This thesis describes novel research using Portobello mushroom spores (PMS) as a biotemplate and reducing agent that may be used to produce nanocomposites and replicas with societal benefits. First, the use of PMS as a green eco-friendly bioreagent for the biosynthesis of Ag, Au and TiOx nanoparticles (NPs) and their hybrids is described. These have been characterised using SEM, TEM, XRD, FTIR, UV, SIMS, DLS and TGA (where a full list of acronyms is to be found on page iv). The spherical shape, location and mean diameter of the PMS-held (5-30nm) Ag and Au NPs were confirmed. PMS functional groups are comparable with those in plant sources and allow them to act as reducing/capping/stabilising agents. Second, the sequential biosynthesis of PMS-held Ca2+, CaCO3 and nanohydroxyapatite (nHAp) is described where surface nucleation and growth are facilitated by biotemplate surface hydrophilic polar groups (-OH and -COO-). XRD and HRTEM suggest that the nHAp so formed has lower crystallinity and greater directed growth in the (002) direction than commercial nHAp (e.g. Bio-Oss), making PMS-routes useful for the delivery of artificial bone (after subsequent PMS removal). Furthermore, PMS-held nHAp showed more rapid in-vitro mineralization in simulated body fluid (SBF). Third, it is shown that ascorbic acid (AA), haemoglobin (Hb) and insulin (In) can be loaded into/released by PMS through its cell walls faster than with synthetic hydrogels (PVA); the transdermal use of PMS nanocomposites is considered in the context of drug delivery nanotechnology, avoiding size-dependent toxicity. Fourth, it is shown by traditional diffusion and novel methods that the antimicrobial activity especially of Ag/PMS, but also TiOx/PMS and Ag-TiOx/PMS (but not Au/PMS) is good in the inhibition of the growth of E.coli and S.aureus bacteria. The highest activity of Ag/PMS is attributed to Agx+ release. Fifth, the synthesis of NPs/PMS and biomimetic TiOx/PMS has shown to lead to good photocatalysis for the removal of coloured organic pollutants (e.g. methyl orange) from water, with faster rates of removal in molecules/mg/s and turnover numbers (TON) (s-1) than commercial anatase-rutile TiO2 (P25) possibly as the texture of the titania replicas raises the number of multiple reflections of light.

Orientador: Lauro Tatsuo Kubota / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-09-11T21:18:50Z (GMT). No. of bitstreams: 1 Silva_CeciliadeCarvalhoCastroe_M.pdf: 2199742 bytes, checksum: e0c39714ed0a9045beffe47b579b8438 (MD5) Previous issue date: 2011 / Resumo: Este trabalho descreve o desenvolvimento de um sensor amperométrico para detecção eletrocatalítica de cisteína, através da construção de uma plataforma funcional para a complexação de íons cobre. O material base desta plataforma foi um nanocompósito obtido por meio da modificação de nanotubos de carbono de paredes múltiplas (MWCNTs) com poli(4-vinilpiridina) PVP, através uma reação de polimerização in situ. Foi realizada uma otimização multivariada, empregando um planejamento composto central de face centrada, para a modificação da superfície do eletrodo de carbono vítreo (ECV), sendo a condição ótima obtida quando se utiliza concentração da dispersão de nanocompósito de MWCNTs-PVP de 6,00 mg L, concentração da solução CuCl2 de 50 mmol L e tempo de complexação dos íons cobre de aproximadamente 83 minutos. A plataforma foi caracterizada por microscopia eletrônica de varredura (MEV), espectroscopia de energia dispersiva de raios-X (EDX), espectroscopia de impedância de eletroquímica (EIE), cronoamperometria e voltametria cíclica. Os valores da constante heterogênea de transferência de elétrons (ks) e da constante cinética da reação entre os íons Cu- cisteína (kobs) foram 5,78 s e 6,96 x 10 L mol s respectivamente. A curva analítica apresentou uma faixa linear de 5 a 60 mmol L para a detecção de cisteína. Já os limites de detecção e quantificação foram 1,50 e 5,00 mmol L, respectivamente. Além disso, o ECV/MWCNTs-PVP/Cu apresentou um tempo de resposta extremamente baixo, 0,10 s e quando aplicado para determinação de cisteína em amostras de suplemento alimentar apresentou resultados estatisticamente iguais em um nível de confiança de 95% com os resultados obtidos pelo método oficial / Abstract: This work describes the fabrication of an amperometric sensor for electrocatalytical detection of cysteine. The developed sensor is based on a functional platform for complexing copper ions on multi-walled carbon nanotubes (MWCNTs) modified with poly-4-vinylpyridine through an in situ reaction of polymerization. A multivariate analysis using a central composite design to investigate the surface modification of glassy carbon electrode (GCE) was employed to optimize the experimental variables. The established optimal conditions for the concentration of MWCNTs-PVP dispersed nanocomposite were, 6,00 mg L, 50 mmol L of concentration CuCl2 and around 83 min. for complexation of copper ions. The platform was characterized performing scanning electron microscopy (SEM), energy dispersive x-ray (EDX), electrochemical impedance spectroscopy (EIS), chronoamperometry and cyclic voltammetry analyses. The obtained values for the kinetic constants for heterogeneous electron transfer rate (ks) and for chemical reaction (kobs) between Cu and cysteine were 5.78 s and 6.96 L mol s, respectively. The analytical curve showed a linear range for detecting cysteine in concentrations from 5 to 60 mmol L. The detection and quantification limits obtained were 1.50 and 5.00 mmol L, respectively. Moreover, the response time of the ECV/MWCNTs-PVP/Cu sensor was 0.1 s. The application of the sensor to detect cysteine in nutritional supplement showed results statistically equal (0.95 confidence level) to those obtained with official methods / Mestrado / Quimica Analitica / Mestre em Química

Orientador: Maria Isabel Felisberti / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-09-27T12:44:40Z (GMT). No. of bitstreams: 1 Contar_LiviaBarbosa_M.pdf: 1831028 bytes, checksum: 9dc6aca0cd0794c653af2498ac17227d (MD5) Previous issue date: 2013 / Resumo: A incorporação de cargas em matrizes poliméricas, visando o desenvolvimento de compósitos e nanocompósitos poliméricos, tem sido foco de intensos estudos e apresentado interesse crescente na área industrial nos últimos anos em função do acréscimo conferido às suas propriedades mecânicas, térmicas e elétricas, dependendo da natureza da carga, e também devido à simplicidade, rapidez e baixo custo na obtenção destes materiais. A associação de cargas de diferentes naturezas em uma mesma matriz polimérica, além de conferir múltiplas funcionalidades ao material, pode contribuir com propriedades sinérgicas, antagônicas ou meramente aditivas. Neste trabalho, foram preparados em diferentes concentrações, compósitos binários de poliamida 6 (PA 6) com argila organicamente modificada, Cloisite® 30 B (C30B) e PA 6 com grafite puro, bem como compósitos ternários de PA 6, argila C30B e grafite, através da mistura mecânica no estado fundido, utilizando extrusora de duas roscas cônicas co-rotacionais, com o objetivo de desenvolver materiais com elevado desempenho mecânico e térmico. Corpos de prova moldados por injeção foram submetidos a ensaios para determinação de suas propriedades mecânicas (ensaios de tração e de resistência ao impacto), térmicas (DMA, TGA e DSC), morfológicas (SEM e TEM) e estruturais (XRD). Tanto os nanocompósitos de PA 6 e argila C30B, quanto os compósitos de PA 6 e grafite, apresentaram maior resistência à tração do que a PA 6 pura, assim como ocorreu com os compósitos ternários. Porém, nestes últimos, foram observados os maiores ganhos na rigidez do material, devido ao efeito co-reforçante de ambas as cargas e suas prováveis interações mútuas que favorecem a dispersão na matriz. As análises morfológicas das misturas binárias e ternárias revelaram a formação de estruturas esfoliadas e de agregados, no caso da argila, enquanto que no caso da grafite apenas se observou partículas correspondentes a agregados de multilaminas de grafeno, mesmo nos sistemas ternários. Apesar disso, contatou-se que a presença da grafite nos nanocompósitos ternários proporciona um aumento da extensão de delaminação da argila. A grafite atua como agente nucleante para a cristalização da poliamida, sem alterar a forma cristalina, no caso a forma 'alfa'. Enquanto que a argila induz a formação da fase 'gama'. / Abstract: The incorporation of fillers in polymeric matrices in order to develop polymer composites and nanocomposites has been highlighted in many works and has showed increasing interest in industrial area in the last years because of enhaced mechanical, thermal and electrical properties, depending on the filler nature, and also because of simplicity, velocity and low costs in the preparation of these materials. The association of different fillers in the same polymeric matrix, beyond multiple functionalities attributed to the material, can also contribute to synergistic, antagonistic or additive properties. In this work, binary composites of polyamide 6 (PA 6) with organic modified clay, Cloisite® 30 B (C30B), and PA 6 with pristine graphite, were prepared in different concentrations as well as ternary composites of PA 6, clay and graphite, through mechanical mixture in the molten state, using a conical co-rotational twin-screw extruder, in order to develop materials with enhaced mechanical and thermal properties. The materials were injection molded to investigate their mechanical (Tensile properties, Izod Impact resistance), thermal (DMA, TGA and DSC), morphological (SEM and TEM) and structural (XRD) properties. Both binary composites, PA 6 with C30B clay and PA 6 with graphite, showed higher tensile properties in relation to pure PA 6, and the same happened with ternary composites. But in these last one the highest gain in the material stiffness was observed, because of the co-reinforcement effect of both fillers and their mutual interations that favoured fillers dispersion. The morphological analysis of binary and ternary systems have revealed the formation of exfoliated structures and aggregates, in the case of the clay, while in the graphite case only particles refered to aggregates of graphene multi-platelets were observed even in the ternary systems. Nevertheless, it was detected that the presence of graphite in the ternary composites promotes an increase in the exfoliation degree of the organoclay. Thermal studies showed that the graphite acts as a nucleating agent for the crystallization of polyamide, without change in the crystalline 'alpha' phase, while the organoclay promotes the 'gama' phase / Mestrado / Físico-Química / Mestra em Química

Hidróxido de níquel é um material amplamente estudado principalmente devido às suas aplicações como cátodo de baterias secundárias de níquel, entretanto tal sistema ainda apresenta problemas devido à progressiva diminuição da capacidade de carga em função do número de ciclos de oxidação/redução. No presente trabalho são descritas a preparação, caracterização e propriedades de nanomateriais de hidróxido de níquel, obtidos pelo processo sol-gel; e também dos nanocompósitos obtidos por meio da interação do sol de Ni(OH)2 com argilas catiônica (hectorita) e aniônica (HDL similar a hidrotalcita). Os materiais foram caracterizados por análise térmogravimétrica, espectroscopia UV-Vis e infravermelho, difração de raios-X, microscopia eletrônica de varredura, voltametria cíclica e microbalança eletroquímica a cristal de quartzo. Os resultados obtidos são claramente consistentes com a forma α-Ni(OH)2, e apresentam uma maior reversibilidade eletroquímica que os nanomateriais análogos preparados por outros métodos. Além disso, essa característica foi melhorada por meio de tratamento térmico a 240 °C, ou por meio da incorporação nas matrizes lamelares hospedeiras, gerando nanomateriais com grande potencialidade para o desenvolvimento de dispositivos eletroquímicos, em particular baterias, dispositivos eletrocrômicos, catalisadores e sensores amperométricos. / Nickel hydroxide has been extensively studied because of its use as active material in the cathode of alkaline secondary batteries, but the main problem related to the progressive decrease of charge capacity as a function of the number of oxidation/reduction cycles still remains unsolved. In this work, the preparation, characterization and electrochemical properties of nickel hydroxide nanomaterials obtained by sol-gel method, and of nanocomposites materials prepared by the combination of nickel hydroxide sol and a cationic clay (hectorita) and an anionic clay (LDH like hydrotalcite) are described. The materials were characterized by thermogravimetric analyses, UV-Vis and IR spectroscopy, X-ray diffractometry, scanning electron microscopy, cyclic voltammetry and electrochemical quartz microbalance. The results were consistent with the α-Ni(OH)2 phase, but showing better electrochemical reversibility than that of similar materials obtained by others methods. Furthermore, this property was enhanced by thermal treatment at 240 °C or by Ni(OH)2 incorporation into the layered hosts. In conclusion nickel hydroxide nanomaterials with possible applications for the development of electrochemical devices such as batteries, electrochromic devices, catalysts and amperometric sensors were prepared and their exceptional electrochemical reversibility demonstrated

Esta tese apresenta um estudo detalhado das propriedades eletroquímicas dos nanocompósitos de V2O5.nH2O e poli(pirrol) sobre a superfície de eletrodos. Demonstramos aqui que pelo controle de parâmetros de síntese é possível alterar a composição das interfaces eletroquímicas dos eletrodos modificados, fazendo com que o poli(pirrol) esteja por cima, por baixo ou dentro do V2O5 que recobre os eletrodos. Esta diferenciação estrutural tem repercussão nas propriedades eletroquímicas e espectroscópicas dos eletrodos modificados. Desenvolvemos além disto um método para gerar matrizes de V2O5.nH2O, assim como nanocompósitos com poli(pirrol) que possuam anisotropia elétrica tridimensional, propriedade útil em eletrônica. Na última parte do trabalho, poli(pirrol) foi inserido em matrizes de intercalação do tipo BV (V2O5.nH2O estabilizado com esmectita) gerando materiais estáveis em meio aquoso e adequados modificadores de eletrodos, viabilizando a exploração das propriedades dos compósitos de V2O5/poli(pirrol) em água. / This thesis focuses on the electrochemical properties of V2O5.nH2O and its poly(pyrrole) nanocomposites over electrodes. We demonstrate that it is possible, by controlling synthetic procedures, to change the composition of the modified electrodes interfaces, leaving poly(pyrrole) over, under or inside the V2O5 films covering the electrodes. This structural differenciation repercutes on the electrochemical and spectroscopic properties of the modified electrodes. We have developed also a method to generate V2O5.nH2O matrices as well as their nanocomposites with poly(pyrrole) showing tridimensional electrical anisotropy, a useful property in electronics. Additionally, poly(pyrrole) has been inserted into BV (smectite stabilized V2O5.nH2O) matrices, generating stable materials in aqueous medium, conveying to this, the properties of V2O5/poly(pyrrole) nanocomposites modified electrodes.

As propriedades dielétricas dos materiais têm ganhado importância na aplicação industrial nas últimas décadas, estas propriedades fornecem informações úteis para melhorar o controle de processamento e qualidade dos produtos alimentícios e outros materiais. A espectroscopia dielétrica é amplamente utilizada para estudar a dinâmica molecular em diversos sistemas, nos quais é comum observar o fenômeno de relaxação dielétrica que tem sido associado por vários pesquisadores ao fenômeno de transição vítrea, importante na estabilidade e propriedades dos materiais. O objetivo da tese foi analisar as propriedades dielétricas de produtos alimentícios e filmes biopoliméricos, dando ênfase ao estudo da mobilidade molecular nos filmes; e ao estudo da dinâmica estrutural de alimentos e sua correlação com fatores de qualidade. O estudo foi dividido em várias etapas com objetivos específicos: A primeira consistiu na montagem e startup do equipamento adquirido para medida das propriedades dielétricas (E4980A com 16451B; E5061B com 85070E, Keysight Technologies); A segunda etapa foi dedicada à análise das propriedades dielétricas de goiabada em pasta e suco de laranja na faixa de frequência de 500-3000 MHz, em função do teor de sólidos solúveis e da temperatura visando a geração de correlações que permitiriam fazer um monitoramento durante o processo de produção; Na última etapa foi estudada a mobilidade molecular de filmes de gelatina e nanocompósitos através da análise dielétrica em função da umidade, temperatura, e teor de plastificante ou nanopartícula, na faixa de frequência de 20 Hz - 2 MHz. Análises de calorimetria diferencial de varredura (DSC) e dinâmica mecânica (DMA) foram realizadas para determinar a temperatura de transição vítrea e de relaxação mecânica nos filmes produzidos. A constante dielétrica e o fator de perda dielétrica de suco de laranja e de goiabada em pasta foram dependentes da temperatura e concentração de sólidos solúveis. A temperatura de transição vítrea (Tg) e os tempos de relaxação dielétrica de filmes de gelatina diminuíram com o aumento da concentração de glicerol e com o aumento da umidade relativa de condicionamento. A temperatura de transição vítrea nos filmes nanocompósitos diminuiu com o aumento da umidade relativa de condicionamento. Filmes com 6% de laponita e sem adição de glicerol apresentaram os maiores valores de Tg. Os tempos de relaxação aumentaram ligeiramente com o aumento na concentração de laponita. Foram gerados dados úteis para estimar as propriedades dielétricas de suco de laranja e goiabada em pasta nas principais frequências de uso comercial, 915 e 2450 MHz, através de equações matemáticas em função da temperatura e concentração de sólidos solúveis. O glicerol e especialmente a água afetaram as propriedades dielétricas dos filmes de gelatina refletidas em menores tempos de relaxação, enquanto que as interações da laponita com a gelatina reduziram ligeiramente a mobilidade molecular nos filmes nanocompósitos proporcionando tempos de relaxação maiores. Este tema fez parte do Pilar 4 do projeto CEPID (2013/07914-8) \"Food Research Center\" (FoRC). / The dielectric properties of materials have gained importance in industrial application over the last decades; these properties provide useful information to improve processing and quality control of food products and related materials. The dielectric spectroscopy is widely used to study molecular dynamics in several systems, where it is common to observe the dielectric relaxation phenomenon that has been associated by many researchers to the glass transition phenomenon, important in stability and material properties. The objective of the thesis was to analyze the dielectric properties of food products and biopolymer films, emphasizing the study of molecular mobility in films; and the study of the structural dynamics of food and its correlation with quality factors. The study was divided into several stages with specific goals: The first was the installation and startup of the equipment for measurement of dielectric properties (E4980A with 16451B; E5061B with 85070E, Keysight Technologies); The subsequent step was dedicated to the analysis of the dielectric properties of guava paste and orange juice in frequencies between 500-3000 MHz, as a function of soluble solids content and temperature in order to generate correlations which allow to make a monitoring during the production process; In the last stage, the molecular mobility of gelatin biodegradable films and nanocomposites was studied through dielectric analysis as a function of moisture content, plasticizer or nanoparticle concentration and as a function of temperature, in frequencies between 20 Hz - 2 MHz. Differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) were performed to determine the glass transition and mechanical relaxation temperatures of the films. The dielectric constant and the dielectric loss factor of orange juice and paste guava were dependent on the temperature and soluble solids concentration. The glass transition temperature (Tg) and the dielectric relaxation times of gelatin films decreased with increasing glycerol concentration and with increasing relative humidity of conditioning. The glass transition temperature of the nanocomposite films decreased with the increase of the relative humidity of conditioning. Films with 6% of laponite and without addition of glycerol had the highest values of Tg. Relaxation times increased slightly with increasing laponite concentration. Useful data were generated to estimate the dielectric properties of orange juice and guava paste in the main commercial frequencies, 915 e 2450 MHz, through mathematical equations as a function of temperature and soluble solids content. Glycerol and especially water affected the dielectric properties of gelatin films reflected in lower relaxation times, whereas laponite and gelatin interactions reduced slightly the molecular mobility of the nanocomposite films by providing longer relaxation times. This topic was part of the Pillar 4 of CEPID project (2013 / 07914-8) \"Food Research Center\" (FoRC).

Philosophiae Doctor - PhD / The main objective of this study was to advance kinetic performances of formation and decomposition of magnesium hydride by design strategies which include high energy ball milling in hydrogen (HRBM), in combination with the introduction of catalytic/dopant additives. In this regard, the transformation of Mg → MgH2 by high energy reactive ball milling in hydrogen atmosphere (HRBM) of Mg with various additives to yield nanostructured composite hydrogen storage materials was studied using in situ pressure-temperature monitoring that allowed to get time-resolved results about hydrogenation behaviour during HRBM. The as-prepared and re-hydrogenated nanocomposites were characterized using XRD, high-resolution SEM and TEM, as well as measurements of the mean particle size. Dehydrogenation performances of the nanocomposites were studied by DSC / TGA and TDS; and the re-hydrogenation behaviour was investigated using Sieverts volumetric technique.

Novos materiais obtidos a partir de polímeros biodegradáveis são uma alternativa para a redução do impacto ambiental causado pelo uso excessivo de polímeros derivados do petróleo. Atualmente, vários estudos têm sido realizados na busca de matéria-prima para o desenvolvimento de filmes biodegradáveis, com boa viabilidade técnica e econômica. Dentre estas matérias-primas, destacam-se as que são provenientes de fontes renováveis, de baixo custo e que tenham grande importância econômica e ambiental, como, por exemplo, o amido, as argilas, e a quitosana. Nos filmes que preparamos, adicionamos como plastificante a glicerina, um subproduto do biodiesel, e que contribui para maior estabilidade térmica dos filmes, em conjunto com o amido. O propósito deste trabalho foi o preparo de um biopolímero a base de quitosana e argila com propriedades de nanocompósitos, pois estes materiais costumam exibir propriedades físico-químicas diferenciadas em relação a outros materiais, devido à redução no seu tamanho. Sendo assim, através do estudo e comparação de duas argilas esmectíticas sódicas naturais, Bentogel e Corral, pôde-se observar o comportamento dos filmes formados em presença de amido e glicerina. Os filmes obtidos, através do método de dispersão em solução do polímero, foram caracterizados através das técnicas de DRX, MEV, IV, TG e DSC. Os resultados obtidos mostraram a formação de filmes nanocompósitos esfoliados de boa estabilidade térmica. / New materials made from biodegradable polymers are an alternative to reducing the environmental impact caused by excessive use of polymers derived from petroleum. Currently, several studies have been conducted in search of raw material for the development of biodegradable films, with good technical and economic feasibility. Among these materials, we highlight those that are from renewable resources, low cost and have great economic and environmental importance, such as, starch, clays, and chitosan. In preparing films, we added glycerol as a plasticizer, a byproduct of biodiesel, and contributes to better thermal stability of the films, together with starch. The purpose of this study was the preparation of a biopolymer based on chitosan and clay nanocomposites properties, because these materials tend to display different physico-chemical properties compared to other materials because of the reduction in size. Thus, through the study and comparison of two natural sodium smectite clays, Bentogel and Corral, it was observing the behavior of films formed in the presence of starch and glycerol. The films obtained by the method of dispersion in the polymer solution, were characterized by techniques of XRD, SEM, FTIR, TG and DSC. The results obtained showed the formation of exfoliated nanocomposites films and good thermal stability.

Polymer composites formed from layered fillers with high surface volume ratio show enhanced reinforcement. Graphite oxide is a high modulus material that can be separated into thin layers with high surface area. The aim of this study is to prepare polymer layered graphite oxide composites using functionalised polyolefin to enhance compatibility with various forms of layered graphite oxide in varying concentration. Functionalised polyolefins reinforced with layered graphite oxides and expanded graphite oxides were prepared using solution blending and melt blending methods. Three different mixing methods with varying shear intensity were employed to prepare polymer layered graphite oxide composites. The crystalline structure, thermal and mechanical properties of the prepared polymer layered graphite oxide composites was studied. Oxidised graphite prepared from the Staudenmaier method and its exfoliated form were dispersed in poly(ethylene-co-methyl acrylate-co-acrylic acid) (EMAA) via solution blending to prepare EMAA layered composites. The thermal stability was determined using thermogravimetric analysis. The EMAA layered composites showed higher thermal stability in comparison with pure EMAA. The mechanical properties of these EMAA layered composites were determined through dynamic mechanical analysis. Shear modulus, yield stress and storage modulus of EMAA in the presence of graphite oxide fillers decreased. A solution blending method was used to prepare poly(propylene-grafted-maleic anhydride) layered expanded graphite oxide composites (PPMA-EGO). Two types of PPMA-EGO were prepared using different mixing methods - low and high shear were employed. The effects of preparative mixing methods on the PPMA-EGO properties were investigated. The mechanical properties of PPMA-EGO obtained from dynamic mechanical analysis indicated that EGO had a reinforcing effect on the elastic behaviour of PPMA-EGO. This is due to strong interfacial adhesion between PPMA and EGO as a result of hydrogen bonding. The elastic behaviour of PPMA-EGO was affected by the surface area of graphite flakes. Low sheared PPMA-EGO elastic behaviour was found to be higher compared with that of high sheared PPMA-EGO. A melt blending method was used to prepare PPMA-EGO with varying EGO concentration. The interconnected network structure of EGO in the PPMA-EGO was not observed as shown by its scanning electron microscopy images. Thermogravimetric analysis of PPMA-EGO indicates increased decomposition temperature of the PPMA matrix. Dynamic mechanical analysis showed enhanced storage modulus of PPMA-EGO. The maximum elastic modulus of PPMA-EGO was observed at 3 %wt of EGO. The electrical conductivity of PPMA-EGO was measured only for EGO concentrations above 2 %wt. The EGO concentration was found to be the most critical factor in the enhancement of the electrical conductivity of PPMA-EGO. Wide angle X-ray diffraction analysis of all polymer layered graphite oxide composites revealed no change in interlayer spacing of graphite layers, indicating the absence of EMAA intercalation in the graphite layers. The crystallisation temperature and crystallinity of all polymer layered graphite oxide composites were determined using differential scanning calorimetry. The results indicated that graphite oxide and expanded graphite oxides acted as nucleating agents in inducing the crystallisation of functionalised polyolefin in the layered composites. However, the degree of crystallinity of functionalised polyolefin decreased in the layered composites.

Différents nanocomposites ont été préparés par polymérisation in situ d'une dispersion de nanosilicates lamellaires dans du méthacrylate de méthyle. L'influence de la nature de la charge et de l'interface nanoparticule-matice sur la plasticité et sur la transition vitreuse a été étudiée en incorporant différents types de nanoparticules : deux argiles phyllosilicates (la cloisite et la laponite) et deux silicates de calcium hybride qui différent, entre autre, par leur facteur de forme. Le couplage charge-matrice varie d'une liaison purement covalente, jusqu'à l'emploi d'agent lié par attraction ionique à la charge et interaction Van der Waals avec la matrice. La dispersion des phyllosilicates nécessite une étape d'échange cationique avec des ions ammoniums comportant une ou deux chaînes alkyles terminée ou non par une double liaison pouvant réagir avec le méthacrylate de méthyle. Quant aux silicates de calcium, ils ont été synthétisés avec des groupements vinyle en surface. Pour chaque type d'échange, le protocole a été optimisé afin d'obtenir la meilleure dispersion des charges dans le nanocomposite ; la diffraction X et la microscopie électronique à transmission ont été utilisées pour contrôler l'état de dispersion. L'étude par analyse mécanique dynamique montre que l'introduction de nanoparticules lamellaires dans une matrice thermoplastique peut conduire soit à une augmentation, soit à une diminution de la température de transition vitreuse. Cette variation semble liée à la nature de l'interface plutôt qu'à la taille de la charge. L'étude de la plasticité met en évidence, pour tous les systèmes, un effet renforçant des nanoparticules qui, cependant, reste inférieur à ceux observés dans d'autres nanocomposites à matrice thermoplastique.