesive bonds with the most inert of engineering polymers, a simple plasma treatment has proven elusive for PTFE. The following studies evaluate two very different plasma processes, activation and deposition, as a means to achieve reliable and high-strength structural adhesive bonds. Sodium naphthalene-etched PTFE is used as a control. Presented are ESCA data which support a theory that improvement is limited by a weakened boundary layer of the PTFE.

An experimental investigation of the surface modification of polytetrafluoroethylene (PTFE) by an Ar and Ar/O₂ plasma created with an atmospheric-pressure radio frequency (r.f.) torch is presented here. The surfaces were analyzed by atomic force microscopy (AFM), XPS and water contact angle (WCA) to get an insight of the surface morphology and chemistry. An increase of roughness is observed with the Ar/O₂ plasma treatment. The WCA analysis shows that these surfaces are more hydrophobic than pristine PTFE; a contact angle of 135° was measured. When a PTFE surface is treated by Ar plasma, no roughening or significant change of the surface morphology and chemistry of PTFE was observed. The effects of the Ar and O₂ fluxes on the PTFE surface treatment were analyzed, as well as the effect of the power and treatment time. The plasma phase was also analyzed by optical emission spectroscopy, and some correlations with the treatment efficiency of the plasma are made. The chemistry on the surface is finally discussed and the competition between etching and re-deposition chemical reactions on the surface is proposed as a possible explanation of the results. Copyright © 2010 John Wiley & Sons, Ltd. https://analyticalsciencejournals.onlinelibrary.wiley.com/doi/10.1002/sia.3384

Filter paper and greaseproof paper have been exposed to hydrogen or oxygen plasma. The paper surface composition was determined by ESCA measurements. The unmodified and modified papers then were laminated with polyethylene and the adhesive strength was measured. The hydrogen plasma treatment reduces the cellulose surface and forms low-molecular-weight degradation products. It is shown that the reduction of the cellulose surface has no influence on the adhesion, but the degradation products strongly decrease the adhesion. Oxygen plasma treatment increases adhesion, probably by removing low-molecular-weight wood resin from the surface and by forming covalent bonds across the interface.

In this paper, we present a study on the surface modification of polyethyleneterephthalate (PET) polymer by plasma treatment. The samples were treated by nitrogen and oxygen plasma for different time periods between 3 and 90 s. The plasma was created by a radio frequency (RF) generator. The gas pressure was fixed at 75 Pa and the discharge power was set to 200 W. The samples were treated in the glow region, where the electrons temperature was about 4 eV, the positive ions density was about 2 × 1015 m−3, and the neutral atom density was about 4 × 1021 m−3 for oxygen and 1 × 1021 m−3 for nitrogen. The changes in surface morphology were observed by using atomic force microscopy (AFM). Surface wettability was determined by water contact angle measurements while the chemical composition of the surface was analyzed using XPS. The stability of functional groups on the polymer surface treated with plasma was monitored by XPS and wettability measurements in different time intervals. The oxygen-plasma-treated samples showed much more pronounced changes in the surface topography compared to those treated by nitrogen plasma. The contact angle of a water drop decreased from 75° for the untreated sample to 20° for oxygen and 25° for nitrogen-plasma-treated samples for 3 s. It kept decreasing with treatment time for both plasmas and reached about 10° for nitrogen plasma after 1 min of plasma treatment. For oxygen plasma, however, the contact angle kept decreasing even after a minute of plasma treatment and eventually fell below a few degrees. We found that the water contact angle increased linearly with the O/C ratio or N/C ratio in the case of oxygen or nitrogen plasma, respectively. Ageing effects of the plasma-treated surface were more pronounced in the first 3 days; however, the surface hydrophilicity was rather stable later. Copyright © 2008 John Wiley & Sons, Ltd.

A study on surface modification of extended PTFE (polytetrafluoroethylene) foil after treatment in oxygen and nitrogen plasma is presented. PTFE was exposed to a weakly ionized, highly dissociated RF plasma with a high density of neutral atoms. The gas pressure was 75 Pa and the discharge power was 200 W. The appearance of the functional groups on the sample surface was determined by using high-resolution XPS. The results showed that oxygen plasma treatment did not cause any noticeable changes in the surface composition, while after nitrogen plasma treatment new functional groups were detected on the surface. Copyright © 2008 John Wiley & Sons, Ltd.

The choice of plasma gas can determine the interaction between material and plasma and therefore the applications of the treated materials. Nitrogen plasma can integrate functional groups such as primary amines and carbon dioxide plasma can incorporate carboxylic groups on the surface of polymers. For specific adhesion such as bio-adhesion, polar groups must be attached to the surface to enhance bio-film formation but the acidic or basic character also controls the adhesion mechanism.

Nitrogen and carbon dioxide plasmas are chosen to treat the surface of polystyrene and to show the effects of different functionalizations, i.e. attachment of acid or basic groups and degradation are compared in the present work.

Nitrogen-containing plasma induces mainly weak degradation at a rate of ∼0.13 µg cm⁻²s⁻¹. The roughness of the treated surface remains mostly unchanged. Functionalization leads to amino group attachment at a concentration of 1.2 sites nm⁻². We found that carbon dioxide plasma treatment shows more drastic degradation with a rate three times higher than that of nitrogen plasma and can create more functional groups (4.5 sites nm⁻²) at mild plasma treatment. However, the roughness of the surface is altered. In both cases the aromatic groups are degraded through the plasma treatment (again this is more evident with the CO₂ plasma) and the induced functionalization was shown to be quick (the upper monolayer of polystyrene film can be functionalized rapidly). Copyright © 2005 John Wiley & Sons, Ltd.
https://analyticalsciencejournals.onlinelibrary.wiley.com/doi/abs/10.1002/sia.2029

Surface treatment of monofilaments of polypropylene (PP), poly (ethylene terephthalate) (PET), and polyamide-6 (PA-6) was carried out by corona discharge. The process was conducted with an inter-electrode distance of 4 mm and treatment time in the range of 10 s to 120 s using a wire-plan system under controlled ambient conditions. The samples, before and after corona, were characterized through contact angle measurements, water absorption, Fourier transform infrared spectroscopy/attenuated total reflectance (FT-IR/ATR), scanning electron microscopy (SEM), and differential scanning calorimetry (DSC). After corona, the PP, PET, and PA-6 samples showed water absorption degrees of 9.4%, 8.5%, and 9.1%, respectively. Meanwhile, their dynamic contact angles reduced by 29.6% (PP), 27.9% (PET), and 18.6% (PA-6), while their corresponding surface energies were 71.1 mJ/m², 77.4 mJ/m², and 75 mJ/m², respectively. The FT-IR/ATR, SEM, and DSC results showed that corona treatment effectively improves the wettability of polymeric surfaces through oxidation and surface morphology alteration, but does not affect the bulk thermal properties.

Preliminary results are presented on hydrophilization, grafting, and metal plating of PP nonwovens using novel types of atmospheric-pressure low-temperature plasma sources, namely the "Surface Discharge Induced Plasma Chemical Processing" source and the plasma source based on a coplanar diffuse surface discharge. The plasma sources generate a thin (~ 0.3 mm) surface layer of plasma and are capable of meeting the basic on-line production requirements for surface activation and permanent hydrophilization of light-weight nonwovens.