Récemment, les recherches scientifiques ont attiré son attention sur les domaines liés à l'énergie en raison de la consommation croissante d'énergie qui a affecté les dernières décennies. Les matériaux magnétiques sont déterminants dans les applications basées sur l'énergie et l'amélioration de leurs performances joue un rôle primordial dans le développement technologique. Le présent travail explore la possibilité de préparer des composites céramiques magnétiques hétéro-nano-structurés à base de constituants d'oxydes. Un oxyde ferromagnétique (F) a été couplé à un antiferromagnétique (AF) à l'échelle nanométrique pour étudier les propriétés magnétiques résultantes, en accordant une importance primordiale au couplage d'échange entre les deux phases. L’établissement de l’effet de biais d’échange à l’interface des phases F-AF est souhaitable pour augmenter l’anisotropie magnéto-cristalline du système et le produit énergétique relatif BHmax. Dans ce but, deux oxydes F différents ont été pris en compte, le Fe3O4 et le CoFe2O4, et trois oxydes différents de la AF, CoO, NiO et l'hématite α-Fe2O3. Des nanoparticules d'oxyde de chaque composant ont été préparées par synthèse de polyol, avec une bonne qualité cristalline et une morphologie uniforme. Ils ont ensuite été utilisés pour préparer des échantillons de céramique de consolidation par la technique SPS. Pour chaque échantillon, un oxyde F a été mélangé à l'un des oxydes AF. Les céramiques résultantes ont été formées selon différents rapports de masse F / AF, variant entre 0,75 / 0,25, 0,5 / 0,5 et 0,25 / 0,75, et selon différentes combinaisons entre les oxydes F et AF considérés. Tous les échantillons ont été frittés à 500 ° C et 100 MPa pendant 5 minutes. Toutes les céramiques ont été étudiées en profondeur, notamment en ce qui concerne leur structure, leur microstructure et leurs propriétés magnétiques. L’analyse HR-TEM réalisée sur des lames raffinées de céramiques Fe3O4-CoO, Fe3O4-NiO et CoFe2O4-NiO, ainsi que des résultats de diffraction XR, a mis en évidence une importante variation de la composition des échantillons après frittage. Une nouvelle phase métallique est formée après frittage dans l'atmosphère fortement réductrice au cours du processus SPS, modifiant ainsi la composition relative des phases F et AF individuelles. L’établissement d’effets de biais d’échange n’a guère été observé à cause de la diffusion des atomes qui affecte l’échantillon. En effet, les nanoparticules AF d'hématite se sont révélées instables dans une large plage de températures et donc inappropriées pour ce type d'application. En particulier, une transformation de phase se produisant à environ 380 ° C a été observée lorsqu'un champ magnétique externe est appliqué. Une telle transition a été étudiée au moyen d’une caractérisation par magnétomètre, d’une analyse HR-TEM et d’une analyse EELS et a révélé qu’elle impliquait la transformation de l’hématite en magnétite. Le mécanisme de cette transformation n’a pas encore été compris et fait l’objet d’une enquête plus approfondie. / Recently the scientific research led its attention towards energy related fields because of the increasing energy consumption that affected the last few decades. Magnetic materials are determining in energy-based applications and the enhancement of their performances has a primary role on the technological development. The present work explores the possibility to prepare hetero-nano-structured magnetic ceramic composites based on oxide constituents. A ferromagnetic oxide (F) was coupled with an antiferromagnetic one (AF) at a nanometric size scale to study the resulting magnetic properties, above all concerting the exchange coupling between the two different phases. The establishing of the exchange-bias effect at the F-AF phases interface is desirable in order to increase the magneto-crystalline anisotropy of the system and the relative energy product BHmax. At this aim, two different F oxides were took into account, the Fe3O4 and the CoFe2O4, and three different AF oxides, CoO, NiO and hematite α-Fe2O3. Oxide nanoparticles of each component were prepared by polyol synthesis, with a good crystalline quality and uniform morphology. They were then employed to prepare consolidate ceramic samples by SPS technique. For each sample, one F oxide was mixed with one of the AF oxides. The resulting ceramics were formed by different F/AF mass ratio, varying between 0,75/0,25, 0,5/0,5 and 0,25/0,75, and by different combinations between the considered F and AF oxides. All the samples were sintered at 500°C and 100 MPa for 5 minutes. All the ceramics were deeply studied, above all concerning their structure, microstructure and magnetic properties. HR-TEM analysis performed on FIB-refined slides of the Fe3O4-CoO, Fe3O4-NiO and CoFe2O4-NiO ceramic samples, together with XRD results, highlighted an important variation of samples’ composition after sintering. A new metallic phase is formed after sintering cause to the strongly reductive atmosphere during the SPS process, thus modifying the relative composition of the single F and AF phases too. The establishing of exchange-bias effects was hardly observed exactly because of the atoms diffusion that affects the sample. The hematite AF nanoparticles, indeed, were found to be unstable in a wide temperature range and thus unsuitable for this kind of application. In particular, a phase transformation occurring at about 380°C was observed when an external magnetic field is applied. Such a transition was studied by mean of magnetometer characterisation, HR-TEM and EELS analysis and was found to involve hematite transforming into magnetite. The mechanism of such transformation hasn’t been understood yet and is under further investigation

Made available in DSpace on 2016-06-02T20:15:28Z (GMT). No. of bitstreams: 1 5160.pdf: 6005480 bytes, checksum: 6aae866e51fab054ffc455e4b0479f2f (MD5) Previous issue date: 2013-02-25 / Financiadora de Estudos e Projetos / Considering the search for miniaturization of electronic devices, the development of new methods and techniques for the production and characterization of nanostructured materials is fundamental, beyond understanding of the effect of grain size on the properties of materials in nanoscale. Therefore, it was proposed in this work the obtaining of nanostructured multiferroic materials, in bulk, with high density and microstructural control, with grains ranging from micrometer to nanometer scale. To achieve this goal, was developed a methodology for obtaining the powder of lead iron niobate, Pb(Fe1/2Nb1/2)O3 (PFN) and lead iron tungstate, Pb(Fe2/3W1/3)O3 (PFW), with average particle size around 150 nm, contamination-free, minimal agglomeration and with highly reproductive results using the micro-milling technique. Regarding consolidation materials, conventional sintering requires higher temperatures and long holding times for a satisfactory densification, resulting in a grain growth higher than the desired. Through the fast sintering technique, only high heating rates are not sufficient to ensure a satisfactory densification and also inhibit the growth of grains. The obtain nanostructured dense samples with average grain size of approximately 200 nm was only possible using spark plasma sintering technique (SPS), which allows sintering at temperatures corresponding to the intermediate sintering stage, inhibiting the grain growth. PFN and PFW samples obtained through the SPS technique showed high conductivity at room temperature due the extreme reduction suffers in the system plus the use of high current densities during sintering, being necessary the samples oxidation. Through the dielectric characterization, the decrease in grain size of micrometer to nanometer scale results in lower permittivity values in phase transition temperature, besides a peak broadening. Moreover, the SPS technique added to the oxidation process makes it possible to obtain PFW samples with high dielectric values (in order of 104) at room temperature, a motivation results with regard to the application. / Considerando a busca pela miniaturização dos dispositivos eletrônicos é fundamental o desenvolvimento de novos métodos e técnicas para a produção e caracterização de materiais nanoestruturados, além do entendimento do efeito do tamanho de grão sobre as propriedades dos materiais em escala nanométrica. Dessa forma, propôs-se neste trabalho a obtenção de materiais multiferróicos nanoestruturados, na forma de bulk com alta densidade e controle microestrutural, com grãos variando de escala micrométrica a nanométrica. Para alcançar este objetivo, foi desenvolvida uma metodologia para a obtenção de pós de niobato de ferro e chumbo, Pb(Fe1/2Nb1/2)O3 (PFN) e tungstanato de ferro e chumbo, Pb(Fe2/3W1/3)O3 (PFW), com tamanhos médios de partículas em torno de 150 nm, livre de contaminação, mínima aglomeração e com resultados altamente reprodutivos por meio da técnica de micromoagem. Em relação à consolidação dos materiais, o procedimento convencional requer altas temperaturas e longos tempos de patamar para uma densificação satisfatória, resultando em um crescimento de grão superior ao desejado. Por meio da técnica de sinterização rápida fast sintering , somente altas taxas de aquecimento não são suficientes para garantir uma densificação satisfatória bem como inibir o crescimento de grãos. A obtenção de amostras densas nanoestruturadas com tamanhos médio de grão de aproximadamente 200 nm só foi possível utilizando a técnica spark plasma sintering (SPS), que permite a sinterização a temperaturas correspondentes ao estágio intermediário de sinterização, inibindo o crescimento de grãos. As amostras de PFN e PFW obtidas por meio da técnica de SPS apresentaram alta condutividade à temperatura ambiente devido às condições extremas de redução que a amostra sofre somada ao uso de altas densidades de corrente durante a sinterização, sendo necessária a oxidação das mesmas. Através da caracterização dielétrica, verifica-se que a diminuição nos tamanhos de grãos de escala micrométrica para nanométrica resulta em menores valores de permissividade na temperatura de transição de fase, além de um alargamento dos picos. Contudo, a técnica de sinterização SPS somada ao processo de oxidação torna possível a obtenção de amostras de PFW com altos valores de constate dielétrica (na ordem de 104), a temperatura ambiente, resultado extremamente motivador no que diz respeito à aplicação.

<p>U ovom radu pripremljeni su različiti polimerni i keramički nanostrukturni materijali, u cilju ispitivanja uticaja vrste i udela nanopunila (čađ, fuleren, silicijum(IV)oksid, aluminijum(III)oksid i titanijum(IV)oksid) na strukturu, reolo&scaron;ko i toplotno pona&scaron;anje kompozita, dobijenih na osnovu stirena, metilmetakrilata i akrilamida, primenom različitih metoda sinteze. Ispitivan je uticaj prisustva različitog udela nanočestica (1, 3 i 5 %<em> m/m</em>) na kinetiku polimerizacije stirena, i na oblast prelaska u staklasto stanje polistirenskih hibridnih materijala. Sintetisana je i serija nanokompozita polimerizacijom metilmetakrilata u prisustvu čestica (silicijum(IV)oksid, aluminijum (III)oksid i titanijum(IV)oksid) različitih dimenzija i hidrofilnosti, ali istog zapreminskog udela (1 %<em> v/v</em>). Na osnovu primene izotermne diferencijalno skanirajude metode (DSC), razvijen je kinetički model za opisivanje dve razičite reakcije tokom polimerizacije vinilnih monomera (reakciju prvog reda i samoubrzanje), i izračunata je debljina međufaznog sloja polimera na čestici u cilju određivanja njegovog uticaja na temperaturu prelaska u staklasto stanje hibridnih materijala. Za ispitivanje strukture i morfologije polistiren/silicijum(IV)oksid nanokompozita dobijenih metodom isparavanja rastvarača, kori&scaron;dene su infracrvena spektroskopija sa Furijeovom transformacijom (FT-IR) i skanirajuda elektronska mikroskopija (SEM). Radi utvrđivanja uticaja udela hidrofobnog silicijum(IV)oksida (2, 5, 10, 15 i 30 %<em> m/m</em>) na toplotnu postojanost polistirenskih materijala, primenjene su istovremena termogravimetrijska i diferencijalno skanirajuda analiza (TG-DSC). Takođe, određen je uticaj veličine čestice fulerena C60 i submikronske čestice čađi na reolo&scaron;ka svojstva polistirenskih kompozita sintetisanih taloženjem polimera iz rastvora. Ispitivanjem reolo&scaron;kog pona&scaron;anja hibridnih materijala, proučavan je uticaj veličine čestica, molekulske mase polimera i indeksa polidisperznosti na viskoznost polistirenskih kompozita. Na osnovu<em> in-situ</em> reolo&scaron;kih analiza polimerizacije u toku želiranja suspenzije nanočestica aluminijum(III)oksida u vodenom rastvoru monomera metakrilamida i N,N&rsquo;-metilenbisakrilamida, utvrđena je jaka katalitička aktivnost povr&scaron;ine aluminijum(III)oksida na nastajanje slobodnih radikala. Radi nalaženja veze između željenih svojstava keramičkih proizvoda i načina njihovog dobijanja, proučavan je uticaj uslova vođenja polimerizacije na slaganje čestica u dobijenom odlivku i na gustinu krajnjeg sinterovanog proizvoda.</p> / <p>In this work, polymeric and ceramic nanostructured materials were prepared using different methods, in order to investigate the influence of nanofiller content and its type (carbon black, fullerene, silica, alumina and titania) on the structure, rheological and thermal behavior of composites, based on styrene, methylmethacrylate and acrylamide. The effect of particles content (1, 3 and 5 wt. %) on the kinetics of styrene radical polymerization and on the glass transition temperature of polystyrene/silica composites was investigated. A series of polymethylmethacrylate nanocomposites containing 1 vol. % of silica, alumina or titania particles (differing in dimensions and surface properties) was obtained. On the basis of isothermal differential scanning calorimetry (DSC), the kinetic model for describing two reactions during vinyl monomer polymerization (first order and autoacceleration) was developed, and the thickness of interfacial layer formed on nanoparticle surface was determined, in order to investigate its influence on the glass transition temperature of polymethylmethacrylate hybrid materials. The structure and the morphology of polystyrene/silica nanocomposites prepared by solvent evaporation were investigated using Fourier transform infrared spectroscopy (FT-IR) and scanning electron microscopy (SEM). The influence of&nbsp; hydrophobic silica content (2, 5, 10, 15 and 30 wt. %) on polystyrene thermal stability was studied by simultaneous thermogravimetry and differential scanning calorimetry (TG-DSC). The effect of fullerene C60 and submicron carbon black particle size on rheological properties of polystyrene composites prepared by the rapid coprecipitation was determined. Following the rheology of hybrid melts, the influence of filler size, molecular weight and polydispersity of polymer matrix on the viscosity of polystyrene composites was studied. On the basis of in-situ rheology analysis of polymerization process during the gelation of alumina nanoparticles suspension in aqueous solution of methacrylamide and N,N&rsquo;- methylene bisacrylamide monomers, the strong catalytic activity of alumina surface on the free radicals formation was determined. In order to find the correlation between desired properties of ceramic products and their preparation procedure route, the influence of polymerization conditions on the green body structure and sintered body density was studied in details.</p>