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Polymer surfaces were modified by exposure to a silent discharge plasma, by exposure to UV radiation and by chemical functionalisation. Additionally, the silent discharge treatment of alkali halide disks was investigated. Employing XPS and IR, the silent discharge treatment of poly (phenylmethylsilane) and poly (cyclohexylmethylsilane) thin films was found to result in the formation of a carbonaceous SiO(_x) layer. Oxidation occurred faster and to a larger degree in the case of the aromatic polysilane. A XPS study of the UV irradiation of poly (phenyhnethylsilane) thin films in the presence of CCI(_4) vapour revealed the formation of a chlorinated silicon species. The analysis of aged samples showed that this initially formed product was unstable in moist air. The silent discharge treatment of alkali halide disks (KCI, KBr, KI) was studied in ambient air, as well as in dried and humidified gases (artificial air. He, N(_2), O(_2)). IR and XPS were used as analytical methods, hi most cases nitrate and halogenate were formed upon treatment in air. Depending on the reaction conditions treated KI disks sometimes showed the presence of nitrite as an additional or as the main product. In oxygen atmospheres halogenate was formed as the exclusive product. Treatments in the remaining atmospheres did not lead to product formation. The presence of water vapour in the feed gas increased the amount of product. Changes in the IR spectra of the nitrate species upon storage in a desiccator and after exposure to heat were found and monitored. Pentafluoropropionic anhydride was tested for its suitability as a vapour phase labelling reagent for hydroxyl groups on polymer surfaces. Derivatised films were analysed by XPS and IR. Using Polyvinyl alcohol as a model polymer the reaction proceeded fast and quantitative. Moreover, the cross-reaction with a number of polymers containing functionalities other than hydroxyl was studied. The reaction with nylon 6,6 was investigated m detail. The vacuum photodegradation of polyethersulfone upon irradiation with the full and a selected part of a Hg (Xe) lamp spectrum was studied. The volatile products were identified with in-situ quadrupole mass spectrometry. Monitoring the intensities of some products in subsequent irradiation phases provided evidence for a crosslinking process. In samples irradiated with the complete lamp spectrum crosslinkmg occurred faster. Additionally, the XP spectra of the corresponding samples revealed a stronger modification which became most obvious in the presence of a reduced sulfur species.

This thesis presents theoretical and experimental study of properties of amorphous diamond-like carbon (DLC) coatings synthesised using discharge plasma methods. There were two objectives in this study. The first objective was to investigate the formation mechanism of hydrogenated DLC films (a-C:H) in an open hydrocarbon plasma source. The inductively coupled plasma (ICP) reactor was used to synthesise the films and the formation of sp2 and sp3 hybridised phases and the combination of these phases in the ICP plasma environment was studied. It was found that for a-C:H films with narrow distribution of the sp3 content the mechanical properties are determined by the degree of disorder of the sp2 fraction. The relationship between the sp3 content in fabricated films and hardness and Young's modulus was established. Raman and multi-wavelength (Vis – UV range) Raman spectroscopy was primarily used together with other suitable analytical methods to examine a-C:H films and it was found that films fabricated at higher ion energies displayed higher degree of clustering and bonding disorder than films produced at lower ion energies. All as fabricated a-C:H films were also found contain basic π-conjugated polymer inclusions as of trans-polyacetylene. The Raman results also reveal that the magnitude of Rayleigh scattered light is related to the relative density of the films, a feature that can be useful for monitoring film growth in-situ. The use of X-ray photoelectron spectroscopy (XPS) as a suitable method for measuring the sp3 content of the bulk DLC was also established. The second objective was to develop a fabrication technique that would allow fabrication of DLC films using graphite target sputtering with a single focused ion beam source and producing films with medium-high sp3 content. This research was motivated by the industrial partner of the project Laserdyne Pty Ltd that required a simple DLC deposition apparatus to be integrated into a standard, stand alone, optical thin film deposition chamber. Such technique was developed on the basis of a conventional ion beam target sputtering. In our experiments hydrogen-free DLC films with medium sp3 content were produced using a single, Kaufmann type ion source operated at low energies. The fabrication technique, denoted a reactive ion beam sputter deposition (RIBSD), was based on sputtering a graphite target at low incident angles and positioning the substrate at the grazing angles to the incoming ions, thus the incident ions (Ar and Xe ions were used) were simultaneously bombarding the target and the growing film. The effect of angle of incidence of an ion beam to the target and to the substrate in creating the sp3 content in DLC was investigated. It was found that the infringement bombardment of the substrate was not favourable for DLC growth as it essentially provided for a secondary re-sputtering process. Quality DLC films with approximately 40 % of the sp3 content were fabricated at the optimal angle of the ion flux to the target of 30º and to the substrate of 0º (parallel to the ion bema axis). The increased ion energy contributed to structural changes in DLC from predominantly sp2 graphitic like bonding to tetrahedral sp3 bonding arrangement.

Thesis (M.S.)--Air Force Institute of Technology, 2007. / AFIT/GCA/ENV/07-MI. "March 2007." Includes bibliographical references (leaves 41-44).

Thesis (M.Sc.) --University of Adelaide, 1951. / Typewritten copy.

Thesis (M.H.A.)--University of Michigan, 1972.

Thesis (Ph. D.)--University of Missouri--Columbia, 1996. / "December 1996." Typescript. Vita. Includes bibliographical references (leaves 107-109). Also available on the Internet.

Thesis (M.S.)--University of Michigan, 1989.

Thesis (M.S.)--University of Michigan, 1987.

Thesis (M.H.A.)--University of Michigan, 1972.