Non-isothermal plasma treatment of organic and inorganic polymers
Increased understanding of plasma-polymer interactions is required to further the technological use of such processes, and elucidates heterogeneous physico-chemical reactions which occur under bombardment by complex combinations of energetic species. This thesis presents a systematic investigation into the effect of exposing organic and inorganic polymeric surfaces to controlled non-isothermal plasmas. Concurrently, a novel process is presented by which metal oxide gas barrier coatings are synthesized on polymer substrates by non- isothermal plasma treatment. Organic polymers exhibiting a range of structures were modified using non-isothermal plasmas at atmospheric and low pressure. The extent of atmospheric discharge oxygenation, measured by X-ray photoelectron spectroscopy (XPS), correlated with the polymers' ozonolysis rate constants. Surface physical disruption, studied using atomic force microscopy (AFM), after atmospheric discharge treatment was more pronounced than after low pressure plasma treatment. During low pressure oxygen plasma treatment, polymers containing phenyl groups were oxygenated to an extent which varied with the strength of π-π* valence band excitation in XPS C(1s) spectra of the untreated polymers, suggesting a dominance of reaction of plasma atomic oxygen at polymer radical sites excited by plasma vacuum ultraviolet radiation. The size of globules, observed by AFM, on the plasma modified surfaces correlated with the extent of surface chemical modification, inkeeping with a mechanism of chemically driven agglomeration of plasma oxidized low molecular weight polymer material. Oxygen plasma was more effective than water plasma in chemically modifying the surface of films of zirconium-normal-butoxide spin coated on polyester substrates, and the resulting optimized treatment produced a significant reduction in gas permeation of the substrate. XPS studies showed that oxygen plasma treatment of a polyphenylsilsesquioxane film on polyester film created a SiO(_2) layer less than 8 nm thin, which reduced O(_2) and Ar permeation of the coated film by 37.5 % and 31.6% respectively.