In this work is described a study of the magnetic anisotropy of a magnesioferrite nanoparticle system (MgFe2O4) obtained by precipitation in solid solution of magnesiowüstite [Mg, Fe]O. The anisotropy field was obtained from system’s resonance spectra as measured in the X band. Such spectra can be considered as composed by two spectral lines: A broad line assigned to blocked particles at the measuring temperature and a thin line, which can be attributed to unlocked (superparamagnetic) particles. The anisotropy field of four samples treated at 700 °C during different annealing times were obtained from the spectra measured with their easy magnetization axes oriented at 0 ° and 45 ° with the applied field. The use of a theoretical model to adjust the obtained anisotropy field data enabled the obtaining of the model’s parameter values and their posterior comparison with those reported by other authors. Beyond the dependence of the anisotropy field with the measurement temperature and the sample’s treatment time, it was observed the presence of low field resonance lines that may be related to transitions usually considered as forbidden, which can be enabled by the degenerescence breaking caused by dipolar magnetic interactions between particles. Such phenomenon, which is considerably rare to observe in magnetic nanoparticles systems, was clearly observed in the studied system not only for the half-field resonance line (2Q), but also for lines appearing at one third of field (3Q) and at one quarter of field (4Q). This feature shows that, at least in the investigated experimental system, the dipolar interactions between nearby particles cannot always be neglected as has been proposed by several other authors. / O presente trabalho aborda o estudo da anisotropia magnética do sistema de nanopartículas de magnesioferrita (MgFe2O4) precipitadas em solução sólida de magnesiowüstita [Mg;Fe]O a partir da análise de seus espectros de ressonância magnética medidos na banda X. Tais espectros podem ser aproximadamente decompostos em duas linhas, sendo uma atribuída às partículas bloqueadas na temperatura de medição (linha larga) e a outra às partículas desbloqueadas (linha estreita). Os campos de anisotropia de quatro amostras tratadas a 700 oC por diferentes tempos de tratamento foram obtidos a partir dos espectros medidos com seus eixos de magnetização fácil orientados a 0° e a 45° em relação ao campo aplicado. O emprego de um modelo teórico de anisotropia magnética para ajustar os dados obtidos possibilitou a obtenção dos valores dos parâmetros considerados no mesmo e a comparação destes valores com os que foram reportados por outros autores. Além da dependência do campo de anisotropia com a temperatura de medição e com o tempo de tratamento térmico das amostras, observou-se a presença de linhas de ressonância na região de baixos campos que podem estar relacionadas a transições normalmente consideradas como proibidas que ser viabilizadas com a quebra da degenerescência causada por interações magnéticas dipolares entre partículas. Tal fenômeno, que é consideravelmente raro de se observar em sistemas de nanopartículas magnéticas, foi claramente observado no sistema estudado não somente para a linha de ressonância a meio campo (2Q), mas também para as linhas a um terço (3Q) e um quarto (4Q) de campo. Isso evidencia que, ao menos no sistema experimental investigado, as possíveis interações dipolares entre partículas próximas não podem ser sempre desprezadas a priori como tem sido proposto por vários outros autores.

Les propriétés spectroscopiques des monocristaux de α-ZnAl2S4, semi-conducteurs de type spinelle avec une large bande interdite, dopées par les ions des métaux de transition sont investigués et leur interprétation est donnée. Les monocristaux, obtenus par la méthode de transport chimique en phase vapeur avec la concentration des impuretés dopantes compris entre 0.01 – 0.1% at., représentent des octaèdres homogènes optique avec des faces orientent (111). Les analyses par les rayons X ont confirmé que tous les échantillons ont cristallisés dans une structure normale de type spinelle avec la symétrie cubique Fd3m (Oh7). Les monocristaux de α-ZnAl2S4 : Ti manifestent des propriétés radiatives dans le domaine spectral du proche infrarouge 0.8–1.4μm. Les résultats spectroscopiques obtenus dans l’intervalle des températures 10-300K (les spectres de la photoluminescence stationnaire et résolue en temps, de l’absorption et de l’excitation de la photoluminescence) sont interprétés dans les termes d’un cluster composé par un ion de Ti4+ dans une configuration octaédrique des six ions de soufre. Les bandes spectrales observées sont attribuées à des transitions électroniques survenues d’un transfert de charge ligand Ti4+ pour les sites octaédriques de titane, qui est en concordance avec la évidence expérimentale de l’absence du RPE signale des ions de Ti. Les constantes vibroniques des niveaux excités et l’auteur de la barrière potentielle entre eux ont étés calculés. La structure des spectres d’absorption et de la luminescence des monocristaux de α-ZnAl2S4 :Co est déterminé par les transitions électroniques des ions de Co2+ localisés dans des sites tétraédriques. Quatre composantes spectrales radiatifs sont révélés en utilisant la spectroscopie résolue en temps sous différentes longueur d’onde d’excitation et il est montré que la photoluminescence des monocristaux de α-ZnAl2S4 : Co est dû aux transitions électroniques entre les niveaux excités des ions de Co2+. Les valeurs calculées des constantes de l’interaction spin – orbite des niveaux excités indiquent une faible influence du part de champ cristallin et une forte interaction spin – orbite. L’absorption optique et la photoluminescence des monocristaux de α-ZnAI2S4 : V sont déterminées des transitions électroniques du vanadium trivalent situé dans des sites octaédriques. L’augmentation de la température est accompagnée par l’amplification de la luminescence intégrale et l’élargissement du spectre centré à λ =1.4μm. Trois composantes spectrales radiatifs de α-ZnAI2S4 : V révélés aux basses températures sont dû aux transitions électroniques des ions de V3+. D’après l’analyse comparative des propriétés spectroscopiques des monocristaux de type spinelle de α-ZnAl2S4 dopés par les ions des métaux de transition Ti, Co, et V, le plus favorable comme milieux actifs laser, est le composée α-ZnAl2S4 : V3+, qui pourrais assurer l’émission dans le domaine des longueurs d’ondes 1.2-1.6μm, ce qui correspondent à la région spectrale utilisée par les systèmes des communications sur fibre optique. / Spectroscopic properties of α-ZnAl2S4 spinel-type single crystals of the wide band gap semiconductor doped by the transition metals Ti, Co and V are investigated and their interpretation is presented. The crystals, grown by the chemical vapour transport method, with activator impurities concentrations 0.01 – 0.1% at., correspond to optically homogeneous octahedrons with (111) - oriented mirror-like faces. The x-ray analyses confirm that all samples crystallised into the normal spinel type structure with Fd3m (Oh7) cubic symmetry. It is found out that α-ZnAl2S4:Ti single crystals exhibit luminescence in the IR spectral range 0.8–1.4μm. The spectroscopic results obtained in the temperature range 10-300K (steady-state and time resolved photoluminescence, optical absorption and excitation luminescence spectra) are interpreted in terms of a cluster composed of the central Ti4+ ion in an octahedral coordination of six sulphur ions. The observed spectral bands are assigned to the electronic transitions arising from the ligand – Ti4+ charge transfer for octahedral sites of titanium that is in agreement with the experimental evidence for the absence of the EPR signal from Ti ions. The vibronic coupling constant for the excited levels and the barrier height between them are calculated. The structure of the absorption and luminescence spectra of α-ZnAl2S4:Co crystals is determined by the electronic transitions of Co2+ ions located in tetrahedral sites. Four radiative spectral components are revealed using the time-resolved spectroscopy at different excitation wavelengths and it is shown that the luminescence of α-ZnAl2S4:Co crystals is due to the electronic transitions between the excited levels of Co2+ ions. The calculated values of the spin-orbit coupling constants of the excited levels indicate a weak crystal field influence and a strong spin-orbit coupling. It is determined that the absorption and luminescent properties of α-ZnAl2S4:V spinel type crystals are the result of electronic transitions of trivalent vanadium ions located in octahedral sites. The rise of temperature leads to the enhancement of the integral luminescence intensity and to the broadening of the spectrum centered at λ =1.4μm. Three main spectral components of the α-ZnAI2S4:V IR spectra revealed at low temperatures are caused by electronic transitions of V3+ ions. The coexistence of a broad band with the narrow lines at low temperatures, when the thermal energy kBT is much less than the height of the potential barrier between the excited states, is explained assuming that there is a phonon assisted tunnelling between these states. On the base of the comparative analysis of spectroscopic properties of α-ZnAl2S4 spinel type crystals doped with transition metals Ti, Co, and V it is established that α-ZnAl2S4:V3+ compounds are the most appropriate for applications as active media for solid state IR-lasers tunable in the 1.2-1.6μm wavelength range, which corresponds to the spectral region used in the fibre-optics communication systems.

Cette thèse porte sur la croissance de films minces d’oxydes de zinc/fer (ZnxFe1-xO1+δ par ablation laser pulsée (PLD) et sur la possibilité de contrôler leurs propriétés structurales et physico-chimiques en variant les conditions d’élaboration : pression d’oxygène et température de croissance, proportions respectives de zinc/fer. Pour de fortes valeurs de x (x > 65%), les films sont monophasés de structure wurtzite type ZnO (films Fe:ZnO), avec une transparence optique dans la gamme UV-visible de 80% mais sans propriété ferromagnétique ; en fonction de leur teneur en fer (1-x), ils évoluent de très bons conducteurs électriques à quasi-isolants. Pour de faibles valeurs de x (x < 15%), les films sont également monophasés de structure spinelle type Fe3O4 (films Zn:Fe3O4). Ils présentent de très bonnes propriétés ferromagnétiques dès la température ambiante ainsi qu’une bonne conductivité électrique, les effets de localisation des porteurs de charge se manifestant en dessous de la température de Verwey. Le nombre de parois d’antiphase peut être diminué par une croissance en deux étapes, comme l’atteste les mesures de magnétorésistance. Aux taux intermédiaires de zinc (15% < x < 65%), les films sont nano-composites. Dans le cas d’une coexistence des phases Fe:ZnO et Zn:Fe3O4, la bonne conductivité de Zn:Fe3O4 jointe à la multiplicité des variantes épitaxiales et donc des interfaces fournit un matériau adapté à la thermoélectricité. Dans le cas d’une coexistence de la phase ferrromagnétique Zn:Fe3O4 avec la phase Zn:FeO antiferromagnétique de type sel gemme, un fort couplage d’échange ainsi qu’une anisotropie magnétique perpendiculaire élevée sont mis en évidence. / This thesis deals with the growth of thin films of zinc/iron oxides (ZnxFe1-xO1+δ) by pulsed laser deposition (PLD) and the possibility of controlling their structural and physicochemical properties by varying the elaboration conditions: oxygen pressure and growth temperature, respective proportions of zinc/iron. For high values of x (x> 65%), the films are single-phase with a ZnO-type wurtzite structure (Fe:ZnO films), with 80% optical transparency in the UV-visible range but without ferromagnetic properties; depending on their iron (1-x) content, they evolve from very good electrical conductors to near-insulators. For small values of x (x <15%), the films are also single-phase with a Fe3O4-type spinel structure (Zn:Fe3O4 films). They exhibit very good ferromagnetic properties at ambient temperature as well as good electrical conductivity, the localization effects of charge carriers occurring below the Verwey temperature. The number of antiphase walls can be decreased by a two-step growth, as evidenced by magnetoresistance measurements. At intermediate zinc rates (15% <x <65%), the films are nano-composites. In the case of a coexistence of the Fe:ZnO and Zn:Fe3O4 phases, the good conductivity of Zn:Fe3O4 combined with the multiplicity of epitaxial variants and thus of the interfaces provides a material suitable for thermoelectricity. In the case of a coexistence of the ferrromagnetic Zn:Fe3O4 phase with the Zn:FeO antiferromagnetic rocksalt phase, strong exchange coupling as well as high perpendicular magnetic anisotropy are demonstrated.

The first part of the thesis discuss general characterization of heterogeneous processes in silicates. This part is focused on kinetics of heterogeneous processes and mathematical description of reactions time behavior. The other part describes important technologies in silicate industry such as sintering, solid matter decomposition, transition modification, etc. Another chapter deals mineralogy, structure and properties of eminent silicate raw materials. Emphases is given to characterization of clay minerals and their utilising. The experimental part handle the analytic techniques used for investigation of thermal decompostion, dehydroxylation, crystalization of Al-Si spinel phase and sintering process of washed kaolin Sedlec Ia from the region Carlsbad (Czech Republic). Concluding chapter reports on results of experimental work.

Nanostructured fayalite (α-Fe2SiO4) with a large volume fraction of interfaces is synthesized for the first time via single-step mechanosynthesis, starting from a 2α-Fe2O3 + 2Fe + 3SiO2 mixture. The nonequilibrium state of the as-prepared silicate is characterized by the presence of deformed polyhedra in the interface/surface regions of nanoparticles. / Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.

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As current environmental challenges are gaining increased attention, development of clean energy solutions is becoming one of the essential strategies to keep within the boundaries of established environmental policies. Solid oxide cell (SOC) technology can provide clean energy conversion and storage when hydrogen is the energy carrier. The high total energy conversion efficiency resulting from the high operation temperature of SOCs make the technology promising, but material costs must be reduced to make it commercially viable. Therefore, this thesis aims to study the long- term performance of a novel cost-optimized cell interconnect at 650 and 850 °C. At high temperatures, chromium evaporation from the interconnect result in electrode poisoning, which may be mitigated by application of a protective coating. The studied interconnect is an AISI 441 steel with some different pre-oxidized copper and iron spinel coatings. Sample analysis was made mainly with scanning electron microscopy coupled with energy dispersive X-ray spectroscopy and X-ray diffraction. It was found that the most promising pre-oxidation treatment was 24 h at 750 °C and that chromium migration was restrained at 650 °C long-term treatment but not at 850 °C where it wasfound available for evaporation at the surface. / När samtida milljöutmaningar får ökad uppmärksamhet blir gröna energilösningar en av de viktigaste strategierna för att hålla sig inom satta gränser från etablerade miljöriktlinjer. Teknologin bakom fastoxidceller, eller solid oxide cells (SOCs), kan bidra med grön omvandling och lagring av energi när energibäraren är väte. Den höga totala omvandlingseffektiviteten, som kommer med den höga verkningstemperaturen, gör SOC till en lovande teknologi, men materialkostnaderna måste först reduceras innan den blir komersiellt gångbar. Därför syftar detta examensarbete till att undersöka prestandan av en ny, kostnadsoptimerad cellinterkonnektor på lång sikt i 650 och 850 °C. Vid höga temperaturer förångas krom från interkonnektorn, vilket leder till elektrodförgiftning, men kan mildras genom applicering av en skyddande beläggning. Den undersökta interkonnektorn är ett stål som betäcknas AISI 441 belagt med några olika föroxiderade beläggningar av koppar- och järnspinell. Proverna analyserades i huvudsak genom svepelektronmikroskopi kobinerat med energidispersiv röntgenspektroskopi och röntgendiffraktometri. Det visades att den mest lovande föroxideringsbehandlingen var 24 h i 750 °C och att krom förblev återhållet vid 650 °men inte vid 850 °C då det fanns tillgängligt för förångning vidytan.

[pt] Ferritas do tipo espinélio têm atraído atenção devido a suas propriedades magnéticas com possibilidade de aplicações em dispositivos spintrônicos e de memória magnética, além de aplicações em catálise. Este trabalho tem como objetivo sintetizar o espinélio de alumínio e ferro (FeAl2O4) pelo método de síntese reação de combustão e avaliar suas características estruturais e morfológicas bem como suas propriedades magnéticas devido a sua ampla possibilidade de aplicações. A síntese deste material foi feita utilizando soluções concentradas dos nitratos metálicos hidratados de ferro e alumínio, variando o tipo e quantidade de combustível no intuito de verificar sua influência na microestrutura do produto. Os combustíveis utilizados neste trabalho foram ureia e ácido cítrico, ambos em quantidade estequiométrica, dita ideal, calculada a partir da teoria química dos propelentes, além de reações com quantidades acima e abaixo do ideal. Uma síntese apenas utilizando os nitratos metálicos, sem combustível, foi feita para comparação. O produto final das diferentes sínteses foram caracterizados em termos de estrutura e composição por meio de difração de raios X (DRX), Microscopia Eletrônica de Varredura (MEV) e Microscopia Eletrônica Transmissão (MET). As propriedades magnéticas foram obtidas por magnetometria de amostra vibrante e a identificação das fases de ferro por espectroscopia Mössbauer. As análises indicaram que a amostra sintetizada sem combustível corresponde a óxidos de ferro e de alumínio, majoritariamente amorfo, com formação de partículas nanométricas de hematita (Fe2O3) e um comportamento paramagnético. As caracterizações das amostras produzidas com ureia apresentam maior cristalinidade em relação a sintetizada sem combustível, com a amostra em quantidade estequiométrica de ureia, resultando em um produto monofásico identificado como o espinélio FeAl2O4, misto. Já as amostras com excesso e deficiência de ureia tiveram como produto, além da formação do espinélio desejado, a formação de outra fase identificada como magnetita (Fe3O4), sendo todas as amostras sintetizadas com ureia manifestando comportamento ferromagnético. As amostras sintetizadas com ácido cítrico, em todas as condições, apresentaram um sistema trifásico constituído pelo espinélio, magnetita e hematita e mostraram comportamento também ferromagnético. Neste trabalho é mostrado que a síntese por reação de combustão se mostrou eficiente para produzir o FeAl2O4, alcançando melhores resultados utilizando ureia como combustível, em quantidade ideal. / [en] Spinel-like ferrites has attracted attention due to its magnetic properties with the possibility of spintronic and magnetic memory devices applications as well as catalysis applications. This work aims to synthesize aluminum and iron spinel (FeAl2O4) by combustion reaction synthesis method and evaluate its structural and morphological characteristics, as well as its magnetic properties due to its wide application possibilities. The synthesis of this material was made using concentrated solutions of hydrated iron and aluminum metal nitrates, varying the type and quantity of fuel in order to verify its influence on the product microstructure. The fuels used in this work were urea and citric acid, both in stoichiometric quantity, said ideal, calculated from the chemical theory of propellants, and reactions with quantities above and below ideal. A synthesis using only metal nitrates without fuel was made for comparison. The final product of the different syntheses were characterized in terms of structure and composition by Xray diffraction (XRD), Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM). Magnetic properties were obtained by vibrating sample magnetometry and the iron phase identification by Mössbauer spectroscopy. The analysis indicated that the sample synthetized without fuel corresponds to iron and aluminum oxides, mostly amorphous, with formation of nanometer hematite particles (Fe2O3) and a paramagnetic behavior. The characterizations of the samples produced with urea show higher crystallinity than the synthesized without fuel, with the sample in stoichiometric amount of urea, resulting in a single phase product identified as FeAl2O4 mixed spinel. The samples with excess and deficiency of urea had as product, besides the formation of the desired spinel, the formation of another phase identified as magnetite (Fe3O4), being all the samples synthesized with urea manifesting ferromagnetic behavior. The samples synthesized with citric acid, under all conditions, presented a triphasic system consisting of spinel, magnetite and hematite and showed also ferromagnetic behavior. In this work it is shown that combustion reaction synthesis was efficient to produce FeAl2O4, achieving better results using urea as fuel, in ideal quantity.

[pt] Devido a grande poluição do meio ambiente, diferentes estratégias devem ser tomadas para remediação ambiental. Dentre as diversas estratégias, é possível citar adsorção de cátions metálicos de soluções aquosas, adsorção de fármacos, utilização e armazanamento de energia verde. Dito isso, o presente estudo relata a utilização das estratégias mencionadas. Portanto, foi utilizada nanofibras de celulose oxidada via TEMPO (2,2,6,6-tetrametil-piperidinil-N-oxil), TCNF, para a remoção de cátions de ferro, zinco e cobalto. Sua capacidade adsortiva para a remoção de ferro e zinco puros apresentou valores de 5902 e 5633 Miligrama por grama−1 , respectivamente. Quando ferro e zinco removidos de uma mesma solução, a capacidade adsortiva de TCNF foi de 5852 e 5622 Miligrama por grama−1 . Para a adsorção de cobalto, sua concentração reduziu de 50 grama por litro−1 para 8,3 grama por litro−1 . Posteriormente, as amostras de TCNF impregnadas com metais foram levadas para calcinação, com objetivo de produção de óxidos nanoestruturados. Em temperaturas a partir de 300 graus C, fases de hematita são identificadas e a partir de 400 graus C fases de zincita e franklinita são identificadas por ajustes de Rietveld nos difratogramas obtidos. Adicionalmente, quando calcinadas em atmosfera inerte, é possível observar o surgimento de óxidos. Além disso, todas as morfologias foram analisadas via MET e MEV, e podem ser comparadas a um nanocoral com espessuras entre 20 e 30 nm. Então, as amotras de ferrita de zinco foram aplicadas em adsorção de tetraciclina, com capacidade adsortiva de 18 miligrama por grama−1 e também como capacitor, atingindo um valor de capacitância de 2031 Farad por grama−1 . A amostra contendo ferrita de cobalto foi utilizada como catalisador para extração de H2 de borohidreto e a quantidade de gás hidrogênio extraída girou em torno de 476,4 Litros de hidrogênio produzido por grama de borohidreto de sódio por grama de catalisador. A energia de ativação para a reação foi calculada em torno de 57 Quilojoules por mol−1 . Portanto, a inovadora rota de síntese de óxidos nanoetruturados aparenta ser promissora. / [en] Due to significant environmental pollution, different strategies require to be implemented for environmental remediation. Among the different approaches, it is possible to cite the adsorption of metallic cations from aqueous solutions, adsorption of pharmaceuticals, and the use and storage of green energy. With this in mind, the present study reports the use of the mentioned strategies. Thus, oxidized cellulose nanofibers, produced via TEMPO (2,2,6,6-tetramethyl-piperidinyl-N-oxyl), TCNF, were used for the removal of iron, zinc, and cobalt cations from aqueous solution. Their adsorptive capacity for the removal of pure iron and zinc was 5902 and 5633 Milligram per gram−1 , respectively. When iron and zinc were removed from the same solution, the adsorptive capacity of TCNF was 5852 and 5622 Milligram per gram−1 , respectively. For cobalt adsorption, its concentration decreased from 50 gram per liter−1 to 8.3 gram per liter−1 . Subsequently, the TCNF samples impregnated with metals were subjected to calcination to produce nanostructured oxides. At temperatures above 300 C degrees, hematite phases were identified, and at 400 C degrees, zincite and franklinite phases were identified through Rietveld refinements of the obtained diffractograms. Additionally, when calcined in an inert atmosphere, the appearance of oxides was observed. Moreover, all morphologies were analyzed via TEM and SEM, resembling a nanocoral with thicknesses between 20 and 30 nm. The zinc ferrite samples were applied to tetracycline adsorption with an adsorptive capacity of 18 miligram per gram−1 and also as a capacitor, achieving a capacitance value of 2031 Farad per gram−1 . The cobalt ferrite sample was used as a catalyst for hydrogen extraction from borohydride, and the amount of extracted H2 was around 476.4 liters of hydrogen produced per gram of sodium borohydride per gram of catalyst. The activation energy for the reaction was calculated to be approximately 57 Kilojoules per mole−1 . Therefore, the innovative route for the synthesis of nanostructured oxides appears to be promising.