Neste trabalho, estudou-se a síntese por sol-gel da ferrita de cobalto (CoFe2O4), variando-se a temperatura de tratamento térmico do xerogel. Nitrato de ferro e nitrato de cobalto foram utilizados como fonte de cátions e ácido cítrico como mineralizador. Os produtos obtidos, tratados a 750, 800 e 850°C, tiveram sua microestrutura e propriedades magnéticas investigadas no intuito de encontrar correlações entre as condições de síntese, as posições ocupadas pelos cátions dentro da estrutura espinélio do composto e as propriedades magnéticas medidas. Estudos de difratometria de raios X exibiram reflexões características da estrutura espinélio, o que sugere que o tratamento térmico não afetou significativamente a estrutura cristalina do material. Uma fração secundária de hematita também foi observada. As ferritas apresentaram área superficial específica (por BET) de aproximadamente 4 m².g-1. Imagens por MEV indicam que o material apresenta-se aglomerado. Quanto às propriedades magnéticas, um máximo de coercividade de 1405.2 Oersted foi encontrado para a amostra tratada a 800°C. Espectros Mößbauer indicaram um baixo grau de inversão nos espinélios formados, o que é incomum para a ferrita de cobalto. Subtraindo do espectro obtido por Mößbauer o excesso de ferro na forma de hematita, há um forte indicativo que a ferrita foi sintetizada de maneira sub-estequiométrica deficiente em ferro. / We herein report a study on the sol-gel synthesis of cobalt ferrite (CoFe2O4) and the effect of treatment temperature on the product outcome. Iron nitrate and cobalt nitrate were used as cation sources and citric acid as mineralizer. Products treated at 750, 800 and 850°C had their microstructure and magnetic properties assessed in order to correlate their synthesis conditions, the positions in which the cations are inserted in the spinel structure and the magnetic behavior displayed by the ferrites. X-ray diffractometry studies exhibit the characteristic reflections of spinel group materials, suggesting that the thermal treatment does not sensibly affect the crystalline structure of the material. A secondary fraction of hematite was also observed. The ferrites exhibit a specific surface area (from BET) of approximately 4 m².g-1. SEM images indicate the material forms agglomerates. As to the magnetic properties, a maximum of 1405.2 Oersted was achieved for the sample treated at 800°C. Mößbauer spectra indicate a fairly low inversion degree in the synthesized materials, which is rather unusual for cobalt ferrite. After deducting the iron fraction present in the form of hematite, there are strong indications that cobalt ferrite was synthesized as a substoichiometric iron-deficient spinel.

This work addresses the growth of ultrathin magnetite (Fe3O4) and cobalt ferrite (CoFe2O4) films and their thorough structural, electronic, and magnetic characterization. In a first step, ultrathin Fe3O4 films are grown on SrTiO3(001) substrates by reactive molecular beam epitaxy (RMBE) and the substrate-induced anomalous strain behavior of the films is investigated by complementary high-resolution transmission electron microscopy (HRTEM) and (grazing incidence) X-ray diffraction [(GI)XRD] measurements. Next, an additional CoO film is deposited on similar Fe3O4/SrTiO3(001) heterostructures to demonstrate an alternative route for the synthesis of cobalt ferrite films through the thermally mediated interdiffusion of both oxide films. The evolution from the initial bilayer stacks to completely reacted cobalt ferrite films is extensively monitored by soft and hard X-ray photoelectron spectroscopy (soft XPS and HAXPES) and (GI)XRD. Complete intermixing and formation of single cobalt ferrite films is confirmed by angular-resolved HAXPES (AR-HAXPES) and X-ray reflectivity (XRR). The study of the cationic distribution resulting from this novel synthesis technique and its effects on the magnetic properties of the cobalt ferrite films is the subject of the subsequent part. Here, X-ray magnetic circular dichroism (XMCD) and superconducting quantum interference device (SQUID) magnetometry serve as key investigation techniques, which are further complemented by AR-HAXPES and atomic force microscopy (AFM) measurements. In a final step, highly crystalline cobalt ferrite films with different cationic stoichiometries are grown on MgO substrates using RMBE while their growth behavior is captured in real-time using operando XRD. Further structural characterization of the films is carried out by low-energy electron diffraction and XRR, whereas HAXPES and SQUID provide fundamental information on the electronic, chemical, and magnetic properties of the films.

No description available.

The work of this dissertation is centered on two non-conventional synthetic approaches to ferromagnetic nanomaterials: high-throughput experimentation (HTE) (polyol process) and continuous flow (CF) synthesis (aqueous reduction and the polyol process). HTE was performed to investigate phase control between FexCo1-x and Co3-xFexOy. Exploration of synthesis limitations based on magnetic properties was achieved by reproducing Ms=210 emu/g. Morphological control of FexCo1-x alloy was achieved by formation of linear chains using an Hext. The final study of the FexCo1-x chains used DoE to determine factors to control FexCo1-x, diameter, crystallite size and morphology. [Ag] with [Metal] provide statistically significant control of crystallite size. [OH]/[Metal] predict 100 % FexCo1-x at > 30. To conclude section 1, a morphological study was performed on synthesis of Co3-xFexOy using the polyol process. Co3-xFexOy micropillars were synthesized at various sizes. The close proximity of the particles in the nanostructure produced an optical anisotropy and was magnetically induced which is evidence for the magneto-birefringence effect. The second non-conventional synthetic approach involves continuous flow (CF) chemistry. Co nanoparticles (Ms=125 emu/g) were newly synthesized by aqueous reduction in a microreactor and had 30 ±10 nm diameter and were produced at >1g/hr, a marker of industrial-scale up viability. The final work was the CF synthesis of FexCo1-x. The FexCo1-x was synthesized with limitation to the composition. The maximum FexCo1-x phase composition at 20 % resulted from the aqueous carrier solvent triggering oxide formation over FexCo1-x.

Atualmente com o advento da nanociência e nanotecnologia, as nanopartículas magnéticas têm encontrado inúmeras aplicações nos campos da biomedicina, diagnóstico, biologia molecular, bioquímica, catálise, etc. As nanopartículas magnéticas funcionalizadas são constituídas de um núcleo magnético, envolvido por uma camada polimérica com sítios ativos, que podem ancorar metais ou compostos orgânicos seletivos. Estas nanopartículas são consideradas materiais híbridos orgânico-inorgânicos de grande interesse em aplicações comerciais devido à particularidade das propriedades obtidas. Entre as aplicações importantes podemos citar: tratamento por magnetohipertermia, carregadores de fármacos para áreas específicas do corpo, seleção de moléculas específicas, biossensores, melhoria da qualidade de imagens por RMN, etc. O trabalho foi desenvolvido em duas partes: 1) a síntese do núcleo constituído de nanopartículas superparamagnéticas de ferrita de cobalto e, 2) o recobrimento do núcleo por um polímero bifuncional o 3-aminopropiltrietoxissilano. Os parâmetros estudados na primeira parte da pesquisa foram: pH, concentração molar da base, tipo de base, ordem de adição dos reagentes, modo de adição dos reagentes, velocidade de agitação, concentração inicial dos metais, fração molar de cobalto e tratamento térmico. Na segunda parte estudou-se: o pH, a temperatura, o catalisador, a concentração do catalisador, o tempo de reação, a relação H2O/silano, o tipo de meio, o agente umectante e a eficiência do recobrimento em relação ao pH. Os produtos obtidos foram caracterizados pelas técnicas de difratometria de raios-X (DRX), microscopia eletrônica de transmissão (MET), microscopia eletrônica de varredura (MEV), espectroscopia de energia dispersiva (EDS), espectroscopia de emissão atômica (ICP-AES), espectroscopia por infravermelho (FTIR), análises termogravimétricas (TGA/DTGA), calorimetria exploratória diferencial (DSC) e curvas de magnetização (MAV) / Nowadays with the appear of nanoscience and nanotechnology, magnetic nanoparticles have been finding a variety of applications in the fields of biomedicine, diagnosis, molecular biology, biochemistry, catalysis, etc. The magnetic functionalized nanoparticles are constituted of a magnetic nucleus, involved by a polymeric layer with active sites, which ones could anchor metals or selective organic compounds. These nanoparticles are considered organic-inorganic hybrid materials and have great interest as materials for commercial applications due to the specific properties. Among the important applications it can be mentioned: magnetohyperthermia treatment, drugs delivery in specific local of the body, molecular recognition, biossensors, enhancement of nuclear magnetic ressonance images quality, etc. This work was developed in two parts: 1) the synthesis of the nucleus composed by superparamagnetic nanoparticles of cobalt ferrite and, 2) the recovering of nucleus by a polymeric bifunctional 3-aminepropyltriethoxysilane. The parameters studied in the first part of the research were: pH, hydroxide molar concentration, hydroxide type, reagent order of addition, reagent way of addition, speed of shake, metals initial concentrations, molar fraction of cobalt and thermal treatment. In the second part it was studied: pH, temperature, catalyst type, catalyst concentration, time of reaction, relation ratios of H2O/silane, type of medium and the efficiency of the recovering regarding to pH. The products obtained were characterized using the following techniques X-ray powder diffraction (DRX), transmission electronic microscopy (MET), scanning electronic microscopy (MEV), spectroscopy of scatterbrained energy spectroscopy (DES), atomic emission spectroscopy (ICP-AES), themogravimetric analysis (TGA/DTGA), Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC) and magnetization curves (VSM)

Ce travail de thèse est consacré à l’étude des propriétés magnéto-optiques de nanoparticules (NP) magnétiques de ferrite de cobalt (CoFe2O4) sous forme liquide et lorsqu’elles sont bloquées dans une matrice de silice produite par voie sol-gel. Cette dernière dispersion constitue un matériau composite à activité magnéto-optique obtenu par un procédé basse température qui le rend totalement compatible avec les technologies d’intégration. A plus long terme, ce matériau pourra contribuer à l’intégration de composants non-réciproques. L’objectif de ce travail est d’une part l’identification du type de NP qui maximise la rotation Faraday et le facteur de mérite (rapport de la rotation Faraday à l’absorption) dans le but d’améliorer la qualité magnéto-optique du matériau composite. Et d’autre part, il s’agit d’améliorer la compréhension des phénomènes physiques liés aux effets magnéto-optiques de ces nanoparticules et le lien avec leurs caractéristiques physiques. L’étude est menée sur des NP magnétiques synthétisées et dispersées en phase aqueuse au laboratoire PHENIX (UMR CNRS 8234). Les mesures optiques et magnéto-optiques réalisées au laboratoire Hubert Curien (UMR CNRS 5516) ont été complétées par des mesures magnétiques XMCD au synchrotron SOLEIL. L’étude des différentes nanoparticules magnétiques a révélé que l’utilisation d’une petite taille de NP permet de multiplier par deux le facteur de mérite du matériau pour une longueur d’onde de 1,5 µm, soit une division par deux des pertes pour les composants magnéto-optiques visés. L’analyse du comportement spectral de l’effet Faraday illustre l’influence de la distribution cationique des ions Co2+ et Fe3+ dans la structure cristalline. Couplée aux mesures XMCD, l’analyse montre le besoin d’une localisation de l’ion Co2+ en site tétraédrique dans la structure spinelle pour maximiser l’effet Faraday à 1,5µm, et obtenir une anisotropie uniaxe qui permette une pré-orientation aisée des NP lors de la gélification / This work is dedicated to the study of the magneto-optical properties of cobalt ferrite (CoFe2O4) nanoparticles (NP) dispersed in liquid as ferrofluid, or blocked in a solid silica matrix realized with a sol-gel method. This last dispersion is a magneto-optical composite material, obtained with a low temperature process which insures its compatibility with photonic integration technologies, to produce, in the future, integrated non-reciprocal devices. The aim of the study is, on one hand, to identify which kind of NP can improve the Faraday effect and the merit factor (ratio between the Faraday effect and the absorption) of the composite material. On the other hand, the aim is to give a better understanding of the link between the magneto-optical properties and the physical characteristics of the NP. The study has been led on NP synthetized and dispersed as ferrofluid in PHENIX laboratory (UMR CNRS 8234). Optical and magneto-optical measurements were made in Hubert Curien laboratory (UMR CNRS 5516) and completed by XMCD analysis in Synchroton SOLEIL. Results show that it is necessary to use a small size of NP (5 nm) to maximize the merit factor at a wavelength of 1,5 µm. The spectral analysis of the Faraday effect shows the influence of the cationic distribution of Co2+ et Fe3+ in the spinelle structure. Coupled to XMCD results, this analysis shows that it is necessary to maximize the quantity of Co2+ in tetraedric sites to maximize the Faraday effect at 1,5 µm and to obtain an uniaxial anisotropy which allows to orientate the NP during the gelification of the sol-gel matrix

Im Rahmen dieser Arbeit wurde der Einfluss von Defekten auf die Eigenschaften von Ferrit-Dünnfilmen untersucht. Die Dünnfilme wurden mit Hilfe von gepulster Laserabscheidung bei verschiedenen Züchtungsparametern hergestellt. Durch Variation der Substrattemperatur und des Sauerstoffpartialdrucks wurden Dünnfilme verschiedener kristalliner Qualität gezüchtet. Diese wurden hinsichtlich ihrer chemischen Komposition mit Hilfe von energie-dispersiver Röntgenspektroskopie und Röntgenphotoelektronenspektroskopie untersucht. Durch Korrelation der Ergebnisse mit Messungen zum zirkularen magnetischen Röntgendichroismus, konnte eine partielle Inversion der Spinellstruktur nachgewiesen werden. Der Grad der Inversion ist höher für geringe Abscheidetemperaturen. Für diese defektreichen Dünnfilme zeigen Röntgenbeugungsuntersuchungen eine geringere kristalline Ordnung der Dünnfilme. Die strukturellen Defekte haben einen maßgeblichen Einfluss auf die elektrischen und magnetischen Eigenschaften der Ferrit-Dünnfilme. So zeigen die Ferrit-Dünnfilme für geringe Züchtungstemperaturen eine erhöhte elektrische Leitfähigkeit, während Dünnfilme, die bei hohen Substrattemperaturen gezüchtet wurden, isolierend sind. Die Temperaturabhängigkeit der elektrischen Leitfähigkeit kann auf thermisch aktivierte Hopping-Leitung oder die Leitung zwischen Clustern, die in einer Matrix eingebettet sind, zurückgeführt werden. Die magnetischen Eigenschaften von Zinkferrit-Dünnfilmen werden maßgeblich durch Defekte in der Spinellstruktur bestimmt, da es nominell in der normalen Spinellstruktur kristallisiert und daher antiferromagnetisch ist. Die partielle Inversion der Eisen- und Zinkionen führt zu Ferrimagnetismus in den Zinkferrit-Dünnfilmen, der mit Hilfe von SQUID-Messungen in dieser Arbeit eingehend untersucht wurde. Durch Korrelation der Ergebnisse der verschiedenen Untersuchungsmethoden konnten Rückschlüsse auf die dominierenden Defekte in den Ferrit-Dünnfilmen geschlossen werden. So sind zum einen Defekte auf atomarer Skala, wie Antisite-Defekte und divalenten Fe-Ionen für die erhöhte elektrische Leitfähigkeit und die größere Magnetisierung der defektreichen Dünnfilme verantwortlich. Zum anderen können ausgedehnte Defekte, im Speziellen Cluster, die in einer amorphen Matrix eingebettet sind, nicht ausgeschlossen werden.

Atualmente com o advento da nanociência e nanotecnologia, as nanopartículas magnéticas têm encontrado inúmeras aplicações nos campos da biomedicina, diagnóstico, biologia molecular, bioquímica, catálise, etc. As nanopartículas magnéticas funcionalizadas são constituídas de um núcleo magnético, envolvido por uma camada polimérica com sítios ativos, que podem ancorar metais ou compostos orgânicos seletivos. Estas nanopartículas são consideradas materiais híbridos orgânico-inorgânicos de grande interesse em aplicações comerciais devido à particularidade das propriedades obtidas. Entre as aplicações importantes podemos citar: tratamento por magnetohipertermia, carregadores de fármacos para áreas específicas do corpo, seleção de moléculas específicas, biossensores, melhoria da qualidade de imagens por RMN, etc. O trabalho foi desenvolvido em duas partes: 1) a síntese do núcleo constituído de nanopartículas superparamagnéticas de ferrita de cobalto e, 2) o recobrimento do núcleo por um polímero bifuncional o 3-aminopropiltrietoxissilano. Os parâmetros estudados na primeira parte da pesquisa foram: pH, concentração molar da base, tipo de base, ordem de adição dos reagentes, modo de adição dos reagentes, velocidade de agitação, concentração inicial dos metais, fração molar de cobalto e tratamento térmico. Na segunda parte estudou-se: o pH, a temperatura, o catalisador, a concentração do catalisador, o tempo de reação, a relação H2O/silano, o tipo de meio, o agente umectante e a eficiência do recobrimento em relação ao pH. Os produtos obtidos foram caracterizados pelas técnicas de difratometria de raios-X (DRX), microscopia eletrônica de transmissão (MET), microscopia eletrônica de varredura (MEV), espectroscopia de energia dispersiva (EDS), espectroscopia de emissão atômica (ICP-AES), espectroscopia por infravermelho (FTIR), análises termogravimétricas (TGA/DTGA), calorimetria exploratória diferencial (DSC) e curvas de magnetização (MAV) / Nowadays with the appear of nanoscience and nanotechnology, magnetic nanoparticles have been finding a variety of applications in the fields of biomedicine, diagnosis, molecular biology, biochemistry, catalysis, etc. The magnetic functionalized nanoparticles are constituted of a magnetic nucleus, involved by a polymeric layer with active sites, which ones could anchor metals or selective organic compounds. These nanoparticles are considered organic-inorganic hybrid materials and have great interest as materials for commercial applications due to the specific properties. Among the important applications it can be mentioned: magnetohyperthermia treatment, drugs delivery in specific local of the body, molecular recognition, biossensors, enhancement of nuclear magnetic ressonance images quality, etc. This work was developed in two parts: 1) the synthesis of the nucleus composed by superparamagnetic nanoparticles of cobalt ferrite and, 2) the recovering of nucleus by a polymeric bifunctional 3-aminepropyltriethoxysilane. The parameters studied in the first part of the research were: pH, hydroxide molar concentration, hydroxide type, reagent order of addition, reagent way of addition, speed of shake, metals initial concentrations, molar fraction of cobalt and thermal treatment. In the second part it was studied: pH, temperature, catalyst type, catalyst concentration, time of reaction, relation ratios of H2O/silane, type of medium and the efficiency of the recovering regarding to pH. The products obtained were characterized using the following techniques X-ray powder diffraction (DRX), transmission electronic microscopy (MET), scanning electronic microscopy (MEV), spectroscopy of scatterbrained energy spectroscopy (DES), atomic emission spectroscopy (ICP-AES), themogravimetric analysis (TGA/DTGA), Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC) and magnetization curves (VSM)

Cobalt Ferrite has important, size-dependent magnetic properties. Consequently, an overview of particle size is important. Co-precipitation in air was the fabrication method used because it is comparatively simple and safe. The effects of three different reaction times including 1, 2, 3 hour(s) on particle size were compared. Also, the effectiveness of three different capping agents (Oleic Acid, Polyvinylpyrollidone (PVP), and Trisodium Citrate) in reducing aggregation and correspondingly particle size were examined. Using Welch’s analysis of variance (ANOVA) and the relevant post hoc tests, there was no significant difference (p=0.05) between reaction times of 1 hour and 2 hours, but there was a significant difference between reaction times of 2 hours and 3 hours. Potentially, because of increased coarsening for the 3 hour reaction time. PVP and Oleic Acid were shown to be effective in reducing aggregation; however, Citrate was not effective. Possibly, the synthesis procedure was inadequate.

[pt] A demanda energética mundial está em constante crescimento e tal cenário faz aumentar a preocupação com os impactos ambientais, muitos deles decorrentes da exploração de combustíveis fósseis e sua utilização desmedida. Neste contexto, o estudo da pirólise da biomassa apresenta uma alternativa para a produção direta de calor que pode vir a ser utilizado em usinas termoelétricas sustentáveis. Uma investigação foi realizada abordando o tema da reciclagem de madeira sobre a possibilidade de aproveitá-la a biomassa principal deste processo. Este trabalho apresenta a caracterização da madeira reciclada bem como da madeira de eucalipto para poder averiguar a similaridade química entre as duas biomassas. Para tanto foram realizadas análises de espectroscopia de infravermelhos (FTIR) e difração de raios-X (DRX), além de análises de microscopia eletrônica de varredura com espectroscopia por dispersão de energia (MEV/EDS). Com o auxílio da técnica de termogravimetria (TG) foram realizados experimentos de pirólise lenta da madeira reciclada, a partir dos quais foram identificados eventos térmicos, caracterizados por perdas de massa. Para verificar um possível efeito oxidante dos óxidos Fe2CoO4 e Co3O4, realizou-se também pirólise lenta da mistura da madeira reciclada com cada um dos óxidos, tendo sido identificados eventos térmicos que não estavam presentes nos experimentos com a madeira pura. Os principais eventos foram avaliados cineticamente por métodos model-free que permitem a determinação da energia de ativação sem a necessidade de assumir uma ordem de reação. Foram utilizados os métodos de Kissinger (KS) e Kissinger-Akahira-Sunose (KAS), empregando os dados de experimentos realizados no TG com cinco taxas de aquecimento diferentes até 1100 graus Celsius. Para o evento térmico de maior importância, entre 200 e 390 graus Celsius tanto na madeira pura quanto na mistura, o ajuste de ambos o métodos foi satisfatório e está de acordo com a literatura. / [en] World s energy demand is constantly growing, and this scenario raises the concern about environmental impacts, many of them resulting from the constant manipulation of fossil fuels and their excessive use. In this context, the study of biomass pyrolysis presents an alternative for the direct production of heat that can be used in sustainable thermoeletric plants. To this end, a research has been carried out on the possibility of taking advantage of recycled wood as the main biomass of this process, an investigation that has been carried out along with a company in the field of wood recycling. This work presents the characterization of a recylced and a typical Brazilian eucalyptus wood with the purpose of proving their chemical similarity. Therefore, analysis of Scanning Electron Microscopy with Energy Dispersive Spectroscopy (SEM/EDS), X-ray diffraction (XRD) and Fourier-transform infrared spectroscopy (FTIR) was performed. Thermogravimetric (TG) experiments were carried out with slow pyrolysis of recycled wood and eucalyptus wood, from wich were identified thermal events, characterized by mass losses. To verify a possible oxidative effect of the compounds Fe2CoO4 and Co3O4, slow pyrolysis of a mixture of the recycled wood with each of the oxides was also performed, and thermal events that were not present in the experiments with the pure wood were identified. The main thermal events were kinetic investigated with model-free methods wich allows the determination of the activation energy without the need of a reaction order pre-stipulated. In this workk were tested the Kissinger (KS) and Kissinger-Akahira-Sunose (KAS) model-free methods and the TG data of five different heating rate were collected until 1100 Celsius degrees. For the most relevant thermal event, wich occurs from 200 to 390 Celsius degrees (for recycled wood and its mixture with the oxides) the adjustment of both methods was fine and accordance with literature.