Atmospheric plasmas have traditionally been used as a non-chemical etching process for polymers, but the characteristics of these plasmas could very well be exploited for metals for purposes more than surface cleaning that is presently employed. This paper focuses on how the corona discharge process modifies aluminium AA 1050 surface, the oxide growth and resulting corrosion properties. The corona treatment is carried out in atmospheric air. Treated surfaces are characterized using XPS, SEM/EDS, and FIB-FESEM and results suggest that an oxide layer is grown, consisting of mixture of oxide and hydroxide. The thickness of the oxide layer extends to 150–300 nm after prolonged treatment. Potentiodynamic polarization experiments show that the corona treatment reduces anodic reactivity of the surface significantly and a moderate reduction of the cathodic reactivity.

This work concerns the ageing effect of the atmospheric plasma and corona treatments when used to treat paper substrates. Pigment coated and surface sized papers were modified using two types of atmospheric plasma equipment; one at the pilot scale and one at the laboratory scale. In addition, the plasma treatments were compared to conventional corona treatment. Surface energy was estimated by contact angle measurements and surface chemistry by X-ray photoelectron spectroscopy (XPS) as a function of the time during three months. The treatments increased surface energy and oxidation level of surface for both papers. The ageing effect could be detected only in the surface energy, whereas the oxidation level remained stable during the twelve weeks. The decay in surface energy was faster during the first weeks of storage and subsequently leveled off leading to a permanent change. The permanent change was explained as a contribution of oxygen containing polar molecular groups, which were detected by XPS. The ageing effect was suggested to originate from already existing polar molecular groups, which have rotated on the surface by plasma-related process and then rotate back into the material in time. A part of the decay was also explained by the plasma cleaning model, in which the ageing effect occurred through re-contamination. Paper is a multicomponent system, where the constituents that have the lowest surface energy were suggested to migrate to paper surfaces.

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 surface chemistry and surface energies of materials are important to performance of many products and processes—sometimes in as yet unrecognized ways. This article has been written for the researchers who wish to calculate solid surface energy (SE) from contact angle data. In this article, we describe various methods of calculations and their assumptions. The theoretical and experimental approaches for understanding the solid surface free energy using various methods are discussed in this article. Researchers concerned with many fields such as printing, dyeing, coating, adhesion, pharmaceuticals, composite materials, textiles, polymers, and ceramics should have interest in this topic. SE calculated by various methods for polyethylene surface treated in air plasma is discussed. Using contact angle data, the values of surface roughness using Wenzels equation, have been obtained and correlated to surface roughness calculated from AFM data.
© 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008 https://onlinelibrary.wiley.com/doi/abs/10.1002/app.27446

The influence of pigment shapes and pigment blends on the surface energy was investigated and compared with the surface chemistry of pigmented latex coatings. The coatings were made of different volume ratios of two pigments: plate-like kaolin clay pigment and prismatic precipitated calcium carbonate (PCC) pigment. These were mixed together with carboxylated styrene–butadiene–acrylonitrile latex (SBA), and applied over nonabsorbent substrates as well as absorbent substrates. The composition of the surface of the coatings was investigated by X-ray photoelectron spectroscopy (XPS). Two approaches were used to estimate the total surface energy and the components of the coatings: a conventional approach—“the Kaelble approach”—and a more modern approach—“the van Oss approach.” Pigment blends with different shapes and increments caused a change in the surface chemistry and the surface energy of the latex coatings. As the prismatic PCC pigment particles increased in the kaolin/SBA coating system, the SBA latex content at the coating surface increased and the total surface energy of the coating decreased. This is valid for both nonabsorbent as well as absorbent substrates. It was found that there was a strong correlation between the surface energy and the surface composition. The surface energy of the coatings estimated by the Van Oss approach was always lower than that estimated by the Kaelble approach. Colloidal interactions between pigment–pigment and/or pigment–binder were thought to play an essential role in determining the final coating surface energy and its components. Changes in the surface latex content and the surface energy due to the different pigment blends investigated were found to fit straight-line equations.

Poly(tetrafluoroethylene) (PTFE) surfaces are modified with remote and direct Ar plasma, and the effects of the modification on the hydrophilicity of PTFE are investigated. The surface microstructures and compositions of the PTFE film were characterized with the goniometer, scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). Results show that the remote and direct plasma treatments modify the PTFE surface in morphology and composition, and both modifications cause surface oxidation of PTFE films, in the forming of some polar functional groups enhancing polymer wettability. When the remote and direct Ar plasma treats PTFE film, the contact angles decrease from the untreated 108–58° and 65.2°, respectively. The effect of the remote Ar plasma is more noticeable. The role of all kinds of active species, e.g. electrons, ions and free radicals involved in plasma surface modification is further evaluated. This shows that remote Ar plasma can restrain the ion and electron etching reaction and enhance radical reaction.

In this work, low-pressure nitrogen plasma has been used to improve wettability in a polyurethane film. Evaluation of wettability changes has been carried out using contact angle measurements. Furthermore, plasma-treated films have been subjected to air aging to evaluate the extent of hydrophobic recovery. X-ray photoelectron spectroscopy (XPS) has been used to study surface functionalization; surface topography changes related with the etching mechanism have been followed by scanning electron microscopy (SEM), atomic force microscopy (AFM) and weight loss study. The results show a considerable improvement in surface wettability even for short exposure times, as observed by a remarkable decrease in contact angle values. The aging study shows a partial hydrophobic recovery due to the re-arrangement of polar species and migration of low molecular oxidized material (LMWOM). In addition to surface activation, SEM and AFM analyses show slight changes in surface topography as a consequence of the plasma-etching mechanism.

It is well known that in extrusion coating, the coating adhesion to the substrate decreases with decreasing thickness. The study on this phenomenon is divided into three parts. Part I explores the reduction in adhesion of LDPE to paper and other porous substrates. Several hypotheses are proposed for the origin of this decrease, including a reduction in oxidation time, faster cooling in the air gap, and more rapid quenching in the nip. A model of the molten polymer penetration into the substrate shows that the greatest effect is cooling in the nip; thinner coatings have less time to flow into the substrate interstices once the chill roll contact is made. The model results agree well with experimental adhesion data from the literature.

In Part II, adhesion to aluminum foil and other nonporous substrates is studied. Several hypotheses are proposed for why peel strength decreases in these structures, including a reduction in the air gap time, faster air gap cooling, more rapid nip quenching, and stress imposed during drawing. Modeling and experimental results show that cooling in the nip and imposed stress have the greatest impact.

In Part III, the peel test is analyzed to understand why the peel strength of better adhering adhesives are more sensitive to changes in coating thickness. The analysis shows that changes in the critical dimension of the deformation region at the peel front may be responsible.

The wettabilities of fluorinated polymers were evaluated using a series of contacting probe liquids ranging in nature from nonpolar aprotic to polar aprotic to polar protic. Fully fluorinated polymers were wet less than partially fluorinated polymers, highlighting the weak dispersive interactions of fluorocarbons. For partially fluorinated polymers, the interactions between the distributed dipoles along the polymer backbone and the dipoles of the contacting liquids were evaluated using both polar and nonpolar probe liquids. The results demonstrate that the surface dipoles of the fluoropolymers generated by substituting fluorine atoms with hydrogen or chlorine atoms can strongly interact with polar contacting liquids. The wettabilities of the partially fluorinated polymers were enhanced by increasing the density of dipoles across the surfaces and by introducing differentially distributed dipoles.

The surfaces of poly(ethylene terephthalate) (PET) and poly(ethylene naphthalate) (PEN) were treated with an atmospheric-pressure oxygen and helium plasma. Changes in the energy, adhesion, and chemical composition of the surfaces were determined by contact angle measurements, mechanical pull tests, and X-ray photoelectron spectroscopy (XPS). Surface-energy calculations revealed that after plasma treatment the polarity of PET and PEN increased 6 and 10 times, respectively. In addition, adhesive bond strengths were enhanced by up to 7 times. For PET and PEN, XPS revealed an 18-29% decrease in the area of the C 1s peak at 285 eV, which is attributable to the aromatic carbon atoms. The C 1s peak area due to ester carbon atoms increased by 11 and 24% for PET and PEN, respectively, while the C 1s peak area resulting from C-O species increased by about 5% for both polymers. These results indicate that oxygen atoms generated in the plasma rapidly oxidize the aromatic rings on the polymer chains. The Langmuir adsorption rate constants for oxidizing the polymer surfaces were 15.6 and 4.6 s(-1) for PET and PEN, respectively.

The objective of this paper was to understand the effects of plasma activation, and thus influence of the surface energy and chemistry changes on offset print quality. Pigment coated and surface sized papers were treated with corona and atmospheric plasma in pilot and laboratory scales. The surface energy and surface chemistry changes were evaluated by contact angle and X-ray photoelectron spectroscopy (XPS). Offset printing was performed in laboratory scale with an IGT unit with predampening and in a pilot scale sheet-fed offset printing press. In addition, the ink setting rate was measured using an ink on paper tack tester. Plasma activation increased the surface energy of the papers. Furthermore, the polarity of the paper surface increased due to formed polar oxygen containing molecular groups. Due to differences in treatment times laboratory scale plasma treatment formed mainly carboxyl and ester groups, whereas pilot scale treatment induced mainly alcohol, ethers, aldehydes and/or ketones on paper surfaces. Printing evaluation showed that plasma activation influences both ink and water absorption properties. According to print tack results plasma activation led to faster ink-setting. With hydrophobic surface-sized paper plasma activation influenced the ink transfer, print gloss and density by changing dampening water absorption properties. The difference in surface chemistry with laboratory scale plasma treated samples was also reflected in the print quality properties. SEM imaging showed that too intense plasma activation can cause topography changes in addition to of the surface chemistry changes.

A new concept for molecular interface design in metal–polymer systems is presented. The main features of this concept are the replacement of weak physical interactions by strong covalent bonds, the flexibilization of the interface for compensating different thermal expansions of materials by using long-chain flexible and covalently bonded spacers between the metal and the polymer as well as its design as a moisture-repellent structure for hindering diffusion of water molecules into the interface and hydrolysis of chemical bonds. For this purpose, the main task was to develop plasmachemical and chemical techniques for equipping polymer surfaces with monotype functional groups of adjustable concentration. The establishing of monotype functional groups allows grafting the functional groups by spacer molecules by applying usual wet-chemical reactions. Four processes were favoured for production of monotype functional groups by highly selective reactions: the plasma bromination, the plasma deposition of plasma polymers, the post-plasma chemical reduction of O-functionalities to OH-groups, and the chemical replacement of bromine groups by NH₂-groups. The grafting of flexible organic molecules as spacers between the metal layer and polymer improved the peel strength of the metal. To obtain maximal peel strength of aluminium coatings to polypropylene films and occurrence of cohesive failure in the polypropylene substrate, about 27 OH groups per 100 C-atoms or 6 COOH groups per 100 C-atoms were needed. Introducing C_6–11-aliphatic spacers 1 OH or COOH group per 100 C-atoms contributed about 60% of the maximal peel strength of the Al–PP system, i.e. 2 or 3 spacer molecules per 100 C-atoms were sufficient for maximal peel strength.

This paper aims to provide an analysis of the correlation between various plasma effects on polymers exposed to atmospheric pressure plasma. The relationship linking the surface polarity, the chemical structure and composition and the crystalline/amorphous phase contribution in the surface modification mechanisms of plasma-exposed polymers is explored. Different polymers were chosen comprising of various structures, functionality, degree of oxidation, crystallinity, and were treated under a particular experimental configuration, and dielectric barrier discharge-type. The plasma parameters and the treatment settings are observed, in relation to relevant surface properties, as surface energy components, surface topography, structural changes and chemical composition, under conditions where the gaseous environment chosen, He-N₂, allows complex surface modification, by combined functionalisation and crosslinking.

Comments are made concerning the recent use of adjectives to describe solid surfaces that exhibit anomalously high water contact angle values. We suggest that the meaning of the word hydrophobic be resolved before it is modified, for example, to superhydrophobic and further modified, for example, to sticky superhydrophobic and before the definitions of these new words become issues of contention. The case is made that the first statement in the title is appropriate with experiments that demonstrate significant attractive interaction between liquid water and the surface of solid Teflon. Four types of experiments are described: the interaction of a silicon-supported covalently attached perfluoroalkyl monolayer (a model Teflon surface) with a sessile water drop (1) and with a thin film of water on a clean silicon wafer surface (2), the interaction of 1 and 12 microm diameter solid Teflon particles with a water droplet surface (3), and the interaction of a thin (<5 microm) Teflon film with a water droplet (4). The concepts of shear and tensile hydrophobicity are introduced, and the recommendation that two numbers, advancing and receding contact angle values, should be considered necessary data to characterize the wettability of a surface. That the words hydrophobic, hydrophilic, and their derivatives can and should only be considered qualitative or relative terms is emphasized.

Surface modification of thermotropic liquid crystalline aromatic polyester (LCP) films was carried out by low-pressure plasma treatment to improve the initial adhesion as well as the long-term adhesion reliability, a measure of durability between the LCP films used as substrates for printed circuit boards. Plasma irradiation was carried out in various plasma gases with different plasma modes such as reactive-ion-etching, and direct-plasma (DP) with pressures ranging from 6.7 Pa to 26.6 Pa. The introduction of polar groups on the film surface such as phenolic hydroxyl groups and carboxyl groups enhanced the initial adhesion by increased chemical interaction. However, if the concentration of polar groups became too high, the longterm adhesion reliability estimated by the pressure cooker test was degraded due to the acceleration of the penetration of water molecules into the interface. A large surface roughness was also effective in preventing the decrease in the long-term adhesion reliability. However, too much increase in surface roughness decreases the long-term adhesion reliability. The DP-treatment in the O₂ atmosphere at a gas pressure of 6.7 Pa was found to be the best plasma condition for both the initial adhesion as well as the long-term adhesion reliability between the LCP films.