This paper describes the photochemical surface modification of polystyrene (PS) substrates using vacuum ultraviolet (VUV) light 172 nm in wavelength. We have particularly focused on the effects of atmospheric pressure during VUV irradiation on the obtained surface's wettability and the stability of the wettability, in addition to its chemical structure, morphology, and photooxidation rate. Samples were photoirradiated with VUV light under pressures of 10, 10(3), or 10(5) Pa. Although, in each case, the originally hydrophobic PS surface became highly hydrophilic, the final water-contact angle and photooxidation rate depended on the atmospheric pressure. The samples treated at 10 Pa were less wettable than those prepared at 10(3) and 10(5) Pa due to the shortage of oxygen molecules in the atmosphere. The minimum water-contact angles of the samples treated at 10, 10(3), and 10(5) Pa were about 8 degrees, 0 degrees, and 0 degrees, respectively. With the samples prepared at 10 and 10(3) Pa, photooxidation reactions proceeded in the topmost region closest to the surface, while at 10(5) Pa photooxidation was found to be greatly enhanced in the deeper regions, as evidenced by angle-resolved X-ray photoelectron spectroscopy. Photoetching rates were determined through atomic force microscope observation of microstructured PS samples prepared by a simple mesh-contact method. As estimated from AFM images of the latticed microstructures obtained, the rates of samples prepared at 10(3) and 10(5) Pa were about 1.5 and 1.3 nm/min, respectively. However, no photoetched features were observable on the sample surface prepared at 10 Pa. Hydrophilic stability also varied greatly depending on atmospheric pressure. The hydrophilicity of samples treated at 10 and 10(3) Pa gradually decreased as they were exposed to air. On the other hand, the sample surface prepared at 10(5) Pa showed excellent hydrophilicity even after being left in air for 30 days.

Contact angle (θ) measurements on poly(tetrafluoroethylene) (PTFE) and polymethyl methacrylate (PMMA) surface were carried out for the systems containing ternary mixtures of surfactants composed of: p-(1,1,3,3-tetramethylbutyl)phenoxypoly(ethylene glycols), Triton X-100 (TX100), Triton X-165 (TX165) and Triton X-114 (TX114), and fluorocarbon surfactants, Zonyl FSN100 (FSN100) and Zonyl FSO100 (FSO100). The aqueous solutions of ternary surfactant mixtures were prepared by adding TX114, FSN100 or FSO100 to binary mixtures of TX100+TX165, where the synergistic effect in the reduction of the surface tension of water (γ(LV)) was determined. From the obtained contact angle values, the relationships between cosθ, the adhesion tension and surface tension of solutions, cosθ and the reciprocal of the surface tension were determined. On the basis of these relationships, the correlation between the critical surface tension of PTFE and PMMA wetting and the surface tension of these polymers as well as the work of adhesion of aqueous solutions of ternary surfactant mixtures to PTFE and PMMA surface were discussed. The critical surface tension of PTFE and PMMA wetting, γ(C), determined from the contact angle measurements of aqueous solutions of surfactants including FSN100 or FSO100 was also discussed in the light of the surface tension changes of PTFE and PMMA under the influence of film formation by fluorocarbon surfactants on the surface of these polymers. The γ(C) values of the studied polymeric solids were found to be different for the mixtures composed of hydrocarbon surfactants in comparison with those of hydrocarbon and fluorocarbon surfactants. In the solutions containing fluorocarbon surfactants, the γ(C) values were different taking into account the contact angle in the range of FSN100 and FSO100 concentration corresponding to their unsaturated monolayer at water-air interface or to that saturated.

Polyethylene films were prepared with phase separation at lower temperatures. The wettability of such films varied from hydrophobicity to superhydrophobicity as the processing temperature decreased owing to the increase of surface roughness. Storing the as-prepared films at subzero temperature (−15 °C), it was found that the water contact angle of the film decreased obviously, and the decrease depended on the corresponding roughness. Further keeping the as-prepared films at room temperature for 30 min, the water contact angle would return to the normal value, which indicated that the reversible switching of surface wettability can be controlled by the environmental temperature.

A theory, based on the presence of an adsorbed film in the vicinity of the triple contact line, provides a molecular interpretation of intrinsic hysteresis during the measurement of static contact angles. Static contact angles are measured by placing a sessile drop on top of a flat solid surface. If the solid surface has not been previously in contact with a vapor phase saturated with the molecules of the liquid phase, the solid surface is free of adsorbed liquid molecules. In the absence of an adsorbed film, molecular forces configure an advancing contact angle larger than the static contact angle. After some time, due to an evaporation/adsorption process, the interface of the drop coexists with an adsorbed film of liquid molecules as part of the equilibrium configuration, denoted as the static contact angle. This equilibrium configuration is metastable because the droplet has a larger vapor pressure than the surrounding flat film. As the drop evaporates, the vapor/liquid interface contracts and the apparent contact line moves towards the center of the drop. During this process, the film left behind is thicker than the adsorbed film and molecular attraction results in a receding contact angle, smaller than the equilibrium contact angle.

Plasma treatment of polyimide surfaces not only causes structural modification during the plasma exposure, but also leaves active sites on the surfaces that are subject to post-reaction. In this work, the effects of atmospheric fluorine plasma treatment on the surface properties and dielectric properties of polyimide thin film were investigated by using X-ray photoelectron spectroscopy (XPS), Fourier transform-IR (FT-IR) spectroscopy, and contact angle measurement. The results indicated that plasma treatment successfully introduced fluorine functional groups on the polyimide surfaces. The polyimides also exhibited good thermal stability and a lower dielectric constant. It appears that the replacement of fluorine led to the decrease of the local electronic polarizability of polyimide. Consequently, it was found that the atmospheric fluorine plasma-treated polyimides possessed lower dielectric characteristics than the untreated polyimides.

The surface chemical and physical character of offset paper was studied before and after application of model fountain solutions based on isopropyl alcohol and an alcohol-free surfactant solution. The paper surface features were characterised with atomic force microscopy and the surface energies were determined by contact angle measurements. Changes in the surface chemical properties induced by the fountain solutions were investigated with X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectroscopy. Coated papers wetted with the surfactant solution revealed a slight increase in the root mean square roughness, but the isopropyl alcohol solution led to no observable changes. The change in sub-micro roughness is ascribed not only to substrate swelling or migration of coating constituents but also to the presence of surfactant on the surface. A change in the surface energy and particularly the polar contribution was observed after application of the surfactant solution. The X-ray photoelectron spectroscopy showed an increase in the oxygen-to-carbon ratio, which confirms the presence of surfactant on the surface. Time-of-flight secondary ion mass spectroscopy showed that the isopropyl alcohol solution did not change the elemental composition of the surface whereas the surfactant solution clearly did so. The distribution of surfactant on the surface was confirmed by mapping the characteristic fragments of the molecule.

The surface characteristics of ethylene-vinyl acetate (EVA) were modified by argon, air, and oxygen plasma at atmospheric pressure. The surface energies of the EVA were evaluated by contact angles according to a sessile-drop method and adhesion energy (G(IC)) was estimated by a 180 degrees peel test with polyurethane (PU). After the plasma treatments, the surface free energies (or specific polar component) of the EVA increased about five times compared to that of virgin EVA. The adhesion between the EVA and the PU is significantly improved by the plasma treatment. Especially, Ar/air/O(2) plasma treatment increases G(IC) of EVA/PU up to about 600% compared to that of the sample using virgin EVA.

In this work, the effect of atmospheric-pressure plasma treatments on surface properties of polyimide film are investigated in terms of X-ray photoelectron spectroscopy (XPS), contact angles, and atomic force microscopy (AFM). The adhesion characteristics of the film are also studied in the peel strengths of polyimide/copper film. As experimental results, the polyimide surfaces treated by plasma lead to an increase of oxygen-containing functional groups or the polar component of the surface free energy, resulting in improving the adhesion characteristics of the polyimide/copper foil. Also, the roughness of the film surfaces, confirmed by AFM observation, is largely increased. These results can be explained by the fact that the atmospheric-pressure plasma treatment of polyimide surface yields several oxygen complexes in hydrophobic surfaces, which can play an important role in increasing the surface polarity, wettability, and the adhesion characteristics of the polyimide/copper system.

In an attempt to modify the hydrophobic surface properties of polypropylene (PP) films, this study examined the optimum process parameters of atmospheric pressure plasma (APP) using Ar gas. Under optimized conditions, the effects of a mixed gas (Ar/O2) plasma treatment on the surface-free energy of a PP film were investigated as a function of the O2 content. The polar contribution of the surface-free energy of the PP film increased with increasing O2 content in the gas mixture. However, slightly more oxygen-containing polar functional groups such as CO, CO, and COO were introduced on the PP film surface by the Ar gas only rather than by the Ar/O2 gas mixture. In addition, AFM analysis showed that the Ar plasma treatment of the PP film produced the smoothest surface as a result of the relatively homogeneous etching process.

A new method for the measurement of apparent contact angles at the global energy minimum on real surfaces has been developed. The method consists of vibrating the surface, taking top-view pictures of the drop, monitoring the drop roundness, and calculating the contact angle from the drop diameter and weight. The use of the new method has been demonstrated for various rough surfaces, all having the same surface chemistry. In order to establish the optimal vibration conditions, the proper ranges for the system parameters (i.e., drop volume, vibration time, frequency of vibration, and amplitude of vibration) were determined. The reliability of the method has been demonstrated by the fact that the ideal contact angles of all surfaces, as calculated from the Wenzel equation using the measured apparent contact angles, came out to be practically identical. This ideal contact angle has been compared with three methods of calculation from values of advancing and receding contact angles.