The surface modification of high density polyethylene by a CO₂ microwave plasma is described with the aim of fixing carboxylic groups. The characterization is discussed in terms of functionalization, degradation, crystallization and cross-linking. The formation of carboxylic acids seems mainly favored by the presence of the CO₂ active species. The degradation leading via chain scissions to the formation of volatile byproducts is shown to be heterogeneous by mainly affecting amorphous zones. The structural modification is associated with a twisting motion of macromolecular chains having defects to more organized conformations. Finally, cross-linking appears weak due to the absence of chromophoric sites and of VUV radiations in the plasma.

The treatment of surfaces by corona discharges is a well-established method to improve surface properties. The surface to be treated is moved continuously and is exposed to transient gas discharges, known as microdischarges, in air at atmospheric pressure between electrodes, where at least one electrode is covered with a dielectric barrier. Because of the short duration, only some 10 ns, the current through the microdischarges is predominantly carried by electrons. The ion temperature remains close to room temperature. Owing to these properties such discharges are qualified to treat surfaces which are sensitive to higher temperatures. For a large number of applications this treatment is adequate, but the adhesion of aqueous glues and inks to some plastic materials is insufficient if the surfaces are treated in this way. Furthermore, it is difficult to meet the requirements of surface properties of, for instance, polyolefine film (e.g. surface tension, adhesion). This material is not based on monomers containing chlorine or fluorine and is preferred for ecological reasons. This paper presents the results of experiments which demonstrate that in comparison to a common corona treatment significant improvements in surface properties of plastic materials can be achieved if repetitively generated pulse trains and reactive gases are used instead of air. If, for instance, the microdischarges are established in acetylene, thin films with a thickness of several namometres are formed on surfaces, which increase and stabilize the surface tension up to a level of 72 mN m−1. The state of the art of this new technology is discussed.

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.

Polypropylene electrets 20-μm thick obtained in a corona discharge were studied. After the electrets were charged, they were put into a vacuum chamber at various pressures and the electret surface potential was measured over a 1-h period. A desorption from the electrets is suggested to explain the results obtained.

High-modulus polyethylene (PE) tapes were grafted with acrylic acid using a two-step procedure. The tapes were first subjected to He/Ar corona discharge, immediately followed by exposure of the corona-treated tapes to acrylic-acid-saturated He gas. Evidence for the grafting was provided by X-ray photoelectron spectroscopy, which showed the surface of the treated tapes to consist of 64% acrylic acid and 36% PE. The grafting of acrylic acid is confined to the outermost surface layers, as indicated by reflection infra-red spectroscopy. Pull-out tests showed that the corona grafting of acrylic acid improves adhesion to epoxy resins by a factor of eight. Moreover, the increased adhesion is not achieved at the expense of a decrease in mechanical properties of the high-modulus PE tapes.

The decrease in the corona treatment effect with time and its influence on the flexographic printability of low-density polyethylene-coated paperboard were studied. After corona treatment, sheets were stored in different ways. Some sheets were stored in a laboratory atmosphere, while others were protected from exposure to light, air, moisture and dust in polyethylene bags. The tendency for ink to spread on the surfaces was studied using contact angle measurements. Printability was evaluated as print density, dot gain, uncovered (white) and mottling. The results obtained show that the surface energy of the protected sheets decreased with time, but not as much and not as quickly as that of the unprotected sheets. In the case of the protected sheets, the percentage uncovered areas and mottling remained constant, but for the unprotected sheets they increased with increasing time after the corona treatment. No significant differences were seen in the other print quality measures. Copyright © 2005 John Wiley & Sons, Ltd.
https://onlinelibrary.wiley.com/doi/abs/10.1002/pts.708

Polytetrafluorethylene (PTFE) was treated with N⁺ , O⁺ and C⁺ ion beams with energies of 20 and 30 keV at 5 mA/cm² current density in the pulse regime. Structural changes were studied by IR ATR, XPS, IR diffuse reflectance spectra and wetting methods. After treatment the PTFE surface became chemically active to isocyanate, acrylamide and epoxy reagents, which caused a change of interface interaction with active adhesives. The durability of the PTFE adhesion joint to an epoxy adhesive increases by more than 100 times. The ion beam treatment can be used to increase adhesion joint durability of PTFE.

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.

The surface free energy of polymeric films of polyvinylchloride (PVC) + poly(ethylene-co-vinylacetate) (EVA) blends was calculated using the van Oss treatment (Lifshitz and electron donor–electron acceptor components of surface free energy) and the Owens–Wendt treatment (dispersive and nondispersive components of surface free energy). Surface free energy results were found to be greatly dependent on the calculation method and on the number of standard liquids used for contact angle measurements. The nondispersive/donor–acceptor surface free energy component and the total surface free energy of polymeric films were always higher when the van Oss treatment was used compared to the Owens–Wendt treatment. Conversely, both methods led to similar apolar/Lifshitz components. All the calculation methods were in good agreement for the surface free energy of PVC; however, a discrepancy between the methods arose as EVA content in the blends increased. It seems that there is not yet a definite solution for the calculation of solid surface free energy. Further developments of existing models are needed in order to gain consistency when calculating this important physicochemical quantity.

Oriented polypropylene treated by atmospheric barrier discharges in air and nitrogen was investigated using several techniques: contact angle measurements, ATR-FT-IR spectroscopy and two adhesion tests based on the stripping of an applied ink layer. The activation in an air discharge was found to be much weaker compared to the activation in industrial grade nitrogen, particularly with respect to adhesion. The adhesion was found to be much better in nitrogen in spite of the common use of air in industrial 'corona discharges'. A new 'abrasive shear-stripping' (AS) test for ink coating adhesion was designed and performed. It was shown that the AS test was much more sensitive than the classical adhesive tape test and was sensitive enough to monitor ageing and overtreatment. The contact angle measurements did not correlate completely with the adhesion properties and could not monitor the overtreatment, while the ATR-FT-IR technique indicated changes just for overtreated foils.

The influence of film roughness on the wetting properties of vacuum-deposited polytetrafluorethylene (PTFE) thin films has been investigated using atomic force microscopy (AFM) and contact angle goniometry. Surface roughness has been characterized by atomic force microscopy in terms of RMS roughness (R_q) and fractal dimensions. A contact angle correlation with surface roughness, as determined by AFM, is evident from these results, which are discussed on the basis of wetting theory. The results also confirm that the high water contact angles (as high as 150°) recently observed at the surface of a new water repulsive coating material (mixture of PTFE and binder) are because of surface roughness. Such measurements clarify the effect of nanometer-size surface asperities on the wetting properties of hydrophobic coating.

This chapter focuses on the drop volume technique. The stalagmometer is the most primitive version of the drop volume method. It allows only a very rough estimate of the surface tension of a liquid. With the drop volume technique an accurate determination of the volume of a drop formed at the tip of a given capillary is obtained. The measuring procedure is realized by means of a precise dosing system, which forms drops continuously at the capillary. The method has restrictions for example with respect to the drop formation time. If drops are formed too fast the measured drop volumes are no longer a measure of the surface tension alone but are in addition governed by chaotic effects leading to so-called drop volume bifurcations. A drop volume experiment is described is this chapter.

A method of preparing modified surfaces, referred to as soft-landing, is described in which intact polyatomic ions are deposited from the gas phase into a monolayer fluorocarbon surface at room temperature. The ions are trapped in the fluorocarbon matrix for many hours. They are released, intact, upon sputtering at low or high energy or by thermal desorption, and their molecular compositions are confirmed by isotopic labeling and high-resolution mass measurements. The method is demonstrated for various silyl and pyridinium cations. Capture at the surface is favored when the ions bear bulky substituents that facilitate steric trapping in the matrix.

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.

Synchronous, real-time optical and electrical diagnostics have been carried out on dielectric barrier discharges in flowing gases (air, He, N₂) at atmospheric pressure. A true “Atmospheric Pressure Glow Discharge” (APGD) is observed in N₂ when O₂ and H₂ concentrations are below ≈500 ppm and 2500 ppm,respectively, and the APGD regime can be beneficially modified by suitably chosen dielectric coatings. X-ray photoelectron spectroscopy (XPS) analyses of some APGD-treated polymer surfaces are presented.

The effect of different nebulized liquids directly introduced into the dielectric barrier discharge (DBD) was compared with simple air DBD treatment of polyethylene foils. Water, alcohols and aqueous solutions of different organic substances (environmentally compatible) and water soluble polymers were applied as aerosols and injected into the DBD zone. The DBD residence time (number of treatment cycles) and the power were varied. The durability of the surface modification effect was studied after removing of Low-Molecular Weight Oxidized Material (LMWOM) by washing the samples with water and ethanol. The modified foils were characterized by XPS and contact angle measurements as a function of the applied plasma conditions. The concentration of functional groups at modified surfaces was estimated by derivatization and subsequent XPS measurement.