As blendas poliméricas são importante alternativa ao mercado para se conseguir de forma economicamente vantajosa ou sob o ponto de vista de processabilidade produtos com propriedades otimizadas para aplicações específicas. Blendas com razões de composição variadas entre diferentes polímeros atendem aplicações muitas vezes com requisitos intermediários entre materiais. Este trabalho revisa sucintamente a literatura sobre blendas poliméricas, a produção em laboratório de uma blenda mecânica de poli(cloreto de vinila) PVC e poli(metacrilato de metila) - PMMA, avalia as propriedades de blendas com frações variadas de PVC/PMMA e discute o potencial de aplicação no mercado. A blenda miscível caracterizada tem custo, resistência à chama e propriedades mecânicas e térmicas intermediárias aos dois polímeros puros. / Polymer blends are an important alternative in the market for achieving, in an economically and advantageous way or just considering processability products with optimized properties for specific applications. Blends with variable composition ratios, between two different polymers, fit to applications with intermediate requirements between two different materials. This paper reviews slightly the literature about polymer blends, the lab scale production of a mechanical blend of poli(vinylene vhloride) - PVC and poly(methyl metacrylate) - PMMA with different PVC/PMMA ratios and the application potential. The miscible blend shows intermediate cost, flame resistance, mechanical and thermal properties then those shown by its neat polymers.

Chapas de poli(metacrilato de metila) podem ser modificadas por meio da adição de um agente promotor de ligações cruzadas e um plastificante objetivando incrementar seu desempenho durante a termoformagem. A interação intermolecular, modificada com a adição de diferentes quantidades de um agente promotor de ligações cruzadas (TEGDMA) e pela presença de um plastificante (DOP) faz com que as macromoléculas sejam ancoradas e afastadas respectivamente. O desenvolvimento deste trabalho objetivou, avaliar as propriedades físicas, mecânicas, térmicas e o processamento via termoformagem para duas diferentes temperaturas de termoformagem em um molde cilíndrico, a uma mesma taxa de deformação e determinado a influência da formulação, para cinco chapas que se diferenciaram nas quantidades de TEGDMA e uma quantidade fixada de DOP para duas das formulações. Os resultados mostraram que há incremento na deformação com as modificações introduzidas quando comparado a uma chapa sem adição de TEGDMA ou DOP e as propriedades destas chapas como dureza superficial, módulo de rigidez e temperatura de transição vítrea apresentaram mudanças sensíveis, que caracterizam vantagens no uso dos dois componentes. / Poly(methyl methacrylate) sheets can be modified adding a cross-linking agent and a plasticizer, to increase performance during thermoforming. The intermolecular interaction modification can be achieved adding different amount of cross-linking agent (TEGDMA) and a plasticizer (DOP). They have an effect on the network polymer system improving the intermolecular interaction and increasing the macromolecular distances, respectively. The aim of this study was to prepare acrylic sheets formulations with differents amounts of TEGDMA and a fixed amount of DOP, and thermoformed using at differents process temperatures and a mould cylinder at the same strain rate. Samples were carried out and their properties physical, mechanical, thermal and thermoformability was characterized. The results have shown strain increases, changes in surface hardness, Young moduli and glass transition temperature, compared to a reference acrylic sheet.

Les polylactides (PLA) sont une famille de polymères biodégradables et biocompatibles de la famille des polyesters aliphatiques. Lorsque le PLA est dans un milieu humide et à une température excédant le 60°C, il se dépolymérise rapidement par hydrolyse, étape préalable à la biodégradation du PLA. Le PLA est utilisé dans le domaine biomédical et dans la fabrication de nombreux produits destinés, entre autres, à l’usage alimentaire tels que des emballages, des ustensiles et de la vaisselle jetable. Cependant, quand des applications à longue durée de vie sont visées, sa dégradation peut devenir une propriété non désirable. À cet égard, le mélanger avec un autre polymère est une des alternatives les plus simples et peu coûteuses afin de limiter cette dégradation. Le polyméthacrylate de méthyle (PMMA), un polymère thermoplastique et biocompatible avec de bonnes propriétés mécaniques et thermiques, est un candidat potentiel. Ce travail de recherche, divisé en deux étapes, consiste en l’étude de l’hydrolyse du PLA puis celle des mélanges PLA/PMMA aux températures supérieures à leur température de transition vitreuse, cela en milieu neutre, en milieu alcalin et, en certains cas, en milieu acide. La première étape de ce travail comprend l’étude de l’hydrolyse du PLA en fonction de sa capacité à cristalliser ainsi que de la température et de l’acidité du milieu d’hydrolyse en phase aqueuse. Pour l’effet de composition, deux PLA commerciaux qui différaient dans leurs ratios de compositions d’énantiomères L- et D- ont été sélectionnés. Le premier de ces PLA avait la capacité de cristalliser jusqu’à un taux d’environ 40% alors que le second était complètement amorphe. L’hydrolyse a été effectuée dans l’eau distillée (pH égal à 5.3) à 60, 70 et 80 °C pour évaluer l’effet de la température. Ensuite, les PLA ont été soumis à l’hydrolyse en milieu acide (pH égal à 1) et alcalin (pH égal à 12) à une température constante de 70°C afin d’évaluer l’effet de l’acidité et l’alcalinité du milieu. L’hydrolyse a été réalisée en suivant l’évolution de la perte de masse, du pourcentage d’eau absorbée, de l’évolution de la distribution de masse molaire et finalement de la température de fusion et du changement d’enthalpie qui y est associé. Les résultats ont montré que l’hydrolyse en milieu acide et neutre procède par un mécanisme d’érosion massique (i.e. érosion dans le cœur de l’échantillon) tandis qu’en milieu alcalin, l’hydrolyse du PLA suit principalement un mécanisme d’érosion surfacique. La cinétique de l’hydrolyse a été modélisée avec succès à l’aide d’un modèle exponentiel à deux étapes qui prend en compte chaque étape du mécanisme d’érosion. Indépendamment de leur composition énantiomérique et même si tous les échantillons étaient amorphes au début des essais, ils ont cristallisé rapidement durant l’hydrolyse. Dans une deuxième étape, l’hydrolyse des mélanges PLA/PMMA a été étudiée. L’ajout du PMMA avait pour but de ralentir la progression de l’hydrolyse puisque ce matériau est un polymère d’addition insensible à l’hydrolyse. Les mélanges préparés par extrusion ont été soumis à l’hydrolyse en milieu neutre et en milieu alcalin à 80°C durant 30 et 5 jours, respectivement. Le milieu acide n’a pas été utilisé, car, dans la première étape du travail, le comportement en hydrolyse y a été trouvé similaire à celui en milieu neutre. Les résultats montrent que le PMMA n’a aucune influence sur le développement de la cristallinité durant l’hydrolyse car le PLA a cristallisé rapidement dans les deux milieux. La réduction de la masse molaire durant l’hydrolyse a causé une réduction de la température et de l’enthalpie de fusion du PLA. La présence du PMMA a fortement amélioré l’intégrité structurelle des mélanges. À cet effet, une teneur aussi faible que 5% de PMMA retardait significativement la fragmentation des échantillons par comparaison au PLA pur. Néanmoins, le PMMA n’a eu aucune influence sur la diffusion de l’eau dans la matrice polymérique. De plus, la présence du PMMA n’a joué aucun rôle sur la cinétique de l’hydrolyse du PLA lorsque le mécanisme en cause était l’érosion massique (i.e. milieu neutre). Par contre, en milieu alcalin, où le mécanisme d’érosion surfacique est prédominant, la perte de masse et la cinétique de l’hydrolyse ont été fortement ralenties par la présence du PMMA. L’enlèvement sélectif du PLA durant l’hydrolyse a laissé une structure poreuse interconnectée d’échelle nanométrique qui n’avait été observée auparavant.

Although existing continuum models for the elasto-viscoplastic response of amorphous polymeric materials phenomenologically capture the large deformation response of these materials in a reasonably acceptable manner, they do not adequately account for the creep response of these materials at stress levels below those causing “macro-yield”, as well as the Bauschinger-type reverse yielding phenomena at strain levels less than ≈ 30% associated with the macro-yield transient. Anand [1] has recently generalized the model of Anand and Gurtin [2] to begin to capture these important aspects of the mechanical response of such materials. In this work, we summarize Anand’s constitutive model and apply it to the amorphous polymeric solid poly(methyl methacrylate) (PMMA), at ambient temperature and compressive stress states under which this material does not exhibit crazing. We describe our compression-tension and creep experiments on this material from which the material parameters in the model were determined. We have implemented the constitutive model in the finite-element computer program ABAQUS/Explicit [3], and using this finite-element program, we show numerical results for some representative problems in micro-indentation of PMMA, and compare them against corresponding results from physical experiments. The overall predictions of the details of the load, P, versus depth of indentaion, h, curves are very encouraging. / Singapore-MIT Alliance (SMA)

A promising technique for the large-scale manufacture of micro-fluidic devices and photonic devices is hot embossing of polymers such as PMMA. Micro-embossing is a deformation process where the workpiece material is heated to permit easier material flow and then forced over a planar patterned tool. While there has been considerable, attention paid to process feasibility very little effort has been put into production issues such as process capability and eventual process control. In this paper, we present initial studies aimed at identifying the origins and magnitude of variability for embossing features at the micron scale in PMMA. Test parts with features ranging from 3.5- 630 µm wide and 0.9 µm deep were formed. Measurements at this scale proved very difficult, and only atomic force microscopy was able to provide resolution sufficient to identify process variations. It was found that standard deviations of widths at the 3-4 µm scale were on the order of 0.5 µm leading to a coefficient of variation as high as 13%. Clearly, the transition from test to manufacturing for this process will require understanding the causes of this variation and devising control methods to minimize its magnitude over all types of parts. / Singapore-MIT Alliance (SMA)

The aim of this project was to study the in vitro release of cephalothin, vancomycin and strontium from hydroxyapatite particles and its PMMA composite. The hydroxyapatite spheres containing strontium were prepared in the laboratory. The in vitro release study for the hydroxyapatite was carried out in phosphate buffer saline solution (PBS) with differing pH value at 37 °C for five days and the PMMA composites for 21 days. All of the releases showed a burst release within the first 24 hours followed by a slow release. The pH value of the release medium had influence on the release rate to some extent for the antibiotic release and the acidic solution had a more significant impact on the strontium release. All of the composite groups had a much lower strontium release rate than the strontium release from the hydroxyapatite spheres.

In this thesis , we studied the photo-chemistry between the green emitter (C545T) and the photo-acid generator (PAG) . When the sample of C545T and PAG in solutions and thin films were exposured to UV-light , we found that a new product was produced due to protonation of C545T with the acid generated by PAG . Therefore , we measured absorption and fluorescence spectra of the samples in solutions (THF) and in polymer (PMMA) thin films . The different concentrations of C545T dopanted photo-acid generator in the solvent (THF) could increase the photo-acid generator at higher concentrations of PAG , the energy could be transferred from unprotonated to protonated . Therefore , we can easily observe the absorption and fluorescence spectra have been changed and the phenomenon of stock¡¦s shift has been found accordingly . At higher concentrations of C545T in solutions , also called concentrations quenching effect was observed because C545T molecules could collide each other easily that causes intensity to decrease in the solvent (THF) . In order to get rid of the collision effect , we use the samples of polymer thin films instead of solutions . The different of the change of spectra between solutions and thin films were observed and compared were also studied .

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Orientadores: Liliane Maria Ferrareso Lona, Fernando Wypych / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química / Made available in DSpace on 2018-08-20T11:49:48Z (GMT). No. of bitstreams: 1 Nogueira_TelmaRegina_D.pdf: 5921921 bytes, checksum: 94d41e3ad2e82662f94aff13bcfef289 (MD5) Previous issue date: 2012 / Resumo: Recentemente, nanocompósitos poliméricos reforçados com argilominerais têm atraído considerável interesse científico. A maioria dos trabalhos publicados sobre a produção de nanocompósitos poliméricos utiliza silicatos naturais lamelares da classe dos filosilicatos do tipo 2:1, como a montmorilonita e a hectorita, como agentes de reforço. Para permitir a compatibilização com polímeros hidrofóbicos, já que os filosilicatos são hidrofílicos, utiliza-se normalmente a montmorilonita modificada com surfactantes catiônicos (sais quaternários de amônio, por exemplo), como reforço. Outra classe de trocadores aniônicos é a dos hidróxidos duplos lamelares (HDLs), que raramente ocorrem na natureza, mas são muito simples e baratos de sintetizar. Neste trabalho de doutorado foi investigada a polimerização "in situ" de metacrilato de metila com hidróxidos duplos lamelares modificados com ânions orgânicos (dodecilsulfato, estearato e laurato). Há poucos estudos em literatura aberta sobre as propriedades mecânicas e térmicas dos nanocompósitos de PMMA reforçados com HDLs e até agora não foram encontrados estudos sobre nanocompósitos de PMMA reforçados com HDLs intercalados com ânions estearato. O laboratório iniciou o estudo nesta área de nanocompósitos recentemente, no entanto, já foram produzidos alguns resultados sobre as propriedades de nanocompósitos de poliestireno e hidróxidos duplos lamelares. No presente trabalho foram produzidos nanocompósitos com alta transparência na região espectral da radiação visível assim como nanocompósitos coloridos, sem a adição de pigmentos ou corantes. Através de resultados de análises termogravimétricas demonstrou-se que a adição de HDLs pode aumentar a temperatura de decomposição do PMMA em mais de 80°C. Os resultados de análise dinâmico-mecânica mostraram que a concentrações de HDLs de 1% em massa nos nanocompósitos foi possível obter módulos elásticos com valores mais do que o dobro daqueles obtidos para o PMMA na maior parte da faixa de temperatura estudada. Com o objetivo de avaliar como a concentração de HDL afetava as propriedades anteriormente avaliadas, foram sintetizados nanocompósitos poliméricos contendo seis diferentes HDLs pré-selecionados, em duas diferentes concentrações (3% e 5%). Estes resultados demonstraram que a maioria destes nanocompósitos apresentou valores de microdureza maiores do que os encontrados para o PMMA / Abstract: Recently, nanocomposites consisting of polymer and mineral clays have attracted considerable scientific interest. Most published works on the production of polymer nanocomposites use clay mineral fillers such as montmorillonite, modified with cationic surfactants. Another class of anionic exchanger is layered double hydroxides (LDH), which rarely occur in nature but are very simple and inexpensive to synthesize, allowing the production of highly defined composition material. In this study we have investigated "in situ" bulk polymerization of methyl methacrylate (MMA) in the presence of LDHs intercalated by organic anions (dodecyl sulfate, laurate, stearate). There are few studies in the open literature on the mechanical and thermal properties of PMMA nanocomposites reinforced with hydrophobic HDLs and so far it was not found in open literature studies about the mechanical and thermal properties of the PMMA nanocomposites reinforced with stearate intercalated LDHs. In our laboratory, the investigation in the nanocomposites area started recently, however, some results on the nanocomposites of polystyrene and layered double hydroxides have already been produced. In the present work were synthesized nanocomposites with high transparence in the visible region as well as nanocomposites with an uniform orange color, without the addition of dyes or pigments. By thermogravimetric analysis, the results showed that the addition of LDHs may increase PMMA decomposition temperature in more than 80°C. The results of dynamic mechanical analysis, for nanocomposites with 1wt% of LDHs, showed that elastic modulus more than 2 times higher than PMMA in the range of studied temperature. In order to verify how the LDH concentration could affect the previously evaluated properties, nanocomposites containing six different pre-selected LDHs, in two different concentrations (3% and 5%) were synthesized. These results demonstrated that most of these nanocomposites presented microhardness values higher than those found for PMMA / Doutorado / Desenvolvimento de Processos Químicos / Doutor em Engenharia Química

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