No description available.

Photo-oxidatative degradation in isotactic polypropylene (PP) has been examined in samples made by both injection and compression moulding and using different moulding conditions. Samples were exposed to ultraviolet (UV) radiation in the laboratory for periods up to 48 weeks. The specimens were tested in tension and the fracture surfaces were inspected by scanning electron microscopy. The extent of chemical degradation was assessed by gel permeation chromatography and Fourier transform infrared spectroscopy. The structural characterization of the as-moulded and UV-exposed materials was conducted by differential scanning calorimetry, X-ray diffraction, pole figure analysis, and polarized light microscopy. Filled grades of PP containing talc were also investigated. The mechanical properties of degraded PP were shown to be highly dependent on aspects like the extent and depth-profile of degradation, the character of the polymer physical structure, and the presence of filler and nucleating agent. Injection moulded bars containing weld lines were also investigated, and their mechanical properties were generally poorer than those for equivalent samples without weld regions. With most samples studied here a partial recovery in tensile properties was observed after 6-9 weeks exposure. Analysis of the fracture surfaces indicated that in the specimens with better properties the surface cracks did not propagate into the undegraded interior. An increase in the polymer crystallinity was observed during exposure, caused by rearrangement of molecule segments released by oxidative scission in the non-crystalline region. This process, called chemi-crystallization, continues until a large number of chemical defects is present within the molecules, and it results in surface cracks formed spontaneously during exposure. In injection moulded samples the pattern of surface cracks featured circular arcs radiating from the injection gate and they were correlated with the flow lines generated during mould filling. The concentration of surface cracks in these samples varied with the location in the test bar, according to local variations in crystal orientation. The crystallization of photodegraded PP from the melt was investigated under isothermal and non-isothermal conditions. The kinetics of crystallization, degree of crystallinity, and morphology were shown to depend on the molecular weight and on the presence of chemical impurities within the molecules. The crystal y-phase was formed in specimens exposed for more than 18 weeks. Double peaks were normally observed in DSC heating experiments of unfilled polypropylene and were assigned to crystal re-organization during heating. The existence of different molecule species was detected by DSC and light microscopy, and might also have contributed to the melting behaviour.

No description available.

In the modern ocean, manganese is oxidized over a timescale of days. To better understand the mechanisms and driving factors for manganese oxidation in the natural environment, experiments were performed with surface water samples collected from the San Antonio Bay. In this study area, the formaldoxime assay was utilized to determine that manganese oxidation is catalyzed via multiple pathways utilizing various catalysts and proximal oxidants. The contribution of catalysts such as colloidal matter, microorganisms and the proximal oxidant superoxide were investigated in the San Antonio Bay. The study suggests that superoxide contributed about 30% of Mn oxidation. The microorganisms and colloids were equal in terms of catalysis and accounted for approximately 100% of Mn oxidation. This study is important because gaining more understanding on the mechanisms by which Mn is oxidized will contribute to its use as a geochemical redox indicator.

No description available.

Graduation date: 1971

Mechano-chemical activation is fundamentally different than chemical activation in that energy is added to alter the state of bond energy instead of exciting electrons to produce a chemical reaction. Mechano-chemical activation has demonstrated to alter the chemical reaction and rates. There remains no development of a model to quantify the changes in reactions due to mechano-chemical activation. This research aims in expanding our understanding of the influence of mechanochemical activation methods. The dynamics and kinetics of mechano-chemically activated surfaces will be studied using x-ray spectroscopy methods. Mechano-chemical interactions can be quantified through the study of electron energies. X-ray spectroscopy is a useful method of analyzing and quantifying electron energy states. X-ray absorbance is used to study the valence state electron shells of iron undergone activation through sliding friction of naturally produced wax. In-situ x-ray photoemission spectroscopy is employed to instantaneously characterize single crystal tantalum samples of each principal crystallographic orientation during oxidation. Sliding friction of the naturally produced wax resulted in a reduction in the binding energy of the iron 2p electrons by approximately one electron-volt. This reduction in binding energy is attributed to ferrocene which is an organo-metallic alloy, Fe(C5H5)2. Mechanical strain of the crystal lattices of tantalum resulted in altered activation energies. Activation energy increased with the application of lattice strain. At increasing strain, oxide properties become more dependent on the lattice strain than the crystal orientation and temperature. A model system is developed incorporating mechanical strain into the prediction of activation energy and rates.

xvii, 135 leaves : ill., graphs / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Thesis (Ph.D.)--University of Adelaide, Dept. of Agricultural Biochemistry, Waite Institute, 1969

Thesis (D. Sc.)--Dept. of Animal Science, University of Adelaide, 1985. / Offprints of 35 journal articles inserted. Includes bibliographical references (leaves 28-29).

Thesis (Ph. D.)--University of New South Wales, 1976. / "Thesis submitted for the Degree of Doctor of Philosophy in the School of Biological Technology, University of New South Wales, 1976." Includes bibliographical references. Also available online.