Alguns polímeros propriedades ópticas não lineares, as quais fazem com que o material responda de forma não linear à luz ou campo aplicado. Estas propriedades são relevantes no estudo da resposta de materiais à luz e tem sido alvo de muitos estudos recentes. Materiais poliméricos que exibem estas propriedades oferecem um grande potencial em aplicações que requerem a transmissão e manipulação de informações, principalmente na área de telecomunicações, processamento de sinais ópticos, computação e armazenamento de dados. Os polímeros com propriedades não lineares têm geralmente um alto custo, não só devido ao alto custo dos cromóforos utilizados, mas também ao baixo rendimento do processo de polimerização (<50%). Assim a utilização de quantidades relativamente baixas do polímero em misturas com polímeros comerciais poderia aumentar a aplicabilidade destes sistemas. Além disso, muitos destes polímeros apresentam pouca flexibilidade formando filmes quebradiços. Uma maneira de melhorar a flexibilidade seria utilizar blendas dos polímeros com propriedades ópticas não lineares com polímeros comerciais. Neste trabalho preparou-se um polímero com propriedades ópticas não lineares, o poliuretano MDI-DR19CI e caracterizou-se por medidas de espectroscopia nas regiões do visível e infravermelho e ressonância magnética nuclear. Preparou-se blendas deste polímero com quatro outros polímeros transparentes na região do visível, estudando-se o efeito da presença dos polímeros comerciais no espectro de absorção na região do infravermelho e nas propriedades de armazenamento óptico do MDI-DR19CI. Os resultados obtidos mostraram a viabilidade da utilização do azopolímero MDI-DR19CI em aplicações que requeiram a diluição do cromóforo para três tipos diferentes de polímeros de natureza química bastante distintas. Preparou-se, em uma segunda etapa do trabalho, misturas de poli(amida-imida) com o poliuretano preparado e com outros três polímeros contendo grupos com propriedades ópticas não lineares (ONL) visando a obtenção de filmes auto-sustentáveis e flexíveis com propriedades ópticas não lineares. Foram obtidos filmes com 5% do polímero contendo grupos ONL, os quais apresentaram boa flexibilidade, alto grau de coloração. Três deles, que pertencem a classe dos azopolímeros tiveram suas propriedades de armazenamento óptico demonstradas, apresentando valores de taxa residual em alguns casos menores que os polímeros puros, mas ainda com valores bastante razoáveis para viabilizar seu uso em aplicações de armazenamento de informação que requeiram filmes flexíveis / property is extremely relevant and has been extensively studied recently. Polymeric materials showing this properties offers a great potential for applications requiring transmission and manipulation of information, mainly in telecommunications, optical signal processing, computation, and optical storage. Polymers with non-linear properties are generally expensive, not only due to the high cost of the chromophores used but alto due to the low yield of the polymerization processes (less than 50%). Therefore, the utilization of rather low quantities of the NLO polymer in mixtures with commercial polymers can open the field of application of these polymers. Besides, several of these polymers present low flexibility and form brittle films. A way to increase the flexibility of the films would be the use o blends of NLO polymers s with commercial ones. In this work, a polymer with non-inear optical properties, the MDI-DR19CI polyurethane was prepared and characterized by ultraviolet-visible and infrared spectroscopies, and nuclear magnetic resonance. Blends of this polymer and four commercial polymers, transparent in the visible region, were prepared. The effect of the commercial polymers in the infrared absorption spectra, and in the optical storage properties of MDI-DR19CI, was studied. The results obtained showed the viability of the use of MDI-DR19CI blends in applications that require the \"dilution\" of the chromophores, for three different types of polymers. In a second stage, mixtures of poly(amideimide) and the polyurethane MDI-DR19CI and with other three polymers with NLO properties were prepared in order to obtain self-standing and flexible films with NLO properties. Films with 5% of NLO polymer were obtained, showing good flexibility and high coloration degree. Three of them were azopolymers and were used in optical storage experiments, showing remaining optical storage values, in some cases; lower than the pure NLO polymer, but with values rather sufficient to show the viability of the use of these mixtures in optical storage application that requires flexible films

During exothermic reactions a significant amount of heat is released. This heat can be further utilized for heating up chemical substances, chemical reaction initiation or welding. The first part of this thesis contains survey of thermodynamics and thermodynamics and thermochemistry of exothermic reactions, overview of commonly used exothermic processes as thermites and NanoFoil, summary of intermetallic systems and possibilites of powder metallurgy as a fabrication process of exothermic powder blends. Based on the survey part is designed experimental powder blend obtained by powder metallurgy. 18 powder samples were analysed; chemical composition was obtained by XRD and EDS analysis, on scaning electron microscope the morphology of powder particles was evaluated and by differential scanning calorimetry (DSC) the temperature of exothermic intermetallic reaction was determined. Furthermore a bulk intermetallic sample was sintered by spark plasma sintering process (SPS).

This work aims to investigate the vapor sensing behavior of conductive polymer composites (CPCs). In connection with the protection of the environment and human beings, sensing of different kinds of chemical vapors is of increasing importance. At the moment, four kinds of vapor sensors are widely investigated and reported, namely semiconducting metal oxide sensors (MO), conjugated polymer sensors, carbonaceous nanomaterial based sensors, and CPC based sensors. Due to their unique component systems, the different sensor types are based on different sensing mechanisms resulting in different potential application ranges. In consideration of cost and processability, CPC based vapor sensors are promising owning to their low cost, excellent processability, and designable compositions. In terms of vapor sensing behavior of CPC sensors, the interaction between the polymer and the organic vapor is a decisive factor in determining the sensing performance of CPCs. Ideally, the chosen polymer matrix should be able to swell without dissolving during vapor exposure so that the conductive network within the matrix can be disconnected, giving rise to the resistance change of CPCs. In some reported cases, polymers such as PLA and polycaprolactone (PCL) are degradable polymers, which are not durable when being exposed to environmental conditions for a long time. Therefore, it is necessary to make sure whether the selected polymers are resistive to vapors or not. There are two options for the polymer selection. One is to select a polymer that is only swellable in a specific or few organic solvents; another one is to select a polymer that is swellable to a variety of solvents. Since CPC sensors are used for detecting as many as possible hazardous chemicals to human beings or environment, the second case is more desired because of its broader window of detection. The solubility parameter is effective to characterize the interaction of polymers and organic solvents/vapors, which was firstly proposed by Charles Hansen. Initially, the Hansen solubility parameter (HSP) was used to predict the compatibility between polymer partners, chemical resistance, permeation rates, and even to characterize the surface of fillers. Liquids with similar solubility parameter (δ) are miscible, and polymers will dissolve in solvents whose δ is similar to their own value. This behavior is recognized as “like dissolves like”. Based on the description above, CPCs that can be used as liquid/vapor sensor materials should meet the following two requirements: 1) the chosen polymer should be swellable to vapors; 2) the CPCs as sensor materials have to be electrically conductive. Therefore, the relationship between conductive network and vapor sensing behavior of CPCs was investigated from the following aspects: 1) According to the previous studies, CB/polymer composites exhibit poor reversibility in cyclic vapor sensing tests because of the susceptible conductive network formed by CB particles. Thus, there is a need to improve the reversibility and increase the relative resistance change (Rrel) of CPCs. MWCNTs, as 1-dimensional carbon fillers with high aspect ratio, have excellent electrical and mechanical properties. Therefore, a hybrid filler system (MWCNT and CB) was utilized and incorporated in polycarbonate (PC) via melt compounding. PC was selected as the polymer matrix of CPCs because it showed high affinity with many commercial organic solvents/vapors as well as high and fast volume change upon organic solvents/vapors. In order to discuss the effect of conductive network formation on the vapor sensing behavior of PC/MWCNT/CB composites, two MWCNT contents were selected, which were lower and higher than the electrical percolation threshold of the PC/MWCNT composites. In the following, three CB contents were selected for the mixtures with MWCNT. The conductive networks composed of either MWCNT or hybrid CB/MWCNT are compared. The morphology of CPCs with different hybrid filler ratios was observed and investigated using SEM and OM. Moreover, to quantify the vapor sensing behavior of CPCs, some organic solvents were chosen and characterized by Flory-Huggins interaction parameter to demonstrate the polymer-vapor interaction. Afterwards, the cyclic vapor sensing was applied to illustrate the vapor sensing behavior of CPCs with different conductive network formations. 2) At moment, the filler dispersion is still a big challenge for MWCNT filled polymer composites due to the fact that the strong Van der Waals force among nanotubes makes them easily to entangle with each other resulting in the formation of agglomerates. A good filler dispersion state is desirable to achieve CPCs with low φc and. In order to reduce the φc of CPCs, immiscible polymer blend systems are introduced, which can have different blend microstructures by adjusting the polymer component ratios. In the second section, an immiscible polymer blend system based on two amorphous component, namely PC and polystyrene (PS), was chosen aiming to explain the influence of the blend morphology on the sensing performance of CPCs. PC/PS blends with different compositions filled with MWCNT were fabricated by melt mixing. The selective localization of MWCNTs in the blends was predicted using the Young’s equation. Moreover, the composite morphology, filler dispersion, and distribution were characterized by SEM and TEM. In the following, three kinds of CPCs ranging from sea-island structure to co-continuous structure were selected for the cyclic sensing measurement. The relationship between composite microstructure and resulting vapor sensing behavior was evaluated and discussed. 3) The poor reversibility of CPCs towards good solvent vapors is still a problem that hinders the cyclic use of CPC sensor materials. As an important class of polymer, crystalline polymers are rigid and less affected by solvent penetration because of the well-arranged polymer chains. Therefore, the effect of polymer crystallinity on the vapor sensing behavior of CPCs is imperative to be studied. In the third section, poly(lactic acid) (PLA), a semi-crystalline polymer, was selected to melt-mixed with PS and MWCNTs with the aim to improve the sensing reversibility of CPCs towards organic vapors, especially good solvent vapors. Thermal annealing was utilized to tune the PLA crystallinity and the polymer blend microstructure of CPCs. The electrical, morphological, and thermal behavior of CPCs after different thermal annealing times is discussed. In the following, the effect of crystallinity on the vapor sensing behavior of the CPCs was studied in detail. Besides, the different sensing performances of the CPCs towards different vapors resulted from the selective localization of MWCNTs and increased polymer matrix crystallinity were investigated and compared. 4) As discussed for the amorphous polymer blends and crystalline polymer blends and their vapor sensing behavior. The comparison of compact and porous structure of CPCs is going to be studied. In the fourth section, studies to further improve the sensing performance and to find out the exact sensing mechanism of CPCs were performed. Therefore, poly(vinylidene fluoride) (PVDF), a solvent resistive polymer, was chosen to be melt-mixed with PC and MWCNTs. In order to compare the MWCNT dispersion and localization in the blends, three kinds of PCs with different molecular weights were selected; hence, the viscosity ratio of immiscible blends was varied. Rheological, morphological, and electrical properties of CPCs were characterized. After that, the cyclic sensing and long-term immersion tests of CPCs towards different vapors were carried out to evaluate the vapor sensing behavior of compact CPCs with different blend viscosity ratios. Moreover, porous CPC sensors were prepared by extracting the PC component. The same sensing protocols were also applied to these porous sensor materials. The sensing mechanisms between compact CPC sensor and porous CPC sensor were compared and investigated.

Thermoplastic polyimides (TPIs) exhibit high glass transition temperatures (Tgs), which make them useful in high performance applications. Amorphous and semicrystalline TPIs show sub-Tg relaxations, which can aid in improving strength characteristics through energy absorption. The a relaxation of both types of TPIs indicates a cooperative nature. The semicrystalline TPI shows thermo-irreversible cold crystallization phenomenon. The polymer liquid crystal (PLC) used in the blends is thermotropic and with longitudinal molecular structure. The small heat capacity change (ACP) associated with the glass transition indicates the PLC to be rigid rod in nature. The PLC shows a small endotherm associated with the melting. The addition of PLC to the semicrystalline TPI does not significantly affect the Tg or the melting point (Tm). The cold crystallization temperature (Tc) increases with the addition of the PLC, indicating channeling phenomenon. The addition of PLC also causes a negative deviation of the ACP, which is another evidence for channeling. The TPI, PLC and their blends show high thermal stability. The semicrystalline TPI absorbs moisture; this effect decreases with the addition of the PLC. The absorbed moisture does not show any effect on the degradation. The addition of PLC beyond 30 wt.% does not result in an improvement of properties. The amorphous TPI + PLC blends also show the negative deviation of ACP from linearity with composition. The addition of PLC causes a decrease in the thermal conductivity in the transverse direction to the PLC orientation. The thermomechanical analysis indicates isotropic expansivity for the amorphous TPI and a small anisotropy for the semicrystalline TPI. The PLC shows large anisotropy in expansivity. Even 5 wt. % concentration of PLC in the blend induces considerable anisotropy in the expansivity. Thus, blends show controllable expansivity through PLC concentration. Amorphous TPI + PLC blends also show excellent film formability. The amorphous TPI blends show good potential for applications requiring high thermal stability, controlled expansivity and good film formability.

Cyclodextrin mediation offers a unique mechanism with the potential for interesting control of reaction parameters. Cyclodextrin mediation of hydrophobic monomers may offer desirable kinetics over conventional free radical polymerizations, and it has been shown in this work that cyclodextrin mediation facilitates polymerization of hydrophobic monomers in aqueous solution and in ethylene glycol. It also may be a facile method for controlling relative reactivity of comonomer mixtures. In addition, complexation of cyclodextrin with guest molecules has been utilized in selective synthesis where the host cyclodextrin has been utilized to sterically hinder the attack of certain reactive sites contained within the host cavity. This aspect of inclusion complexation could also be utilized in free radical polymerizations of monomers with multiple reactive double bonds to preferentially reduce the reactivity of the hindered reactive sites. This thesis involves the use of methylated(1.8)-beta-cyclodextrin (MeCD) as a mediator for polymerizations in solvents that would not facilitate polymerization of the pure monomer in the absence of cyclodextrin. This study focuses on the carbohydrate mediation of a series of methacrylic monomers. t-Butyl methacrylate, n-butyl methacrylate, cyclohexyl methacrylate, and 2-ethylhexyl methacrylate were complexed with methylated(1.8)-beta-cyclodextrin and subsequently dissolved in either water or ethylene glycol. The complexes were studied by 1H and 13C NMR spectroscopy, thin layer chromatography, CPK modeling, and thermogravimetric analysis, and were found to have molar ratios of cyclodextrin to monomer as high as 1.0 to 0.72. These complexes were then free radically polymerized in either water or ethylene glycol and resulted in high molecular weight polymers that precipitated out of solution, allowing for facile polymer isolation through filtration. Isolated yields were found to be as high as 86 %. The majority of the cyclodextrin remained in solution after polymerization. It was also recovered and found to be recyclable. Heterogeneous polymerizations were also performed with 2-ethylhexyl methacrylate in which linear dextrin and methylated (1.8)-beta-cyclodextrin were used in emulsifier quantities. It was found that linear dextrin, at concentrations of 3.0 wt% produced a stable latex product with high molecular weight and an isolated yield of >90%. MeCD on the other hand failed to produce a stable emulsion at concentrations between 0.9-3.0 wt%, but remarkably MeCD at 3.0 wt% gave high molecular weight coagulated polymer with a yield of >90%. It is proposed that a heterogeneous mechanism inconsistent with the four major types discussed by Arshady is taking place. Unlike typical suspension or emulsion polymerizations, the cyclodextrin mediated polymerizations are completely homogeneous at the onset, making them more like a dispersion or precipitation polymerization. However, in dispersion and precipitation polymerizations the pure monomer is soluble in the reaction media. In the absence of cyclodextrin, the monomers utilized in this study possessed no appreciable solubility in the reaction media. Therefore, it is proposed that cyclodextrin acts as a phase transfer agent, effectively solublizing the hydrophobic monomer and allowing for the aqueous dispersion or precipitation type polymerization to occur, depending on the relative solubility of the components. Bulk polymerizations of t-butyl methacrylate, cyclohexyl methacrylate, and 2-ethylhexyl methacrylate and their subsequent use in the preparation of carbohydrate/poly(alkyl methacrylate) blends was also performed in this project. Bulk polymers were utilized as references for physical properties for the polymers produced through polymerization of the MeCD/monomer complexes in either aqueous solution or in ethylene glycol. 1H NMR analysis of the polymers from both the cyclodextrin mediation and bulk polymerizations indicated that the tacticity of the polymers produced in both cases were identical. The bulk polymers were also used in the preparation of carbohydrate/methacrylic blends with potential applications in the areas of selective barriers, biodegradable films. Inclusion of drug molecules or antioxidants into these cyclodextrin containing films also may have potential in drug delivery, or food packaging applications. In addition, the side chain liquid crystalline monomer, 6-(4-hexyloxy-biphenyl-4-yloxy)hexyl methacrylate was synthesized in high purity via a three-step procedure and confirmed by a combination of mass spectrometry, thin layer chromatography, and 1H and 13C NMR. This hydrophobic liquid crystalline monomer was subsequently complexed with 1.0-3.0 equivalents of methylated(1.8)-beta-cyclodextrin in an attempt to alter the water solubility of the monomer. Complexes of this side-chain liquid crystalline monomer have not been studied previously and it is proposed that complexation with cyclodextrin will lead not only to novel polymerizations routes for this monomer, but also to novel smectic phases for this thermotropic liquid crystalline polymer. / Master of Science

Skim milk was ultrafiltered to three lactose/protein ratios and spray dried. The skim milk powder was extruded with pearled corn starch at different moisture contents, protein contents, lactose/protein ratios, and feed rates (control variables). Response surface methodology and a central composite in cube experimental design were used. This design required 30 experimental runs with 16 factorial points, 8 axial points, and 6 center points for replication. The physical and functional properties evaluated were expansion ratio, product temperature, bulk density, color, shear stress, viscosity, and water absorption index (response variables). Scanning electron microscopy was done to evaluate the microstructural attributes of the extrudates. A quadratic model was used to express the response variables in terms of the control variables. Response surfaces were generated by assigning center point values to 2 of the 4 control variables and then solving the fitted equations as a quadratic in the remaining 2 control variables. An increase in moisture content decreased expansion ratio, product temperature, color, and water absorption index, and increased bulk density, shear stress, and viscosity. An increase in protein content decreased product temperature, shear stress, viscosity, and water absorption index, increased color, and had no effect on expansion ratio and bulk density. An increase in lactose/protein ratio decreased product temperature, viscosity, and water absorption index, and had no effect on expansion ratio, bulk density, color, and shear stress. Feed rate did not have significant individual effect on any response variable. Expansion ratio had a negative correlation with bulk density (r = -0.61) and shear stress (r = -0.62) and a positive correlation with product temperature (r = 0.52). Bulk density and shear stress were positively correlated (r = 0.69), and product temperature and water absorption index were positively correlated too (r = 0.81). Expansion ratio, bulk density, color, and shear stress were chosen to determine a combined set of extrusion conditions most likely to produce an extrudate with properties suitable for a snack-type product.

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