Neste trabalho foi estudada a influência da adição de quitosana e sílica a monômeros dimetacrílicos, BisEMA e TEGDMA, por meio das técnicas de fotocalorimetria, termogravimetria e análise dinâmico mecânica. Os resultados dos experimentos de fotocalorimetria demonstraram que a quitosana pode aumentar a velocidade de polimerização e o máximo de conversão para alguns sistemas em determinadas concentrações da mesma, já a sílica tem pouco efeito nas reações de fotopolimerização das amostras. Para os experimentos de termogravimetria, a quitosana tem pouca influência na degradação das amostras não alterando significativamente as curvas TGA/DTG, por outro lado a sílica acelerou a degradação térmica das amostras. A avaliação das propriedades mecânicas demonstrou que a quitosana diminui a temperatura de transição vítrea e a resposta elástica dos sistemas não afetando os valores dos módulos de armazenamento e módulos de perda. A sílica apresentou a tendência de aumento de temperatura de transição vítrea e não alteração da resposta elástica das amostras. / In this work we studied the influence of the addition of chitosan and silica in dimethacrylic monomers, BisEMA and TEGDMA, by photocalorimetry, thermogravimetric analysis and dynamic mechanical analysis. The results of photocalorimetry experiments demonstrated that chitosan can increase the polymerization rate and the degree of conversion for some concentrations. Silica has little effect on photopolymerization reactions of samples. For thermogravimetric experiments, chitosan has little influence on the degradation of samples and does a slightly change the TGA / DTG curves, on the other hand silica accelerated thermal degradation of the samples. The evaluation of mechanical properties showed that chitosan reduces the glass transition temperature and elastic response of the samples but does not affect the values of the storage modulus and loss modulus. Silica showed an effect of increasing glass transition temperature and almost no change in the elastic response of the samples.

The viscoelastic relaxation dynamics of a series of poly(methyl methacrylate) [PMMA] based nanocomposites filled with carbon nanotubes have been studied using dynamic mechanical analysis and broadband dielectric spectroscopy. The networks were prepared using four methods: (i) melt mixing, (ii) solution processing, (iii) in-situ polymerization, and (iv) polymer grafting. Nanotube modifications included surface oxidation via acid exposure and surface functionalization for polymer grafting. The effect of variations in processing method and nanotube modification on glass transition temperature (Tg) and relaxation dynamics was investigated. The relaxation behavior of the nanocomposites was sensitive to processing method and nanotube functionalization. Nanotube loading (to 5 wt%) led to a progressive increase in rubbery modulus, with the increase more pronounced in the solution-processed samples owing to enhanced nanotube dispersion. In the case of the oxidized nanotubes, loading led to an increase in modulus, but also a systematic decrease in Tg of ~ 15°C with 3 wt% nanotubes. For in-situ polymerized (PMMA/MWNT-ox) nanocomposites, there was no readily discernable trend in Tg. Composites prepared via in-situ polymerization in the presence of methyl methacrylate functionalized tubes (i.e., polymer grafting) displayed a positive shift in Tg of nearly 20°C at 1 wt% loading. Investigation of the dielectric relaxation of the PMMA/MWNT composites indicated a percolation threshold between 0.3 and 0.4 wt% MWNT.

The structural adhesives widely used in structural strengthening applications are thermoset ambient cure adhesive polymers. At ambient temperatures, these polymers are in a relatively hard and inflexible state. At higher temperatures, the material becomes soft and flexible. The region where the molecular mobility changes dramatically is known as the glass transition temperature Tg and often is presented as a single value. Epoxy polymers exhibit a significant reduction in mechanical properties near glass transition temperature Tg when they are exposed to elevated temperatures. Glass transition temperature Tg is used to characterise the change in epoxy adhesive properties with changing temperature. The mechanical properties of epoxies tend to improve with curing temperature. This is because the crosslink density between the adhesive molecular structures increases during the curing process consequently the Tg improves. The aims of this work are first to demonstrate the importance of curing temperature. Second, to investigate the influence of glass transition temperature !! improvement on the performance of EB-FRP strengthened steel structures in flexure at ambient and elevated temperatures. Third, to compare analytical results with experimental results from the flexure tests results. Finally, to compare the current design guideline recommendations with the flexure tests results. The most commonly used methods to evaluate Tg Dynamic Mechanical Analysis (DMA) and Differential Scanning Calorimetry (DSC) were used to study Tg. Two off-shelf structural adhesives were investigated to understand their property variation with temperature. Epoxy coupons were cured at different elevated temperature and humidity environments up to 28 days. A combination of two extreme relative humidity of 0 and 100% and variable curing temperatures between 15 to 80°C were considered. From a test matrix of 300 DMA and over 250 DSC coupons these conclusions were drawn. First, ambient cured thermosets have a linear relationship between Tg and curing temperature, but Tg is reduced if a certain temperature is reached. Second, a fully cured adhesive requires heating treatment. Without a curing regime, designed Tg may never be achieved. Finally, curing time is crucial at the low curing temperatures while it is less significant at the higher curing temperature. The results of Tg investigation were used to select appropriate curing temperature that the adhesives resistance to temperature can be maximised without damaging the mechanical properties. The study helps designs to understand and assess the behaviour of these two adhesives when they are exposed to extreme temperatures. The study increases the awareness that a fully cured adhesive may never be achieved at ambient or low temperatures. It is important to find the mechanical properties and Tg when the coupons are exposed to the same curing temperature. To investigate the influence of glass transition temperature Tg improvement on the performance of EB-FRP strengthened steel structures in flexure at ambient and elevated temperature, nine three metre length beams were designed to behave as a concrete-steel composite bridge deck. The beams were tested in four-point bending. Lap shear, DMA test, and pull-off adhesion samples were prepared and cured at the same conditions and tested at ambient temperature. Six beams were tested under only mechanically loading at ambient temperature, including the control specimen. Five beams were tested at ambient temperature to show the effects of adhesive curing on FRP strengthened sections. A significant increase of load capacity of the adhesive joints was achieved due to the curing of the joints at elevated temperature. The failure occurred was in the same manner. An increase in the load capacity was observed with increasing curing temperature. An increase of approximately 25% was noticed in the ultimate load capacity of the specimens cured at 50°C compared to the specimens cured at 30°C. The load capacity of lap-shear specimens cured at 50°C was 28% higher than the specimens cured at 30°C. Three specimens were tested under mechanical and thermal loading. A bespoke thermal chamber was designed and fabricated to apply a controlled thermal loading. The beams were loaded mechanically up to 350kN, first. The temperature of the specimens was then increased at a rate of 0.8°C/min. The sustained load 350kN remained constant during the heating phase. Digital Image Correlation (DIC) technique was used to detect the slippage of the tip of the FRP plates. The only specimen cured at 30°C showed relatively poor performance compared to the two specimens cured at 50°C. The plate ends started to slip when the adhesive storage modulus from the DMA runs reduced approximately by 15 and 18% for the beams cured at 30 and 50°C respectively. Pull-off adhesion tests confirmed that adequate surface preparation of over 25 MPa was achieved The flexural model for the composite steel section represented to predicate load-deflection behaviour of the specimens using semi-experimental constitutive material law. The model successfully predicts the load-deflection behaviour of specimens, considering the strain hardening contribution. A bond stress analysis is also presented, which counts for the effect of FRP plate moment effect. The experimental and theoretical FRP plate slippage assuming only adhesive degradation with temperature are compared. The analytical bond models cannot predict the experimental failure because the linear elastic material properties were assumed and the failure was adhesion.

In this work differential scanning calorimetry, dynamic mechanical analysis, Fourier-Transformed Infrared Spectroscopy [FT-IR] and polarized light microscopy will be employed to characterize polymeric systems. The first chapter broadly covers polymer synthesis and important characterization methods. In the second chapter, a polyamide (PA12) will be sintered via a novel additive manufacturing (AM) technology developed here at USF termed LAPS (Large Area Projection Sintering). LAPS uses extended sintering timespans to ensure complete melting and densification of the polymer powder over the entire two-dimensional area of the part’s footprint. Further, it allows for the printed layer to crystallize and shrink in its entirety as the temperature falls below the crystallization temperature prior to the next layer being added. The printed parts (termed coupons) will be assayed by DSC and polarized light microscopy to determine sintering efficacy. Additionally, the parts will be compared to coupons printed with conventional methods to show that the USF AM technology shows superior elongation at break (EaB), with comparable ultimate tensile strength (UTS) and Young’s Modulus to laser sintered coupons. This is notable as conventional AM methods produce parts which usually compromise between EaB and modulus. The EaB of LAPS-printed parts is comparable to injection molding (IM) grade PA12, which is remarkable as IM grade PA12 powder normally has higher molecular weight and limited crystallinity. The reduced crystallinity of IM grade PA12 parts is thought to be due to the high shear rates during injection and fast cooling rates post-fabrication. Further, the USF LAPS parts show minimal or no detectable porosity. Porosity is an artifact of the sintering process which conventional techniques like laser sintering (LS) have little ability to mitigate, as higher energy wattages simply burn and degrade the polymer surface with insufficient time available for heat transfer and bulk melt flow. Porosity is documented as one of the leading causes of part failure and decreased mechanical properties in the literature, and as such the USF AM technology is in the process of being patented as of March, 2018. Chapters three through six will explore a phenomenon first noticed by clinicians at the James A. Haley Veterans Hospital. They observed that starch-thickened drinks for patients suffering from dysphagia became dangerously thinned down upon addition of the osmotic drug polyethylene glycol (PEG) 3350, marketed as Miralax®. Starch-based hydrocolloids are common thickeners used for patients with dysphagia, and so any incompatibility with such a ubiquitous drug as PEG 3350 poses an immediate danger. Patients with the disorder can suffer increased rates of aspiration-related pneumonia, incurring up to nearly a 60% fatality rate within a year. Chances for aspiration greatly increase for food items which are too inviscid to safely swallow. Rheology and FT-IR spectroscopy will be used to show that the breakdown of the starch network in aqueous solution is dependent upon the molecular weight of PEG. As the molecular weight of PEG is reduced to that of a small molecule (~300MW) from its large drug form (3350MW), the structure stabilizes and can resist shearing forces in a steady shear rheological experiment. Spectroscopy will show that PEG molecular weight also influences syneresis and the crystallinity of the starch hydrocolloid solutions. It is postulated that the molecular weight of PEG influences its miscibility in starch solutions, and its ability to interrupt the hydrogen bonding and entanglements which maintain the elastic framework which allow starch thickeners to impart viscosity and resist shearing forces. When this framework collapses, absorbed water is expelled as evidenced as a biphasic separation where water collects on top of the starch suspension. This was the phenomenon observed by the clinicians at the Veterans’ Hospital.

Syntactic foams are hollow particles-filled lightweight composites that are widely used in areas that require high strength while maintaining low weight and density. These foams are highly tailorable materials whose properties can be altered during the manufacturing process by changing various parameters like matrix and microballoon material type, size, distribution, as well as the volume fraction and wall thickness of microballoons. Therefore, understanding the effect of these parameter changes in the behavior of syntactic foams is very important to manufacture the foam for different applications. In the present study, syntactic foams of various volume fractions of microballoons were fabricated and different mechanical testing was conducted to study their elastic and viscoelastic behavior. Moreover, density, void content, and microstructure of the syntactic foam with varying volume fractions of microballoons were also studied to better characterize these foams. Results show that changes in the volume fraction of the microballoons had a significant impact on the elastic and viscoelastic behavior of the foams. The introduction of the microballoons into the epoxy resin decreased the density of the epoxy resin by up to 43.36% and at the same time increasing the specific modulus by up to 21.059%. In addition, representative 3D models of these syntactic foams were also developed to further study the elastic behavior of these materials which were found to be in good agreement with the experimental results. These findings will help in designing and optimizing the material properties of the syntactic foam required for different applications.

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Silicone hydrogels are receiving considerable interest due to their important biomedical application areas such as contact lenses and wound dressings. The applications of such materials are usually in the hydrated state, as hydrogels. However, manufacturing and molding processes are mostly carried out in the organically solvated state, as organogels. This thesis investigates the effects of some of the manufacturing parameters such as curing time and thermal processing on thermal, mechanical, viscoelastic and adhesive/cohesive fracture properties of silicone semi-interpenetrating polymer network organogels. Curing time may affect the extent of reaction and the crosslink density of a gel network. In order to investigate the effect of this parameter, materials were photo-cured for different times within the range of 150s to 1800s. Gel content, uniaxial tensile, dynamic mechanical, adhesive fracture and cohesive fracture properties were obtained as a function of photo-curing time and results were correlated with each other in order to have a better understanding of the effects on the material properties. Additionally, thermal properties of the gels were studied in detail. Crystallization and melting behavior of one of the solvents in the organogel were investigated by differential scanning calorimetry and thermal optical microscopy. Correlation between the thermal properties of the solvent and the gel network structure was shown. Dynamic mechanical analysis experiments were performed to investigate the effect of solvent crystallization on the mechanical properties. Finally, the effect of thermal processing parameters such as the heating  rate and the minimum cooling temperatures on the crystallization and the thermo-mechanical properties were studied. / Master of Science

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