Les nanocomposites suscitent un intérêt croissant depuis leur développement dans les années 90 par Toyota. Par conséquent, l'amélioration des propriétés de ce type de matériaux est un enjeu fort tant d'un point de vue fondamental qu'industriel. Cette amélioration peut passer par un choix pertinent des charges renforçantes ajoutées à la matrice notamment en ce qui concerne le type, la géométrie, la proportion et le traitement de ces charges. L’optimisation des paramètres d’élaboration du mélange y joue aussi un rôle important. L’objectif de ce travail est de contribuer à l’identification et à la compréhension des mécanismes à l'origine du renforcement des matrices thermoplastiques par des nanocharges. Cet aspect est abordé à travers l’étude des propriétés thermiques et mécaniques des nanocomposites formés d’une matrice Polyamide 12 (PA12) chargées par des nanoparticules d’argile organiquement modifiée. Plus précisément, nous avons analysé les effets de la fraction massique des charges et du vieillissement naturel sur les propriétés structurales, thermiques et mécaniques de ces nanocomposites. L’influence des conditions de mélangeage sur ces propriétés ont aussi été examinées. Nous avons particulièrement mis l’accent sur l’identification des liens qui existent entre les propriétés macroscopiques et la structure des nanocomposites. Nous avons aussi fait une étude comparative des propriétés viscoélastiques de ces matériaux à l'état fondu et à l'état solide, ce qui représente une des originalités forte de ce travail. / Nanocomposites are interestingly growing since their development in the 1990s by Toyota Company. Therefore, improving the properties of such materials is a major issue from fundamental and industrial point of view. This improvement can pass through a relevant choice of reinforcing loads added to the matrix particularly regarding the type, geometry, the proportion, and the treatment of these fillers. The processing parameters of the mixture play also a key role. The objective of this work is to contribute to the identification and understanding of the mechanisms at the origin of the reinforcing thermoplastic matrices by nanofillers. This aspect presented through the study of the thermal and mechanical properties of nanocomposites formed by a polyamide 12 matrix (PA12) filled with organically modified clay nanoparticles. More specifically, we analysed the effects of the filler mass fraction and environmental aging on structural, thermal and mechanical properties of these nanocomposites. The mixing conditions on these properties were also examined. A particular attention has been paid to the study of relationships between the macroscopic properties and the structure of nanocomposites. Viscoelastic properties of these materials in both melt and solid states were compared, which represents one of the originalities of this work.

L’objectif premier de ce travail de thèse concerne la réalisation et la caractérisation de différents films multicouches afin d’étudier l’impact du phénomène de confinement des couches de polymères sur les propriétés barrières du polymère confiné et du film multicouche. Des films multicouches constitué de polycarbonate (PC) et de poly(m-xylène adipamide) (MXD6), polymères actuellement utilisés par les industries de l’emballage, ont tout d’abord été étudiés. Puis, dans un second temps, des films multicouches composés de polyesters biodégradables, à savoir des films multicouches d’acide polylactique (PLA) avec comme polymère confiné soit du poly(butylène succinate-co-butylène adipate) (PBSA) ou du poly(butylène succinate) (PBS), ont été élaborés.Une fois la structure multicouche obtenue et avoir confirmé l’amélioration de l’effet barrière grâce au phénomène de confinement, le deuxième objectif a été d’incorporer des charges lamellaires de type montmorillonite (Cloisite® 30B) dans la couche de polymère confiné dans le but d’accroitre davantage l’effet barrière du film multicouche sélectionné.Pour comprendre l’amélioration des propriétés barrières aux gaz et à l’eau des films multicouches élaborés, une analyse de la microstructure par DSC et DRX ainsi qu’une analyse des propriétés mécaniques ont été menées conjointement avec une observation par microscopie. / The objective of the work was the elaboration and the characterization of different multilayer films in order to study the impact of the confinement effect of the polymer layers on the barrier properties. Multilayer films of polycarbonate (PC) and poly(m-xylene adipamide) (MXD6), which are usual polymers for packaging industries, have been studied. Then, multilayer films composed of biodegradable polyesters, such as polylactic acid (PLA) with poly(butylene succinate-co-butylene adipate) (PBSA) or poly(butylene succinate) (PBS) as the confined layers, have been prepared and characterized.For the multilayer structure presenting improved barrier performances due to the confinement effect, the second objective was to insert lamellar clays (Cloisite® 30B) into the confined polymer layers to again improve the barrier properties of the multilayer film. To understand the gas and water barrier improvement of the multilayer films, a microscopic observation of the films and an analysis of the microstructure by DSC and XRD have been performed with mechanical properties measurements.

Orientador: Fauze Ahmad Aouada / Resumo: Neste trabalho, primeiramente foram desenvolvidos hidrogéis nanocompósitos baseados em poli(ácido metacrílico) (PMAA) e nanoargilas cloisita-Na+, laponitas RD (Lpt RD) e RDS (Lpt RDS) por meio de polimerização via radical livre. A formação do nanocompósito e o grau de dispersão das nanoargilas junto a matriz polimérica foram investigados por análise de FTIR, MEV e DRX. A presença do argilomineral se apresentou um fator importante no que diz respeito ao aumento da capacidade de absorver água (Q) dos hidrogéis, atingindo um máximo em 5% de incorporação das Lpts no PMAA, além de uma melhora na estabilidade térmica dos nanocompósitos comprovada por TG. Assim como as nanocargas, o pH do meio também é um fator determinante para o controle do intumescimento. Pois, os grupos carboxílicos do PMAA sofrem ionização dependendo do pH da solução, aumentando assim o intumescimento do hidrogel. Segundo, foi realizado um estudo relativo à eficiência da adsorção pelos nanocompósitos (nanoargilas Lpt RD, Lpt RDS e cloisita-Na+) do herbicida paraquat (PQ) e sua posterior liberação em solução aquosa. Mais uma vez a presença do argilomineral se mostrou relevante, aumentando para 100% de eficiência no carregamento para nanocompósitos constituídos por 20% de nanoargilas. As adsorções em todas as formulações dos nanocompósitos se ajustaram à isoterma de Langmuir. Enquanto o modelo de isoterma de Freundlich foi o melhor modelo para a matriz sem nanoargila. Todas as isotermas apresentaram perfil de ads... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: In this work, initially, nanocomposite hydrogels based on poly(methacrylic acid) (PMAA), closite-Na+, laponite RD (Lpt RD) and laponite RDS (Lpt RDS) nanoclays were synthesized from free radical polymerization. The formation of the nanocomposite and the degree of dispersion of the nanoclays into polymeric matrices were investigated by FTIR, SEM, and XRD techniques. The presence of the clay mineral was a significant factor because it increased the capacity of water absorption (SD) of the hydrogels, reaching a maximum of 5% of Lpts into PMAA. Besides, the thermal stability of the nanocomposites, confirmed by TG, was increased by clay presence. As the nanofillers, the pH of the environment is also a determinant factor for the control of swelling. Because the carboxyl groups of the PMAA undergo ionization depending on the pH of the solution, increasing the swelling of the hydrogel. Then, a study was carried out on the adsorption efficiency of the herbicide paraquat (PQ) using hydrogel nanocomposites (with Lpt RD, Lpt RDS, and cloisite-Na+ nanoclays) as adsorbent materials. After, its release properties were investigated in aqueous solution. The presence of nanoclay was again relevant, increasing to 100% its loading efficiency for nanocomposites made up of 20% nanoclays. Adsorption in all nanocomposite formulations fitted the Langmuir isotherm. Already, the paraquat sorption results followed the Freundlich isotherm model. All isotherms had favorable adsorption profiles, and it pre... (Complete abstract click electronic access below) / Doutor

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In-situ polymerization is one of the most efficient methods for production of polymer clay nanocomposites. In-situ polymerization of olefins using coordination catalysts is a type of heterogeneous polymerization. In order to achieve acceptable clay nanolayer dispersion in the polyolefin matrix, the clay layer exfoliation and particle break up during the polymerization are essential requirements. A literature review on polyolefin/clay nanocomposite is given in Chapter 2. In Chapter 3, we present a new mathematical model, which is as an extension of the multigrain model (MGM), to describe the intercalative polymerization and expansion of clay interlayer spaces during polymerization using clay-supported metallocenes. The results from the model show that, under the studied conditions, mass transfer is not a strong factor controlling clay exfoliation and particle break up. If the polymerization active sites are supported uniformly on all clay surfaces, effective exfoliation will be achieved after a relative short polymerization time. In practice, obtaining good dispersion of clay nanolayers with uniform properties requires that the active sites be exclusively located on the clay nanolayer surfaces, and not extracted by the solvent to form a homogeneous solution. Factors favouring active site extraction would result in nanocomposites with poor properties. In addition, high polymerization activities, stable polymerization runs, and ease of supporting are other criteria for a successful in-situ polymerization. For this purpose we established a catalyst supporting method by which most of these requirements were met. In this method, the water content on the clay surface, which is considered as poison for the metallocene catalyst, was used to produce MAO upon reaction with trimethylaluminum (TMA). Using this method, polymerization was highly active in absence of MAO cocatalyst, knowing that MAO cocatalyst promotes active site extraction from the clay surface and results in poor powder morphology. Chapter 4 describes the development of this supporting methodology. Chapter 4 also investigates the effect of the organic modification type existing on the clay surface on the success of catalyst supporting and in-situ polymerization. We found that using the proposed supporting procedure, only tertiary ammonium type modification enhanced the in-situ polymerization, whereas the quaternary ammonium worsened the catalyst supporting efficiency and led to catalyst with poor or no polymerization activity. It is suggested that, in addition to enhancing clay surface-organic solvent compatibility (which facilitates catalyst supporting), the tertiary ammonium cation reacts with the in-situ produced MAO and increases the stability of the cocatalyst bonded to the clay surface. The effect of different polymerization conditions on the polymerization behavior and nanocomposite structural properties, such as catalyst loading during supporting, polymerization temperature and triisobutylaluminum (TIBA) concentration, were studied in Chapter 5. It was found that TIBA acts merely as scavenger. High polymerization activities were obtained with low Al/Zr ratios (Al from TIBA) and increased Al concentration decreased the polymerization activity and also the quality of powder morphology. Catalyst loading in the supporting step showed to have an important role in determining the final properties. The clay particles with higher catalyst loading resulted in better exfoliation and powder morphologies The effect of solvent type during catalyst supporting and polymerization was studied in Chapter 6. It was shown that catalyst supporting in n-hexane resulted in polymerizations with higher activities and polymers with higher molecular weight were produced. Polymerization with catalyst supported in hexane showed different ethylene uptake profiles, suggesting different mechanism of exfoliation. It is suggested that using this catalyst, the clay is mostly exfoliated before polymerization started. Similar to the original clay, the catalyst supporting efficiency on the organically modified clay was close to 100 percent. However, comparing the polymerization activities of these catalysts to those that were supported directly in the reactor just before the polymerization (in-reactor, or in-situ, supported catalysts) shows that a considerable fraction of the active sites are deactivated during the prolonged contact between catalyst and clay support surface. In Chapter 5, it was shown that the in-reactor supported catalyst had considerably higher polymerization activities, up to 40 percent of that of the homogeneous catalyst. Nanocomposites made with in-reactor supported catalysts had powder morphology and nanaolayer dispersion comparable to those made with clay-supported catalysts.

In-situ polymerization is one of the most efficient methods for production of polymer clay nanocomposites. In-situ polymerization of olefins using coordination catalysts is a type of heterogeneous polymerization. In order to achieve acceptable clay nanolayer dispersion in the polyolefin matrix, the clay layer exfoliation and particle break up during the polymerization are essential requirements. A literature review on polyolefin/clay nanocomposite is given in Chapter 2. In Chapter 3, we present a new mathematical model, which is as an extension of the multigrain model (MGM), to describe the intercalative polymerization and expansion of clay interlayer spaces during polymerization using clay-supported metallocenes. The results from the model show that, under the studied conditions, mass transfer is not a strong factor controlling clay exfoliation and particle break up. If the polymerization active sites are supported uniformly on all clay surfaces, effective exfoliation will be achieved after a relative short polymerization time. In practice, obtaining good dispersion of clay nanolayers with uniform properties requires that the active sites be exclusively located on the clay nanolayer surfaces, and not extracted by the solvent to form a homogeneous solution. Factors favouring active site extraction would result in nanocomposites with poor properties. In addition, high polymerization activities, stable polymerization runs, and ease of supporting are other criteria for a successful in-situ polymerization. For this purpose we established a catalyst supporting method by which most of these requirements were met. In this method, the water content on the clay surface, which is considered as poison for the metallocene catalyst, was used to produce MAO upon reaction with trimethylaluminum (TMA). Using this method, polymerization was highly active in absence of MAO cocatalyst, knowing that MAO cocatalyst promotes active site extraction from the clay surface and results in poor powder morphology. Chapter 4 describes the development of this supporting methodology. Chapter 4 also investigates the effect of the organic modification type existing on the clay surface on the success of catalyst supporting and in-situ polymerization. We found that using the proposed supporting procedure, only tertiary ammonium type modification enhanced the in-situ polymerization, whereas the quaternary ammonium worsened the catalyst supporting efficiency and led to catalyst with poor or no polymerization activity. It is suggested that, in addition to enhancing clay surface-organic solvent compatibility (which facilitates catalyst supporting), the tertiary ammonium cation reacts with the in-situ produced MAO and increases the stability of the cocatalyst bonded to the clay surface. The effect of different polymerization conditions on the polymerization behavior and nanocomposite structural properties, such as catalyst loading during supporting, polymerization temperature and triisobutylaluminum (TIBA) concentration, were studied in Chapter 5. It was found that TIBA acts merely as scavenger. High polymerization activities were obtained with low Al/Zr ratios (Al from TIBA) and increased Al concentration decreased the polymerization activity and also the quality of powder morphology. Catalyst loading in the supporting step showed to have an important role in determining the final properties. The clay particles with higher catalyst loading resulted in better exfoliation and powder morphologies The effect of solvent type during catalyst supporting and polymerization was studied in Chapter 6. It was shown that catalyst supporting in n-hexane resulted in polymerizations with higher activities and polymers with higher molecular weight were produced. Polymerization with catalyst supported in hexane showed different ethylene uptake profiles, suggesting different mechanism of exfoliation. It is suggested that using this catalyst, the clay is mostly exfoliated before polymerization started. Similar to the original clay, the catalyst supporting efficiency on the organically modified clay was close to 100 percent. However, comparing the polymerization activities of these catalysts to those that were supported directly in the reactor just before the polymerization (in-reactor, or in-situ, supported catalysts) shows that a considerable fraction of the active sites are deactivated during the prolonged contact between catalyst and clay support surface. In Chapter 5, it was shown that the in-reactor supported catalyst had considerably higher polymerization activities, up to 40 percent of that of the homogeneous catalyst. Nanocomposites made with in-reactor supported catalysts had powder morphology and nanaolayer dispersion comparable to those made with clay-supported catalysts.

Made available in DSpace on 2016-03-15T19:36:56Z (GMT). No. of bitstreams: 1 Thiago Ramos Stellin Malagrino.pdf: 4441654 bytes, checksum: 6ca4cb745da024c77c96b57a51ae6f04 (MD5) Previous issue date: 2016-01-26 / Polycarbonate, an amorphous engineering polymer, has excellent mechanical strength and although it s good chemical resistance, its interaction with some types of alkali and some organic solvents is weak. The main objective of this work was to study the effect of the inclusion of nanometric particle size of natural sodium clay (named Nanolite) and sodium clay treated with quaternary ammonium salt (named Cloisite 15A) in resin processing in order to investigate the variations in chemical properties, transparency and molecular structure. The characterization of nanocomposite was performed using methods of Scanning Electron Microscopy (SEM), Molar Mass Characterization by Mark-Houwink-Sakurada equation, Differential Scanning Calorimetry (DSC), Melt Flow Rate (MFR), Differential Thermal Analysis (DTA), Fourier Transform Infrared Spectroscopy (FTIR), X-Ray Diffraction (XRD) and Chemical Resistance obtained by the contact angle technique / Fowkes method. Optical, thermal, physical and chemical testing indicated that the molecular structure of PC after the inclusion of clays remained unchanged showing no irreversible degradation. The analysis of chemical resistance through the contact angle method showed significant improvement in the surface free energy of the nanocomposites when using the organoclay (Cloisite 15A) and partial improvement when used natural sodium clay (Nanolite). The decrease in surface free energy, indicates a likely improvement in the chemical resistance of the nanocomposites. / O Policarbonato, polímero de engenharia de estrutura amorfa, possui excelente resistência mecânica, e embora possua boa resistência química, deixa a desejar no que se refere ao contato com alguns tipos de álcalis e solventes orgânicos. O objetivo principal deste trabalho foi de estudar comparativamente o efeito da inclusão de partículas nanométricas de argila sódica natural (Nanolite) e argila sódica tratada com sal quaternário de amônio (Cloisite 15A), no processamento da resina a fim de investigar as variações ocorridas nas propriedades químicas e consequentemente, na transparência e estrutura molecular. A caracterização do nanocompósito foi realizada por meio de métodos de Microscopia Eletrônica de Varredura (MEV), massa molar calculada pela equação de Mark-Houwink-Sakurada, Calorimetria Diferencial por Varredura (DSC), Índice de Fluidez (IF), Análise Térmica Diferencial (DTA), Espectroscopia no Infravermelho por Transformada de Fourier (FTIR), Difração de Raios X (DRX) e Resistência Química calculada através da técnica de ângulo de contato / método de Fowkes. Os ensaios óticos, térmicos, físicos e químicos indicaram que a estrutura molecular do PC após a inclusão das argilas permaneceu inalterada, sem degradação irreversível. A análise da resistência química através do método de ângulo de contato apresentou significativa melhora na energia livre superficial dos nanocompósitos quando utilizada a argila organofílica (Cloisite 15A) e, melhora parcial quando utilizada a argila sódica natural (Nanolite). A queda da energia livre superficial, indica que existe uma provável melhora na resistência química dos nanocompósitos.

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