L'ajout de charges (agrégat de taille submicronique) dans une matrice élastomère apporte des propriétés physiques qualitativement différentes de celles de la matrice pure : module complexe dépendant de la température, forts effets non linéaires, forte dissipation... Ces propriétés sont liées à la nature de la matrice et des charges, à leur fraction volumique, et enfin à la force des interactions charge / matrice. Nous présentons d'abord les différents systèmes et la caractérisation de leurs propriétés mécaniques, de façon à clarifier le rôle des différents paramètres.La cristallisation sous traction du caoutchouc naturel a un effet important sur ses propriétés mécaniques. Nous l'avons donc mesurée quantitativement dans chacune des formulations. Nous montrons que le taux de cristallisation à la rupture est toujours de l'ordre de 13%. La nature de l'interface silice / matrice a un effet sur les propriétés mécaniques mais pas sur la cristallisation. Nous avons ensuite étudié le comportement en traction simple d'échantillons pré-entaillés. Nous montrons que la plus grande résistance à la propagation d'entaille du caoutchouc naturel renforcé est corrélée à la présence d'instabilités de propagation (rotation d'entaille). Les mécanismes physiques à l'origine de la rotation d'entaille ne sont pas compris. Nous décrivons la dynamique de propagation des rotations à différentes échelles, et les caractéristiques des rotations.La combinaison de la cristallisation induite et de la présence des charges induit dans le matériau une très grande anisotropie qui pourrait être à l'origine des rotations.

L'objectif de cette thèse a été l'optimisation de la synthèse et des performances catalytiques des matériaux lamellaires au W et Mo dans les réactions d'oxydation de plusieurs composés organiques en présence d'H2O2. Le travail réalisé au cours de cette thèse est le développement de nouveaux catalyseurs hétérogènes pour la réaction d'oxydation qui est réalisée sélectivement en systèmes catalytiques homogènes, mais pour un développement durable, la catalyse hétérogène demeure beaucoup plus porteuse d'avenir au niveau industriel. La réaction d'oxydation de composés soufrés a un grand intérêt, en particulier dans l'élimination des composés organiques soufrés (thiophènes, sulfures) contenus dans les carburants et les coupes pétrolières, réalisée dans des conditions douces de température et pression, en présence de l'eau oxygénée. Les objectifs principaux de cette étude ont été les suivants: 1. élaboration des matériaux catalytiques : a) préparation des précurseurs de type hydrotalcites (HDL) à base de Mg-Al-NO3, Mg-Al-terephthalate et Ni-Mg-Al-NO3. b) préparation des matériaux hybrides par intercalation des espèces de Mo et W par deux voies de synthèse : réaction d'échange anionique et synthèse hydrothermale. 2. caractérisation de la structure, la texture et la nature des sites catalytique par différentes techniques : DRX, adsorption d'azote, ATG, spectroscopie Raman et UV-Vis, MEB etc. 3. applications de ces catalyseurs à la réaction d'oxydation des composes soufrés (sulfures, thiophènes, sulfoxydes), epoxydation de cyclooctene et oxydation d'anthracène. Les catalyseurs ont été stables au recyclage et aucun phénomène de leaching n'a été observé. / The objective of this thesis was the optimization of the synthesis and catalytic performances of nanocomposites materials containing W and Mo in the oxidation with H2O2 of a wide range of model organic compounds. The work achieved during this thesis is the development of new heterogeneous catalysts for the oxidation reaction who is carried out selectively in homogeneous catalytic systems, heterogeneous catalysis is still much more promising in future. The oxidation reaction of sulfur compounds has great interest, especially in the removal of organic sulfur compounds (thiophene, sulfide) contained in fuels and petroleum fractions, performed in mild conditions of temperature and pressure in the presence of H2O2. In this study were as follows : 1. elaboration of materials : a) preparation of precursors of type hydrotalcites (HDL) based on Mg-Al-NO3, Mg-Al-Ni-terephthalate and Mg-Al-NO3. b) preparation of hybrid materials by intercalation species of Mo and W by two synthetic routes : reaction of anion-exchange and hydrothermal synthesis. 2. characterization of the structure, texture and nature of catalytic sites by different techniques : XRD, nitrogen adsorption, TGA, Raman spectroscopy and UV-Vis, SEM, etc. 3. application of these catalysts in the reaction of oxidation of sulfur compounds (sulfides, thiophenes, sulfoxides), epoxidation of cyclooctene and oxidation of anthracene. The catalysts were stable under operating conditions.

The superior material properties of polymer/clay nanocomposites have attracted much research interests in the past years. The hypothesis of polymer stiffening in the vicinity of the nano-c1ay described using the "core-shell" model has not been fully investigated yet. The investigation of the interfacial region by atomic force microscopy (AFM) has provided us with details of the physical state of this region. It was found that the polymer stiffening region could extend as far as 200nm and 100nm from the face and the edge of a nano-clay respectively. Two different degrees of polymer stiffening have been observed from AFM micrographs with the help of amplitude and phase contrasting techniques. The temperature dependant property of the stiffened polymer has been studied using a heating stage, which showed the stiffened polymer was softened with increasing temperature between the studied range, 60°C and 91°C. The relative polymer crystallinity derived from the X-ray diffraction (XRD) data showed a general trend that increases with the clay content, regardless of the clay modification. However, an exception has been observed with the set of bi-axially drawn specimens, of which the highest polymer crystallinity was found to be the neat polymer when compared with the nanocomposites counterpart. It is believed that the presence of nano-c1ay particles restricted the reorientation of the polymer chains upon stress. From the in situ isothermal investigation of polymer crystal growth, it has been found the crystal grown from a nano-clay particle is larger than that from the bulk. This indicated that the crystallisation began at a lower temperature. The nano-clay and polymer crystal orientations have been further studied with X-ray texture analysis. It was found that the polymer chains were not completely aligned alone the extrusion direction as expected. Also, from the annealed specimens it was found that the orientation of the nano-clay particles had been influenced by the relaxation of the polymer chains.

Submitted in fulfillment of the academic requirements of the degree of Master of Applied Sciences in Chemistry, Durban University of Technology, Chemistry Department, Durban, South Africa, 2016. / Cellulose is a sustainable, abundant biopolymer derived from a variety of living species such as plants, animals, bacteria and some amoebas. An attractive source of cellulose for industrial uses is agricultural waste, as this use does not jeopardize food supplies and improves the local rural economy. Sugarcane bagasse (SCB) is one of the main biomass wastes from sugar production and represents 30–40 wt % of sugar production waste. In 2008, South Africa produced on average 22 million tons of sugar cane each season from 14 sugar mill supply areas which resulted in 7,9 million tons of “waste” bagasse. In this study cellulose nanocrystals were prepared from soda pulped sugarcane bagasse by acid hydrolysis followed by separation using centrifugation, ultrasonication and dialysis. Transmission Electron Microscopy (TEM) images showed nanocrystals of approximately 300 nm in length and 20 nm in width. Thermogravimetric Analysis and Differential Thermogravimetry (TGA and DTG) profiles of FD CNC, MCC and Pulped bagasse all had characteristic onset and decomposition temperatures indicating a change in the structure after chemical treatments. Particle size distribution measurements corroborated with the TEM and FE - SEM results and showed that the majority of the nanocrystals were in the 100 – 300 nm range. Attenuated Total Reflectance – Fourier Transform Infra Red (ATR - FTIR) analysis showed functional group changes as the amorphous regions of the polymer were removed revealing the ordered crystalline portions. These were further confirmed by an increase in the Lateral Orientation Index (LOI) of the samples as the nanocrystals were isolated. X - Ray Diffraction (XRD) Crystallinity Index (CrI) calculations showed a steady increase in the crystallinity of the materials from pulped bagasse to MCC to FD CNC. / M

Philosophiae Doctor - PhD / Magnesium hydride has long been regarded as a promising candidate for lightweight hydrogen storage applications, owing to reasonably high theoretical capacity (7.6 wt. %). It is burdened by slow absorption/desorption kinetics which has been the target for improvement of many research groups over the years. Nanostructured MgH2 prepared by high energy reactive ball milling (HRBM) of Mg under hydrogen atmosphere with the addition of V or Ti results in modified MgH2 that demonstrates superior hydrogenation/dehydrogenation kinetics without a crippling compromise in storage capacity. Mg – FeV nanocomposites prepared via ball milling of Mg and FeV raw materials demonstrated up to 96.4% of the theoretical storage capacity and comparable kinetics to Mg - V prepared via the same method using pure refined V (which is far costlier than FeV). In both cases, the hydrogenation/dehydrogenation kinetics was much improved than pure Mg alone, as evidenced by faster hydrogenation times. In terms of cyclic stability, Mg – 10FeV demonstrated improvement over pure Mg with final absorption and desorption capacities of 4.93 ± 0.02 wt. % and 4.82 ± 0.02 wt. % respectively over 30 cycles. When compared against Mg – V, Mg – FeV showed slightly inferior improvements, attributed to incomplete hydrogenation of V in the presence of Fe. However, they share similar crystalline BCC, BCT – V2H and FCC - VH phases with the size of less than 10 nm and demonstrated the same behaviour at high temperatures; at temperatures approaching 400 °C, particle sintering became an issue for both nanocomposites resulting in a drop in absorption capacity even in the first cycle. The further inclusion of carbonaceous species showed several effects, one of which was an improvement in hydrogen uptake speed as well as kinetics for the addition of 5 wt. % activated carbon. For the sample with 5 wt. % graphite, the appearance of an initial incubation period of up to 60 minutes was noted, presumably corresponding to the duration of time when the carbon was sheared and crushed before hydrogenation commences.

A dissertation submitted to the Faculty of Engineering and the Built Environment, University of the Witwatersrand, in fulfilment of the requirements for the degree of Master of Science in Engineering 25 May 2017 / Two of the main contributors to high voltage insulation failure are thermal and electrical stresses. The failures may be mitigated by using nanodielectrics. The enhanced effect of nanoparticles in nanodielectrics is attributed to an interaction zone/interphase around each individual nanoparticle between the nanoparticle and host polymer. However, particle clumping or agglomerates are a major challenge in nanodielectric technology. In this work mitigation of the clumping challenges was explored through Rheology in determining optimal particle loading levels. The nanodielectrics studies were Boron Nitride and Carbon Nanospheres in Araldite Epoxy. The rheology results indicated an optimal loading level of 1.09 vol % to 1.35 vol% for Boron Nitride in Epoxy and 0.33 vol% for Carbon Nanospheres in Epoxy. Microscopy, dielectric spectroscopy, electrical tree characterisation, thermal expansion and laser flash analysis were used to validate the efficacy of the rheology results. The results indicated improved properties of the resultant dielectric such as; increased mechanical stiffness, increased electrical resistance and the percolation threshold, partial discharge suppression and increased thermal conductivity at the glass transition temperature. This study has established a rheology-based technique incorporated in the manufacturing process to determine the optimal filler loading of C/Epoxy and BN/Epoxy nanodielectrics. Future work is recommended as investigating either new particle types such as Sulphur hexafluoride in Carbon Nanospheres or mixtures of Carbon Nanospheres and Boron Nitiride. / MT 2017

Ao contrário de muitos polímeros, as resinas fenólicas se caracterizam por possuir um grande número de aplicações por conta de sua superior resistência ao fogo e baixa emissão de fumos e ao seu excelente nível de resistência térmica e química, além de seu baixo custo. No entanto, devido à sua estrutura tridimensional, caracterizada pelo alto grau de reticulação, este tipo de resina apresenta baixas tenacidade e resistência à fratura. Com isso, para garantir seu bom desempenho, faz-se necessário promover modificações em sua formulação ou acrescentar agentes de reforço de modo a compensar essas deficiências resultantes de sua estrutura. São inúmeros os materiais que, usualmente, são incorporados à matriz fenólica. Além da preparação de blendas poliméricas em que uma das fases consiste em um elastômero ou um termoplástico, a introdução de agentes de reforço como materiais fibrosos também são utilizados. São exemplos de agentes de reforço: fibras vegetais, fibras de vidro e de carbono, negro de fumo, argilas entre outros. A mistura de polímeros e argilas pode levar à formação de nanocompósitos de modo a obter excelentes combinações de resistência à fratura, tenacidade, condutividade, resistência ao calor e redução da permeabilidade a gases e líquidos quando comparados com o polímero puro. Neste trabalho, argilas do tipo montmorilonita modificadas foram utilizadas como agente de reforço na preparação de filmes de nanocompósitos de matriz fenólica com o objetivo de melhorar as propriedades mecânicas deste material polimérico quando comparado com o material puro. A resina fenólica utilizada neste trabalho é a do tipo resol, utilizada comercialmente para a formulação de vernizes para revestimento de embalagens metálicas. No estudo foram utilizadas três argilas comerciais: Cloisite® sódica (Na) e argilas Cloisite® modificadas com sais quaternários de alquilamônio, de códigos 15A e 30B, objetivando verificar qual apresentaria melhor compatibilidade com a matriz fenólica. Para a preparação de filmes poliméricos uniformes, isentos de defeitos como bolhas, foi feita, de forma preliminar, a seleção de um ciclo de cura apropriado. Como a formação de bolhas é intrínseco à cura da resina fenólica resol, a definição de um esquema de tratamento térmico de cura apropriado constituiu-se em etapa crítica no processo de preparação dos compósitos de resina fenólica/argila montmorilonita modificada. Os filmes curados isentos de defeitos foram caracterizados por difração de raios X, análise termomecânica dinâmica (DMA) e calorimetria exploratória diferencial (DSC). Os resultados das análises de DRX mostraram para os compósitos preparados com as argilas modificadas 15A e 30B manutenção e até mesmo redução do espaçamento basal da estrutura cristalina das argilas, indicando não ter ocorrido intercalação do polímero nessas argilas; enquanto que para a argila Cloisite® Na ocorreu aumento do espaçamento basal. Os resultados de DMA mostraram para a maioria das amostras aumento no módulo de armazenamento em baixa e alta temperatura. Por último, a análise de DSC mostrou redução na temperatura de transição vítrea nos compósitos preparados com as argilas modificadas 15A e 30B, e elevação na composição de 5% da argila Cloisite® Na. Os resultados indicam o potencial de reforço mecânico de resinas fenólicas com argilas lamelares do tipo montmorilonita sem a necessidade de modificação química. / Unlike most polymers, phenolic resins are characterized by having a large number of applications because of its superior fire resistance and low emission of smoke and its excellent level of thermal and chemical resistance, and low cost. However, due to its three dimensional structure, characterized by a high degree of crosslinking, this type of resin has low toughness and fracture resistance. Thus, to ensure their good performance, it is necessary to make enhancements in their formulation or adding strengthening agents so as to compensate for these deficiencies due to its structure. There are numerous materials that usually are incorporated into the phenolic matrix. Besides the preparation of polymer blends in which one phase consists of an elastomer or a thermoplastic, the introduction of agents such as fibrous reinforcement is also used. Examples of reinforcing agents: vegetable fibers, glass and carbon fibers, carbon black, clay and others. The mixture of polymer clays may cause the formation of nanocomposites in order to obtain excellent combination of fracture strength, toughness, conductivity, heat resistance and reduced permeability to gases and liquids when compared with the pure polymer. In this work, modified montmorillonite clays were used as a reinforcing agent in the preparation of nanocomposite films of phenolic matrix with the aim of improving the mechanical properties of polymer materials when compared with the pure material. The phenolic resin used in this work is that of the resol type, used commercially for the formulation of varnish for coating metal containers. The study used three types of commercial clay: Cloisite® sodium (Na) and Cloisite® clays modified with quaternary alkylammonium salts, codes 15A and 30B in order to verify which present better compatibility with the phenolic matrix. For the preparation of uniform polymeric films, free of defects such as bubbles, was preliminarily selected a suitable cure cycle. As the bubble formation is intrinsic to the cure of resol phenolic resin, the definition of a heat treatment scheme is a critical step in the process of preparing composites of phenolic resin/montmorillonite clay. The cured films free of defects were characterized by X-ray diffraction (DRX), dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC). The results of XRD analysis showed the composites prepared with the modified clays 15A and 30B maintained and even reduced the basal spacing within the clay crystal structure, indicating not having occurred polymer intercalation of the clay; for the Cloisite® Na clay DRX has shown increased basal spacing. DMA results showed for most of the samples increase in storage modulus at low and high temperatures. Finally, DSC analysis showed a reduction in glass transition temperature of the composites prepared with the modified clays 15A and 30B, and an increase in the composition of 5% in the Cloisite® Na clay. The results indicate the potential of enhancement of phenolic resins mechanical properties with layered clays of montmorillonite without chemical modification.

A celulose é o polímero natural renovável disponível em maior abundância atualmente. Por possuir estrutura semicristalina, é possível extrair seus domínios cristalinos através de procedimentos que ataquem sua fase amorfa, como a hidrólise ácida, obtendo-se assim partículas cristalinas chamadas nanopartículas de celulose (NCs). Estas nanopartículas têm atraído enorme interesse científico, uma vez que possuem propriedades mecânicas, como módulo de elasticidade e resistência à tração, semelhantes a várias cargas inorgânicas utilizadas na fabricação de compósitos. Além disso, possuem dimensões nanométricas, o que contribui para menor adição de carga à matriz polimérica, já que possuem maior área de superfície, quando comparadas às cargas micrométricas. Nanocompósitos formados pela adição destas cargas em matrizes poliméricas podem apresentar propriedades comerciais atraentes, como barreira a gases, melhores propriedades térmicas e baixa densidade, quando comparados aos compósitos tradicionais. Como se trata de uma carga com dimensões nanométricas, obtida de fontes renováveis, uma das principais áreas de interesse para aplicação deste reforço é em biopolímeros biodegradáveis. O poli(ácido lático) (PLA), é um exemplo de biopolímero com propriedades mecânicas, térmicas e de processamento superiores a de outros biopolímeros comerciais. No presente trabalho foram obtidas nanopartículas de celulose (NCs), por meio de hidrólise ácida, utilizando-se três métodos distintos, com o objetivo de estudar o método mais eficiente para a obtenção de NCs adequadas à aplicação em compósitos de PLA. Os Métodos I e II empregam extração das NCs por meio do H2SO4, diferenciando-se apenas pela neutralização, a qual envolve diálise ou neutralização com NaHCO3, respectivamente. No Método III a extração das NCs foi realizada com H3PO4. As NCs foram caracterizadas por diferentes técnicas, como difração de raios X (DRX), análise termogravimétrica (TG), espectroscopia vibracional de absorção no infravermelho (FTIR), microscopia eletrônica de transmissão (MET) e microscopia de força atômica (MFA). Os resultados de caracterização das NCs indicaram que, a partir de todos os métodos utilizados, há formação de nanocristais de celulose (NCCs), entretanto, apenas os NCCs obtidos pelos Métodos II e III apresentaram estabilidade térmica suficiente para serem empregados em compósitos preparados por adição da carga no polímero em estado fundido. A incorporação das NCs em matriz de PLA foi realizada em câmara de mistura, com posterior moldagem por prensagem a quente. Compósitos obtidos por adição de NCs obtidas pelo Método II foram caracterizados por calorimetria exploratória diferencial (DSC), análise termogravimétrica, microscopia óptica, análises reológicas e microscopia eletrônica de varredura (MEV). A adição de NCs, extraídas pelo Método II, em matriz de PLA afetou o processo de cristalização do polímero, o qual apresentou maior grau de cristalinidade. Além disso, a adição de 3% em massa de NCs no PLA foi suficiente para alterar seu comportamento reológico. Os resultados reológicos indicaram que a morfologia do compósito é, predominantemente, composta por uma dispersão homogênea e fina da carga na fase matriz. Micrografias obtidas por MEV corroboram os resultados reológicos, mostrando, predominantemente a presença de partículas de NC em escala nanométrica. Compósitos de PLA com NCs obtidas pelo Método III apresentaram aglomerados de partículas de NC em escala micro e milimétrica, ao longo da fase matriz, e não foram extensivamente caracterizados. / Cellulose is the renewable natural polymer currently available in greatest abundance. Cellulose is a semicrystalline polymer, and it is possible to extract its crystalline domains through a procedure that destroys its amorphous phase, such as acid etching, so obtaining crystalline cellulose particles called cellulose nanoparticles (NC). These nanoparticles have attracted great scientific interest because they have mechanical properties similar to those of many inorganic types of filler used in polymer matrix composites, like elastic modulus and tensile strength. Moreover, they have nanometric dimensions, which contribute to lower filler contents in the polymer matrix, due to its increased surface area when compared to the one of micrometric fillers. Nanocomposites formed by adding these fillers into polymeric matrices can present attractive commercial properties such as gas barrier, improved thermal properties, and low density, when compared to traditional composites. As NC are nanometric scale fillers, obtained from renewable sources, there is a great interest in their application into biodegradable biopolymer matrixes. Poly (lactic acid), PLA, is an example of biopolymer that presents improved thermal, mechanical and processing properties, when compared to the ones of other commercial biopolymers. In this work, cellulose nanoparticles (NC) were obtained, via acid hydrolysis, using three different methods, in order to study the most efficient method to obtain NC suitable to be used in polymer matrix composites. NC obtention methods I and II employ extraction by H2SO4. Methods I and II differ only in the neutralization step, which involves dialysis, for Method I, and neutralization with NaHCO3, for Method II. In Method III, the extraction of the NCs was performed using H3PO4. The NC were characterized by different techniques such as X-ray diffraction (XRD), thermogravimetric analysis (TG), infrared absorption spectroscopy (FTIR), transmission electron microscopy (TEM) and atomic force microscopy (AFM). The characterization results indicated that all methods yielded cellulose nanocrystals. However, only NC obtained by methods II and III showed sufficient thermal stability to be used in composites prepared by melt mixing. The NC/PLA composites were prepared in a mixing chamber, followed by hot press molding. The composites with addition of NC obtained by Method II were characterized by differential scanning calorimetry (DSC), TG, optical microscopy, rheological analysis and scanning electron microscopy (SEM). The cellulose nanoparticles extracted by Method II affected the crystallization process of the PLA. The composite presented a higher degree of crystallinity than the pure matrix. Furthermore, the addition of 3 wt% of the NC in PLA was enough to change its rheological behavior. The rheological results indicated that the morphology is predominantly composed by a fine and homogeneous dispersion of the filler in the matrix. The SEM micrographs corroborate the rheological data, showing, predominantly, NC particles in nanometric scale. Composites with NC obtained by Method III presented micro and milimetric scale clusters of NC particles in the matrix phase and were not extensively characterized.

Nanocompósitos poliméricos foram preparados por meio da incorporação de 1, 2, 5 e 10% das argilas montmorilonita organofílicas Cloisite 15A e 30B em poliamida-6, pelo método de fusão numa extrusora dupla rosca. Em seguida, foram reprocessados numa extrusora mono-rosca gerando folhas pelo método balão e caracterizados por meio de técnicas espectroscópicas, de análise térmica e difração de raio-X. Os estudos mostraram a formação de nanocompósitos com uma boa dispersão e esfolheamento, principalmente em concentrações de argila inferiores a 5%. Nas amostras com 5 e 10%, nanocompósitos intercalados também foram observados. Portanto, quando a concentração de argila aumenta no nanocompósito, fica cada vez mais difícil obter nanocompósitos totalmente esfoliados. Além disso, verificou-se que a incorporação de 1% da Cloisite 15A ou 30B induzem a cristalização do polímero, predominando a fase γ nos filmes. Entretanto, a medida que a concentração de argila aumenta a fração de fase amorfa tende a aumentar, provavelmente em decorrência da diminuição da velocidade do processo de recristalização em torno de 194 ºC, que gera a fase cristalina γ. Foi demonstrado a presença de um excesso de surfactante em uma das argilas organofílicas, tanto na parte exterior dos tactóides como na região interlamelar, aumentando o espaçamento basal e facilitando o processo de intercalação/esfolheamento. Todavia, o excesso de surfactante interfere nos processos de incorporação pois sofrem decomposição em temperaturas relativamente baixas (200 ºC) enquanto o cátion amônio intercalado se decompõe a 240 ºC. De fato, os estudos realizados comprovam que o surfactante tem influência direta sobre as propriedades das argilas organofílicas e grande importância no processo de incorporação. Melhorias significativas foram observadas nas propriedades de barreira a gases e mecânicas, principalmente com relação a resistência a tração, que aumenta a medida que se aumenta a concentração de argila. As propriedades de perfuração não foram significativamente modificadas, mas também verificou-se um aumento significativo da estabilidade mecânica em função da temperatura. Porém, a absorção de umidade interfere negativamente tanto nas propriedades mecânicas quanto na de barreira a gases, sendo que a Cloisite 15A é menos suscetível que a Cloisite 30B, provavelmente devido ao cátion de amônio quaternário ser mais hidrofóbico. Assim, os filmes de nanocompósitos de poliamida- 6/argila devem ter aplicações diversas na indústria de embalagens / Polymeric nanocomposites were obtained by incorporation of 1, 2, 5 e 10% of the organophilic clays Cloisite 15A e 30B in polyamide-6, using a twin-screw extruder and the melting process. Then, the pellets were reprocessed as films in a single-screw extruder coupled with the blow method, and those materials were characterized by means of spectroscopic, thermal and X-ray difraction techniques. The results were consistent with the formation of nanocomposites with excellent dispersion and exfoliation, especially when the concentration of clay was below 5%. In the samples containing 5 e 10%, the presence of tactoids were observed showing the formation of intercalated nanocomposites as well. Thus, as the concentration of organophillic clay increases, the fraction of completely exfoliated clay decreased. Furthermore, the incorporation of clays (Cloisite 15A or 30B) in concentrations as low as 1% induced the crystallization of polyamide-6, such that it was found in the films predominantly in the γ phase. However, as the concentration of clay increases there is a steady increase of the amorphous phase, probably due to the decrease of the rate of the recrystallization process at 194 ºC, responsible for the formation of the γ phase. Also, the presence of an excess of surfactant was confirmed for both, Clositite 15A and 30B, around the tactoids and in the interlamelar space also, increasing the basal distance and facilitating the intercalation/exfoliation process. However, such an excess interfere in the nanocomposite preparation process since decomposes at relatively low temperatures (200 ºC) while the intercalated quaternary ammonium cation decomposes at 240 ºC. In fact, we showed that the structure of the surfactant directly influences the properties of the organophilic clays, and has strong influence on the nanocomposite preparation process. Significant improvements in the barrier effect to gases and in the mechanical properties were noticed for the nanocomposites, particularly on the resistance to traction and on the mechanical stability as a function of temperature, but the resistance to perforation didnt change significantly as the concentration of clay increased. The absorption of water by the nanocomposites influenced negatively the mechanical properties and the barrier effect as well. However, the nanocomposites prepared with Cloisite 15A were less susceptible than those obtained with Cloisite 30B, probably because the quaternary ammoniun salt in the first one is more hydrophobic and repels more effectively the water molecules

Neste trabalho foram investigados a obtenção de argilas organofílicas e nanocompósitos de Poliestireno com estas argilas. A primeira parte deste trabalho teve como objetivo a modificação de argilas esmectíticas naturais brasileiras, tornando-as organofílicas e adequadas à aplicação em nanocompósitos de matriz poliméricas. Para modificação foram utilizados sais quaternários e foi avaliado quais parâmetros do processo de obtenção mais influenciam nas propriedades das argilas organofílicas. Para tanto foi utilizada a argila Brasgel (fornecida pela BUN, e naturalmente cálcica), e foram propostos diferentes métodos de preparo de argilas, onde quatro parâmetros foram avaliados: os sais quaternários amônio; a granulometria da argila (#400 e coloidal), a temperatura de processamento (ambiente e a 70oC) e os tempos utilizados durante o processo de incorporação dos sais quaternários na estrutura dos materiais argilosos. Os materiais obtidos foram caracterizados por difração de raios-X (DRX), ensaios de inchamento de Foster e analise térmica diferencial (DTA). Obteve-se incremento do espaçamento basal com todas as argilas utilizadas. Mostrou-se que os dois principais parâmetros determinantes na incorporação das argilas são o tempo de mistura e a temperatura (de 70oC) empregada. A segunda parte do trabalho teve como objetivo obter nanocompósitos de PS com argilas organofílicas (sendo uma argila obtida na primeira parte e uma comercial, Cloisite 20A) via intercalação no polímero fundido. Os nanocompósitos foram preparados em extrusora de rosca dupla e em misturador interno. As argilas foram adicionadas ao polímero fundido na forma de um pó e em suspensão de etanol. Os nanocompósitos obtidos foram moldados por compressão e injeção (com variações nas condições de injeção para avaliar a influencia na estrutura final), para realização da caracterização. A principal técnica de caracterização utilizada foi a caracterização reológica com ensaios de cisalhamento de pequenas amplitudes (COPA) e de varredura de tempo. Os materiais foram caracterizados também por técnicas auxiliares como DRX, microscopia eletrônica de transmissão (MET), analises térmicas diferenciais (DTA) e ensaios mecânicos. Obteve-se nanocompósitos de estrutura intercalada. Os materiais obtidos no misturadores mostraram as melhores dispersões de argila. . Verificou-se que o tempo de residência dos materiais é um dos fatores mais importantes na obtenção dos nanocompósitos. Os ensaios mecânicos não mostraram alteração significativa. / In this work, the obtention of organoclays and nanocomposites of polystyrene (PS) using these modified clays was studied. In a first part Brazilian smectites clays were modified to be used in clay containing polymer nanocomposites. Several quaternary ammonium salts and experimental methods to modify the clays were used. In particular four parameters were evaluated: the type of ammonium salt, the particle clay size, the temperature and time used during the process of modification. The samples obtained were characterized by X-ray diffraction (XRD), Foster swelling test and differential thermal analysis (DTG). The results indicated that the most two important parameters in the process of modification are the time and the temperature used. In a second part nanocomposites of PS with organoclays (one obtained in the first part, and commercial clay, named cloisite 20A) were obtained by melt intercalation method using a twin screw extruder and an internal mixer. The clays were incorporated to the polymer as a fine dried powder and as a suspension of ethanol. Nanocomposites were molded by compression and injection. The injection conditions were modified to evaluate their influence on the morphology of the samples. The nanocomposites samples were characterized by XRD, transmission electronic microscopy (TEM), DTG and mechanical tests. Small amplitude oscillatory shear (SAOS) and time sweep tests were carried out. Nanocomposites of intercalated structure were obtained. The ones obtained using the internal mixer were shown to present a finer microstructure. The experimental results revealed that the residence time was showed the most important parameter in obtention of nanocomposites.