Low- and atmospheric-pressure plasma co-polymerisations of binary gas mixtures of C2H4 and NH3 or N2, respectively, were investigated for depositing N-rich plasma polymer coatings for biomedical applications. Deposition kinetics and relevant surface characteristics of resulting plasma polymerised ethylene enriched with nitrogen, PPE:N, coatings were investigated as a function of the gas mixture ratio, X = NH3(N2)/C2H4. Physico-chemical properties of the coatings were determined using a combination of complementary surface-sensitive techniques: for example, total nitrogen concentrations, [N], up to 40 at.% were measured by X-ray Photoelectron Spectroscopy, XPS, while those of primary amines, [NH2], were determined by performing chemical derivatisation followed by XPS analyses. PPE:N films were further characterised by UVVIS Ellipsometry, Near Edge X-ray Absorption Fine Structure Spectroscopy, IR Spectroscopy and by Contact Angle Goniometry measurements. The stability of the coatings was tested, both in terms of water solubility and of ageing in ambient atmosphere. For the latter, selected samples were stored in the laboratory for different durations, in order to assess possible changes in their chemical structures.
Selected FTIR, XPS and NEXAFS spectroscopy results obtained with films deposited with different plasma polymerization processes and different monomers (styrene, acetylene, ethylene and butadiene) are presented. In detail FTIR spectra, XPS surveys, XPS valence bands and core level signals including shake-up features as well as carbon K-edge absorption spectra are qualitatively and, in some cases, semi-quantitatively considered. Information on the film formation, the chemistry of the films and the film stability against air exposure are derived from spectroscopic features. With styrene chemically rather well defined plasma polymer layers can be formed with rather high deposition rates applying a pulse plasma process. Using ethylene, acetylene or butadiene as a monomer in the plasma deposition process the deposition rates are smaller. Using these monomers plasma polymer films can be obtained with a primary chemical structure which is similar to each other but more or less different from those of the respective conventional polymers. The main difference between these samples is their individual concentration of unsaturated carbon species. Finally, a technologically relevant example, i.e. a plasma deposited polymer barrier layer deposited on the inner wall of a poly(ethylene) vessel is briefly considered.
Static ToF-SIMS analysis of plasma chemically deposited ethylene/allyl alcohol co-polymer films
(2006)
A plasma co-polymerization of ethylene as a chain extending monomer and allyl alcohol as a carrier monomer for hydroxyl groups was studied. The composition of the feed gas was systematically varied and the plasma co-polymers were analyzed in terms of their relative concentrations of OH functional groups by static Time of Flight Secondary Ion Mass Spectrometry (ToF-SIMS) immediately after their preparation without any air contact, i.e., under so called in situ conditions.
The relative OH group concentration involved in the CH2OH groups was derived from the normalized yields of the CH3O+ secondary fragment ion. The density of functional groups in the plasma co-polymers was found to vary non-linearly with respect to the mole percentage of the monomers in the feed gas.
Co-polymerization phenomena, i.e. chemical interactions and recombination reactions taking place between monomer molecules in the plasma and/or during the deposition process, become evident in ToF-SIMS spectra.
Ripeness and senescence of climacteric fruits are strongly related to the emission of ethylene gas. The ethylene emission of apples can be detected by a new developed ripeness indicator. This indicator is based on the reduction effect of ethylene causing colour changes in selected metal ions. The used molybdenum (Mo) chromophores change under the impact of ethylene in a colour spectrum from white/light yellow to blue because of a partial reduction of Mo(VI) to Mo(V). The sensitivity of molybdenum colour change reactions can be varied by composition and pH values (pH 1.4–pH 1.5) of used ammonium molybdate solution and thus adopted to different fruits and storage conditions. The indicator can be combined with a colour recognition sensor for quantitative measurements of colour change in the frame of the L*a*b* model. The b*-coordinate, reflecting changes from yellow to blue, and the luminance L* continuously vary with increasing ethylene emission. Results obtained with the indicator system were compared with direct determination of ethylene concentrations by gas chromatography (GC-FID). Furthermore, a descriptive sensory test was used to estimate the degree of ripeness. The indicator can be applied for ripeness gauge on single fruit or in paperboard crates.