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The purpose of this thesis was to determine which contaminants were present in washed and dried shredded poly(ethylene terephthalate) (PET, flake) obtained from curbside collection and to determine whether their concentrations were above the US FDA threshold of 215 ppb. Over thirty semi-volatile contaminants were extracted from the treated flake by Soxhlet extraction using dichloromethane as a PET swelling solvent and gas chromatography-mass spectroscopy for identification and quantification. Soxhlet extraction of flake ground to 0-300 �m was effectively completed by 24 h, whereas sonication reduced the extraction time to 3 h. In contrast Soxhlet extractions on flake ground to a larger particle size range (>300-425 �m and >425-700 �m) were completed within four hours, possibly due to less aggregation in the extraction thimble. In the finely ground flake (0-300 �m) the levels of most contaminants were below 215 ppb, but six were not. Dodecanoic acid was present at about 1200 ppb, 2-butoxyethanol was approximately 1000 ppb, limonene, benzophenone and methylsalicylate were above 800 ppb and 2-methylnaphthalene near 215 ppb. After analogous method development the levels of all diffusible compounds in extruded PET pellets were below the threshold of 215 ppb. The Soxhlet extraction technique was validated by comparison with total dissolution by TFA for two of the three particle size ranges obtained by grinding the PET flake (>300-425 �m and >425-700 �m) and for the unground flake. Further validation was achieved by the comparison of contaminant levels determined by total dissolution with TFA and sonication with DCM using flake ground to the 0-300 �m size range. The levels of contaminants were found to increase with decreasing particle size range, but XRD measurements of degrees of crystallinity were similar for each PET particle size range, thus showing that the differences in contaminant levels were not due to variable percentages of the amorphous material from the tops and bottoms of shredded bottles, relative to the amounts of crystalline PET from the mid-sections of the bottles. Hence it was postulated that the variations in contaminant levels were due to selective grinding of the more highly contaminated surfaces, whilst the larger particles incorporated the less contaminated interior material. The analysis of the more homogenous annealed (extruded) pellets indicated that contaminant levels between the analogous particle size ranges were equivalent. This observation validated our interpretation of the high levels of contaminants found in finely ground flake being due to selective surface grinding where high levels are expected. When analysing volatiles, static headspace analysis was performed on flake and extruded pellets due to the limitations surrounding SPME. External standardisation was used as the method of quantification and the levels of toluene, undecane and p-xylene in extruded pellets were found to be below 38 ppb and therefore within the 215 ppb FDA-set threshold for flake and pellets.

published_or_final_version / Mechanical Engineering / Master / Master of Philosophy

published_or_final_version / abstract / Ecology and Biodiversity / Master / Master of Philosophy

Organic electrode materials, as sustainable and environmental benign alternatives to inorganic electrode materials, show great promise for achieving cheap, light, versatile and disposable devices for electrical energy storage applications. Conducting redox polymers (CRPs) are a new class of organic electrode materials where the charge storage capacity is provided by the redox chemistry of functional pendent groups and electronic conductivity is provided by the doped conducting polymer backbone, enabling the production of energy storage devices with high charge storage capacity and high power capability. This pendant-conducting polymer backbone combination can solve two of the main problems associated with organic molecule-based electrode materials, i.e. the dissolution of the active material and the sluggish charge transport within the material. In this thesis, diethyl terephthalate and polythiophenes were utilized as the pendant and the backbone, respectively. The choice of pendant-conducting polymer backbone combination was based on potential match between the two moieties, i.e. the redox reaction of terephthalate pendent groups and the n-doping of polythiophene backbone occur in the same potential region. The resulting CRPs exhibited fast charge transport within the polymer films and low activation energies involved charge propagation through these materials. In the design of these CRPs an unconjugated link between the pendant and the backbone was found to be advantageous in terms of the polymerizability of the monomers and for the preservation of individual redox activity of the pendants and the polymer chain in CRPs. The functionalized materials were specifically designed as anode materials for energy storage applications and, although insufficient cycling stability was observed, the work presented in this thesis demonstrates that the combination of redox active functional groups with conducting polymers, forming CRPs, shows promise for the development of organic matter-based electrical energy storage materials.

Since decades, nucleation, or the ability of certain organic or inorganic substances to trigger the crystal growth, has been empirically used in the plastics industry. Talc, for instance, is a well-known nucleating agent of poly(ethylene terephthalate) (PET) and other polymers, that allows one to enhance the crystallisation rate of the polymer material and to control its spherulites size. The exact mechanism involved in this nucleation had however remained unknown at the onset of this thesis. Through electron diffraction, performed on thin PET films nucleated by macroscopic talc particles as model samples, this work demonstrates an epitaxial relationship between polymer and substrate and thus confirms the seemingly ubiquitous role of epitaxy in the nucleation of polymers. However, in order to compare the talc-nucleated morphology of PET with the virgin one, new methods of sample preparation for transmission electron microscopy (TEM) have also been developed. Coupled with theoretically justified image analysis techniques, they allow the direct observation of PET crystalline lamellae, both in the bulk and in thin films. Analyses of the semicrystalline structure in the reciprocal and direct spaces were performed from small-angle X-ray scattering (SAXS) data and from observations by TEM on melt-crystallised samples. These independent results were shown to be in good agreement and bring strong evidence in favour of a semicrystalline space-filling model, where the average crystalline thickness is slightly smaller than the average width of the amorphous regions. Discrepancies between characteristic distances derived by several methods from the same experimental results were attributed to the broad distribution of thicknesses, in contrast with the ideal linear stack model commonly used to analyse the data.

Differential scanning calorimeter (DSC) and temperature modulated differential scanning calorimeter (TMDSC) were used to study the isothermal crystallization kinetics and the melting behaviors at heating rates of 2, 10, 50, and 80

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