Highly hydrophobic surfaces have numerous useful properties; for example, they can shed water, be self-cleaning, and prevent fogging (1, 2). Surface hydrophobicity is generally characterized with contact angle (CA) goniometry. With a history of more than 200 years (3), the measurement of CAs was and still is considered the gold standard in wettability characterization, serving to benchmark surfaces across the entire wettability spectrum from superhydrophilic (CA of 0°) to superhydrophobic (CA of 150° to 180°). However, apart from a few reports [e.g., (4–8)], the inherent measurement inaccuracy of the CA goniometer has been largely overlooked by its users. The development of next-generation liquid-repellent coatings depends on raising awareness of the limitations of CA measurements and adopting more sensitive methods that measure forces.

BACKGROUND: Polytetrafluoroethylene (PTFE) is utilized in many engineering applications, but its poor wettability and adhesion properties with other materials have limited its use. The study reported was aimed at achieving surface modification of PTFE films by radiofrequency NH₃ and N₂ plasma treatment, followed by graft copolymerization, in order to improve the interfacial adhesion of PTFE and bismaleimide.

RESULTS: X-ray photoelectron spectroscopy results showed that a short-time plasma treatment had a distinct defluorination effect and led to nitrogen functional group formation. The nitrogen chemical bonding form was different for NH₃ and N₂ plasma treatments. Under the same experimental conditions, the NH₃ plasma exhibited a better etching effect than did the N₂ plasma. Contact angle measurement showed an improvement in both surface energy and wettabliity by short-time plasma treatment. The concentration of the surface-grafted bismaleimide on PTFE increased after the plasma pretreatment. The lap shear strength between PTFE and bismaleimide increased significantly after surface modification.

CONCLUSION: This study found that plasma treatment caused changes in surface chemistry, thus leading to an increase of the wettability of PTFE surfaces. Hence, the adhesion properties of PTFE with bismaleimide were significantly improved. Copyright © 2008 Society of Chemical Industry

The aim of this study was to analyze how corona dosages above recommended levels affect film surface energy and hydrophobic recovery of such treated film surfaces as well as laminate bond strength of laminates made of these films. The adhesive for lamination was a polyurethane-adhesive with a dry film thickness of ∼5 µm. Polar and dispersive parts of the surface energy were measured frequently according to DIN 55660-2 (Owens–Wendt–Rabel-and-Kaelble method) for up to 140 days after corona treatment. The corona dosage had a value of up to 280 W min/m². Laminate bond strength was measured according to DIN 55543-5. The effect of corona treatment was highest for low-density polyethylene (PE-LD) films, mean for biaxial-oriented polypropylene (PP-BO) films, and lowest for biaxial-oriented poly(ethylene terephthalate) (PET-BO) films. With increasing storage time, surface energy decreased, as expected. The higher the effect of corona treatment, the faster the polar part of surface energy decreased. At PE-LD, laminate bond strength increased with a higher corona dosage from 0.05 to 8.87 mN/15 mm, whereas at PET-BO and PP-BO laminate bond strength was so high that samples teared before delamination during bond strength testing. By our results is shown that corona dosages above recommended levels resulted in higher laminate bond strength. Only at PP-BO a reduction of laminate bond strength due to “overtreatment” was be observed. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 45842. https://onlinelibrary.wiley.com/doi/abs/10.1002/app.45842

The role of roughening and functionalization processes involved in modifying the wettability of poly(ε-caprolactone) (PCL) after treatment by an atmospheric pressure glow discharge plasma is discussed. The change in the ratio of CO/C–O bonds is a significant factor influencing the wettability of PCL. As the contact angle decreases, the level of CO bonds tends to rise. Surface roughness alterations are the driving force for lasting increases in wettability, while the surface functional species are shorter lived. We can approximate from ageing that the increase in wettability for PCL after plasma treatment is 55–60% due to roughening and 40–45% due to surface functionalization for the plasma device investigated.

One of the main differences between low-pressure and atmospheric-pressure plasma treatments is that there is little moisture involved in the low-pressure plasma treatment, although moisture could exist at the wall of the vacuum chamber or react with the substrate after plasma treatment, while in the atmospheric-pressure plasma treatment moisture exists not only in the environment but also in any hygroscopic substrate. In order to investigate the influence of environmental moisture on the effect of atmospheric pressure plasma treatment, ultra-high-modulus polyethylene (UHMPE) fibers were treated using an atmospheric-pressure plasma jet (APPJ) with 10 l/min helium gas-flow rate, treatment nozzle temperature of 100°C and 5 W output power. The plasma treatments were carried out at three different relative humidity levels, namely 5, 59 and 100%. After the plasma treatments, the surface roughness increased while the water-contact angle decreased with increasing relative humidity. The number of oxygen containing groups increased as the environmental moisture content increased. The interfacial shear strength of the UHMPE fiber/epoxy system was significantly increased after the plasma treatments, but the moisture level in the APPJ environment did not have a significant influence on the adhesion properties. In addition, no significant difference in single fiber tensile strength was observed after the plasma treatments at all moisture levels. Therefore, it was concluded that the environmental moisture did not significantly influence the effect of atmospheric-pressure plasma treatment in improving interfacial bonding between the fiber and epoxy. The improvement of the interfacial shear strength for the plasma-treated samples at all moisture levels was mainly due to the increased surface roughness and increased surface oxygen and nitrogen contents due to the plasma etching and surface modification effect.

Polyacrylonitrile fibers were treated with a nitrogen glow-discharge plasma. The surfaces of untreated and treated fibers were examined with contact angle measurements, atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). Surface energy calculations of the fibers were carried out from contact angle measurements using the relationships developed by Fowkes. It is found that plasma treatment causes a reduction in water contact angle on the fiber surfaces. The dispersion component of surface energy changes slightly, while the polar component is increased significantly from 14.6 mN/m to 58.7 mN/m and the total surface energy increase is 139%. The increase of surface energy is mainly caused by the introduction of hydrophilic groups on the fiber surfaces after plasma treatment.

Polyethylene (PE) samples were activated by an atmospheric pressure plasma jet. The improvement in adhesive bond strength is attributed to the incorporation of oxygen-containing functional groups into the PE surface. Optical emission spectroscopy in combination with XPS analysis shows differences in the surface reactions for a plasma jet operated with air or pure nitrogen. The results indicate that the surface modifications take place in two different environments with respect to location and time: (a) reactions while the substrate is hit by the plasma jet, and (b) reactions outside the plasma jet after the treatment.

Polyethylene terephthalate (PET) plates have been exposed to different nitrogen containing plasmas with the purpose of incorporating nitrogen functional groups on its surface. Results with a dielectric barrier discharge (DBD) at atmospheric pressure and a microwave discharge (MW) at reduced pressure and those using an atom source working under ultrahigh vacuum conditions have been compared for N₂ and mixtures Ar + NH₃ as plasma gases. The functional groups have been monitored by X-ray Photoemission Spectroscopy (XPS). Nondestructive oxygen and carbon depth profiles for the plasma treated and one month aged samples have been determined by means of the nondestructive Tougaard’s method of XPS background analysis. The surface topography of the treated samples has been examined by Atomic Force Microscopy (AFM), while the surface tension has been determined by measuring the static contact angles of water and iodomethane. It has been found that the DBD with a mixture of Ar+NH₃ is the most efficient treatment for nitrogen and amine group functionalization as determined by derivatization by reaction with chlorobenzaldehyde. It is also realized that the nitrogen functional groups do not contribute significantly to the observed increase in surface tension of plasma treated PET.

Plasma treatment is one of the methods currently used to obtain polymeric materials with surface properties appropriate to the functionality for which they were designed. However, the effects achieved after surface modification are not always long lasting and involve chemical and physical changes in the outermost layer. In this context, the effects of both argon and oxygen plasma on polylactic acid (PLA) films deposited on titanium were studied to determine which physical and chemical processes occur at the surface, and their duration. Regarding physical surface changes, there were scarcely any differences between both plasmas: roughness was very similar after treatments, root mean square height (Sq) being 10 times higher than the control, without plasma. Water contact angle (WCA) showed that the surface became more hydrophilic after application of the plasma, although hydrophilization was longer lasting in the case of argon treatment.

With regard to chemical changes, it was observed that the argon plasma treatment caused greater fragmentation of the polymer chains, and increased crosslinking between them. ToF-SIMS analysis made it possible to propose mechanisms to explain the formation of the fragments observed.