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Dynamical heterogeneity (DH) has been observed in many systems approaching the glass or jamming transition. Whether DH has a structural origin is under heated debate. To provide a deeper understanding, in this thesis I investigate the microscopic dynamics in weakly attractive colloidal systems by confocal fluorescence microscopy. The van Hove density-density correlation function is applied to our systems. Separable fast and slow populations emerge in the self part (svH), while the distinct part shows a strong signature of DH close to the gel transition. At intermediate time, svH shows a purely exponential tail, mainly arising from the fast population. I show that this broad tail is a direct consequence of the occurrence of rare large jumps that are statistically distributed. The slow population tends to form a space-spanning backbone, and its mean squared displacement close to the gel transition exhibits a plateau, whose height is consistent with the range of attraction, suggesting a bonding mechanism for the dynamical arrest. I further examine various quantities characterizing local structure and local dynamics and a strong correlation is identified between them. Subsequently, I develop order parameters for quantifying amorphous structure and apply them to our systems. I find that attractive colloidal systems exhibit higher order under higher attraction tension, while hard spheres become more ordered under higher compression. Finally, I investigate the effect of the range of attraction on the structure and dynamics of attractive colloidal systems. I observe that the system with shorter range of attraction forms a denser and more heterogeneous structure. Meanwhile, I observe an even stronger dynamical heterogeneity. These observations provide further evidence of a connection between structural heterogeneity and dynamical heterogeneity in these systems, providing guidance for a theoretical description of the dynamical arrest as well as the relaxation mechanisms upon gelation and its relation to solidification in glasses. / In order to do all of this, I first implemented full 3D subpixel resolution localization of particles and improved particle tracking algorithms tailored for the sorts of heterogenous dynamics these systems exhibit, that otherwise confounds existing methods such that the very relaxation mechanisms would be missed. This allows us to obtain unprecedented precision in positions of all of the particles and complete tracking, both of which are essential for correctly determining system properties that depend on measured particle dynamics.

In this thesis we describe two separate experiments involving the use of gold nanoparticles. The first experiment looks at the use of gold nanoparticles as a localized heat source and the potential application as a cancer treatment. The second experiment, which is the real focus of this thesis, applies gold nanoparticles in the study of the free surface dynamics of glassy thin films. Gold nanoparticles have the ability to strongly absorb the energy in an incident laser beam and convert that energy into heat. Photothermal therapy is a proposed cancer treatment which exploits this ability to irreparably damage cancerous tissues surrounding gold nanoparticles. In the first chapter of this thesis we explain an experiment designed to probe the local temperatures achieved in such a process. Gold nanoparticles are used to stabilize the boundary of an inverse micelle system which contains an aqueous fluorescent dye solution on it's interior. A temperature dependent fluorescence intensity allows us to probe the temperature changes induced by laser irradiation. In the remainder of this thesis we describe a separate experiment involving the use of gold nanoparticles to study the free surface dynamics of thin glassy films. There is a growing body of evidence in the literature that thin polymer films in the glassy state exhibit heterogeneous dynamics; specifically that the first few nanometers from an air-polymer interface exhibit enhanced mobility relative to the interior of the film. The underlying mechanism responsible for this enhanced mobility remains elusive, however some believe it to be a direct consequence of the polymeric nature of these films. We describe in detail an experiment aimed at addressing this concern. We deposit gold nanoparticles onto the surface of a molecular (non-polymeric) glassy film and monitor their behaviour upon heating using atomic force microscopy. Our results clearly show the existence of enhanced surface mobility in the system studied and provide strong evidence that enhanced surface mobility should be expected in all glass forming systems.

The production of free flowing powder by spray drying of sugar-acid rich foods requires an appropriate carrier. High molecular weight materials such as maltodextrins are commercially used as a drying aid because of their high glass transition temperature (Tg). Alternatively, fibre-rich by-products from fruit and vegetable juice processing might provide high molecular weight elements that are suitable as a drying support. This study aimed to understand the variables affecting the spray-dried product of fruit juice so that non-sticky fibre-based juice powder could be obtained. Freeze dried carrot fibre was centrifically-milled to 50-100 µm sizes. Three sugar determination methods; enzymatic, enzyme membrane and HPLC with RID, were compared. The freeze drying performance of fructose, fructose + carrot fibre and fructose + carrot fibre + malic acid had the glass transition temperatures measured by differential scanning calorimetry (DSC) at 0.1 °C min-1. The results from the freeze drying were used as a key for the possibility of spray dried apple juice + carrot fibre. Similar methods were used to study freeze dried fructose + maltodextrin (DE max 9.8) and fructose + maltodextrin + malic acid. Dried sucrose, glucose and fructose were used to study glass transition temperature of melted amorphous sugars and mixtures by the visual experiment and DSC at 0.1°C min-1 of heating and cooling scans. The Gordon-Taylor equation was used to predict the Tg of anhydrous two-sugar mixtures from experimental and literature data. The Coachman and Karaze equation was used to predict Tg of three-sugar mixtures and compared to the experimental data. Spray dried powders of fructose + carrot fibre of 30, 40, 50, 60 and 70% w/w and apple juice concentrate + carrot fibre of 30, 40, 50, 60, 70% w/w at 165/75°C inlet/outlet temperature in a laboratory scale drier were compared to that of fructose + maltodextrin (DE max 9.8) and apple juice concentrate + maltodextrin of 50, 60 and 70% w/w (dry basis). Dielectric analysis in the range 200 Hz -1 MHz between 10-105 °C were applied to find the onset Tg (based on DSC results) from freeze dried mixtures of 14, 21, and 28% w/w (dry basis) carrot fibre+ fructose. The enzymatic method was found to be the most accurate method for sugar determination of fruit juice but the HPLC method was the most practical one. The results of Tg values of sugars and mixtures melted showed that the Tg values from heating and cooling scans of fructose, glucose and sucrose were in good agreement with literature. Fructose acted as a plasticizer; an increase in the fructose fraction decreased the Tg of sugar mixtures. Sucrose increased the Tg of the mixtures while the Tg of the three-sugar mixtures was less variable when there was a moderate to high proportion of glucose. The visual Tg values of sugars and mixtures were 7-28 °C higher than the onset DSC heating and cooling Tg values. This result suggested that more than one method should be used to study the glass transition of substances. The Gordon-Taylor equation did not fit well the Tg values of the dry sugars and their mixtures from this experiment. The variations might have been due to the degradation of sugar samples on the melting process. The Coachman and Karaze equation gave a good prediction of the three-sugar mixtures from this experiment. The carrot fibre was found to be crystalline. Carrot fibre increased the Tg of freeze dried fructose and decreased stickiness of fructose. Increasing malic acid fraction decreased Tg of the mixtures. Freeze dried fructose + maltodextrin showed higher hygroscopicity than freeze dried fructose + carrot fibre. It was not possible to determine Tg of fructose + maltodextrin + malic acid due to the swelling and hygroscopicity of the freeze dried samples. Tg values of freeze dried fructose + carrot fibre and fructose + maltodextrin were found to high enough to allow spray drying of these mixtures. The minimum fraction of carrot fibre to facilitate spray drying of fructose and apple juice concentrate was found to be 30%. Mixtures with maltodextrin at a fraction lower than 50% could not be successfully spray dried. When spray drying fructose + carrot fibre, apple juice + carrot fibre, fructose + maltodextrin and apple juice + maltodextrin at the appropriate ratios most of the powder stuck to the drier walls. The powder swept from the wall was free flowing with moisture content of approximately 2-4%. The Tg values of these powder indicated the wall build-up might be avoided in larger scale drying. Tg values of spray dried powder from the mixtures with fibre and maltodextrin were found to be not very different. The yield from mixtures with carrot fibre was three times higher than those of mixtures with maltodextrin. This cast doubts that Tg alone could be a good indicator for the stickiness of spray dried material. The microscope images and DSC scans of spray dried powders of fructose + carrot fibre and apple juice + carrot fibre showed crystalline material. The particle of spray dried fructose + maltodextrin and apple juice + maltodextrin were mostly amorphous. The crystals are more physically and chemically stable than the amorphous form. Thus carrot fibre is a good additive in spray drying of fruit juice. Dielectric analysis at low frequency was able to possible detect Tg of single and double components. For food polymer with many components it was found that Tg value was not consistently dependent on frequency. In conclusion, carrot fibre was a more effective carrier for spray drying than maltodextrin when compared on a mass basis and spray drying condition. Since edible fibre is an essential element needed by the human body, spray drying of fruit juice using fibre as a carrier showed the great potential of fibre in the application of fruit juice spray drying. In the case of clear juice, after reconstitution, the fibre can be easily separated from the juice as there seemed to be no chemical binding between the juice and the fibre during the spray drying process.

Thesis (M.Eng.)--University of Wollongong, 2005. / Typescript. Includes bibliographical references: leaf 113-121.

Thesis (Ph. D.)--University of Missouri-Columbia, 1998. / Typescript. Vita. Includes bibliographical references (leaves 139-150). Also available on the Internet.

Thesis (Ph. D.)--University of Missouri-Columbia, 1998. / Typescript. Vita. Includes bibliographical references (leaves 139-150). Also available on the Internet.

Thesis (Ph.D.)--Hong Kong University of Science and Technology, 2004. / Includes bibliographical references. Also available in electronic version.

Thesis (Ph.D.) - University of Queensland, 2003. / Includes bibliography.

Rotational-translational decoupling, in which translational motion is apparently enhanced overrotational motion in violation of Debye-Stokes-Einstein predictions, has been observed in a wide variety of materials near their glass transition temperatures (Tg). This has been posited to result from ensemble averaging in the context of dynamic heterogeneity. In this thesis, single fluorescent probe molecules are tracked rotationally and translationally to interrogate this explanation. In one study, ensemble and single molecule experiments are performed in parallel on the ideal fluorescent probe N,N’-dipentyl-3,4,9,10-perylenedicarboximide (pPDI) in high molecular weight polystyrene near its Tg. Ensemble results show decoupling onset at approximately 1.15Tg, increasing to over three orders of magnitude at Tg. Single molecule measurements also show a high degree of decoupling, with typical molecules at Tg showing translational diffusion coefficients nearly 400 times higher than expected from Debye-Stokes-Einstein predictions. The same experiments were performed on a microscope with somewhat lower spatial resolution to investigate the role of localization accuracy in apparent degree of breakdown. Here similar, though slightly larger, degrees of breakdown were found, consistent with the idea that averaging across heterogeneous regions, even within a single molecule’s trajectory, is the primary driver of rotational-translational breakdown, while the lower degree of localization accuracy of the microscope additionally leads to some sub-ensemble selection that further inflates apparent breakdown. Across all single molecule experiments, higher degree of breakdown is associated with particularly mobile molecules and anisotropic trajectories, providing support for anomalous diffusion as a critical driver of rotational-translational decoupling and Debye-Stokes-Einstein breakdown. In a final study, single molecule translational simulations are performed with varying types (spatial and dynamical) and degrees of heterogeneity to assist in interpreting results of single molecule translation experiments. These reveal that fast portions of translational trajectories inflate diffusion coefficients and that, taken together with experimental results, the majority of rotational- translational decoupling in glassy systems occurs through dynamic exchange consistent with wide underlying distributions of diffusion coefficients and exchange coupled to local spatiotemporal dynamics.