Submitted by Milena Rubi (milenarubi@ufscar.br) on 2017-08-09T12:48:03Z No. of bitstreams: 1 NAKASHIMA_Gabriela_2016.pdf: 18948386 bytes, checksum: c4adf2165784091a5371108a8c2bd529 (MD5) / Approved for entry into archive by Milena Rubi (milenarubi@ufscar.br) on 2017-08-09T12:48:12Z (GMT) No. of bitstreams: 1 NAKASHIMA_Gabriela_2016.pdf: 18948386 bytes, checksum: c4adf2165784091a5371108a8c2bd529 (MD5) / Approved for entry into archive by Milena Rubi (milenarubi@ufscar.br) on 2017-08-09T12:48:18Z (GMT) No. of bitstreams: 1 NAKASHIMA_Gabriela_2016.pdf: 18948386 bytes, checksum: c4adf2165784091a5371108a8c2bd529 (MD5) / Made available in DSpace on 2017-08-09T12:48:26Z (GMT). No. of bitstreams: 1 NAKASHIMA_Gabriela_2016.pdf: 18948386 bytes, checksum: c4adf2165784091a5371108a8c2bd529 (MD5) Previous issue date: 2016-04-29 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / In the sugarcane plantation it was common to use fire to facilitate the cutting and harvesting of sugarcane. However, Law 11,241 / 02 in São Paulo State provides the gradual elimination of this straw burning of sugarcane. The largest producer of sugarcane in Brazil is the São Paulo State, which has about 4.7 million hectares of planted area. It is estimated that one hectare produces about 14 tons of trash. Therefore, the mills have been trying to incorporate this trash in burning with the bagasse for power generation. However, high concentrations of mineral impurities are impossible its use for energy purposes. The aim of the study was to investigate the influence of storage time and particle size in the physicochemical characterization of the sugarcane trash. It was used the sugarcane trash inside and outside of the bale collected at different storage time (0, 1 and 2 years). The collected material was separated into four different particle sizes (> 0.420mm, 0.250-0.420mm, < 0.250mm and mix). The analyzes involved particle size distribution, proximate analysis, the high heating value (HHV), the chemical analysis of the components of the ashes, the images in the Scanning Electron Microscope (SEM), the Klason lignin content, the holocellulose content and extractives. There were variations in the results of the ash content with different particle sizes. It was observed a higher concentration of mineral impurities in smaller particles (< 0.250mm). The HHV varied from 15.9 to 18.3 MJ.kg-1 and showed no statistical difference for the treatments. The results indicate that the sugarcane trash presents problems related to mineral impurities which constrain its use as a solid fuel in the industry. The particle size interferes in their physicochemical characteristics. The trash can be stored in field and the time storage did not affect the quality for use as solid biofuel. / No manejo da cana-de-açúcar era comum a utilização do fogo para facilitar o corte e colheita da cana. No entanto, a Lei 11.241/02 do estado de São Paulo prevê a eliminação gradual da queima da palha da cana-de-açúcar. O maior produtor de cana-de-açúcar do Brasil é o estado de São Paulo, que possui aproximadamente 4,7 milhões de hectares de área plantada. É estimado que 1 hectare produza cerca de 14 toneladas de palha. Logo, as usinas vêm tentando incorporar esta palha na queima para geração de energia, juntamente com o bagaço. Porém, as altas concentrações de impurezas minerais estão impossibilitando seu uso para fins energéticos. O trabalho teve como objetivo o estudo da influência do tempo de estocagem e da granulometria na caracterização físico-química do palhiço da cana-de-açúcar. Foi utilizado o palhiço de canade-açúcar da superfície e do interior do fardo coletados em diferentes períodos de estocagem, 0, 1 e 2 anos. O material coletado foi separado em 4 granulometrias diferentes (> 0,420mm, 0,250-0,420mm, < 0,250mm e mix). As análises realizadas foram a distribuição granulométrica, a análise imediata, o poder calorífico superior (PCS), a análise química dos componentes das cinzas, as imagens no Microscópio Eletrônico de Varredura (MEV), o teor de lignina Klason, a holocelulose e os extrativos. Houve variações nos resultados do teor de cinzas com as diferentes granulometrias. Observou-se maior concentração de impurezas minerais nas partículas mais finas (< 0,250mm). O PCS variou entre 15,9 a 18,3 MJ.kg-1 e não apresentou diferença estatística para os tratamentos. Os resultados indicam que a palha de cana-de-açúcar apresenta problemas relacionados às impurezas minerais, que dificultam e restringem seu uso como combustível sólido na indústria. A granulometria da palha interferiu nas suas características físico-químicas. O palhiço pode ser estocado no campo e o tempo de estocagem não interferiu na qualidade para o uso como combustível sólido.

The objectives of this project were to synthesise semi-conducting ceramic nanoparticles including zinc oxide (ZnO) and aluminium doped zinc oxide (AZO) through a wet chemistry route to obtain nanoparticles with a controlled size and morphology. Wet chemistry methods (co-precipitation method and hydrothermal method) were used to synthesise ZnO and AZO particles. In the synthesis, various compounds and morphologies were synthesised. ZnO, Zn(OH)2 and unknown phases were co-precipitated, with only ZnO obtained following hydrothermal treatment. Morphologies ranging from platelets, flower-like, nanorods and microflowers were obtained. Particle sizes as small as 11 nm were characterised. Nanorod and nanosphere AZO particles were also synthesised with the results indicated the average grain size decreasing with increasing Al atomic content. Three orthogonal arrays were carried out to investigate the effects of the reaction parameters on the size and morphology of ZnO particles. The applicability of the orthogonal array was successful, with the optimum parameters of both hydrothermal experiments showing an increase in aspect ratio. The L/D ratio of ZnO nanorods obtained in the confirmation experiment increased to 9.4 which was larger than the ZnO synthesised using other reaction conditions (1.0 8.0). Scanning electron microscopy, transmission electron microscopy and X-ray diffraction were used to characterise the properties of the obtained particles. Morphology, crystallinity and particle size were all characterised.

Made available in DSpace on 2016-06-21T13:45:02Z (GMT). No. of bitstreams: 2 9.pdf: 5002800 bytes, checksum: 1aab555cfe6db1a0cf1577ab298c8017 (MD5) license.txt: 1748 bytes, checksum: 8a4605be74aa9ea9d79846c1fba20a33 (MD5) Previous issue date: 2014 / Made available in DSpace on 2016-07-05T22:38:04Z (GMT). No. of bitstreams: 3 9.pdf.txt: 252589 bytes, checksum: b070d500ec1baafb988fc3fbf27085c1 (MD5) license.txt: 1748 bytes, checksum: 8a4605be74aa9ea9d79846c1fba20a33 (MD5) 9.pdf: 5002800 bytes, checksum: 1aab555cfe6db1a0cf1577ab298c8017 (MD5) Previous issue date: 2014 / Fundação Oswaldo Cruz. Instituto de Tecnologia em Fármacos/Farmanguinhos. Rio de Janeiro, RJ, Brasil. / O escalonamento no processo de fabricação de comprimidos é um processo complexo e ainda bastante empírico, feito por método de tentativas e erros, cujos desafios são ainda maiores quando trata-se de formulação obtida por granulação úmida. Este trabalho realizou a transposição de escala de uma formulação de comprimidos revestidos contendo diclofenaco de sódio, fármaco de ação antiinflamatória,não esteroide e inibidor não seletivo das COX 1 e 2, avaliando os fatores relevantes para a obtenção tanto de uma formulação robusta, no que diz respeito ao processo de escalonamento em si, quanto de um medicamento que atendesse às exigências legais necessárias ao registro junto ao órgão regulador.Como resultado, o medicamento originário da formulação proposta apresentou-se aprovado em todos os ensaios exigidos, inclusive mostrando-se bioequivalente ao de referência. Este resultado ratificou a importância dos trabalhos preliminares,como a caracterização do ativo e os estudos referentes aos parâmetros a serem observados na transposição de escala. Na caracterização, as análises mostraram que a forma polimórfica do diclofenaco de sódio utilizado na formulação era a anidra,forma mais solúvel do fármaco; nas etapas de transposição de escala, identificou-se problemas com a alteração dos tempos de mistura do lote experimental para o lote piloto, pois não obteve-se uma boa compressibilidade para o lote piloto. Foi verificada, nas análises do granulado, uma diferença de granulometria que poderia justificar a diferença de desempenho entre os dois lotes. Um novo piloto foi manipulado, com a manutenção dos tempos de mistura do lote experimental, sendo que, dessa forma, os resultados satisfatórios do referido lote experimental foram reproduzidos para o segundo piloto, tanto em processabilidade quanto na avaliação granulométrica e demais ensaios. / Scaling up in the tabletting process is still a rather complex and empirical process carried out by trial and error methods, whose challenges are even greater when the formulation is obtained through wet granulation. Through this work, the development of large-scale production of a formulation of coated tablets containing diclofenac sodium, an anti-inflammatory drug, non-steroidal and non-selective inhibitor of COX 1 and 2, was conducted, evaluating the relevant factors for obtaining both a robust formulation with regard to the scale-up process itself and a drug which meets the legal requirements necessary for registration with the regulatory body. As a result, the product originating from the proposed formulation passed all of the required tests, and it was also proven to be bioequivalent to the reference drug. This result confirmed the importance of preliminary work, such as the characterization of active and studies concerning the parameters to be observed in the development of largescale production. In the characterization, the analysis showed that the polymorphic form of diclofenac sodium used in formulating was the anhydrous one, the more soluble form of the drug. In the steps of the development of large-scale production, there were problems with the alteration of the mixing times from the experimental batch to the pilot batch, as there was no good compressibility for the pilot batch. In the analyzes of the granulate, a difference of particle size was identified. It could explain the difference in performance between the two batches. Therefore, a new pilot batch was manipulated, with the maintenance of the mixing times of the experimental batch, and thus satisfactory results of the experimental batch were reproduced for the second pilot batch, regarding processability, particle assessment and other tests.

Made available in DSpace on 2016-07-01T11:59:26Z (GMT). No. of bitstreams: 2 license.txt: 1748 bytes, checksum: 8a4605be74aa9ea9d79846c1fba20a33 (MD5) 1.pdf: 7298045 bytes, checksum: 81f5fe7a39c309b83b7b15679d38d8b6 (MD5) Previous issue date: 2014 / Made available in DSpace on 2016-07-21T14:39:33Z (GMT). No. of bitstreams: 2 1.pdf: 7298045 bytes, checksum: 81f5fe7a39c309b83b7b15679d38d8b6 (MD5) license.txt: 1748 bytes, checksum: 8a4605be74aa9ea9d79846c1fba20a33 (MD5) Previous issue date: 2014 / Fundação Oswaldo Cruz. Instituto de Tecnologia em Fármacos/Farmanguinhos. Rio de Janeiro, RJ, Brasil. / A Etionamida (ETA) é um fármaco usado no tratamento da tuberculose pulmonar e extrapulmonar, junto com outros tuberculostáticos, nos casos de falência de tratamentos, resistência ou intolerância a outros fármacos, ou abandono de tratamento. A ETA está descrita na literatura como praticamente insolúvel em água e possui rápida absorção por via oral, o que sugere ser um fármaco de classe II do sistema de classificação biofarmacêutica (SCB), ou seja, baixa solubilidade e alta permeabilidade. Para estes fármacos, é importante o conhecimento dos fatores físicos que influenciam na sua dissolução a partir do produto final, além de se investigar condições para ensaios de perfis de dissolução que possam discriminá-los, isoladamente ou em formulações, com o objetivo de se obter um produto final elegível para um estudo de bioequivalência frente ao medicamento de referência. Foi realizado estudo de solubilidade em HCl 0,1 N, tampão acetato pH 4,5 e tampão fosfato pH 6,8, com amostra de ETA obtida no mercado. Estes estudos demonstraram que a ETA possui alta solubilidade em HCl 0,1 N e baixa solubilidade em tampão acetato pH 4,5 e tampão fosfato pH 6,8, considerando-se o critério de solubilidade do SCB, sugerindo que estes últimos meios seriam mais discriminativos para estudos de perfil de dissolução. O tamanho de partícula da ETA foi reduzido utilizando-se os processos de moagem (ETA-MOÍDA) e micronização (ETA-MICRO). As amostras de ETA, ETA-MOÍDA e ETA-MICRO, foram avaliadas quanto suas características de dissolução (molhabilidade, dispersão e intrínseca), físicas (distribuição granulométrica, microscopia, fluidez, DSC, TGA, DRXP, FTIR e FTNIR) e físico-químicas (teor, pH, umidade e substâncias relacionadas), além de serem utilizadas em formulações de núcleos de comprimidos revestidos produzidos pelos processos de compressão direta e granulação úmida. Os processos de moagem e micronização impactaram em alterações na distribuição granulométrica, morfologia dos cristais, fluidez e dissolução da ETA, porém não resultaram em alterações físico-químicas e de arranjo cristalino interno (polimofismo). As formulações fabricadas por granulação úmida apresentaram melhores características de fluidez, quando comparados os valores do índice de compressibilidade, razão de Hausner e fluxo por orifícios. Entretanto, as formulações fabricadas por compressão direta não apresentaram variação de peso durante o processo de compressão que indicasse fluidez inapropriada, com exceção daquela que utilizou ETAMICRO. Foram avaliados os perfis de dissolução das formulações frente ao medicamento de referência Trecator®, sendo evidenciado que a condição descrita nos compêndios oficiais, HCl 0,1 N, não foi suficiente para discriminá-las, sendo os perfis de dissolução considerados semelhantes quando calculados os fatores diferença (F1) e semelhança (F2). Quando alterado o meio de dissolução para tampão acetato pH 4,5 e tampão fosfato pH 6,8, foi possível evidenciar diferença entre as formulações, tendo aquelas que utilizaram ETA-MOÍDA maior semelhança frente ao Trecator®. Portanto, pôde-se concluir que para obtenção de formulações futuramente elegíveis a um estudo de bioequivalência, é necessário tamanho de partícula específico para a ETA, sugerindo-se d90 ~ 113,26 µm e d50 ~ 32,32 µm, sendo obtidas duas formulações candidatas a continuidade do desenvolvimento, não finalizado neste trabalho, uma fabricada por compressão direta e outra fabricada por granulação úmida. / The Ethionamide (ETA) is a drug used to treatment of pulmonary and extrapulmonary tuberculosis, together with other antituberculosis drugs in cases of failure of treatment, resistance or intolerance to other drugs, and abandonment of treatment. ETA is described as practically insoluble in water and has rapid oral absorption, which suggests that it a drug class II in the biopharmaceutical classification system (BCS), low solubility and high permeability. For these drugs, it is important to know the physical factors that influence in dissolution from the final product, and investigate conditions for the dissolution profiles that could discriminate them, alone or in formulations, with the goal of obtaining one product eligible for the bioequivalence study, compared to the reference product. Solubility studies were performed in 0.1 N HCl, acetate buffer pH 4.5 and phosphate buffer pH 6.8, with a sample of ETA obtained on the market. These studies have shown that the ETA has a high solubility in 0.1 N HCl and low solubility in acetate buffer pH 4.5 and phosphate buffer pH 6.8, considering the criteria of solubility of BCS, suggesting that these last mediums will be more discriminative for studies of the dissolution profile. The particle size of the ETA was reduced using the process of milling (ETA-MILLED) and micronization (ETA-MICRO). Samples of ETA, ETA-MILLED, and ETA-MICRO were evaluated for their dissolution characteristics (wetting, dispersing dissolution and intrinsic dissolution), physical properties (particle size distribution, microscopy, flow, DSC, TGA, XRPD, FTIR and FTNIR) and physicochemical characteristics (assay, pH, moisture and related substances), besides being used in formulations of cores coated tablets produced by direct compression and wet granulation. The processes of milling and micronization resulted in changes in particle size distribution, crystal morphology, flowability and dissolution of ETA, but did not result in physicochemical and internal crystalline arrangement (polymorphism) changes. The formulations manufactured by wet granulation showed better flow characteristics, when comparing the values of the compressibility index, Hausner ratio and flow through holes. However the formulations manufactured by direct compression did not show weight variation during the compression process to indicate inappropriate flowability, except that they used ETA-MICRO. The dissolution profiles front reference product (Trecator®) were evaluated and shown that the condition described in official compendium, 0.1 N HCl, was not enough to discriminate against them, and the dissolution profiles were similar when calculated factors difference (F1) and similarity (F2), for all formulations. When the dissolution medium was changed (acetate buffer pH 4.5 or phosphate buffer pH 6.8) was possible to identify differences between formulations and those used ETAMILLED resulted in a greater similarity to the front Trecator®. Therefore, we concluded that to obtain future formulations eligible to a bioequivalence study would require specific particle size for the ETA (d90 ~ d50 ~ 113.26 µm and 32.32 µm), and were obtained two formulations candidates to continue the development, one manufactured by direct compression and other manufactured by wet granulation.

L'objectif de ce travail est de mettre au point une technique de séparation de nanoparticules de milieux liquides. L'étude bibliographique a montré l'étendue potentielle du problème environnemental et a dégagé une problématique industrielle immédiate, celle du rejet de nanosilice. Des tests de séparation par flottation sont menés sans additif, en présence de AlCl3, de CTAB, et en tentant de modifier la charge de surface des bulles. Ces essais ne sont pas très concluants. La flottation a pu être observée, mais uniquement quand l'additif a conduit à la création de flocs qui ont, eux, été flottés. Les résultats des tests avec additifs ont montré que l'interaction entre l'hétérocoagulation (flottation) et l'homocoagulation est très importante, conduisant à l'étude de la coagulation sous l'effet d'AlCl3, puis du CTAB. Les résultats ont mis en évidence des mécanismes de coagulation complexes, car la taille des particules joue un rôle important. Pour chaque phénomène observé, un mécanisme a été proposé, en essayant de relier les observations à la modélisation des mécanismes d'agrégation. Du point de vue du procédé de séparation, la coagulation, suivie d'une sédimentation, permet de séparer les nanoparticules de silice avec une efficacité remarquable (diminution de 99% de la turbidité) / The objective of this work is to develop a technique for separating nanoparticles from liquid media. The literature has shown the potential hazard of nanoparticules and a large quantity of the nanosilica release has been entering in water resources. Tests flotation separations are carried out without additive, in the presence of AlCl3, CTAB, and trying to change the surface charge of the bubbles. These tests are not very conclusive. Flotation has been observed, but only when the additive has led to the formation of flocs which have themselves been floated. The results of tests with additives showed that the interaction between heterocoagulation (flotation) and homocoagulation is very important, leading to the study of coagulation under the effect of AlCl3 and CTAB. The results revealed complex mechanisms of coagulation, because the particle size plays an important role. For each observed phenomenon, a mechanism has been proposed, trying to link the observations to modeling mechanisms of aggregation. From the standpoint of the separation process, coagulation followed by sedimentation to separate the silica nanoparticles with remarkable efficiency (decrease of 99% of the turbidity)

O dióxido de titânio, TiO2, é o pigmento branco mais importante na indústria de tintas devido à sua capacidade de refletir o espectro da radiação solar nas regiões do visível e do infravermelho. Ao refletir os comprimentos de onda da região do visível, o observador percebe a cor branca. A região do infravermelho é percebida pelo ser humano na forma de calor e a radiação ao ser refletida pelo pigmento diminui o aquecimento da superfície pintada. Neste trabalho foram investigados os aspectos morfológicos do TiO2 e avaliado o seu impacto nas propriedades ópticas de tintas base água. Quatro tipos de TiO2 foram utilizados, um de tamanho nanométrico, dois pigmentos comercias com diferentes tamanhos de partículas e o quarto obtido da calcinação do pigmento nanométrico. A calcinação objetivou a alteração da estrutura cristalina da fase anatase para rutilo do TiO2 nanométrico. Os pigmentos e carga (CaCO3) utilizados foram caracterizados através de análises morfológicas (tamanho e formato das partículas, estrutura cristalina, área superficial), absorção de óleo e espectroscopia de refletância difusa (regiões do ultravioleta, visível e infravermelho próximo). Foram produzidas tintas com diferentes teores de pigmentos (5%, 10%, 15% e 20%) As tintas foram caracterizadas através dos seguintes ensaios: viscosidade, espessura do filme seco, determinação de cor e brilho e espectroscopia de refletância difusa. Constatou-se que as propriedades ópticas das tintas são fortemente dependentes do tamanho de partícula do pigmento TiO2. A refletância da região do visível (400 a 700 nm) apresentou valores ótimos nas tintas produzidas com 15 e 20% dos pigmentos comerciais com tamanho médio de partícula entre 140 e 600 nm, produzindo um filme branco com elevada opacidade. A tinta com TiO2 nanométrico (15 a 60 nm para as partículas unitárias) apresentou baixos valores de refletância difusa nas regiões do visível e do infravermelho. As tintas produzidas com TiO2 calcinado, com elevado tamanho de partícula, refletiram mais eficientemente a região do infravermelho (700 – 2500 nm). O tratamento térmico do TiO2 nanométrico resultou num pigmento com tamanho de partícula adequado para aplicação de tintas reflexivas ao calor. / Titanium dioxide, TiO2, is the most important white pigment in coating industry due to its ability to reflect solar radiation spectrum in visible and infrared regions. When TiO2 reflects the light wavelengths in the visible region, the observer perceives the white color. The infrared region is perceived by human being in the form of heat and when the radiation is reflected by pigment decreases the heating of painted surface. In this work, the morphological aspects of TiO2 were investigated and evaluated their impact on optical properties of waterborne paints. Four types of TiO2 were used; one nanosized pigment, two commercial pigments with different particle sizes and the last one was obtained from the calcination of nanoparticles pigments. The main objective of calcination was to alter the crystalline structure of anatase phase to rutile phase of nanometric TiO2. The pigments and filler used (CaCO3) were characterized by morphological analysis (particle size distribution and shape analysis, crystalline structure, surface area), oil absorption and diffuse reflectance spectroscopy (ultraviolet, visible and near-infrared regions) Paints were prepared using different pigments concentrations (5%, 10%, 15% and 20%). The followings tests were carried out to characterize the paints: viscosity, dry film thickness, color and brightness determination and diffuse reflectance spectroscopy. It was observed that the optical properties of the paints are strongly dependent on TiO2 pigment particle size. The reflectance of the visible region (400 to 700 nm) showed better results in the paints produced with 15% and 20% of commercial pigment whose average particle size ranges were between 140 and 600 nm, producing a white film with high opacity. The paint with nanosized TiO2 showed lowest values of diffuse reflectance in visible and infrared regions. The paints formulated with calcined TiO2, pigment showing higher particle sizes, reflected more efficiently the infrared region (700 to 2500 nm). Thermal treatment of nanometric TiO2 resulted in a pigment with particle size suitable for application of heat reflective paints.

Atualmente a decrescente disponibilidade de carvões de excelente qualidade e seus preços elevados levam as coquerias a utilizarem carvões mais baratos e consequentemente com propriedades inferiores. Ao mesmo tempo, ocorre à necessidade de se manter as elevadas especificações de qualidade exigidas para o coque pelos altos-fornos. Nesse contexto, independente da escolha dos carvões a serem utilizados, o controle granulométrico dos carvões e misturas, realizado durante a britagem, pode manter ou até melhorar a qualidade do coque a ser produzido. O presente estudo teve como objetivo geral avaliar de que forma as propriedades dos carvões variam em relação a suas principais frações granulométricas após a cominuição, e estudar qual o efeito de diferentes distribuições de tamanhos de partículas sobre as propriedades de coques produzidos em escala de laboratório. Para isso, dois carvões coqueificáveis individuais e uma mistura foram amostrados, separados em frações granulométricas e caracterizados. Após a caracterização das matérias-primas, foram confeccionados coques em escala de laboratório, a partir de diferentes misturas de granulometrias para os carvões individuais amostrados. A caracterização dos coques foi realizada segundo análise imediata, textura, reatividade ao CO2 em termobalança, resistência a frio em tambor tipo I e microresistência. Os resultados obtidos da caracterização das matérias-primas mostraram que a cominuição dos carvões leva a concentrações de cinzas, matéria volátil e composição maceral em diferentes frações granulométricas produzindo alterações nas propriedades coqueificantes das frações granulométricas. O resultado da caracterização dos coques mostrou que cada carvão apresenta uma distribuição de tamanhos de partículas mais adequada, que irá gerar um coque de boa qualidade. Em termos de reatividade ao CO2, uma grande quantidade de partículas finas nas misturas levou a um aumento da reatividade dos coques produzidos. Além disso, a resistência mecânica foi mínima para as misturas grosseiras, enquanto uma mistura mais fina tendeu a produzir coques de resistência mecânica superior. / Nowadays, the decreasing availability of excellent quality coals and their high prices lead cokemakers to use cheaper coals, consequently with inferior properties. At the same time, there is the need to maintain the high coke quality specifications required for the blast furnace. In this context, independent of the choice of coal to be used, the particle size control of coals and blends, created during crushing, can maintain or even improve the quality of coke to be produced. The present study had as main objective to assess how the properties of coals vary in relation to its particle size fractions after crushing, and study what effect different particle size distributions can cause on the properties of coke produced in laboratory scale. Thus, two individual coking coals and a blend were sampled, separated into particle size fractions and characterized. After the characterization of raw materials, cokes were made on a laboratory scale, from blends of different particle sizes for an individual coals. The characterizations of cokes were done by proximate analysis, texture, thermobalance CO2 reactivity, cold strength in a CSR drum, and microstrength. The results of the characterization of raw materials showed that the comminution of coal leads to concentrations of ash, volatile matter and macerals on different size fractions, causing changes in coking properties of size fractions. The results of the characterization of the cokes showed that each coal used has a more suitable particle size distribution which will generate a good quality coke. In terms of CO2 reactivity, a large amount of small particles in the blend led to an increase of coke reactivity. Furthermore, the mechanical strength of cokes was sharply affected by coarse particle, while a blend with high fine proportion produced a coke with high mechanical strength.

Made available in DSpace on 2014-06-11T19:33:24Z (GMT). No. of bitstreams: 0 Previous issue date: 2006-07-13Bitstream added on 2014-06-13T19:23:16Z : No. of bitstreams: 1 reis_w_dr_botfmvz.pdf: 184462 bytes, checksum: 5f5c576d65a1f089737e2cdacf2f315d (MD5) / Universidade Estadual Paulista (UNESP) / O objetivo deste trabalho foi de avaliar o efeito do processamento (moagem) em dois híbridos de milho (textura dura e mole), conservados secos e grãos úmidos ensilados, sobre a degradabilidade in situ da matéria seca (MS) e da proteína bruta (PB). Determinou-se a granulometria do material onde foi verificada diferença no DGM (Diâmetro Geométrico Médio) dos ingredientes processados, quando submetidos à moagem com diferentes peneiras. Foram utilizados três ovinos adultos fistulados no rúmen, distribuídos em um delineamento inteiramente casualizado, em esquema fatorial 2 x 2 x 3, sendo dois híbridos de milho (textura dura e mole), dois métodos de conservação e três formas de processamento (moído grosso, médio e fino), com cinco tempos de incubação (3, 6, 12, 24 e 48 horas). Os valores verificados para a fração A na SMM (silagem de milho mole) da MS foram superiores ao GMM (grão de milho mole) em todas as granulometrias. O processo de ensilagem aumentou a solubilidade da MS dos ingredientes, diminuindo a fração B quando comparado com o grão seco; disponibilizando mais facilmente para o ataque microbiano. Os valores referentes às frações DP e DE a 5%/h da proteína, foram maiores para SMM e GMM, apresentando maior desaparecimento quando avança o tempo de incubação. Para a MS o processo de ensilagem aumentou a degradabilidade ruminal da MS do milho com textura mole. O mesmo não se verifica com relação ao milho com textura dura. A taxa de fermentação (kd) mostra-se superior para SMM e GMM. O processo de ensilagem tem efeito positivo no desaparecimento da MS e PB quando se compara com o GMM. / The objective of this work was to evaluate the effect of the processing (grinding) in two corn hybrids (flint and dent) conserved, dry and humid grains, on the dry matter (DM) and crude protein (PB) degradability in situ. Was determined the material particle size and difference was verified in DGM (Medium Geometric Diameter) of the processed ingredients, when submitted to the grinding with different sieves. Three adult sheeps were used with rumen canulated, distributed in a compltely randomized design, using a factorial outline 2 x 2 x 3, being two corn hybrid (flint and dent), two conservation methods and three processing forms (whole, coarsely and finely ground), with five times of incubation (3, 6, 12, 24 and 48 hours). The values verified for the fraction A in SMM (silage of dent corn) of DM were superior to GMM (grain of dent corn) in all of the particles size. The ensiling process increased the DM solubility of the ingredients, reducing the fraction B when compared with the dry grain; making available more easily for the microbial attack. The values regarding the fractions DP and DE the 5%/hour of the protein, were larger for SMM and GMM, it presents a larger disappearance when it advances the incubation time. For DM show that the ensiling process has increased the DM degradability ruminal of the corn with soft texture. The same is not verified regarding the corn with flint texture. The fermentation rate (kd) is superior for SMM and GMM. The ensiling process has positive effect in the disappearance of DM and CP when it is compared with GMM.

abstract: Lithium ion batteries prepared with a ceramic separator, have proven to possess improved safety, reliability as well as performance characteristics when compared to those with polymer separators which are prone to thermal runaway. Purely inorganic separators are highly brittle and expensive. The electrode-supported ceramic separator permits thinner separators which are a lot more flexible in comparison. In this work, it was observed that not any α-alumina could be used by the blade coating process to get a good quality separator on Li4Ti5O12 (LTO) electrode. In this work specifically, the effect of particle size of α-alumina, on processability of slurry was investigated. The effect of the particle size variations on quality of separator formation was also studied. Most importantly, the effect of alumina particle size and its distribution on the performance of LTO/Li half cells is examined in detail. Large-sized particles were found to severely limit the ability to fabricate such separators. The α-alumina slurry was coated onto electrode substrate, leading to possible interaction between α-alumina and LTO substrate. The interaction between submicron sized particles of α-alumina with the substrate electrode pores, was found to affect the performance and the stability of the separator. Utilizing a bimodal distribution of submicron sized particles with micron sized particles of α-alumina to prepare the separator, improved cell performance was observed. Yet only a specific ratio of bimodal distribution achieved good results both in terms of separator formation and resulting cell performance. The interaction of α-alumina and binder in the separator, and its effect on the performance of substrate electrode was investigated, to understand the need for bimodal distribution of powder forming the separator. / Dissertation/Thesis / Masters Thesis Chemical Engineering 2017

Les particules en suspension transportées dans les réseaux hydrographiques résultent des processus de rivière et des apports depuis les versants. Nous avons étudié dans cette thèse la dynamique des tailles de particules le long du continuum versant-rivière afin d'apporter des éléments de réponse à la réflexion aujourd'hui menée sur les distances de transport et sur le concept de connectivité sédimentaire. Des observations de terrain sont menées à l'exutoire d'un bassin versant de tête (~20 km²). Elles mettent en évidence une corrélation positive entre débit liquide et taille des particules. L'établissement et la mise en oeuvre d'un protocole de mesure original montre que les particules sont agrégées. A cette échelle, les apports des versants semblent importants pour expliquer les variations de taille des particules. Des expériences de laboratoire utilisant un canal annulaire sont menées et indiquent qu'une partie de ces variations peut être attribuée à la désagrégation ou à la floculation des particules dans l'écoulement. Des variations de taille notables sont dues au type de sol. Elles sont moindres à la fin des évènements schématiques simulés en canal, suggérant que l'écoulement prend une part prépondérante pour expliquer les variations de taille des particules. Cet effet du type de sol a motivé l'étude des processus de versant, et en particulier ceux de la pluie. Des expériences de simulations de pluie menées en laboratoire (~1 m²) sur deux sols révèlent que l'augmentation de l'énergie cinétique de la pluie a tendance à générer des agrégats plus fins. Une paramétrisation du détachement par la pluie par fraction granulométrique est développée sur la base de ces expériences et implémentée au sein de deux modèles numériques d'érosion hydrique à base physique. Les simulations numériques confirment que cette tendance a des impacts sur les exports à l'échelle du versant. Enfin, des variations de granulométrie en lien avec l'énergie cinétique de la pluie sont perceptibles lors d'observations de terrain à l'échelle du versant (~ 100 m²), confirmant l'importance d'une description correcte du forçage pluviométrique. / The suspended particles of catchment networks are dependent on both river and hillslope erosion processes. During this thesis, the particle size dynamics was studied along this continuum in order to improve the understanding of particle delivery from hillslopes to the outlets of headwater catchments. Field measurements were conducted at the headwater catchment scale (~20 km²). The discharge displayed a positive correlation with the particle size. An original measurement protocol has been set up and it demonstrated that particles were mostly aggregated. The inputs from hillslopes were possibly involved in some of the variations of the measured particle size. Laboratory experiments carried out using an annular flume demonstrated that a part of these variations could be explained by disaggregation or flocculation within the flow. Important variations due to the soil type were observed. However, they were less pronounced in the falling limbs of the schematic flood events, suggesting that flow conditions progressively became more important than the soil signature. The latter encouraged the analysis of hillslope processes, among which a special attention was given to the rainfall effects. Rainfall simulation experiments (~1 m²) demonstrated for two soils that an increase in the rainfall kinetic energy resulted in smallest aggregates detached from the soil matrix. The importance of this mecanism at the hillslope scale (~ 100 m²) with regard to runoff selectivity was demonstrated developing a size-dependent detachment parametrisation included in two physically based numerical models. Finally, the effects of the rainfall kinetic energy on the particle size were observed during field measurements made at the plot scale as well, underlining the need to adequatly describe the rainfall forcing field at this scale.