No description available.

Orientador: Maria Isabel Felisberti / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-12T11:50:16Z (GMT). No. of bitstreams: 1 Faria_ElaineCristina_M.pdf: 2819560 bytes, checksum: 35692ba489585c42469cd45337f16702 (MD5) Previous issue date: 2008 / Resumo: Neste trabalho, foram preparadas blendas de poli(cloreto de vinila), PVC, com elastômero termoplástico poli[estireno-g(etileno-co-propileno-co-dieno)-g-acrilonitrila), AES. O AES é uma mistura complexa de poli(estireno-co-acrilonitrila), SAN, poli(etileno-co-propileno-co-dieno), EPDM e do copolímero de enxertia EPDM-g-SAN. As blendas com 10, 20 e 30% de AES foram obtidas em extrusora dupla-rosca cônica. As blendas PVC/AES são heterogêneas, apresentando uma fina dispersão da fase EPDM na matriz da blenda. Análise dinâmico-mecânica e calorimetria diferencial de varredura mostraram fortes indícios de que há um certo grau de miscibilidade da fase SAN do AES e o PVC. Mais especificamente, foram observadas duas transições vítreas para as blendas; a da fase EPDM, deslocada para temperaturas menores em relação à fase EPDM do AES; a da matriz, deslocada para temperaturas intermediárias entre as transições do do PVC e do SAN. Esta miscibilidade entre a fase SAN do AES e o PVC, que resultou em uma boa adesão entre a fase PVC e a fase EPDM da blenda, levando a uma melhora significativa nas propriedades de resistência ao impacto e alongamento do PVC. As blendas de 10, 20 e 30% de AES apresentaram um aumento de 240, 460 e 160% respectivamente, no alongamento do PVC e as blendas de 20 e 30% de AES apresentaram respectivamente um aumento da resistência ao impacto de 2000 e 2700% se comparadas ao PVC original. / Abstract: Abstract: In this work blends of polyvinyl chloride, PVC and the thermoplastic elastomer poly[acrylonitrile-g-(ethylene-co-propylene-co-diene)-g-styrene] were prepared. AES is a complex mixture of poly[stiren-co-acrylonitrile), SAN, and poly (ethylen-co-propylene-co-diene), EPDM and the graft copolymer EPDM-g-SAN. These blends were prepared ina twin-screw conic extruder in the following compositions: 10, 20 and 30% wt of AES. The blends are heteroneneos, presenting a thin phase dispersion of EPDM in the matrix. Dinamic-mechanical analysis (DMA) and Differential Electronic Calorimitry (DSC) showed miscibility between PVC and SAN phase of AES. Two glass transitions were observed for blends: one related to EPDM phase, shifted to lower temperatures in comparison to EPDM in the neat AES and another to matrix, intermediate to PVC and SAN glass transition temperatures. The miscibility between SAN phase and PVC, which promotes a good adhesion between PVC and EPDM significantly improved the impact resistance and elongation. The blends of 10, 20 and 30% of AES present an increase in elongation values in 240, 460 and 160% respectively and the blends of 20 and 30% of AES present an improvement of impact resistance of 2000 and 2700% respectively comparing to the original PVC / Mestrado / Físico-Química / Mestre em Química

Abstract Synthetic routes were developed for the preparation of 2-alkoxy-4-hydroxybenzoic acids and 2-alkoxyhydroquinones, and a large-scale synthesis was developed for the preparation of 2-thioalkoxyhydroquinones. The 2-alkoxy-4-hydroxybenzoic acids, which contained alkyl side chains of different length, were used in the synthesis of new main chain liquid crystalline (LC) homo-, random, and block co-oligomers. In addition, oligomers of terephthaloyl chloride and 2-thioalkoxyhydroquinones and oligomers of terephthaloyl chloride and 2-alkoxyhydroquinones were produced. All the oligomers were blended with aliphatic polyamide 11 (PA 11). The effect of alkyl side chain length on the compatibility behavior of the LC oligomers towards the aliphatic polymer was characterized by DSC and FTIR, and the effect of side chain length on the flexural properties of the blends was investigated with a three-point bending test. The miscibility studies showed variable interfacial adhesion between the blended compounds. The strongest adhesion was achieved between PA 11 and the homo-oligomers of 2-alkoxy-4-hydroxybenzoic acids with short or medium long substituents (C4-C10), but the interactions between PA 11 and the oligomer with long aliphatic side chain (C18) were poor, as were those between PA 11 and the wholly aromatic oligomer of 4-hydroxybenzoic acid. The compatibility between PA 11 and the co-oligomers of 2-alkoxy-4-hydroxybenzoic acids was slightly lower than the compatibility of the corresponding homo-oligomers. DSC and FTIR analyses of the blends of oligomers of terephthaloyl chloride and 2-thioalkoxyhydroquinones and oligomers of terephthaloyl chloride and 2-alkoxyhydroquinones with PA 11 implied that the interactions between the blended compounds were poor. FTIR spectra and viscosity measurements confirmed that all the oligomeric structures could self-associate, with effect on the final mechanical properties of the polyamide. The strength of PA 11 in a three-point bending test was increased by the addition of only 1% of LC oligomers to the matrix. The results also showed that the strengthening ability of the oligomers is directly proportional to the total amount of aliphatic carbons. The best strengthening results were obtained with unsubstituted oligomers, random co-oligomers of 2-alkoxy-4-hydroxybenzoic acids, and homo-oligomer of 2-butoxy-4-hydroxybenzoic acid. DSC investigations of a ternary blend of the oligomer of 2-decanyloxy-4-hydroxybenzoic acid, PA 11, and wholly aromatic commercial LC polymer showed the promising compatibilizing effect of the oligomer.

Composites based on binary polymer blends of polystyrene (PS)/poly(ethylene-co-vinyl alcohol) (EVOH) (70/30 wt%) containing natural Montmorillonite, Na-MMTs (Nanomer PGW or Cloisite Na+) and organically modified Montmorillonite clays, OMMTs (Nanomer I.30T, Cloisite 30B or Cloisite 10A) were prepared via melt compounding. The interactions between the polymers and clays were studied using flow micro-calorimetry (FMC). Data obtained from FMC indicated that the probe molecule mimicking EVOH (butan-2-ol) interacted with the MMTs and OMMTs much more strongly than PS. Scanning electron microscopy (SEM) revealed that composites based on binary blends had dispersed/continuous morphologies, in which EVOH was dispersed in a PS matrix. The size of the EVOH droplets in the PS matrix increased with increasing clay loading. Transmission electron microscopy (TEM) and wide angle X-ray diffraction (WAXD) were used to determine the extent of dispersion and location of clay in the PS/EVOH/clay composites. These techniques confirmed the formation of intercalated clay structures. As predicted by FMC, the clay platelets were selectively located in the EVOH phase, independent of the blending sequence and the type of organic modifier in the OMMT. Composites containing OMMTs showed better dispersion of platelets within the EVOH phase than those containing Na-MMTs. Differential scanning calorimetry (DSC); showed the crystallisation behaviour of EVOH to depend on the clay loading and the nature of the organic modifier in the OMMT. Nanomer PGW, Cloisite Na+ and Cloisite 30B acted as weak nucleating agents. In contrast, Nanomer I.30T and Cloisite 10A significantly hindered the crystallisation of EVOH in the blends due to the restriction of chain segment mobility. Dynamic mechanical thermal analysis (DMTA) confirmed that the presence of clay increases the storage modulus of the composites compared to an unfilled blend. In addition, the improvement in storage modulus reflected the dispersion state of the different clays and their interaction with the polymers of the blend. Ternary-blend based composites were formed by adding poly(styrene-co-acrylonitrile) (SAN) to the composites based on binary PS/EVOH blends. This resulted in a finer dispersion of the EVOH phase and the development of a core-shell morphology, in which SAN encapsulated and formed shells around EVOH droplets. In contrast to binary blend composites, the clay platelets were found at the interface between SAN and EVOH in the ternary blends.

No description available.

<p> Self-consistent field theory (SCFT) is a well established theoretical framework for describing the thermodynamics of block copolymer melts and blends. Combined with numerical methods, the SCFT can give useful and accurate predictions regarding the phase behavior of polymer blends. </p> <p> We have applied SCFT to study the phase behavior of blends composed of diblock copolymers (AB) and homopolymers (C). Two cases are studied in detail. In the first case the homopolymers have a repulsive interaction to the diblock copolymers. We found an interesting feature in the phase diagram that there exists a bump of the phase boundary line when A is the majority-component. In the second case, the homopolymers have an attractive interaction to one of the blocks of the diblock copolymers. A closed-loop of microphase separation region forms for strong interactions. For both cases, we have investigated the effects of homopolymer concentration, homopolymer chain length, and monomer-monomer interactions, on the phase behavior of the system. </p> <p> We also investigated micelle formation in polymer blends. Diblock copolymers (AB) blended with homopolymers (A) can self-assemble into lamellar, cylindrical and spherical micelles. The critical micelle concentrations for different geometries are determined using self-consistent field theory. The effect of varying copolymer block asymmetry, homopolymer molecular weight and monomer-monomer interactions on micelle morphology are examined. \\Then the blends are confined between two flat surfaces, the shape of the micelles may differ from that of the bulk micelles. We study the shape variation of a. spherical micelle under confinement and its dependence on the film thickness and surface selectivity. </p> / Thesis / Doctor of Philosophy (PhD)

No description available.

Este trabalho apresenta o estudo de vidros e vitro-cerâmicas oxifluoretos de composição PbGeO3 CdF2 PbF2 (Fluorgermanatos de cádmio e chumbo) e de blendas poliméricas formadas entre o eletrólito polimérico PEO:LiC104 (Poli-óxido de eltileno com perclorato de lítio) e o polímero condutor POMA (Poli-orto metoxianilina). Foram utilizadas as técnicas de ressonância magnética nuclear (RMN), ressonância paramagnética eletrônica (RPE), calorimetria exploratória diferencial (DSC) e impedância complexa. Dentre várias aplicações, estes materiais são importantes devido ao grande potencial como eletrólitos sólidos. Este estudo tem como principal objetivo esclarecer os mecanismos de transporte iônico do flúor e do lítio. Os resultados mostraram que os mecanismos da condução iônica nos vítreos oxifluoretos são caracterizados diferentemente em cada região de temperatura estudada. Em baixas temperaturas (T&#60;300K), o processo de relaxação foi atribuído às excitações de baixas-frequências dos modos desordenados. Acima de 300K, porém abaixo da temperatura de transição vítrea, os movimentos do flúor modulam as interações dipolares F-F. As vitro-cerâmicas, obtidas através de tratamentos térmicos dos vidros de oxifluoretos, são materiais compósitos onde nano ou micro-cristais estão dispersos na matriz vítrea. Os resultados de RMN mostraram no intervalo 100 800K, pelo menos três processos de relaxação, que foram associados com (i) movimentos difusionais dos íons de flúor nos cristais de &#946;-PbF2, (ii) mobilidade iônica na matriz vítrea e (iii) íons de flúor de baixa mobilidade (provavelmente PbGeO3-xFx). Os resultados de RMN 1H mostraram que os tempos de correlação associados aos movimentos das macromoléculas nas blendas poliméricas xii são comparáveis aos encontrados na literatura para o PEO/PMMA. A fim de se garantir resultados reprodutíveis, um cuidadoso método de preparação deve ser seguido, assegurando a estabilidade química e a homogeneidade da blenda / This work reports the study of oxifluorides glasses and glass-ceramics of composition PbGeO3 CdF2 PbF2 (Lead cadmium fluorgermanate) and blends formed by the polymer electrolyte PEO:LiC104 (poly etilene oxide and lithium perclorate) and the conducting polymer POMA (poly ortho methox aniline). Nuclear magnetic resonance (NMR), electron paramagnetic resonance (EPR), differential scanning calorimetry (DSC) and complex impedance techniques were used. Among several applications, these materiais are important as solid electrolytes. The main objective of this work is to study the fluor or lithium ionic transport mechanisms. Results show that the ionic conduction mechanism in oxifluoride glass systems is characteristic of each temperature region. In low temperatures (T &#60; 300K), the relaxation processes were attributed to low-frequency excitations of disorder modes intrinsic to the glassy state of mater. Above 300 K and below of the glass transition temperature the fluorine motions modulate the dipolar F-F interactions. The glasscerarnics, produced form their respective glasses, are composite materiais where nano- or micro-crystals are dispersed on the glassy matrix. The NMR results, in the range 100-800 K, evidenced three separate relaxation process: (i) diffusional motions of fluorine ions in &#946;-PbF2 crystals; (ii) fluorine mobility in the glass matrix and (iii) fluorine ions of low mobility (probably PbGeO3-xFx). The i ll NMR results shown that the correlation time values, associated to the polymeric chains motion in polymer blends, are comparable to those found for PEO/PMMA. In order to get reproducible results, a careful sample preparation process must be undertaken to ensure chemical stability and blend homogeneity.

Neste trabalho uma blenda foi criada utilizando poliestireno de alto impacto (PSAI) e polietileno de alta densidade (PEAD), ambos pós consumo, com o intuito de empregar esta blenda na fabricação de um produto de tecnologia assistiva para deficientes visuais. Os polímeros foram processados por extrusão e injeção, individualmente, sob diferentes condições de temperatura de processamento e velocidade da rosca a fim de avaliar a influência destes parâmetros em suas propriedades de fluidez, resistência ao impacto, resistência à tração, módulo de elasticidade, dureza e estabilidade térmica. O método estatístico denominado projeto de experimentos (DOE) foi utilizado, através do software Statgraphics Centurion®, para que se pudesse obter dados quantitativos sobre a influência de cada parâmetro de processamento sobre as propriedades avaliadas. Através do delineamento estatístico foi possível a definição dos coeficientes de regressão para cada propriedade, o que possibilita a previsão dos resultados ante o processamento. Blendas foram preparadas variando a concentração de cada polímero, em massa, e compatibilizadas utilizando copolímero de estireno-(etileno-butileno)-estireno (SEBS) com o intuito de avaliar sua miscibilidade, propriedades mecânicas e térmicas, além de demonstrar a viabilidade da utilização de uma destas para fabricação do produto desenvolvido. Ficou evidenciado a imiscibilidade dos polímeros utilizados devido à redução das propriedades após a mistura, no entanto os resultados se mostraram adequados ao produto em questão. A blenda PSAI/PEAD/SEBS contendo 25/75/2 %, em massa, apresentou melhores resultados para resistência ao impacto e dureza e foi escolhida para fabricação do produto final. Este trabalho demostrou a viabilidade da utilização de resíduos poliméricos pósconsumo para a fabricação de um produto de tecnologia assistiva, contribuindo, simultaneamente, para a inclusão social e sustentabilidade. / In this work, a blend was created using HIPS and HDPE, both post-consume, with the intent of using this blend in the creation of an assistive technologic product for visually impaired subjects. The polymers were, individually, processed by extrusion and injection under different processing temperature and screw speed to assess the influence of these parameters on its own flow properties, impact strenght, tensile strenght, elasticity modulus, hardness and thermal stability. The statistical method known as design of experiments (DOE) was used, through the software Statgraphics Centurion®, so that one could obtain quantitative data on the influence of each parameter processing on the assessed properties. Through statistical design it was possible to define the regression coefficients for each property which enables, before processing, the prediction of the results. Blends were prepared by varying the concentration of each polymer by weight and compatibilized using SEBS in order to evaluate their miscibility, mechanical properties and thermal ones, apart from demonstrating the feasibility of using one of these for the manufacture of the developed product. It was evidenced immiscible polymers used due to the reduction of properties after mixing, nevertheless the results were suitable for the product. The HIPS/HDPE/SEBS blend containing 25 /75/ 2%, in weight, showed the best results for resistance of impact and hardness and it was chosen to produce the final product. This work demonstrated the feasibility of using post-consume polymer waste to manufacture an assistive technology product while contributing to social inclusion and sustainability.

Neste trabalho uma blenda foi criada utilizando poliestireno de alto impacto (PSAI) e polietileno de alta densidade (PEAD), ambos pós consumo, com o intuito de empregar esta blenda na fabricação de um produto de tecnologia assistiva para deficientes visuais. Os polímeros foram processados por extrusão e injeção, individualmente, sob diferentes condições de temperatura de processamento e velocidade da rosca a fim de avaliar a influência destes parâmetros em suas propriedades de fluidez, resistência ao impacto, resistência à tração, módulo de elasticidade, dureza e estabilidade térmica. O método estatístico denominado projeto de experimentos (DOE) foi utilizado, através do software Statgraphics Centurion®, para que se pudesse obter dados quantitativos sobre a influência de cada parâmetro de processamento sobre as propriedades avaliadas. Através do delineamento estatístico foi possível a definição dos coeficientes de regressão para cada propriedade, o que possibilita a previsão dos resultados ante o processamento. Blendas foram preparadas variando a concentração de cada polímero, em massa, e compatibilizadas utilizando copolímero de estireno-(etileno-butileno)-estireno (SEBS) com o intuito de avaliar sua miscibilidade, propriedades mecânicas e térmicas, além de demonstrar a viabilidade da utilização de uma destas para fabricação do produto desenvolvido. Ficou evidenciado a imiscibilidade dos polímeros utilizados devido à redução das propriedades após a mistura, no entanto os resultados se mostraram adequados ao produto em questão. A blenda PSAI/PEAD/SEBS contendo 25/75/2 %, em massa, apresentou melhores resultados para resistência ao impacto e dureza e foi escolhida para fabricação do produto final. Este trabalho demostrou a viabilidade da utilização de resíduos poliméricos pósconsumo para a fabricação de um produto de tecnologia assistiva, contribuindo, simultaneamente, para a inclusão social e sustentabilidade. / In this work, a blend was created using HIPS and HDPE, both post-consume, with the intent of using this blend in the creation of an assistive technologic product for visually impaired subjects. The polymers were, individually, processed by extrusion and injection under different processing temperature and screw speed to assess the influence of these parameters on its own flow properties, impact strenght, tensile strenght, elasticity modulus, hardness and thermal stability. The statistical method known as design of experiments (DOE) was used, through the software Statgraphics Centurion®, so that one could obtain quantitative data on the influence of each parameter processing on the assessed properties. Through statistical design it was possible to define the regression coefficients for each property which enables, before processing, the prediction of the results. Blends were prepared by varying the concentration of each polymer by weight and compatibilized using SEBS in order to evaluate their miscibility, mechanical properties and thermal ones, apart from demonstrating the feasibility of using one of these for the manufacture of the developed product. It was evidenced immiscible polymers used due to the reduction of properties after mixing, nevertheless the results were suitable for the product. The HIPS/HDPE/SEBS blend containing 25 /75/ 2%, in weight, showed the best results for resistance of impact and hardness and it was chosen to produce the final product. This work demonstrated the feasibility of using post-consume polymer waste to manufacture an assistive technology product while contributing to social inclusion and sustainability.