Thesis advisor: Zhifeng Ren / Thermoelectric (TE) technology is an environment-friendly one due to reduction of carbon emission, which can be widely used either for power generation or for refrigeration. Basically applications of TEs are based on TE effects, which involve the transition between heat and electricity. Despite the superior advantages of being solid state and providing a clean form of energy, TE technology so far only finds its niche area of application due to the relatively less efficiency compared to traditional methods. The efficiency of a thermoelectric device is solely determined by the dimensionless figure-of-merit (ZT) of thermoelectric materials. According to the definition, ZT is equal to square of Seebeck coefficient times electrical conductivity times absolute temperature divided by thermal conductivity. Therefore, a good thermoelectric material should possess high Seebeck coefficient and electrical conductivity while low thermal conductivity, so called phonon glass electron crystal (PGEC). In bulk materials, it is challenging to further improve ZT or independently vary individual parameters without affecting others, mainly due to the interrelated relationships among these three parameters. Fortunately, nano approach gives us some independent control in parameters adjustment. One important aspect of nano idea lies in the fact that enhanced boundary scattering due to the increased intensities of interfaces arising from nano-sized grains could reduce the thermal conductivity more than the electrical conductivity, which is practically realized in our material system. Since the introduction of nano idea, large ZT as high as above two has been achieved in the superlattice system. Due to the high fabrication cost of superlattices, they are not scalable for mass production. Theoretical calculations indicate that thermal boundary resistance is the main mechanism for the low thermal conductivity in superlattices, rather than the periodicity. Basically, we hope to achieve the supplattice-like ZT in the less costly bulk nanograined materials, based on the idea that reduction of thermal conductivity which is responsible for ZT enhancement in superlattices can be realized in bulk materials with embedded nanostructures as well. Inspired by the nanocomposite idea, in my thesis work I applied the technique of ball milling and then hot press to various thermoelectric materials, from low temperature to high temperature, demonstrating the feasibility of the approach. By ball milling alloyed ingot into nanopowders and DC hot pressing them, we have achieved a 62-89% ZT improvement for p-type half-Heusler samples, mainly due to the significantly enhanced Seebeck coefficient and partially due to the moderately reduced thermal conductivity. Microstructure studies indicated that increased boundaries due to smaller nano-sized grains is the cause for change of parameters. For our ball milled samples, the trend of decreasing thermal conductivities with increasing ball milling time is observed, further substantiating our nano-approach idea because longer ball milling time gives rise to smaller grain sizes and thus stronger boundary scattering. By applying the same technique to n-type half-Heuslers, we also successfully obtained pronounced enhancement in ZT especially at medium and low temperature ranges, which might be useful in medium temperature power generation. By ball milling a mixture of individual constituent elements into alloyed nanopowders and then DC hot pressing them, we did not gain improvement in ZT initially for n-type BiTeSe system mainly due to the simultaneous reduced power factor with the thermal conductivity. Considering anisotropic properties of the n-type BiTeSe single crystal and randomization effect of ball milling process, we repressed the as-pressed bulk samples in a bigger diameter die, during which lateral flow took place, resulting in preferred grain orientation. As a result, a 22% improvement in the peak ZT from 0.85 to 1.04 at 125 oC in n-type Bi₂Te_2.7Se_0.3 has been successfully achieved, arising from the more enhanced power factor than the thermal conductivity. Compared with single crystal, we benefit from the small nano-sized grains in bulk materials. Taking into account the in-plane power factor of single crystal, we still have much room for further ZT improvement if more ab orientation is promoted into the disk plane and/or the crystal plate size and thickness are reduced. By applying our technique of ball milling and then hot press to p-type skutterudites system, we have achieved a peak ZT of 0.95 at 450 <super>o</super>C in NdFe_3.5Co_0.5Sb₁₂, which is comparable to that of the state-of-the-art ingot. Our approach has the advantage of being less costly and more time-efficient compared to traditional fabrication methods. Besides, even lower thermal conductivity and hence higher ZT can be expected, provided that the nanosize of the precursor powder is preserved during hot press. The nanocomposite idea has been substantiated and the feasibility and generality of our ball milling and then hot press approach has been demonstrated, based on the thermoelectric properties data we obtained and the microstructure studies we carried out from various thermoelectric material systems, from low temperature to high temperature. We believe that continued effort in the area of thermoelectrics by our approach should be paid with superlattice-like ZT if ingenious methods are devised to control the grain growth during consolidation. / Thesis (PhD) — Boston College, 2010. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Physics.

Este trabalho aborda o estudo do comportamento mecânico e térmico do nanocompósito híbrido de polipropileno com uma argila brasileira bentonítica do Estado da Paraíba (PB), conhecida como \"chocolate\" com concentração de 1, 2 e 5 % em massa com a adição de 1 e 2 % em massa de celulose proveniente de papel descartado. Foi utilizado nesse nanocompósito o agente compatibilizante polipropileno graftizado com anidrido maleico PP-g-AM com 3 % de concentração em massa, através da técnica de intercalação do fundido utilizando uma extrusora de dupla-rosca e, em seguida, os corpos de prova foram confeccionados em uma injetora. O comportamento mecânico foi avaliado pelos ensaios de tração, flexão e impacto. O comportamento térmico foi avaliado pelas técnicas de calorimetria exploratória diferencial (DSC) e termogravimetria (TGA). A morfologia dos nanocompósitos foi estudada pela técnica de microscopia eletrônica de varredura (MEV). A argila, a celulose e os nanocompósitos híbridos foram caracterizados por difração de raios X (DRX), fluorescência de raios X (FRX) e espectroscopia no infravermelho (FTIR). Nos ensaios mecânicos de tração houve um aumento de 11 % na tensão máxima em tração e 15 % no módulo de Young, para o nanocompósito com argila, PPA 5 %. No ensaio de impacto Izod, o nanocompósito com argila, PPA 2 % obteve um aumento de 63 % na resistência ao impacto. Para o nanocompósito híbrido PPAC 1 % houve aumento de 8 % na tensão máxima em tração e para o nanocompósito híbrido PPAC 2 % houve aumento de 14 % na resistência ao impacto. / This work concerns to the study of the mechanical and thermal behavior of the hybrid polypropylene nanocomposite with a Brazilian bentonite clay from State of Paraíba (PB), known as \"Chocolate\" in concentrations of 1, 2 and 5 % by weight with addition of 1 and 2 % in weight cellulose discarded bond paper. The compatibilizer agent based on maleic anhydride grafted polypropylene, known as PP-g-MA, was added at 3 % weight concentration through the melt intercalation technique using a twin-screw extruder, and afterwards, the specimens were prepared by injection process. The mechanical behavior was evaluated by strength, flexural strength and impact tests. The thermal behavior was evaluated by the differential scanning calorimetry (DSC) and thermogravimetry (TGA). The morphology of the nanocomposites was studied by the technique of scanning electron microscopy (SEM). The clay, cellulose and the hybrid nanocomposites were characterized by X-ray diffraction (XRD), X-ray fluorescence (XRF) and infrared spectroscopy (FTIR). Results of mechanical tests showed an 11 % and 14 % increase in the tensile strength and Young\'s modulus, respectively, for the nanocomposite PPA 5 % with clay. The nanocomposite PPA 2 % with clay obtained a 63 % increase in strength Izod impact test. The hybrid nanocomposite PPAC 1 % obtained an 8 % increase in tensile strength. In the Izod impact test, the hybrid nanocomposite PPAC 2 % obtained 14 % increased in the impact strength.

No presente trabalho, é apresentado o desenvolvimento de novos nanocompósito híbridos orgânico-inorgânico, especificamente MnO2/Blendas poliméricas condutoras (BPC) e nanofibras de V2O5 e V2O5/Pani, com propriedades diferenciadas. Estes óxidos nanoestruturados com morfologia definida, bem como a sua combinação com matrizes de polímeros condutores, apresentaram as características necessárias para um bom desempenho como material para catodos de baterias secundárias de lítio e/ou supercapacitores. Através dos resultados obtidos, foi possível demonstrar, de maneira inequívoca, que é possível alcançar um nanocompósito de óxido de metal de transição/polímero condutor, eletroativo e com morfologia definida mediante a síntese por micela reversa. A caracterização das BPC (Pani/PMMA e Ppy/PMMA) mostrou suas vantagens como matrizes para suportar e dispersar nanopartículas de MnO2, evitando o uso de carbono para aumentar a condutividade eletrônica do óxido. Particularmente, a utilização de nanocompósitos MnO2/(Ppy/PMMA), como material para supercapacitores, demonstrou que a distribuição homogênea das nanopartículas de MnO2 na BPC favorece a rápida difusão dos íons, o que indica que as nanopartículas, imobilizadas numa matriz polimérica condutora, tornam o material mais acessível à inserção de ambas as espécies (íons e elétrons). Comprovou-se a diferença de estabilidade mecânica entre as nanofibras de V2O5 e V2O5/Pani, revelando que a presença do polímero minimiza as variações, nas propriedades mecânicas da matriz inorgânica, durante o processo de intercalação de Li+. As nanofibras de V2O5/Pani revelaram uma maior capacidade especifica e uma cinética de intercalação mais rápida (devido ao caminho difusional mais curto no sólido nanoestruturado), que as nanofibras de V2O5. A presença de Pani, nas nanofibras, diminui a queda ôhmica e fornece um caminho condutor alternativo para unir as partículas isoladas do óxido, tornando-as eletroquimicamente ativas. De uma maneira geral, observou-se um sinergismo entre os materiais, isto é, a combinação de características positivas dos polímeros condutores eletrônicos junto às dos óxidos geraram um novo material com propriedades melhoradas, quando comparados aos componentes originais. / In this work, new nanostructures formed from a mixture of MnO2 and conducting polymer blends (CPB), and new materials with specific morphology (nanofibers), constituted of V2O5 and V2O5/Pani have been investigated for application in energy storage devices, specifically, as cathode material for secondary lithium batteries and supercapacitors. Different nanostructures were prepared by reverse micelle method. Colloidal assemblies are used to control the size and the shape of the particles. The growth of the obtained particles was controlled by two condition: (i) time of the synthesis and (ii) size of the polar core. The characterization of CPB (Pani/PMMA and Ppy/PMMA) shown that this blends give an opportunity for the design of materials with improved properties, (stability, charge propagation dynamics) affording an ultimate degree of dispersion for the nanoparticles (MnO2). We also describe the preparation of electrodes with hybrid films formed by MnO2 dispersed into CPB. The resulting modified electrodes have been used for the fabrication of a supercapacitor and cathodes for lithium batteries. On the other hand, we explore the relationship between the nanoscale morphology and electrochemical performance of V2O5 and V2O5/Pani nanofibers. Both type of sample were examined by several techniques to characterize their structure and morphology. It was found that V2O5/Pani shows improved cycling behavior compared to the V2O5 one. The polymer looks to improve capacity of the nanohybrid electrodes due to the homogeneous distribution of the induced stress during cycling. The rate capabilities of the nanostructured electrodes were compared with the obtained value for thin-film electrodes containing the same type of the electrode material. Spectroscopy electrochemical impedance and cyclic voltammetry experiments have shown that the nanostructured electrode affords higher solid state kinetic and capacities than thin film electrodes. Therefore, the general notion behind these efforts is to combine the attractive properties of each material (conducting polymers and metal transition oxides)while taking advantage of synergistic effects that might mitigate against unattractive features observed for the individual materials.

Le S-nitrosoglutathion (GSNO), donneur d’oxyde nitrique (NO) physiologique, présente une application potentielle dans le traitement des maladies cardiovasculaires (CVD). Cependant, avec une demi vie supérieure à celle de NO, GSNO reste labile limitant ainsi son application. Cette étude vise au développement de particules nanocomposites (NCP) incluant des nanoparticules polymériques chargées en GSNO (GSNO-NP) dans une matrice polysaccharidique pour la voie orale. Bien que les GSNO-NP encapsulant efficacement GSNO, le libèrent rapidement in vitro, elles retardent la S-nitrosation (biomarqueur de NO) des protéines de cellules musculaires lisses en culture (18 h). Par conséquent, pour une libération prolongée, les GSNO-NP ont été incluses dans une matrice d’alginate (a), chitosan (c) ou un mélange des deux (acNCP). Les GSNO-acNCP avec une encapsulation élevée (76%) et une libération in vitro jusqu’à 24 h, ont significativement favorisé le passage de GSNO au travers d’un modèle de barrière intestinale (Caco-2). A la lumière de cette compatibilité avec un traitement oral journalier, le gavage de rats Wistar avec ces GSNO-acNCP 17 h avant prélèvement de l’aorte a diminué la contraction maximale phényléphrine (PHE) dépendante d’anneaux aortiques isolés. De plus, la N-acétylcystéine (NAC) (thiol déstockant NO tissulaire) produit la relaxation d’anneaux précontractés avec la PHE, prouvant le stockage de NO au sein de la paroi vasculaire. En augmentant le temps de résidence gastrointestinale et donc le passage de GSNO au travers de l’intestin, les GSNO-acNCP produisent un effet prolongé (17 h après administration) par l’intermédiaire du stockage de NO au niveau tissulaire / As a physiologic nitric oxide (NO) donor, S-nitrosoglutathione (GSNO) has potential therapeutic application for the treatment of cardiovascular disease (CVD). With a longer in vivo half-life than NO, GSNO is still sensitive to many factors leading to poor applicability. This study aimed at the development of nanocomposite particles (NCP) based on synthetic polymeric nanoparticles encapsulating GSNO (GSNO-NP) embedded in a polysaccharidic matrix for oral delivery of GSNO. Although GSNO-NP, with a high encapsulation efficiency, showed an in vitro burst release, they succeeded in the preservation of GSNO stability and bioavailability for smooth muscle cells as they delayed in vitro protein S-nitrosation (NO biomarker) until 18 h. Therefore, to reach the sustained release, GSNO-NP were embedded in a matrix of alginate (a), chitosan (c) or a blend (acNCP). GSNO-acNCP with high encapsulation efficiency (76%) and an in vitro release until 24 h, promoted the highest permeation rate of GSNO through an intestinal barrier model (Caco-2). With this daily oral treatment compatibility Wistar Rat pretreatment by gavage with GSNO-acNCP 17 h before aorta removal decreased the maximal contractile effect induced by phenylephrine (PHE) on isolated aortic rings. Furthermore, the N-acetylcysteine (a thiol displacing NO stores from tissues) produced the relaxation of PHE precontracted aortic rings, proving NO storage in the vessel wall. By increasing the residence time in the gastrointestinal tract thus promoting GSNO crossing through the intestinal barrier, GSNO-acNCP induced a long lasting effect (17 h after administration) through NO storage in vessels

Dentre os materiais de fontes naturais e renováveis, a celulose se destaca pela sua abundância, podendo ser encontrada em diversos organismos vivos, como plantas, amebas, bactérias, fungos e alguns animais marinhos. Suas dimensões podem ser reduzidas por quebra das cadeias amorfas, com possibilidade de atingir escalas nanométricas, obtendo-se assim as chamadas nanopartículas de celulose ou nanocelulose. Devido à alta cristalinidade, a nanocelulose possui altos valores de módulo elástico, proporcionando alta capacidade de reforço em matrizes poliméricas, combinados com baixo peso, área superficial elevada e biodegradabilidade. A borracha natural é uma matéria-prima de fonte natural, sendo extraída das seringueiras na forma de látex - dispersão coloidal de partículas de borracha e substâncias não-borrachas em um meio aquoso, com aspecto leitoso. No presente trabalho foram estudados compósitos de borracha natural e nanocelulose. Inicialmente, foi realizada uma análise do látex de nacionalidade brasileira, centrifugado, contendo 60% em massa de sólidos. Os resultados de caracterização do látex centrifugado comercial, a qual consistiu na análise de concentração de sólidos totais e na medida do pH, estavam de acordo com os dados apresentados pelo fornecedor. Além disso, a análise de distribuição de tamanho de partícula indicou que o material apresenta uma população, com tamanho médio de 1,0 ?m. A borracha coagulada com ácido acético apresentou, após mastigação em cilindro aberto, viscosidade Mooney e extrato acetônico igual a, respectivamente, 52,8 e 2,57%. As nanoceluloses foram obtidas por hidrólise com ácido ortofosfórico (NC P) e sulfúrico (NC S), sendo classificadas como nanocristal de celulose (NC). NC P apresentaram comprimento médio, razão de aspecto e cristalinidade igual a, respectivamente, 270 ± 89 nm, 50 ± 24 e 78%; e as NC S apresentaram 209 ± 51 nm, 29 ± 10 e 75%.. Os compósitos de borracha natural com nanocristais de celulose apresentaram, nos ensaios de tração, aumentos nos valores de todas as propriedades analisadas, quando comparados à borracha natural pura. Ao adicionar-se 10 phr de nanocelulose preparada com ácido fosfórico na borracha natural, os valores de resistência à tração na ruptura, alongamento na ruptura e módulo a 300% aumentaram, respectivamente, em 90%, 16% e 52%. Já com a adição de 10 phr de NC S, essas propriedades aumentaram, respectivamente, em 68%, 5% e 109%. O mesmo foi observado para a dureza Shore A. Com a adição de 10 phr de nanocelulose obtida por ácido fosfórico à composição da borracha natural, a dureza Shore A aumentou em cerca de 22%; já com a adição de 10 phr de NCs S, a dureza da borracha natural aumentou em 36%. / Among the natural and renewable sources\' materials, cellulose stands out for its abundance, it can be found in many living organisms, such as plants, amoebas, bacteria, fungi and some marine animals. Its dimensions can be reduced by breaking the amorphous chains, with the possibility of reaching nanometric scales, obtaining the nanocellulose or cellulose nanoparticles. Due to the high crystallinity, the nanocellulose has high elastic modulus value, providing high reinforcement capacity combined with low weight, high surface area and biodegradability. Natural rubber is a raw material from a natural source, extracted from the latex - colloidal dispersion of rubber particles and non-rubbers in a milkylooking aqueous solution. At this work, composites of natural rubber and nanocellulose were studied. Initially, a Brazilian centrifuged latex with 60% of its weight in solids was characterized, by analyzing if the total solids concentration and the pH measurement is in agreement with the data presented by the supplier. In addition, particle size distribution analysis demonstrated that the material had an average size of 1.0 ?m. Then, the mastication in the open cylinder and the Mooney viscosity and acetone extract was measured and them were equal to, respectively, 52.8 and 2.57%. The nanocelluloses obtained by hydrolysis with phosphoric and sulfuric acids are classified as cellulose nanocrystal. NC P present average length, aspect ratio and crystallinity equal to 270 ± 89 nm, 50 ± 24 and 78%; and the NC S had 209 ± 51 nm, 29 ± 10 and 75%. In the tensile test, it was observed that there was an increase in all the mechanical properties analyzed for natural rubber when adding the nanocellulose in its composition. By adding 10 phr of prepared nanocellulose with phosphoric acid in the natural rubber the values of tensile strength at rupture, strain at rupture and modulus at 300% increased, respectively, by 90%, 16% and 52%. When added 10 phr of NC S, these properties increased, respectively, by 68%, 5% and 109%. The same was observed for Shore A hardness. When adding 10 phr of nanocellulose obtained by phosphoric acid in its composition, the Shore A hardness increased by about 22%; When adding 10 phr of NCs S, the hardness increased by 36%.

Cerâmicas à base de alumina pertencem à classe de materiais denominados estruturais, muito utilizados em ferramentas de corte. A alumina possui boas propriedades para uso como cerâmica estrutural e com o objetivo de melhorar suas tenacidade à fratura e resistência mecânica, são produzidos compósitos com diferentes aditivos. Novos estudos apontam para os micro-nanocompósitos, onde a adição de partículas micrométricas deve auxiliar no aumento da resistência mecânica, e de partículas nanométricas, no aumento da tenacidade à fratura. Neste trabalho foram obtidos micro-nanocompósitos à base de Al2O3 com inclusão de partículas nanométricas de NbC e micrométricas de WC com proporções de 2:1, 6:4, 10:5 e 15:10 e micro-nanocompósitos à base de Al2O3 com inclusão de partículas nanométricas de NbC e micrométricas de TaC com proporção de 2:1 em relação à alumina. Para o estudo de densificação, os micro-nanocompósitos foram sinterizados em dilatômetro com taxa de aquecimento de 20 °C / min até a temperatura de 1800 °C, em atmosfera de argônio. Com base nos resultados de dilatometria, corpos de prova foram sinterizados entre 1500°C e 1700°C, com patamar de 30 minutos, em forno resistivo de grafite e atmosfera de argônio. Foram determinadas as densidades, fases cristalinas formadas, durezas e tenacidades, e analisadas as microestruturas dos micro-nanocompósitos. As amostras Al2O3:NbC:TaC sinterizadas a 1700°C atingiram as maiores densidades aparentes (~95%DT) e a amostra sinterizada a 1600°C apresentou microestrutura homogênea e valor de dureza (15,8 GPa) em comparação à alumina pura. As composições com 3% de inclusões são as mais promissoras para aplicações futuras como ferramentas de corte. / Alumina based ceramics belong to a class of materials designated as structural, which are widely used in cutting tools. Although alumina has good properties for application as a structural ceramics, composites with different additives have been produced with the aim of improving its fracture toughness and mechanical strength. New studies point out micro-nanocomposites, wherein the addition of micrometric particles should enhance mechanical strength, and nano-sized particles enhance fracture toughness. In this work, alumina based micro-nanocomposites were obtained by including nano-sized NbC and micrometer WC particles at 2:1, 6:4, 10:5 and 15:10 vol% proportions, and also with the inclusion of nano-sized NbC and micrometer TaC particles at 2:1 vol% proportion. For the study of densification, micro-nanocomposites were sintered in a dilatometer with a heating rate of 20°C/min until a temperature of 1800°C in argon atmosphere. Based on the dilatometry results, specimens were sintered in a resistive graphite furnace under argon atmosphere between 1500°C and 1700°C by holding the sintering temperature for 30 minutes. Densities, crystalline phases, hardness and tenacity were determined, and micro-nanocomposites microstructures were analyzed. The samples Al2O3: NbC: TaC sintered at 1700 ° C achieved the greater apparent density (~ 95% TD) and the sample sintered at 1600 ° C showed homogeneous microstructure and increased hardness value (15.8 GPa) compared to the pure alumina . The compositions with 3% inclusions are the most promising for future applications.

Cerâmicas à base de alumina pertencem à classe de materiais denominados estruturais, muito utilizados em ferramentas de corte. A alumina possui boas propriedades para uso como cerâmica estrutural e com o objetivo de melhorar suas tenacidade à fratura e resistência mecânica, são produzidos compósitos com diferentes aditivos. Novos estudos apontam para os micro-nanocompósitos, onde a adição de partículas micrométricas deve auxiliar no aumento da resistência mecânica, e de partículas nanométricas, no aumento da tenacidade à fratura. Neste trabalho foram obtidos micro-nanocompósitos à base de Al2O3 com inclusão de partículas nanométricas de NbC e micrométricas de WC com proporções de 2:1, 6:4, 10:5 e 15:10 e micro-nanocompósitos à base de Al2O3 com inclusão de partículas nanométricas de NbC e micrométricas de TaC com proporção de 2:1 em relação à alumina. Para o estudo de densificação, os micro-nanocompósitos foram sinterizados em dilatômetro com taxa de aquecimento de 20 °C / min até a temperatura de 1800 °C, em atmosfera de argônio. Com base nos resultados de dilatometria, corpos de prova foram sinterizados entre 1500°C e 1700°C, com patamar de 30 minutos, em forno resistivo de grafite e atmosfera de argônio. Foram determinadas as densidades, fases cristalinas formadas, durezas e tenacidades, e analisadas as microestruturas dos micro-nanocompósitos. As amostras Al2O3:NbC:TaC sinterizadas a 1700°C atingiram as maiores densidades aparentes (~95%DT) e a amostra sinterizada a 1600°C apresentou microestrutura homogênea e valor de dureza (15,8 GPa) em comparação à alumina pura. As composições com 3% de inclusões são as mais promissoras para aplicações futuras como ferramentas de corte. / Alumina based ceramics belong to a class of materials designated as structural, which are widely used in cutting tools. Although alumina has good properties for application as a structural ceramics, composites with different additives have been produced with the aim of improving its fracture toughness and mechanical strength. New studies point out micro-nanocomposites, wherein the addition of micrometric particles should enhance mechanical strength, and nano-sized particles enhance fracture toughness. In this work, alumina based micro-nanocomposites were obtained by including nano-sized NbC and micrometer WC particles at 2:1, 6:4, 10:5 and 15:10 vol% proportions, and also with the inclusion of nano-sized NbC and micrometer TaC particles at 2:1 vol% proportion. For the study of densification, micro-nanocomposites were sintered in a dilatometer with a heating rate of 20°C/min until a temperature of 1800°C in argon atmosphere. Based on the dilatometry results, specimens were sintered in a resistive graphite furnace under argon atmosphere between 1500°C and 1700°C by holding the sintering temperature for 30 minutes. Densities, crystalline phases, hardness and tenacity were determined, and micro-nanocomposites microstructures were analyzed. The samples Al2O3: NbC: TaC sintered at 1700 ° C achieved the greater apparent density (~ 95% TD) and the sample sintered at 1600 ° C showed homogeneous microstructure and increased hardness value (15.8 GPa) compared to the pure alumina . The compositions with 3% inclusions are the most promising for future applications.

Neste trabalho, materiais nanocompósitos de poli(imida) (PI) derivada de BTDA-pFDA-Mel e argila do tipo montmorilonita, organicamente modificada (O-MMT), foram sintetizados usando a metodologia de two-steps. O componente inorgânico do nanocompósito foi adicionado nas concentrações de 3,3, 5,3 e 8,3% em massa. As membranas sintetizadas foram caracterizadas por Espectroscopia de Absorção na Região do Infravermelho com Transformada de Fourrier (FTIR), Difração de Raio X (DRX), Termogravimetria (TG), Espectroscopia de Fotoelétrons Excitados por Raio X (XPS) e Microscopias Ótica (MO), Eletrônica de Varredura (MEV) e de Transmissão (MET). Os resultados comprovam a formação de PI e uma estrutura de nanocompósito do tipo intercalado, onde a cadeia polimérica expulsa o surfactante do espaço interlamelar; além de apresentar estruturas de argila parcialmente esfoliadas. Os materiais sintetizados foram avaliados como polieletrólito em célula a combustível alcalina (Alkaline Fuel Cell - AFC), obtendo condutividades iônicas em torno de 0,032 S cm-1 e de 0,017 S cm-1 para as membranas de PI pura e de nanocompósito com 3,3% de argila em massa, respectivamente, ambas a 60 &deg;C, as quais são na ordem ou até mesmo superior que os polieletrólitos comercias (Tokuyama&reg;, 0,014 S cm-1) para eletrólito alcalino. Apesar de condutividades razoáveis, a performance obtida para as AFCs em operação não foram satisfatórias, desta forma, membranas de nanocompósitos com PI de cadeia principal de maior mobilidade foram sintetizadas, caracterizadas e avaliadas nas AFCs. Ademais, neste segundo nanocompósito, a adição de grupamentos amino na cadeia principal foram realizados para aumentar a condutividade iônica. Assim, este segundo material apresentou uma maior performance nas AFCs quando comparado com o nanocompósito de PI de cadeia mais rígida e com a membrana comercial Tokuyama&reg; nas mesmas condições. Além disso, a carbonização superficial das amostras foi realizada por meio de tratamento térmico. A formação de estruturas grafitizadas nos materiais de PI pura e dos nanocompósitos foram investigadas por FTIR, DRX, TG, XPS e EPR. Foi encontrado que a formação de estruturas do tipo grafite nas amostras ocorrem principalmente nas primeiras camadas (grafitização superficial), preservando a estrutura interna da poli(imida). Com isso, estruturas poliméricas ou nanocompósitos com superfícies grafitizadas podem atuar tanto como polieletrólitos e ser um caminho promissor para o desenvolvimento de arranjos eletrodo-membrana (Membrane Electrode Assembly - MEA) mais eficientes para células a combustíveis alcalinas, como em processos de catálise heterogênea e processos de separação com membranas. / In this work, Poli(imide)/clay (PI/clay) nanocomposite membranes were synthesized by employing a two-steps method using organically modified montmorillonite clay (O-MMT) with different amounts of O-MMT loading (3.3, 5.3 and 8.3 wt.%). Fourier transform infrared spectroscopy (FTIR), X-ray power diffraction (XRD), thermogravimetric analysis (TG), X-ray photoelectron spectroscopy (XPS), optical microscopy (OM), scanning electron microscope (SEM) and transmission electron microscopy (TEM) measurements, confirmed the formation of pure PI and intercalated-nanocomposite structures. The results revealed parallel clay layers with interlamellar PI and some organoclay partially exfoliated. In addition, the polyelectrolyte membranes of PI and PI/O-MMT (3.3 wt.%) showed that the ionic conductivity were 2- and 1-fold, respectively, higher than that of commercial membrane (Tokuyama&reg;, 0.014 S cm-1), in alkaline fuel cells (AFC) at 60 &deg;C. Despite the fact that the membranes of pure PI and PI/O-MMT demonstrated a good degree of ionic conductivity, rapid fuel cell performance deactivation occurred for the temperature higher than 75 &deg;C. Furthermore, the lack of prepared polyelectrolyte ionic groups, led us to consider alternative synthesis of PI/clay nanocomposite membranes. Thus, the performance for second polyelectrolyte was superior when compared to pure PI, PI/O-MMT and commercial Tokuyama&reg; membranes at same conditions. Moreover, the samples were also surface carbonized by thermal treatment. Combining FTIR, XRD, TG, XPS and electron paramagnetic resonance (ESR) analysis, the results suggested that graphitized nanostructures formation occurred mainly on the surface, maintaining the PI bulk structure. Therefore, graphitized PI/clay membranes may act as one promising way for enhancing both membrane electrode assembly in alkaline fuel cells and gas separation or catalysis.

Submitted by Rosivalda Pereira (mrs.pereira@ufma.br) on 2017-09-12T20:09:04Z No. of bitstreams: 1 MartaRodrigues.pdf: 1092531 bytes, checksum: 1276140edb499ab5e3990cb0818ef871 (MD5) / Made available in DSpace on 2017-09-12T20:09:04Z (GMT). No. of bitstreams: 1 MartaRodrigues.pdf: 1092531 bytes, checksum: 1276140edb499ab5e3990cb0818ef871 (MD5) Previous issue date: 2017-07-27 / This work aimed to prepare a material, from the intercalation of a Maranhense clay with a polymer, able to adsorb oil derivatives in aqueous media. The polymer was synthesized from a copolymerization reaction between a tertiary amine and an organic halide, known as Ionene, which was characterized by hydrogen nuclear magnetic resonance (1 H-NMR). The preparation of the clay-ionene adsorbent occurred by the exchange of the interlamellar inorganic cations by the organic cations of the polymer, after the clay in natura receive acid and alkaline treatment. X-ray Diffraction (XRD), Infrared Spectroscopy (FTIR), Surface Area, Thermogravimetry (TG) and Foster Swelling performed the characterization of the new material. The results showed that the cation exchange process occurred, confirmed by the increase of the basal distance (d001) observed in the XRD and by the appearance of the characteristic bands of the organic cations detected by the infrared spectra. The Foster swelling results show that the nanocomposite has higher interaction with organic solvents. In the adsorption tests the organophilic clays, as expected, presented higher efficiency in relation to the in natura material, with removal rate of approximately 90%. The kinetic modeling studies showed that the adsorption is of pseudo second order, indicating that the process is chemical. / Este trabalho teve por objetivo preparar um material, a partir da intercalação de uma argila maranhense com um polímero, capaz de adsorver derivados de petróleo em meio aquoso. O polímero foi sintetizado a partir de uma reação de copolimerização entre uma amina terciária e um haleto orgânico, conhecido como Ioneno, e caracterizado por ressonância magnética nuclear de hidrogênio (RMH- 1H). O preparo do adsorvente argila-ioneno ocorreu pela troca dos cátions inorgânicos interlamelares pelos cátions orgânicos do polímero, após a argila in natura receber tratamento ácido e sódico. A caracterização do novo material foi realizada por Difratograma de Raios-X (DRX), Espectroscopia de Infravermelho (FTIR), medidas de Área Superficial, termogravimetria (TG) e Inchamento de Foster. Os resultados mostraram que ocorreu o processo de troca de cátions, confirmado pelo aumento da distância basal (d001) observado no DRX e pelo aparecimento das bandas característicos dos cátions orgânicos detectados pelos espectros de Infravermelho. Os resultados do inchamento de Foster mostram que o nanocompósito possui maior interação por solventes orgânicos. Nos testes de adsorção as argilas organofilicas, como esperado, apresentaram maior eficiência em relação ao material in natura, com taxa de remoção de aproximadamente 90 %. Os estudos de modelagem cinética mostraram que a adsorção é de pseudo segunda ordem, indicando que o processo é químico.

>Magister Scientiae - MSc / This project focuses on the simple, fast and highly sensitive adsorptive stripping voltammetry detection of Nickel and Cobalt complexed with DMG and Nioxime respectively at a Reduced Graphene Oxide modified pencil graphite electrode in water samples. This research as well demonstrates a novel electrochemically reduced graphene oxide (ERGO)/mercury film (MF) nanocomposite modified PGE, prepared through successive electrochemical reduction of graphene oxide (GO) sheets and in-situ plated mercury film. The GO and graphene were characterized using FT-IR, HR-SEM, HR-TEM, XRD and Raman spectroscopy. The FT-IR results supported by Xray diffraction analysis confirmed the inclusion of oxygen moieties within the graphitic structure during the chemical oxidation step. Microscopic and spectroscopic analysis was used to confirm the stackings of graphene on the pencil electrode. The ERGO-PG-MFE, in combination with a complexing agents of [dimethylglyoxime (DMG) and Nioxime] and square-wave cathodic stripping voltammetry (SW-CSV), was evaluated towards the individual determination of Ni2+ and Co2+ respectively and simultaneous determination of both metals from the combination of DMG and Nioxime mixture. A single-step electrode pre-concentration approach was employed for the in-situ Hg-film electroplating, metal-chelate complex formation and its non-electrolytic adsorption at – 0.7 V for the individual analysis of Ni2+ and Co2+. The current response due to metal-ligand(s) complex reduction were studied as a function of experimental variables; deposition/accumulation potential, deposition/accumulation time, rotation speed, frequency and amplitude and carefully optimized for the individual determination of Ni2+and Co2+ and simultaneous determination of Ni2+ and Co2+ at low concentration levels (μg L-1) in 0.1 M NH3- NH4Cl buffer solution (pH 9.4) solution. The recorded limit of detection for the individual analysis of Ni2+and Co2+ was found to be 0.120 μg L-1 and 0.220 μg L-1 respectively, at an accumulation time of 120 s for both metals. The recorded limit of detection of the simultaneous analysis of Ni2+ and Co2+ was found to be 6.1 μg L-1 and 1.8 μg L-1 respectively. The ERGO-PG-MFE further demonstrated a highly selective stripping response toward all trace metal analysis. The testing of the applicability of graphene-based sensor and method in laboratory tap water samples was evaluated. This electrode was found to be sensitive enough to detect metal ions in the tap water samples at the 0.2 μg L-1 level for individual analysis and 0.001 μg L-1 for simultaneous, well below WHO standards.