ABSTRACT SYNTHESIS AND CHARACTERIZATION OF POLY(DIHALOPHENYLENE OXIDE)S AND ITS DERIVATIVES FROM DIAMMINE BIS(TRIHALOPHENOLATO) Cu(II) COMPLEXES Sonsuz, Muammer M.S., Department of Chemistry Supervisor: Assoc. Prof. Dr. G&uuml / ls&uuml / n G&ouml / kaga&ccedil / Co-Supervisor: Prof. Dr. Duygu Kisak&uuml / rek September 2004, 62 pages In this study, synthesis and characterization of poly(dihalophenylene oxide)s were done by thermal decomposition of diamminebis(trichlorophenolato) copper(II) and diamminebis(tribromophenolato) Cu(II) complexes in solid state. 2,4,6-trichlorophenol (TCP), 2,4,6-tribromophenol (TBP) and ammonia were used as ligands in the complex syntheses. The complexes were characterized by means of X-ray diffraction, FTIR, DSC, mass spectroscopy, magnetic susceptibility and C, H, N elemental analyses. Synthesized complexes were decomposed thermally in solid state for the production of poly(dihalophenylene oxide)s. Polymerizations were carried out at two different conditions. In the first condition, the decomposition time was kept constant at 3 hours and temperature was varied for each sample to observe the effect of temperature on decomposition. In the second condition, the decomposition temperature was kept constant at maximum conversion temperature and the period of time was varied from 3 hours to 48 hours in order to define the effect of time on the decomposition. Synthesized polymers were characterized by FTIR, 1H-NMR, 13C-NMR, DSC, SEM, FAAS and viscometric measurements. At the end of the study, it was observed that, the percent conversion and the structure of the polymeric product depend on polymerization condition and the type of the starting complex.

[pt] Com aumento da preocupação político-ambiental, torna-se imperativo desenvolver processos eficientes em termos econômicos e energéticos para a produção sustentável de combustíveis e produtos químicos. A liquefação hidrotérmica (HTL) é um processo para a transformação de materiais orgânicos, tais como bio-resíduos ou biomassa, em óleo bruto, em temperaturas usualmente inferiores a 400 graus Celsius sob altas pressões na presença de água, e, dependendo do processo, de um catalisador. Nesse contexto, é importante entender o comportamento de degradação térmica do material em atmosfera inerte, no sentido de se investigar a possibilidade de quebra das cadeias poliméricas inicias em moléculas menores, que, mediante pressão, poderão ser convertidas em novos produtos. Assim sendo, os objetivos do presente trabalho estão associados ao estudo termogravimétrico (TG) da degradação térmica da fibra do coco verde na presença de ferrita de cobalto (Fe2CoO4), utilizada no intuito de gerar um efeito catalítico, acelerando a degradação térmica das estruturas poliméricas presentes, e, que possa ser usada posteriormente em uma rota HTL. Os catalisadores foram produzidos a 1000 graus Celsius em diferentes tempos de calcinação (3h, 6h e 9h), sendo, nas misturas com a fibra, a fração mássica de óxido igual a 50 por cento. As amostras de interesse para a pesquisa foram caracterizadas mediante diferentes técnicas, tais como, a microscopia eletrônica de varredura, para o estudo da morfologia e composição elementar, difração de raios X, para a quantificação das fases presentes nas amostras de ferrita, e espectroscopia de infravermelho, visando à identificação das principais ligações químicas nas fibras, tanto antes quanto durante o tratamento térmico. Dentre todos os ensaios de TG realizados, os experimentos com o catalisador calcinado durante 9h homogeneizado com gral de ágata foi o que mostrou uma melhor resposta com relação à degradação térmica das fibras. Os resultados sugerem ainda que, tanto o tempo de calcinação, quanto a natureza do processo de mistura apresentam efeitos significativos sobre a cinética de degradação. / [en] With increasing political-environmental concern, it becomes imperative to develop efficient processes in economic and energy terms for the sustainable production of fuels and chemical products. Hydrothermal liquefaction (HTL) is a process for the transformation of organic materials such as bio-waste or biomass into crude oil at temperatures usually below 400 degrees Celsius under high pressures in the presence of water and, depending on the process, of a catalyst. In this context, it is important to understand the behavior of thermal degradation of the material under inert atmosphere, in order to investigate the possibility of breaking the initial polymer chains into smaller molecules, which, under pressure, can be converted into new products. The objectives of the present work are associated to the thermogravimetric study (TG) in the thermal degradation of the green coconut fiber in the presence of a cobalt ferrite (Fe2CoO4), used to generate a catalytic effect, accelerating the thermal degradation of the polymeric structures present, and which can be used later on an HTL route. The catalysts were produced at 1000 degrees Celsius at different calcination times (3h, 6h and 9h) and in the fiber mixtures, the oxide mass fraction was equal to 50 percent. The samples of interest for the research were characterized by different techniques, such as scanning electron microscopy, for the study of the morphology and elemental composition, X-ray diffraction, for the quantification of the phases present in the ferrite samples, and spectroscopy of Infrared, in order to identify the main chemical bonds in the fibers, both before and during the heat treatment. Among all the TG assays performed, the experiments with the catalyst calcined for 9h homogenized with mortar and pestle showed the best to the thermal degradation of the fibers. The results further suggest that both the calcination time and the nature of the blending process have significant effects on the degradation kinetics.

Master of Science / Food Science Institute - Animal Sciences and Industry / J. Scott Smith / The popularity of convenience foods and consumer awareness have indirectly increased the demand for novel and naturally occurring compounds that can delay oxidative deterioration and maintain nutritional quality of foods. Natural antioxidants from certain herbs and spices such as rosmarinic acid from rosemary, thymol from oregano, eugenol from clove, curcumin from turmeric are rich in polyphenolic compounds that provide long term oxidative stability as well as offer additional health benefits. High antioxidative capacity of herbs and spices phenolics could potentially substitute synthetic antioxidants such as butylated hydroxytoluene (BHT), butylated hydroxyanisole (BHA), propyl gallate (PG), octyl gallate, and tert-butylated hydroquinone (TBHQ) in the food system. Synthetic antioxidants such as butylated hydroxytoluene (BHT) and butylated hydroxyanisole (BHA) are thermally unstable and decompose at higher temperatures. However, widely used cooking methods such as baking, frying, boiling, and roasting use high thermal temperature that can chemically degrade herbs and spices and diminish their antioxidative capacity, but they have been little studied. In this context, this review deals with the need of natural antioxidants, spices and herbs as natural antioxidants, their origin, chemical composition, pharmacological, and antioxidant properties. Moreover, the impact of temperature on total antioxidant capacity (TAC) of various herbs and spices such as cinnamon, clove, nutmeg, mace, oregano, rosemary, sage, and turmeric is highlighted. Different antioxidant assays are also studied and this approach revealed that there is a clear correlation between total phenolic content (TPC) and TAC of herbs and spices and specific phenolic compounds are responsible for the antioxidative capacity of particular herb and spice. These findings identified the optimum cooking temperature-time combination which results in the highest retention of antioxidative capacity and assures higher quality of food for the maintenance of human health.

Conselho Nacional de Desenvolvimento Científico e Tecnológico / The use of cellulose nanocrystals (CN) as a reinforcing agent for polymeric matrices has attracted considerable attention because the cellulose nanocrystal-based nanocomposites typically exhibit thermal, mechanical and superior barrier properties compared to the pure polymer or conventional composites and additionally provide environmental benefits. In order to use these to the CN as a reinforcing agent polymer matrix, the thermal stability of these crystals is a key factor in that they can be used as effective reinforcement materials, since the thermoplastic processing temperatures often exceeds 200°C. In this work CN were obtained from different sources, cellulose of purified mango seed (PMS), eucalyptus kraft pulp (PK) and cellophane (CELL) by acid hydrolysis with HCl and H2SO4. The chemical compositon of PMS, PK and CELL used in the hydrolysis were determined for the levels of -cellulose, hemicelluloses, holocellulose, lignin and ash All NC were characterized by elemental analysis (C,H,N,S), x - rays diffraction (XRD), atomic force microscopy ( AFM ) and thermogravimetry analysis ( TGA ) . Through thermogravimetric analysis kinectic study of thermal decomposition of the CN was carried out, it was possible to determine the conversion ( ) of the thermal decomposition of each sample of NCC under different heating rates of 5 , 10 , 20 and 40 ° C.min-1 . Through these data was possible to estimate the activation energy involved in the thermal decomposition process by applying kinetic method ASTM E 1641 , and the kinetic method of Kissinger . / A aplicação de nanocristais de celulose (NCC) como agente de reforço para matrizes poliméricas tem atraído considerável atenção, pois os nanocompósitos baseados em NC geralmente exibem propriedades térmicas, mecânicas e de barreira superiores em relação ao polímero puro ou compósitos convencionais, e adicionalmente oferecem benefícios ambientais. Tendo em vista a utilização desses NCC como agente de reforço para matrizes poliméricas, a estabilidade térmica destes cristais é um fator chave para que os mesmos possam ser usados como materiais de reforço eficazes, uma vez que as temperaturas de processamento de termoplásticos muitas vezes excede os 200°C. Neste trabalho foram extraídos NCC de diferentes fontes, celulose de manga purificada (CP), celulose de polpa Kraft de eucalipto (PK) e celofane (CEL), através de hidrolise ácida com H2SO4 e HCl. As composições químicas dos CP, PK e CEL utilizadas na hidrólise foram determinadas quanto aos teores de -celulose, holocelulose, hemicelulose, lignina e cinzas. Todos os NCC foram caracterizados através de análise elementar (C,H,N,S), difração de raios-x, microscopia de força atômica (AFM) e análise termogravimétrica (TGA). Através das análises termogravimétricas, foi realizado o estudo cinético de degradação térmica dos NCC, onde foi possível se determinar a conversão ( da decomposição térmica para todas as amostras de nanocristais de celulose. E sob diferentes taxas de aquecimentos 5, 10, 20 e 40°C.min-1. Através desses dados pôde-se estimar a energia de ativação envolvida no processo de decomposição térmica aplicando-se os métodos cinéticos ASTM E 1641 e o método cinético de Kissinger. / Mestre em Química

No desenvolvimento deste estudo avaliou-se o comportamento térmico do bagaço de cana-de-açúcar, dois carvões minerais (CE4500 e PSOC1451), e suas misturas (75%carvão/25%bagaço) nas seguintes atmosferas: 80%N2/20%O2 (combustão convencional), 80%CO2/20%O2 (simulando oxi-combustão), 100% CO2, 100% N2 e 100% O2. Por meio da caracterização físico-química dos materiais e da análise térmica foram avaliados os perfis de decomposição térmica dos materiais, eventos entálpicos, determinação da energia de ativação, a influência da atmosfera na decomposição, emissões de SO2, CO2, NO e CO, a capacidade de queima, os resíduos e o efeito de sinergismo. As principais técnicas empregadas neste estudo foram análise elementar, análise termogravimétrica (TGA), análise térmica diferencial (DTA) e um reator tubular de queda livre (DTF - Drop Tube Furnace), desenvolvido no decorrer deste estudo. Os resultados termogravimétricos mostraram que a decomposição térmica do bagaço ocorre com maiores taxas de reação e picos exotérmicos mais intensos comparados aos carvões. Tal comportamento é atribuído ao alto teor de material volátil presente no bagaço. Esta característica do bagaço também promove a obtenção de menores valores de energia de ativação (Eα) na etapa inicial da decomposição térmica (30 kJ mol-1 comparados a 126 kJ mol-1 para o CE 4500 e 100 kJ mol-1 para o PSOC 1451), que confirmam a maior facilidade no processo de ignição do bagaço em relação aos carvões. Em relação ao efeito da atmosfera, quando N2 é substituído por CO2 observa-se aumento de 6 vezes nos valores iniciais de energia de ativação para o bagaço de cana (E inicial passa de 30 kJ mol-1 para 170 kJ mol-1). Contudo, efeito contrário é observado para os carvões (E inicial diminui de 200 para 130 kJ mol-1 para o CE 4500 e de 100 para 75 kJ mol-1 para o PSOC 1451). A diferença de comportamento do bagaço em relação aos carvões é atribuída ao mecanismo de difusão do material volátil durante a decomposição térmica considerando a escala de análise aplicada. Os resultados obtidos em DTF mostraram que, quando o processo ocorre sob atmosfera contendo CO2 (típica de oxi-combustão), para todos os materiais as emissões de NO são até 34% inferiores àquelas feitas sob atmosfera de ar. Entretanto, efeito contrário é observado para as emissões de CO. Em relação às emissões de SO2, nenhuma tendência pode ser observada. O rendimento da queima do bagaço foi 50% superior em atmosfera de ar devido à facilidade da ignição nesta atmosfera. Para o carvão CE 4500, os maiores rendimentos de queima foram obtidos em atmosferas contendo CO2 (8% a menos de material não queimado comparado aos resíduos obtidos em ar sintético). Em relação ao estudo de sinergismo, as técnicas de análise utilizadas no desenvolvimento desta pesquisa não apresentaram embasamento suficiente para comprovar positivamente a interação entre os materiais. Para ambas as misturas também não se evidenciaram alterações de comportamento em função da atmosfera utilizada. / This study evaluates the thermal behavior of sugar cane bagasse, two bituminous coals (CE 4500 and PSOC 1451) and blends composed of 75%coal/25%bagasse under 80%N2/20%O2 (conventional combustion), 80%CO2/20%O2 (oxy-fuel combustion simulation), 100% CO2, 100% N2 and 100% O2 atmospheres. The evaluations were conducted by means of ultimate analysis, Thermogravimetric analysis (TGA), Differential Thermal Analysis (DTA) and DTF (developed in this study) – which includes thermal decomposition profiles, determination of activation energy, evaluation of atmosphere and interaction effects on the blends, evaluation of SO2, CO2, NO e CO emissions, burning yield and residues analysis. The results show the high content of volatile matter in the bagasse leads to a high rate reaction during the thermal decomposition of the material in comparison to coals, hence, a higher intensity of exothermic events. Such a characteristic of the bagasse also influences the first step of the thermal decomposition and leads to a lower activation energy (Eα) (30 kJ mol-1) in comparison with the values obtained for coals (126 kJ mol-1 for CE 4500 and 100 kJ mol-1 for PSOC 1451). When N2 was replaced by CO2, the activation values obtained in the first step of the bagasse decomposition increased from 30 kJmol-1 to 170 kJ mol-1. However, an opposite effect was observed for both coals (E decreased from 200 to 130 kJ mol-1 for CE 4500 and from 100 to 75 kJ mol-1 for PSOC 1451). The difference was attributed to the volatile mechanism of the matter diffusivity during the thermal decomposition. The atmospheres applied did not affect the thermal decomposition behavior of the blends. Regarding the DTF results, under CO2 atmosphere, all materials showed lower NO emissions in comparison to air atmosphere - NO emissions were up to 34% lower than those in air atmosphere. However, the CO emissions were lower in the CO2 environment. No trend could be observed regarding SO2 emissions. The bagasse burning efficiency was 50% higher in air environment due to the easy ignition under such atmosphere. For coals, higher burning efficiency and lower activation values were achieved under CO2 atmosphere (8% higher). Regarding the study of synergism, the analytical techniques applied did not confirm the interaction between the materials.

Submitted by Sandra Pereira (srpereira@ufrrj.br) on 2017-06-27T14:38:40Z No. of bitstreams: 1 2010 - Adierson Gilvani Ebeling.pdf: 3744657 bytes, checksum: 0458139e287a489573818b522e4c02de (MD5) / Made available in DSpace on 2017-06-27T14:38:40Z (GMT). No. of bitstreams: 1 2010 - Adierson Gilvani Ebeling.pdf: 3744657 bytes, checksum: 0458139e287a489573818b522e4c02de (MD5) Previous issue date: 2010-08-27 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico, CNPq, Brasil. / The Histosols have a small geographic extension in the Brazilian territory; however, they are intensively used in family agriculture systems and have a great environmental importance. The drainage of Histosols leads to the subsidence process and other changes in the soil organic matter (SOM), with consequences in their characteristics and potential. The nature of humic substances (HSs) is determinant in the alterations of the Histosols. The characterization of the HSs allows the understanding of processes of SOM transformation in the Histosols, and their environmental impact. The objectives of this study were: to characterize Histosols from different environments and land usage intensity; and to evaluate alterations in humic fractions of SOM, by using elemental composition analyses, spectroscopic, thermal degradation, and nuclear magnetic resonance (NMR) techniques. The study was developed in eight Histosols, from the States of Rio de Janeiro, Maranh?o and Paran?, in Brazil. Their chemical properties: total organic carbon (TOC), pH, sum of bases (SB), H+, Al3+, cation exchange capacity (CEC), and V%; and physical properties: bulk density (BD), MR, MM, and OMD, were evaluated. Also, the quantitative fractionating of the HSs: fulvic acid (C-FAF), humic acid (CHAF), and humin (C-HUM), and C-FAH/C-FAF relations, C-EA/C-HUM (C-EA = C-FAF + C-FAH). The humic acids were extracted using the method of the International Humic Substances Society (IHSS), and evaluated by different techniques. The chemical attributes varied with the intensity of burning and agricultural usage. Though, in general, the Histosols presented low natural fertility, and it was related to the humic acid fraction (high ratio CFAH/ C-FAF). Amongst the SOM fractions the HUM predominated, with an average value of 59.98% of total carbon determined by the CHN; followed by the FAH. The C-FAH/C-FAF ratio diminished with the increase of agriculture usage intensity. The results of the TGI (Thermal Gravimetric Index) suggested strong resistance to thermal degradation of majority of the organic horizons. The elemental composition (%C, %H, %N, %O) of the humic acids showed large amplitude of variation between the horizons, but no pattern was observed between the Histosols. The increase of carbon content, the high values of TGI, and the reduction of oxygen content in the humic acids (HA) might explain the high thermal decomposition resistance found in the HA extracted form the Histosols. A correlation between H/C and TGI was observed, where the lower values of H/C were related to the highest resistance of the humic acids to thermal degradation. The spectroscopic and NMR techniques allowed characterizing compounds and groups of substances in the HA, showing the great potential of these tools in studies of HS from Histosols. The multivariate methods allowed a combined analysis of techniques applied in the study, showing a group of labile and recalcitrance materials in the soils. The results, in general, indicated the fragility of the Histosols areas, in terms of agricultural management and the formation environment. Their importance for the environment should be priority in comparison to agricultural usage, mainly due to their relevant part in the aquifers preservation. / Os Organossolos t?m pequena representatividade geogr?fica no Brasil, entretanto, s?o utilizados intensamente em modelos de agricultura familiar e t?m grande import?ncia ambiental. Por?m, a sua drenagem conduz ao processo de subsid?ncia e outras modifica??es na mat?ria org?nica do solo (MOS), com implica??es nas caracter?sticas dos Organossolos e em sua potencialidade. A natureza das subst?ncias h?micas (SHs) ? determinante nessas altera??es nos Organossolos. A caracteriza??o das SHs permite a compreens?o dos processos de transforma??o da MOS nos Organossolos e seu impacto no ambiente. Os objetivos deste trabalho foram: caracterizar Organossolos em v?rios ambientes e intensidade de uso agr?cola e avaliar altera??es nas fra??es humificadas da MO, atrav?s de t?cnicas de an?lise da composi??o elementar, espectrosc?picas, termodegradativas e de resson?ncia magn?tica nuclear (RMN). Foram estudados oito perfis de solos, nos Estados do Rio de Janeiro, Maranh?o e Paran?. Foram avaliadas as suas propriedades qu?micas: carbono org?nico total (COT), pH, soma de bases (SB), H+, Al3+, CTC e V%; e propriedades f?sicas: densidade do solo (Ds), RM, MM e DMO. Al?m do fracionamento quantitativo das SHs: ?cidos f?lvicos (C-FAF), ?cidos h?micos (C-FAH) e humina (C-HUM), e rela??es C-FAH/C-FAF, C-EA/CHUM (C-EA = C-FAF + C-FAH). Os ?cidos h?micos (AH) foram extra?dos pelo m?todo da Sociedade Internacional de Subst?ncias H?micas (IHSS) e avaliados por distintas t?cnicas. Os atributos qu?micos variaram com o efeito das queimadas e da intensidade de uso agr?cola; por?m, em geral, os Organossolos apresentaram baixa fertilidade natural, a qual, em geral, esteve relacionada ? fra??o ?cido h?mico (maior raz?o C-FAH/C-FAF). Dentre as fra??es da MO, a HUM predominou, com valor m?dio de 59,98% do carbono total determinado pelo CHN, seguida da FAH. A rela??o C-FAH/C-FAF diminuiu a medida que o uso agr?cola ? intensificado. Os dados do ITG (?ndice Termogravim?trico) sugeriram forte resist?ncia ? termodegrada??o para a maioria dos horizontes org?nicos. A composi??o elementar (%C, %H, %N, %O) dos ?cidos h?micos apresentou grande amplitude entre os horizontes, por?m sem padr?o diferenciado entre os Organossolos. O aumento do conte?do de carbono, os altos valores de ITG e a diminui??o do conte?do de oxig?nio nos ?cidos h?micos podem explicar a maior resist?ncia a termodecomposi??o dos AH extra?dos dos Organossolos. Foi observada correla??o entre a raz?o H/C e o ITG, onde os menores valores de H/C estiveram relacionados a maior resist?ncia dos AH ? termodegrada??o. As t?cnicas espectrosc?picas e de RMN permitiram caracterizar compostos e grupamentos nos AH, demonstrando o potencial dessas ferramentas nos estudos de SHs provenientes de Organossolos. Os m?todos de an?lise multivariada permitiram uma avalia??o conjunta das t?cnicas utilizadas, mostrando um grupo de amostras l?beis e recalcitrantes nos solos. Os resultados encontrados, em geral, indicam a fragilidade das ?reas de Organossolos, em fun??o do manejo para agricultura e do seu ambiente de forma??o. A sua import?ncia em termos ambientais deveria ser priorizada em rela??o ao uso agr?cola, principalmente pelo papel relevante na preserva??o de aqu?feros.

[pt] Oxido de níquel e hematita nanoestruturadas foram sintetizadas a partir da decomposição térmica de nitrato de níquel hexahidratado e nitrato férrico nonahidratado respectivamente, na faixa de temperatura de 350-450°C com variações no tempo reacional. Os tamanhos de cristalito do NiO e Fe2O3 foram estimados a partir dos difractogramas de Difração de Raios-X (XRD) utilizando os software PowderCell e Topas. Foi observado que o tamanho de cristalito varia em função da temperatura de sínteses. O resultado mais significante foi observado nos cristalitos de NiO os quais aumentam de 31 nm (T=350°C, 3hr) a 98 nm (T=450°C, 5hr). Foram realizados estudos cinéticos da redução NiO e Fe2O3 por hidrogênio na faixa de temperatura de 250-600°C. Ligas ferroníquel nanoestruturadas com composições FexNi100-x (x = 25, 50, and 75 w%) têm sido preparadas com sucesso por decomposição térmica de nitratos (formação de óxidos) e posterior redução com hidrogênio a 700ºC (formação das ligas). As ligas Fe-Ni, caracterizadas por difração de raios-X mostraram tamanhos de cristalito da ordem de 25nm. A fase rica em Ni, liga Fe25Ni75, apresentou uma estrutura γ(FCC). A liga Fe50Ni50 apresentou a existência de uma estrutura tetragonal. A fase rica em Fe, liga Fe75Ni25, contém uma mistura de fases α(BCC) e γ(FCC). A coexistência das fases e atribuída à segregação de fases que acontece nestas ligas como resultado da difusão atômica. A partir dos resultados das medições magnéticas efetuadas a 300K, pode-se estabelecer que as ligas Fe-Ni nanoestruturadas tem um comportamento superparamagnético. / [en] Nickel oxide and hematite nanostructured were successfully prepared by thermal decomposition from nickel nitrate hexahydrate and ferric nitrate nonahydrate in the temperature range of 350-450°C with variation of the time. The average crystallite sizes of NiO and Fe2O3 were estimated from X-ray diffraction (XRD) peaks using the PowderCell and Topas software. We observed that the crystallite size changes as a function of synthesis temperature. The significant result was the large size of the resulting NiO crystallites, which increased from 31nm (T=350°C, 3hr) to 98nm (T=450°C, 5hr). Kinetic studies of the reduction of NiO and Fe2O3 by hydrogen in the temperature range 250-600°C have been investigated. Nanostructured Fe-Ni alloys with compositions FexNi100-x (x = 25, 50, and 75 w%) have been successively prepared by thermal decomposition from mixtures of nitrates (formation of oxides) and reduction by hydrogen at 700ºC (formation of alloys). The Fe-Ni alloys, characterized by X-ray diffraction show crystallites sizes about 25nm. The Nirich phase, Fe25Ni75 alloys show the existence of γ(FCC) phase. The Fe50Ni50 alloy show the existence of tetragonal phase. The Fe-rich phase, Fe75Ni25 alloy, contain a mixture of α(BCC) and γ(FCC) phases. The coexistence of these phases is attributed to phase segregation occurring in these alloys as a result of enhanced atomic diffusion. It was inferred from results of magnetic measurements at 300K, that nanostructured Fe-Ni alloys were in a superparamagnetic state.

Les oxydes mixtes d'uranium et de plutonium sont les matières premières privilégiées des combustibles nucléaires de nouvelles générations. Les mécanismes de leur élaboration par décomposition thermique d'oxalates mixtes, précurseurs de référence, font l'objet des présentes recherches, en vue d'une maîtrise plus aboutie des caractéristiques physico-chimiques du solide produit. La décomposition thermique de différents précurseurs oxalates en oxydes a donc été analysée expérimentalement sous atmosphères inerte et oxydante, les processus réactionnels ont été clarifiés, les paramètres thermodynamiques et cinétiques déterminés et des modèles physico-chimiques prédictifs ont été proposés. La méthodologie d'étude expérimentale de ce processus jusqu'à sa modélisation a tout d'abord été développée à l'aide de composés modèles à base de lanthanides, de complexité croissante. La conversion en oxyde des oxalates simples de Nd et Ce, comparée à celle de l'oxalate de Pu(III), a permis de cerner l'effet du redox du métal. Des oxalates doubles lanthanide-hydrazinium, par un comportement spécifique dû à leur structure cristallographique singulière, ont ensuite illustré de manière exacerbée l'importance des interactions gaz-gaz et solide-gaz en présence notamment de gaz réactifs azotés. La résolution globale des mécanismes de décomposition des oxalates mixtes d'actinides en oxydes a bénéficié ensuite d'une approche comparative des systèmes U-Ce, Th-Pu et U-Pu, compte tenu d'analogies structurales ciblées. Un mécanisme général en cinq étapes élémentaires principales a été proposé, associé à des données thermodynamiques et cinétiques. Ceci a notamment permis de simuler les diagrammes de spéciation de la phase solide suivant différentes programmations de température (linéaire ou de type double-four industriel), aussi bien pour le système simulant U-Ce utilisé dans les essais systématiques d'optimisation technologique du procédé que pour le système d'intérêt U-Pu. Enfin, une première ébauche de modèle « procédé » a été réalisée en considérant les phénomènes de transport associé à deux réactions-clés pour ces systèmes : l'étape de décomposition thermique de l'oxalate anhydre en oxyde et l'équilibre de Boudouard entre gaz carbonés. La réactivité du système et les phénomènes prépondérants concernant les flux de gaz de calcination dégagés et la formation de carbone élémentaire au sein d'un lit de poudre statique ont pu être simulés globalement / Mixed uranium-plutonium oxides are preferential raw materials for news generation nuclear fuels. The research project presented herein deals with their elaboration process by thermal decomposition of mixed oxalates, as reference precursors, in order to improve the physicochemical characteristics of the resulting product. The thermal decomposition of several oxalate precursors into oxides was thus experimentally studied under both inert and oxidizing atmospheres, the reaction mechanisms were determined, as well as the thermodynamics and kinetics, and predictive physicochemical models were proposed. The methodology of the study up to the modelling was first developed using lanthanide model compounds with increasing complexity. The conversion into oxides of simple Nd and Ce oxalates, compared with Pu(III) oxalate, allowed to understand the role of the metal cation redox properties. Double lanthanide-hydrazinium oxalates, displaying a specific behaviour due to their peculiar crystallographic structure, underlined the importance of gas-gas and solid-gas interactions. Then, the global resolution of the decomposition mechanisms of mixed actinide oxalates into oxides was carried out through a comparative approach of U-Ce, Th-Pu and U-Pu systems, given ... analogies. A general mechanism including five main steps was proposed, with the corresponding thermodynamic and kinetic parameters. This especially enabled to simulate the speciation diagrams of the solid phases according to different temperature programs (linear or double industrial oven) for the U-Ce surrogate system (used in systematic technological process optimisation tests) as well as for the U-Pu system of interest. Finally, a first attempt at process modelling was undertaken, taking into account transport phenomena associated with two key-reactions for these systems: the thermal decomposition of anhydrous oxalate into oxide and the Boudouard equilibrium between carbonaceous species. The overall system reactivity and the predominant phenomena concerning evolved gas fluxes and elemental carbon formation, within a static powder bed, were simulated

This diploma thesis deals with issues of fine and ultrafine particles formation during thermal decomposition and combustion of biomass. An introduction is devoted to a utilization of biomass as fuel. A following part describes the gas products emerging generally during combustion process. A current emission and air pollution situation in the Czech Republic as well as the health impacts of solid pollutants on human are also mentioned. Within an experimental measurement three basic factors that have impact on fine particles formation during combustion of beech wood (i. e. oxygen content in combustion atmosphere, type of the sample and size of the sample) were thoroughly analyzed. Attention was paid to a progress of thermal decomposition and combustion of sample with respect to the particles formation. Finally, a measurement of fine particles amount was accomplished in a real boiler successively with four different biomass pellet types.

Multifunctional superparamagnetic iron oxide nanoparticles (SPIONs) coated with silica are a promising research field for lots of biomedical applications. The scope of this work is a preparation of SPIONs and coating them with silica to form core-shell structured nanoparticles for nanomedicine applications. SPIONs were synthesized by two chemical methods – co-precipitation and thermal decomposition of organic iron precursor. Prepared nanoparticles were carefully characterized –average size, size distribution, morphology, crystallinity, colloidal stability and magnetic properties were studied. After comparing SPIONs synthetized by two routes the most suitable method for biomedical applicable nanoparticles preparation is determined. The nanomedicine requires nanoparticles of the highest quality. The next step was coating SPIONs with silica shell. For this purpose inverse microemulsion method was chosen. TEOS was used as a silica precursor. Mean size, size distribution, magnetic properties, structure of silica shell were studied.