Industrial applications based on plasma polymerization require reliable processes that can be transferred to production‐scale reactors. To enable an inexpensive access to control plasma deposition processes, macroscopic kinetics were investigated to describe plasma polymerization, which is based on the concept of chemical quasi‐equilibrium. The evaluation of deposition rates was carried out in order to obtain the apparent activation energy for a specific process. Influencing factors, such as substrate temperature, energetic particles, reactor geometry, plasma expansion, pressure, monomer, carrier/reactive gas, power modulation, and plasma source were thoroughly examined. The obtained activation energy was correlated to the plasma‐chemical processes, such as dissociation and radical formation, which are taking place within the active plasma zone. Since these processes are also contributing to the film growth, the activation energy was used for the scale‐up of plasma polymerization processes.
A d.c. oxygen glow discharge was used to modify medical-grade poly(vinyl chloride) (PVC) to study how surface chemistry and hydrophilicity influence Pseudomonas aeruginosa adhesion. The effects of plasma exposure time on the resulting surface, including chemical composition, wettability and roughness, were assessed using x-ray photoelectron spectroscopy, contact angle measurements and atomic force microscopy analysis. A significant alteration in the hydrophilicity of the native PVC surface was observed after oxygen glow discharge treatment. The water contact angle decreased from ∼80• to 8-20• , with a weak dependence of the exposure time used. The change in surface wettability resulted from the incorporation of oxygenated functional groups, including esters, ketones and acids, as indicated by XPS analysis. The amount of oxygen incorporation was shown to be essentially independent of plasma exposure time. However, prolonged plasma exposure resulted in increased surface roughness. Bacterial adhesion efficiency was evaluated for PVC modified by 120 s of plasma exposure, because this exposure time was determined to yield the maximum decrease in contact angle. Oxygen plasma treatment of native PVC was found to yield a 70% reduction in bacterial adhesion for the four strains of Pseudomonas aeruginosa tested.
Biomaterials releasing silver (Ag) are of interest because of their ability to inhibit pathogenic bacteria including antibiotic-resistant strains. In order to investigate the potential of nanometre-thick Ag polymer (Ag/amino-hydrocarbon) nanocomposite plasma coatings, we studied a comprehensive range of factors such as the plasma deposition process and Ag cation release as well as the antibacterial and cytocompatible properties. The nanocomposite coatings released most bound Ag within the first day of immersion in water yielding an antibacterial burst. The release kinetics correlated with the inhibitory effects on the pathogens Pseudomonas aeruginosa or Staphylococcus aureus and on animal cells that were in contact with these coatings. We identified a unique range of Ag content that provided an effective antibacterial peak release, followed by cytocompatible conditions soon thereafter. The control of the in situ growth conditions for Ag nanoparticles in the polymer matrix offers the possibility to produce customized coatings that initially release sufficient quantities of Ag ions to produce a strong adjacent antibacterial effect, and at the same time exhibit a rapidly decaying Ag content to provide surface cytocompatibility within hours/days. This approach seems to be favourable with respect to implant surfaces and possible Ag-resistance/tolerance built-up.
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