As adaptable as polymeric materials are in their many applications to our daily lives, the need exists to tailor the polymer surfaces to provide even more flexibility in regard to their uses. Plasma treatments offer an unprecedented spectrum of possible surface modifications to enhance polymers, ranging from simple topographical changes to creation of surface chemistries and coatings that are radically different from the bulk polymer. Furthermore plasma treatments are environmentally friendly and economical in regard to their use of materials.

Plasma processing can be classified into at least four categories that often overlap. These are the following: (1) surface preparation by breakdown of surface oils and loose contaminates, (2) etching of new topographies, (3) surface activation by creation or grafting of new functional groups or chemically reactive, excited metastable species on the surface, and (4) deposition of monolithic, adherent surface coatings by polymerization of monomeric species on the surface. Key features of these processes will be briefly discussed, with a rudimentary introduction to the chemistries involved, as well as examples. Focus is placed on capacitively coupled radio-frequency (rf) plasmas (see Figure 1 in the article by Lieberman et al. in this issue of MRS Bulletin) since they are most commonly used in polymer treatment.

Polytetrafluoroethylene (PTFE) was treated with hydrogen and ammonia microwave plasmas and the effects of treatment were evaluated by means of advancing and receding contact angle measurements, X-ray photoelectron spectroscopy, secondary-ion mass spectroscopy and atomic force microscopy analysis. Hydrogen plasma downstream treatment principally leads to defluorination and creation of CC and CH groups. This surface modification results in a slight decrease of the water contact angle and a large decrease of the methylene iodide contact angle. No evolution of the surface properties occurs over a period of at least two months following treatment. Ammonia plasma downstream treatment leads to defluorination and creation of CC and CH groups, as already observed with the H₂ plasma, but also to the introduction of nitrogen-containing groups. The modification produces a decrease of both water and methylene iodide contact angles. A large hysteresis is found with water contact angles due to the reorientation of the polar groups when the surface is in contact with a polar liquid. The surface modifications that result after a NH₃ plasma treatment are less stable than after a H₂ treatment. Nevertheless, after two days of ageing the water contact angle reaches a constant value, which is largely inferior to that of the untreated PTFE.

The solid-vapour surface tension has been determined by contact angle measurements with polar and non-polar liquids on flat solid surfaces using Axisymmetric Drop Shape Analysis (ADSA) and by capillary penetration experiments on rough and porous solids. For smooth and inert, well prepared solid surfaces (PTFE, FC 721 on mica, FEP, PET) the plot of γ_lvcosΘ versus γ_lv yields smooth curves which are consistent with the equation of state approach to calculate solid-vapour and solid-liquid interfacial tensions. Other experimental patterns of contact angle data are caused by surface roughness and non-inert solids which may result in contact angles incompatible to Young’s equation. An alternative way to obtain the solidvapour surface tension of rough and porous solids are capillary penetration experiments. The determination of the penetration velocity of liquids into rough and porous solids yields Kγ_lv coΘ versus γ_lv plots, which provide γ_sv values for these systems; K is an unknown parameter of the constant geometry of the porous solid. The application of this concept was demonstrated for a hydrophobic PTFE powder and for hydrophilic Cellulose membranes.

A study was conducted which showed that the Lifshitz-van der Waals / acid-base approach yielded liquid-liquid interfacial tensions which were incompatible with experimental results. The approach allowed correct prediction of interfacial tensions for only four completely miscible liquid/liquid pairs. This result calls into question traditionally held interfacial tension theories, and points up the need for caution in the application to solid/liquid contact angle systems if an approach should fail the liquid/liquid test.

The kinetics of modification of a fluoropolymer coating (FC 722, 3M Company) during its contact with octane, dodecane, and hexadecane is studied via measurement of quasi-static (velocity independent) advancing and receding dynamic contact angles. A decrease in both angles with the time of contact between solid and liquid is observed and it is interpreted as the result of swelling of the polymer. By means of a theoretical extrapolation of the θ_R(t) data tot= 0, based on an equation relating θ_R(t) to swelling kinetics, the experimentally inaccessible receding contact angle on dry coating, θ⁰_R, is determined. The contact angle hysteresis on such a surface, θ⁰_A− θ⁰_R, is found to be less than the hysteresis, θ^∞_A− θ^∞_R, obtained on samples that were soaked in the alkanes long enough to reach saturation. This increase is thought to be due to loosening of the polymer chains during the swelling, leading to an exposure of higher-energy segments to the nonpolar liquid and to an enlargement of the solid surface pores filled with liquid. The contact angle data are also interpreted in terms of interfacial free energies.

In this paper, we report our unexpected finding about the correlation between Lewis acid−base surface interaction components and linear solvation energy relationship (LSER) solvatochromic parameters α and β. In 1987, van Oss, Chaudhury, and Good proposed to split the asymmetric acid−base parts of a bipolar system into separate surface tension components:  Lewis acid (electron acceptor) γ⁺ and Lewis base (electron donor) γ^-. It was assumed that the ratio of γ⁺ and γ^- for water at 20 °C was to be 1.0. With that ratio as a reference, the base components, γ^- for other liquids, biopolymers, polymers, and solids appeared to be overestimated. Recently, we unexpectedly found a correlation for liquids between γ⁺ and γ^-, and α (solvent hydrogen-bond-donating ability) and β (solvent hydrogen-bond-accepting ability) introduced since 1976 by Taft and Kamlet. From that correlation, we obtained a more realistic ratio for the normalized α and β values for water at ambient temperature to be 1.8 instead of 1.0. Based on this new ratio, we calculated total surface tensions for related materials at 20 °C. They are generally unchanged as expected, despite the considerable, favorable change in the γ⁺ and γ^- values in the direction of lowering the Lewis basicity. The predicability of solubility with interfacial tension is also unaffected. For example, the sign of those negative interfacial tensions that favor solubility remains the same. In addition, the implications of other LSER parameters, e.g. Π* and δ_H², on surface properties will be briefly mentioned.

An ultraviolet-ozone oxidation process is shown to be an effective adhesion pretreatment for polyethylene (PE) and polyetheretherketone (PEEK). The data obtained indicate that the treatment gives considerable oxidation and improved wettability for PE and PEEK surface types. Treated surfaces were analysed using X-ray photoelectron spectroscopy (XPS) and water contact angles. XPS was also used to follow the chemistry and mechanism of the oxidation. Adhesion with a two-part epoxy was measured for PE and PEEK and was observed to improve significantly after pretreatment.

The effect of activation of the surface of polypropylene sheet, by a corona discharge, upon the contact angles of liquids and on the surface free energy parameters γ^LW, γ^⊕ and γ^⊖, was determined. Both advancing and retreating contact angles were measured. The “acid/base” theory of the components of surface free energy was employed.

The contact angles of water and glycerol were initially lower by as much as 30°, after treatment, and that of diiodomethane was lower by about 5°. With time, the advancing angles rose, and the γ^⊕ and γ^⊖ parameters fell, towards the values on the untreated solids, and attained more or less steady values after 5 to 10 days. The basic component, γ^⊖, was the most strongly affected by the corona treatment; it rose, typically, from 2.2 to as high as 25 mJ/m². The acidic component, γ^⊕, rose from zero to as high as 1.9 mJ/m². Its decay with time was only qualitatively the same as that of γ^⊖. The retreating angles, and the corresponding energy components, were changed in the same direction, and somewhat more strongly, than were the “advancing” data.

The well-known improvement in the property of forming strong joints or adherent coatings, after corona treatment, is no doubt due to the formation of sites or areas on the polymers where hydrogen bonds can be formed. The decay of the strength of adhesion with time is, no doubt, due to the decay of these sites or areas.

The influence of u.v. irradiation on the surface morphology of some commercial polymers was investigated using scanning electron microscopy (SEM). The photodegraded samples exhibited a high degree of surface damage. The formation of cracks and holes resulting from the degradation and evolution of volatile products was observed. In polymers undergoing photocrosslinking, the agglomeration of particles was clearly seen. Polymer photodegradation in the presence of hydrogen peroxide as an acceleration agent revealed its etching action.

Plasma treatment of silicone surfaces is a useful, environmentally-sound method of increasing wettability to improve adhesion. A thin, wettable silica-like layer is produced with various plasma gases such as argon, helium, oxygen and nitrogen. However, in each case the surfaces gradually recover their hydrophobicity. The silica-like layer is brittle and microcracking is evident at more severe levels of plasma treatment. The onset of cracking is a function of plasma gas, RF power, pressure and treatment time. Scanning electron microscopy has been used to characterize the cracks.

The hydrophobic recovery has been monitored by water contact angle changes. It occurs with both cracked and uncracked treated surfaces. There is an initial jump in hydrophobicity at the onset of cracking. Thereafter, the recovery of both cracked and uncracked surfaces broadly parallels each other with virtually complete recovery of original hydrophobicity within one week. These effects can be accounted for by rapid surface diffusion of low molecular weight material out of fresh cracks followed by slower bulk diffusion through the polymer matrix. Significant differences in recovery rates are also evident between different plasma gases.

In the last 25 years, surface sensitive analytical techniques have made a major contribution to our understanding of adhesion phenomena and problems. There are several areas where these techniques have provided important information including the identification of failure modes, the chemistry of a substrate before and after pretreatments, the stability of surfaces and interfaces, the identification of surface contaminants, the interaction across an interface and the nature of interphases. X-ray photoelectron spectroscopy (XPS or ESCA), Auger electron spectroscopy (AES) and static secondary ion mass spectrometry (SSIMS) have proved to be especially useful. Many examples of the usefulness of these techniques are given.

A surface treating method is described, which method comprising applying, between electrodes, a potential sufficient to cause corona discharge to occur in the presence of a gas which comprises molecules containing at least one atom selected from the group consisting of halogen atom, oxygen atom and nitrogen atom. The resultant corona discharge is applied to an object to be treated for the surface treatment of the object, said object being outside said electrodes. The excellent adhesive surface can be obtained when said object is separated from said electrodes at a distance in the range of 10 mm to 5 m.

Polymer materials such as film and fabrics, woven, non-woven and meltblown, may be non-destructively surface treated to improve water wettability by exposure to a glow discharge plasma sustained at substantially atmospheric pressure in a modified gas atmosphere comprising helium or argon.

Polyacetal-copolymer (POMB), polycarbonate (PC), polybutylene terephthalate (PBT), and nylon 6, 6 (PA6, 6) have been treated in an electron cyclotron resonance (ECR) plasma chamber to improve their adhesion properties towards ink. The chemical composition, the surface free energy, and the macroscopic adhesion have been studied by X-ray photoelectron spectroscopy (XPS), contact angle measurements, cross-cut tests, and the Scotch Tape test. Their dependence on the neutral gas, the treatment time, the pressure, and the ageing in air have been investigated. The XPS results reveal that the plasma treatment allows one to clean the surface and, if reactive gases are used, to incorporate new chemical species. The static and dynamic contact angles decrease with the plasma treatment and continue to decrease after contact with air. Very slow hydrophobic recovery is visible in the advancing contact angle, whereas the receding contact angle remains non-measurable even after more than a week of air exposure. Lower pressures and longer treatment times (120 s) lead to better macroscopic adhesion and reproducibility. For optimal treatment conditions (0.5 Pa, 120s N₂ plasma treatment time), the improvement of the adhesion remains excellent after seven days exposure of the sample in air.

The theory of wetting is reviewed with respect to ink transfer which is based upon measured dynamic surface tension and calculated dynamic spreading coefficient. Laboratory gravure ink transfer results are presented for model water based inks with and without isopropanol as the cosolvent on untreated and corona treated polyethylene film. A mechanism of surface tension driven convection is proposed which is consistent with experimental results. The conclusion, which is based upon the proposed mechanism, is that uniform coverage of a water based ink on a nonpermeable substrate is facilitated by the presence of a high vapor pressure low surface tension cosolvent such as isopropanol. When no cosolvent is present, de-wetting and degree of ink mottling appears to be controlled by dynamics longer than one second.

A hexamethyldisiloxane (HMDSO)-RF plasma was used to treat polypropylene (PP) fabrics to achieve an inorganic type surface. The properties of the plasma modified PP were investigated through demand wettability and contact angle techniques. ESCA and ATR-IR spectroscopy indicated the presence of Si  O  Si and Si  O  C based structures. The influence of treatment time on the level of deposition and surface atomic composition was established. Plasma induced molecular fragmentation of HMDSO was determined through GC-MS and high resolution MS analyses of the molecular structures produced from recombination of active species, in the cold trap.

Method of improving wetting and adhesive properties of dielectric materials by injecting electrical charges into the substrate under conditions such that the primary effect on the surface is that of charging so that improved wettability of the surface will be achieved. Flowable materials are then applied to the surface and cured in situ to permanently adhere the flowable materials to the surface.

The influence of release agents, impurities and light stabilizers on the mechanisms of pretreatment operations, such as flame or plasma treatment, of thermoplastic materials used in the automotive industry has been investigated by X-ray photoelectron spectroscopy (XPS), zeta potential and contact angle measurements. It is shown that the presence of release agents on thermoplastic polyurethane can be detected by contact angle and zeta potential measurements. Sterically hindered amines (HALS) used as light stabilizers in polypropylene-ethylene-propylene-dienemonomer rubber blends (PP-EPDM) enhance the result of flame treatment whereas the effect of oxygen plasma treatment is not changed by the presence of HALS products.