Perfluorosulfonate ionomer (PFSI) membranes were annealed at elevated temperature for various periods of time in order to investigate the morphological effects of thermal treatments. For Nafion® 117, the DSC thermograms of Na+-, Cs+- and tetramethylammonium(TMA+)-form membranes show an endothermic peak develops upon annealing at 200ºC, indicating the development of crystallinity in the membrane. For these three samples annealed under same conditions, the heat of fusion (ΠH) values of the endothermic event increases with increasing counterion size. Larger tetraalkylammonium ions, tetraethylammonium(TEA+) and tetrapropylammonium(TPA+), result in no significant peak upon annealing at 200ºC. DSC thermograms of annealed Na+-form 3M Ionomer show no peak upon annealing and DSC thermograms of annealed TMA+-form 3M Ionomer show a very small peak that develops with annealing time at high equivalent weights. Annealed TMA+-form Dow Ionomer, which has a side chain shorter than both Nafion® and 3M Ionomer and a smaller mole% of side chains at the same equivalent weight, shows a relatively high ΠH value, which might also be related to its blocky nature. These results show that the isothermal crystallization kinetics of PFSI is affected by the counterion attached to the sulfonate group, the length of side chain, the mole% of side chains and the nature of the membrane. Water uptake analysis has been performed on annealed membranes, and the result shows that water uptake decreases with increasing degree of crystallinity. / Master of Science

Diferentes estratégias de flotação (reagentes, pH e rota) têm sido utilizadas na separação entre apatita e carbonatos em todo o mundo. Há evidências na literatura de que a cristalinidade afeta a flotação de apatitas e calcitas com oleato de sódio. Além disso, a dissolução dos sais semi-solúveis pode influenciar a interação entre a superfície dos minerais e os reagentes de flotação, uma vez que o mecanismo de adsorção mais importante é a precipitação de oleato de cálcio na interface sólido/líquido. Portanto, o objetivo deste trabalho é investigar a relação entre cristalinidade, cinética de dissolução e resposta à flotação de apatitas e calcitas de diferentes gêneses (ígnea, metamórfica e sedimentar) e origens. Quatro tipos de minerais foram utilizados: purificados a partir de minérios, previamente purificados, naturalmente puros e amostras de coleção. As amostras foram caracterizadas por fluorescência de raios-X e microanálise (WDS/EDS). Características físicas como densidade (d), área superficial (S) e porosidade (P) também foram determinadas. O método de Rietveld aplicado à difração de raios-X foi usado tanto para comprovar a pureza das amostras como para estudar a cristalinidade dos minerais por meio da determinação dos parâmetros de rede (distâncias a e c, e volume da cela unitária- VCU), além do grau de cristalinidade (GC), tamanho de cristalito (TC) e microdeformação (MD). Ensaios de dissolução, conduzidos na ausência de CO2, forneceram a quantidade (mol) de íons Ca2+ (nCa2+) dissolvidos em função do tempo (t) e normalizada em relação à área superficial. Os resultados se ajustam a um modelo de primeira ordem: nCa2+ = Ca2+MAX(1- e-kt). Este procedimento permitiu calcular os valores da quantidade máxima de íons Ca2+ dissolvidos (Ca2+MAX), bem como da constante cinética (k). Além disso, a velocidade de dissolução foi determinada para a etapa rápida (VR), que caracteriza o início da reação, e para a etapa lenta (VL), que ocorre nas proximidades do estado estacionário. A resposta à flotação com oleato de sódio foi determinada por meio de experimentos de microflotação. Várias relações de causa e efeito são encontradas: flotabilidade (F) versus VR, e VR versus características intrínsecas (parâmetros de rede, de cristalinidade e físicos). VR foi selecionado para participar de tais modelos, pois, caracteriza o intervalo de tempo em que o condicionamento (1 minuto) e a microflotação (1 minuto) ocorrem. Observa-se que a flotabilidade dos minerais aumenta com o aumento de VR, sugerindo que apatitas e calcitas que disponibilizam mais íons Ca2+ em solução para interagir com o oleato, exibem mais elevada flotabilidade. Equações lineares de F em função de VR em pH 8 (R = 0,97 para apatitas e R = 0,66 para calcitas) e pH 10 (R = 0,95 para apatitas e R = 0,63 para calcitas) foram encontradas. Correlações lineares múltiplas foram utilizadas para relacionar VR (em pH 8 e 10) com as características intrínsecas que exercem maior influência sobre este parâmetro. Para as apatitas, VR foi equacionado em função de GC, TC e c, enquanto para as calcitas, os parâmetros GC, TC, d e P foram selecionados para compor o modelo. Os valores de VR calculados se ajustam aos observados dentro de um intervalo de confiança de 95%. As equações lineares propostas para as apatitas foram usadas para se estimar F das amostras de Anitápolis-SC e Tapira-MG, que não foram submetidas aos ensaios de dissolução. Os valores de F calculados estão em concordância com aqueles experimentalmente determinados. / Different flotation strategies (reagents, pH and route) have been adopted to separate apatite from carbonates around the world. Literature provides evidences that crystallinity affects flotation response of apatite and calcite with sodium oleate. Furthermore, dissolution of salt-type minerals influences the interaction between mineral surface and flotation reagents, because the most important adsorption mechanism is the surface precipitation of calcium oleate onto mineral/water interface. Therefore, the objective of this research is to investigate the relationship between crystallinity, dissolution kinetics and flotation response of apatites and calcites from different genesis (igneous, metamorphic and sedimentary) and origins. Four sorts of minerals were utilized: minerals purified from ores, minerals previously purified, naturally pure minerals and collection samples. They were characterized by X-ray fluorescence and X-ray microanalysis (WDS/EDS). Physical characteristics, as specific gravity (d), surface area (S) and porosity (P), were also determined. The Rietveld method applied to X-ray diffraction data was used either to probe the purity of samples or to study the crystallinity of the minerals by means of determining their lattice parameters (a and c dimensions plus lattice volume-VCU), in addition to crystallinity degree (GC), crystallite size (TC) and microstrain (MD). Dissolution experiments, conducted in the absence of CO2, yielded curves which relate the amount (mol) of dissolved Ca2+ ions (nCa2+) versus time (t), normalized by the surface area. They fit a first order model: nCa2+ = Ca2+MAX(1- e-kt). Curve fitting via exponential adjustment was accomplished to calculate values of the maximum amount of dissolved Ca2+ ions (Ca2+MAX) and the kinetic constant (k). In addition, the dissolution rate was determined for the fast step (VR), which characterizes the beginning of the reaction, and for the slow step (VL), as it tends to the steady state. Flotation response with sodium oleate was determined by microflotation experiments. Several cause-effect relationships are found: floatability (F) versus VR, and VR versus intrinsic characteristics of minerals (lattice, crystallinity and physical parameters). VR was selected to participate in the model because it characterizes the length of time along which reagent conditioning (1 minute) plus microflotation (1 minute) take place. It is observed that F increases as VR becomes greater, suggesting that samples of apatites and calcites which place more Ca2+ ions in solution to interact with oleate exhibit higher flotation performance. Linear equations of F versus VR at pH 8 (R = 0,97 for apatites and R = 0,66 for calcites) and pH 10 (R = 0,95 for apatites and R = 0,63 for calcites) were found. Likewise, multiple linear correlations were used to relate VR (at pH 8 and 10) with the intrinsic characteristics of apatites and calcites that affect VR to a greater extent. For apatites, VR was modeled as a function of GC, TC and c, while for calcites, the parameters GC, TC d and P were selected to compose the model. The calculated VR values fit the experimental ones within 95% of confidence. The linear equations developed for apatites were used to estimate floatability of the samples from Anitápolis-SC and Tapira-MG, which were not submitted to dissolution experiments. The values of calculated floatability are in agreement with the experimental ones.

ABSTRACT Injection stretch blow moulded PET bottles are the most widely used container type for carbonated soft drinks. PET offers excellent clarity, good mechanical and barrier properties, and ease of processing. Typically, these bottles have a petaloid-shaped base, which gives good stability to the bottle and it is the most appropriate one for beverage storage. However, the base is prone to environmentally induced stress cracking and this a major concern to bottle manufacturers. The object of this study is to explain the occurrence of stress cracking, and to prevent it by optimising both the geometry of the petaloid base and the processing parameters during bottle moulding. A finite element model of the petaloid shape is developed in CATIA V5 R14, and used to predict the von Mises stress in the bottle base for different combinations of three key dimensions of the base: foot length, valley width, and clearance. The combination of dimensions giving the minimum stress is found by a statistical analysis approach using an optimisation and design of experiments software package ECHIP-7. A bottle mould was manufactured according to the optimum base geometry and PET bottles are produced by injection stretch blow moulding (ISBM). In order to minimise the stresses at the bottom of the bottle, the ISBM process parameters were reviewed and the effects of both the stretch rod movement and the temperature profile of the preform were studied by means of the process simulation software package (Blow View version 8.2). Simulated values of the wall thickness, stress, crystallinity, molecular orientation and biaxial ratio in the bottle base were obtained. The process parameters, which result in low stress and uniform material in the bottle base, are regarded as optimum operating conditions. In the evaluation process of the optimum bottle base, bottles with standard (current) and optimized (new) base were produced under the same process conditions via a two-stage ISBM machine. In order to compare both the bottles, environmental stress crack resistance, top load strength, burst pressure strength, thermal stability test as well as crystallinity studies ¬¬¬via modulated differential scanning calorimetry (MDSC) and morphology studies via environmental scanning electron microscopy (ESEM) and optical microscopy were conducted. In this study carried out, the new PET bottle with the optimised base significantly decreased the environmental stress cracking occurrence in the bottom of the bottle. It is found that the bottle with optimised base is stronger than the bottle with standard base against environmental stress cracking. The resistance time against environmental stress cracking are increased by about % 90 under the same operating process conditions used for standard (current) bottles; and by % 170 under the optimised process conditions where the preform re-heating temperature is set to 105 oC.

Wood is our most important renewable resource. We need better quality and quantity both according to the wood itself and the processes that are using wood as a raw material. Hence, the understanding of the chemical composition of the wood is of high importance. Improved and new methods for analyzing wood are important to achieve better knowledge about both refining processes and raw material. The combination of NMR and multivariate analyses (MVA) is a powerful method for these analyses but so far it has been limited mainly to 1D NMR. In this project, we have developed methods for combining 2D NMR and MVA in both wood analysis and metabolomics. This combination was used to compare samples from normal wood and tension wood, and also trees with a down regulation of a pectin responsible gene. Dissolving pulp was also examined using the same combination of 2D-NMR and MVA, together with FT-IR and solid state 13C CP-MAS NMR. Here we focused on the difference between wood type (softwood and hardwood), process type (sulfite and sulfate) and viscosity. These methods confirmed and added knowledge about the dissolving pulp. Also reactivity was compared in relation to morphology of the cellulose and pulp composition. Based on the method and software used in the wood analysis projects, a new method called HSQC-STOCSY was developed. This method is especially suited for assignment of substances in complex mixtures. Peaks in 2D NMR spectra that correlate between different samples are plotted in correlation plots resembling regular NMR spectra. These correlation plots have great potential in identifying individual components in complex mixtures as shown here in a metabolic data set. This method could potentially also be used in other areas such as drug/target analyses, protein dynamics and assignment of wood spectra.

No description available.

Bioactive glasses react with the human physiological solution in control of their biofunctionality. The stress state in bioactive glasses determines the chemomechanical reaction and their biofunctionality. Using the microindentation technique, the effect of the indentation deformation on the surface damage and material dissolution of 45S5 bioglass was investigated. The indentation-induced residual stresses were calculated. Complete anelastic recoveries of the indentation depths and the impression marks were observed for the first time, which was likely driven by the stored strain energy over the anelastic deformation zone. The indentation-induced local surface damages were revealed before and after the immersion tests in phosphate buffer solution (PBS). The growth of the cracks in the PBS solution displayed the stress-corrosion behavior with the crack-growth speed being a linear function of the indentation load. 45S5-bioglass was crystallized at temperature of 650 ºC. Microindentation technique also was used to study the localized mechanical behavior of the crystallized 45S5-bioglass. The crystallization had little effect on the indentation hardness, and the indentation hardness of the crystallized 45S5-bioglass is the same as that of the corresponding material in vitreous state. The fracture toughness is about 3 times less than that of annealed 45S5-bioglass in vitreous state, suggesting the preference of using bioactive glasses of vitreous state in the implant applications. Also, the effect of crystallization on the material dissolution was examined in phosphate buffer solution. We also studied the growth and mechanical behaviors of the Ca-P precipitate layers formed on 45S5 bioglass in simulated body fluid. The thickness of the Ca-P precipitate layers was proportional to the square root of the immersion time, and the ratio of Ca/P in the Ca-P precipitate layers increased with the immersion time and approached 1.67, corresponding to the stoichiometric hydroxyapaptite (HA).Using the indentation technique, the indentation behavior of the Ca-P precipitate layers was investigated. The indentation hardness of the HA layers formed in SBF was found to be 0.40 GPa, and the contact modulus was 12.0 GPa. The contact modulus of 12.0 GPa is close to that of cortical bone. In this thesis, the primary mechanical properties of the non-crystalline and crystalline bioglass 45S5 were revealed. The relationship between the dissolution rate and localized residual stresses are discussed. With such knowledge, the evaluation of implants with respect to manufacturing processes, control, and service conditions now has another variable to consider and evaluate against performance.

Layered Double Hydroxide (LDH) belongs to a class of ceramic materials that present structure formed by stacked layers of double metals hydroxides and an anion into the lamellar space. They present a large variety of applications possibilities, as industrial, environment, medicine, among others. Non-calcined Mg-Al layered double hydroxide (LDH) with molar ratio, x = Al / (Mg + Al), 0.20, 0.25 and 0.30 were synthesized using co-precipitation method, followed by hydrothermal treatment at a fixed temperature 80ÂC and different aging from 2 to 35 days. The material obtained was characterized by XRD, IR, TG, SEM and EDS. The samples crystallinity was evaluated and particle size was calculated using Scherrer equation. Sorption of anionic acid blue 25 and reactive blue 4 dyes from aqueous solution was investigated for some of the 0.25 molar ratio samples. The purpose of this research was to study the effect of hydrothermal treatment aging conditions on textural properties of synthetic hydrotalcite with different molar ratios and propose a mathematical function to predict crystallite size and crystallinity. This function takes just two of many parameters in consideration: hydrothermal treatment aging time and molar ratio. The obtained as-synthesized samples with a molar ratio 0.20 and 0.25 showed good crystallinity for all the samples. On the other hand the third samples with molar ratio 0.30 showed poor crystallinity, a pronounced shift in the correspondent basal planes peaks 003 and 006, and a broadening in all peaks. The shift in the basal planes was shown to be statistically significant to the others. A non-expected result was found in disagreement with literature: a new crystalline phase was observed in two 0.20 molar ratio samples. MEV and EDS results indicate the existence of a probable amorphous phase in the 0.30 molar ratio samples. The amorphous phase would explain the reduction in crystallinity of this series samples. Just the function to predict the crystallinity was obtained and showed in a 3D and hypsometric graphics. This function may be used to predict a characteristic of a synthesized LDH for an industrial application, like adsorption. / HidrÃxidos Duplos Lamelares (HDL) pertencem a uma classe de materiais cerÃmicos formados por camadas empilhadas de hidrÃxidos metÃlicos com um Ãnion entre os espaÃos lamelares. Apresentam uma grande variedade de possÃveis aplicaÃÃes, na Ãrea industrial, ambiental, medicinal, entre outras. HidrÃxidos Duplos Lamelares (HDL) nÃo calcinados de MagnÃsio e AlumÃnio com razÃo molar x = Al / (Mg + Al), 0,20, 0,25 e 0,30 foram sintetizados utilizando o mÃtodo de co-precipitaÃÃo, seguido por tratamento hidrotÃrmico em temperatura fixa de 80  C e diferente tempos de maturaÃÃo de 2 a 35 dias. O material obtido foi caracterizado por DRX, IV, TG, MEV e EDS. A cristalinidade das amostras foi avaliada e tamanho de partÃcula foi calculado usando a equaÃÃo Scherrer. Foram investigadas adsorÃÃo de corantes Ãcido azul 25 e azul reativo 4 para algumas amostras de razÃo molar 0,25. O objetivo deste trabalho foi estudar o efeito do tratamento hidrotÃrmico e condiÃÃes de tempo de maturaÃÃo nas propriedades texturais de hidrotalcita sintetizada com diferentes razÃes molares e propor uma funÃÃo matemÃtica para prever o tamanho de cristalito e cristalinidade. Esta funÃÃo leva apenas dois de muitos parÃmetros em consideraÃÃo: tempo de tratamento hidrotÃrmico e razÃo molar. As amostras obtidas com uma razÃo molar 0,20 e 0,25 apresentaram boa cristalinidade para todas as amostras. Por outro lado, as amostras com razÃo molar 0,30 apresentaram baixa cristalinidade, um pronunciado deslocamento nos picos basais 003 e 006, e um alargamento em todos os picos. O deslocamento desses picos para essa Ãltima amostra foi mostrado ser estatisticamente significativo em relaÃÃo Ãs outras duas. Um resultado nÃo esperado foi encontrado em desacordo com a literatura: uma nova fase cristalina foi observada em duas amostras de razÃo molar 0,20. Os resultados do MEV e EDS indicam que hà uma provÃvel fase amorfa nas amostras de razÃo molar 0,30. A fase amorfa explicaria a reduÃÃo da cristalinidade das amostras dessa sÃrie. Apenas a funÃÃo para prever a cristalinidade foi obtida e mostrada em grÃficos 3D e hipsomÃtricos. Esta funÃÃo pode ser usada para prever caracterÃsticas de um HDL sintetizado para uma aplicaÃÃo industrial, tal como a adsorÃÃo.

Diferentes estratégias de flotação (reagentes, pH e rota) têm sido utilizadas na separação entre apatita e carbonatos em todo o mundo. Há evidências na literatura de que a cristalinidade afeta a flotação de apatitas e calcitas com oleato de sódio. Além disso, a dissolução dos sais semi-solúveis pode influenciar a interação entre a superfície dos minerais e os reagentes de flotação, uma vez que o mecanismo de adsorção mais importante é a precipitação de oleato de cálcio na interface sólido/líquido. Portanto, o objetivo deste trabalho é investigar a relação entre cristalinidade, cinética de dissolução e resposta à flotação de apatitas e calcitas de diferentes gêneses (ígnea, metamórfica e sedimentar) e origens. Quatro tipos de minerais foram utilizados: purificados a partir de minérios, previamente purificados, naturalmente puros e amostras de coleção. As amostras foram caracterizadas por fluorescência de raios-X e microanálise (WDS/EDS). Características físicas como densidade (d), área superficial (S) e porosidade (P) também foram determinadas. O método de Rietveld aplicado à difração de raios-X foi usado tanto para comprovar a pureza das amostras como para estudar a cristalinidade dos minerais por meio da determinação dos parâmetros de rede (distâncias a e c, e volume da cela unitária- VCU), além do grau de cristalinidade (GC), tamanho de cristalito (TC) e microdeformação (MD). Ensaios de dissolução, conduzidos na ausência de CO2, forneceram a quantidade (mol) de íons Ca2+ (nCa2+) dissolvidos em função do tempo (t) e normalizada em relação à área superficial. Os resultados se ajustam a um modelo de primeira ordem: nCa2+ = Ca2+MAX(1- e-kt). Este procedimento permitiu calcular os valores da quantidade máxima de íons Ca2+ dissolvidos (Ca2+MAX), bem como da constante cinética (k). Além disso, a velocidade de dissolução foi determinada para a etapa rápida (VR), que caracteriza o início da reação, e para a etapa lenta (VL), que ocorre nas proximidades do estado estacionário. A resposta à flotação com oleato de sódio foi determinada por meio de experimentos de microflotação. Várias relações de causa e efeito são encontradas: flotabilidade (F) versus VR, e VR versus características intrínsecas (parâmetros de rede, de cristalinidade e físicos). VR foi selecionado para participar de tais modelos, pois, caracteriza o intervalo de tempo em que o condicionamento (1 minuto) e a microflotação (1 minuto) ocorrem. Observa-se que a flotabilidade dos minerais aumenta com o aumento de VR, sugerindo que apatitas e calcitas que disponibilizam mais íons Ca2+ em solução para interagir com o oleato, exibem mais elevada flotabilidade. Equações lineares de F em função de VR em pH 8 (R = 0,97 para apatitas e R = 0,66 para calcitas) e pH 10 (R = 0,95 para apatitas e R = 0,63 para calcitas) foram encontradas. Correlações lineares múltiplas foram utilizadas para relacionar VR (em pH 8 e 10) com as características intrínsecas que exercem maior influência sobre este parâmetro. Para as apatitas, VR foi equacionado em função de GC, TC e c, enquanto para as calcitas, os parâmetros GC, TC, d e P foram selecionados para compor o modelo. Os valores de VR calculados se ajustam aos observados dentro de um intervalo de confiança de 95%. As equações lineares propostas para as apatitas foram usadas para se estimar F das amostras de Anitápolis-SC e Tapira-MG, que não foram submetidas aos ensaios de dissolução. Os valores de F calculados estão em concordância com aqueles experimentalmente determinados. / Different flotation strategies (reagents, pH and route) have been adopted to separate apatite from carbonates around the world. Literature provides evidences that crystallinity affects flotation response of apatite and calcite with sodium oleate. Furthermore, dissolution of salt-type minerals influences the interaction between mineral surface and flotation reagents, because the most important adsorption mechanism is the surface precipitation of calcium oleate onto mineral/water interface. Therefore, the objective of this research is to investigate the relationship between crystallinity, dissolution kinetics and flotation response of apatites and calcites from different genesis (igneous, metamorphic and sedimentary) and origins. Four sorts of minerals were utilized: minerals purified from ores, minerals previously purified, naturally pure minerals and collection samples. They were characterized by X-ray fluorescence and X-ray microanalysis (WDS/EDS). Physical characteristics, as specific gravity (d), surface area (S) and porosity (P), were also determined. The Rietveld method applied to X-ray diffraction data was used either to probe the purity of samples or to study the crystallinity of the minerals by means of determining their lattice parameters (a and c dimensions plus lattice volume-VCU), in addition to crystallinity degree (GC), crystallite size (TC) and microstrain (MD). Dissolution experiments, conducted in the absence of CO2, yielded curves which relate the amount (mol) of dissolved Ca2+ ions (nCa2+) versus time (t), normalized by the surface area. They fit a first order model: nCa2+ = Ca2+MAX(1- e-kt). Curve fitting via exponential adjustment was accomplished to calculate values of the maximum amount of dissolved Ca2+ ions (Ca2+MAX) and the kinetic constant (k). In addition, the dissolution rate was determined for the fast step (VR), which characterizes the beginning of the reaction, and for the slow step (VL), as it tends to the steady state. Flotation response with sodium oleate was determined by microflotation experiments. Several cause-effect relationships are found: floatability (F) versus VR, and VR versus intrinsic characteristics of minerals (lattice, crystallinity and physical parameters). VR was selected to participate in the model because it characterizes the length of time along which reagent conditioning (1 minute) plus microflotation (1 minute) take place. It is observed that F increases as VR becomes greater, suggesting that samples of apatites and calcites which place more Ca2+ ions in solution to interact with oleate exhibit higher flotation performance. Linear equations of F versus VR at pH 8 (R = 0,97 for apatites and R = 0,66 for calcites) and pH 10 (R = 0,95 for apatites and R = 0,63 for calcites) were found. Likewise, multiple linear correlations were used to relate VR (at pH 8 and 10) with the intrinsic characteristics of apatites and calcites that affect VR to a greater extent. For apatites, VR was modeled as a function of GC, TC and c, while for calcites, the parameters GC, TC d and P were selected to compose the model. The calculated VR values fit the experimental ones within 95% of confidence. The linear equations developed for apatites were used to estimate floatability of the samples from Anitápolis-SC and Tapira-MG, which were not submitted to dissolution experiments. The values of calculated floatability are in agreement with the experimental ones.

Rapid advances continue in the acquisition 6f new fundamental knowledge of starch and a vigorous expansion in the use of starch is proceeding in both food and non-food applications. Results are here reported on starch-filled high density polyethylene which reveal reinforcement effects of starch on the thermoplastic. This significant development makes starch a most promising organic filler. This work is primarily a study of the mechanical and thermal properties of starch-filled high density polyethylene and attempts to identify changes caused in the structure of this polymer due to starch filler. Particular attention has also been given to changes in crystallinity and microscopic appearance. Because preliminary studies showed that enhanced effects were obtained when using starches of small particle size, much effort was given to developing a simple method of extraction of starches from the many varieties of Taro (Colocasia esculenta) plants in order to get the best possible yield and freedom from agglomerates. Because of the absence of recorded data it was necessary to study the physical properties of these starches. The theory and application of small-angle light scattering was reviewed because of its value as a technique for the characterization of starches and spherulitic polymer studies. One hundred and twelve Taro starches were characterized in terms of average particle sizes by the above technique. Starches with particle sizes ranging from 3 micron to 50 micron were investigated in order to establish the size/effect relationship in starch polymer composites. Methods of increasing the adhesion between filler and polymer matrix have also been studied, as has also the stripping of amylopectin from starch grains by cold acid treatment. Acid treatment, surprisingly, produced composites of increased mechanical strength in high density polyethylene, implying that a true reinforcing filler has been created. Results from differential scanning calorimetry and x-ray diffraction studies revealed that an increase in degree of crystallinity in high density polyethylene was associated with the presence of starch.

Lanthanide-based nanoparticles (Ln3+-based NPs) are promising candidates as magnetic resonance imaging (MRI) contrast agents. The present thesis aims to investigate the effect of the crystalline phase of Ln3+-based NPs on their MRI contrast performance. Understanding the phase-dependent MRI contrast behaviour of Ln3+-based NPs will provide insights into the development of brighter MRI contrast agents for future in vivo biomedical applications. A set of NaGdF4 NPs (6-8 nm) in cubic and hexagonal phases in the same size range was synthesized by employing a microwave-assisted approach, allowing the influence of host crystallinity on MRI T1 relaxivity to be investigated (chapter 4). The results showed that cubic NaGdF4 NPs exhibited superior performance as MRI T1 contrast agents than their hexagonal analogues, irrespective of the chosen surface modification, e.g. small citrate groups or longer chain poly(acrylic acid). NaDyF4 NPs (3 nm) were synthesized in both phases to assess whether phase-dependent MRI contrast behaviour consistently exists in other Ln3+-base NPs of the NaLnF4 family (chapter 5). Again, it was demonstrated that cubic NaDyF4 NPs had a better contrast performance as T2 contrast agents than the hexagonal NPs. Alternatively, cubic NaEuF4 NPs, exhibiting additional optical properties (e.g. red emission under UV excitation), were prepared as potential candidates for the preparation of chemical exchange saturation transfer (CEST) contrast agents (chapter 5). Chapter 6 introduces preliminary dispersion stability studies of cubic NaGdF4 NPs dispersed in different buffer solutions, the obtained hydrodynamic diameters indicated that NaGdF4 NPs possessed better dispersity in saline than that in PBS solution.