Zdeněk Krtouš

Plasma polymer films typically consist of very short fragments of the precursor molecules. That rather limits the applicability of most plasma polymerisation/plasma-enhanced chemical vapour deposition (PECVD) processes in cases where retention of longer molecular structures is desirable. Plasma-assisted vapour thermal deposition (PAVTD) circumvents this limitation by using a classical bulk polymer as a high molecular weight “precursor”. As a model polymer in this study, polylactic acid (PLA) has been used. The resulting PLA-like films were characterised mostly by X-ray photoelectron spectroscopy (XPS) and nuclear magnetic resonance (NMR) spectroscopy. The molecular structure of the films was found to be tunable in a broad range: from the structures very similar to bulk PLA polymer to structures that are more typical for films prepared using PECVD. In all cases, PLA-like groups are at least partially preserved. A simplified model of the PAVTD process chemistry was proposed and found to describe well the observed composition of the films. The structure of the PLA-like films demonstrates the ability of plasma-assisted vapour thermal deposition to bridge the typical gap between the classical and plasma polymers.

Poly(ethylene oxide) (PEO)-like thin films were successfully prepared by plasma-assisted vapor thermal deposition (PAVTD). PEO powders with a molar weight (Mw) between 1500 g/mol and 600,000 g/mol were used as bulk precursors. The effect of Mw on the structural and surface properties was analyzed for PEO films prepared at a lower plasma power. Fourier transform (FTIR-ATR) spectroscopy showed that the molecular structure was well preserved regardless of the Mw of the precursors. The stronger impact of the process conditions (the presence/absence of plasma) was proved. Molecular weight polydispersity, as well as wettability, increased in the samples prepared at 5 W. The influence of deposition plasma power (0–30 W) on solubility and permeation properties was evaluated for a bulk precursor of Mw 1500 g/mol. The rate of thickness loss after immersion in water was found to be tunable in this way, with the films prepared at the highest plasma power showing higher stability. The effect of plasma power deposition conditions was also shown during the permeability study. Prepared PEO films were used as a cover, and permeation layers for biologically active nisin molecule and a controlled release of this bacteriocin into water was achieved.