A exata composição e a micromorfologia do esmalte de dentes decíduos ainda são pouco estudadas e conhecidas, e a literatura existente apresenta achados controversos. Os resultados de pesquisas realizadas em dentes permanentes são frequentemente extrapolados para dentes decíduos, sendo que a maioria dos trabalhos explora estes substratos de maneira isolada. É necessário, portanto, conhecer a composição e a estrutura do esmalte de dentes decíduos e determinar em quais aspectos este tecido realmente difere do esmalte de dentes permanentes. A comparação dos dois substratos é fundamental para que sejam estabelecidos protocolos preventivos e restauradores, bem como no desenvolvimento de materiais e técnicas específicos e efetivos para dentes decíduos e permanentes. Assim, o objetivo do presente estudo foi realizar uma análise comparativa in vitro do esmalte de dentes decíduos e permanentes, avaliando suas propriedades físicas e químicas. As propriedades químicas foram avaliadas por meio das análises de mapeamento de superfície do esmalte por Microfluorescência de Raios-X por Energia Dispersiva (&mu;FRX) (n=10) e Espectroscopia no Infravermelho por Transformada de Fourier (FTIR) (n=10). As propriedades físicas analisadas foram Permeabilidade (n=12), Microdureza (n=12), Radiodensidade (n=10) e Resistência Coesiva (n=15). Nos testes de &mu;EDX e FTIR, os dados da amostra não apresentaram distribuição normal, empregando-se o teste não paramétrico de Mann-Whitney. Para os demais testes, a distribuição apresentou-se normal e homogênea. Assim, na análise de Permeabilidade os dados foram submetidos à ANOVA a um critério: tipo de substrato (p<0,05) e na análise de Microtração os dados foram submetidos à ANOVA a dois critérios: tipo de substrato e direção dos prismas (p<0,05). Para os dados de Radiodensidade e Microdureza, foi utilizado o teste t de Student para comparação entre as médias. Considerando-se as limitações de um estudo in vitro, os achados demonstraram que em relação às propriedades físicas, o esmalte de dentes decíduos apresentou maior permeabilidade, maior radiodensidade, menor resistência coesiva e microdureza quando comparado ao esmalte de dentes permanentes. Para as propriedades químicas avaliadas, 20 constatou-se que o conteúdo em peso de cálcio (%), fósforo (%) e da proporção Ca/P (%) bem como os conteúdos de carbonato e água foram semelhantes entre os dois substratos avaliados. Portanto, as propriedades físicas do esmalte de dentes decíduos apresentaram características distintas em relação ao esmalte de dentes permanentes, apesar da semelhança nas propriedades químicas analisadas. / There is still little research and information on the precise composition and the micromorphology of the enamel of deciduous teeth, and the existing literature reveals controversial findings. The results of studies in permanent teeth are frequently extrapolated to deciduous teeth, and the majority of works explores these substrates alone. It is thus necessary to know the composition and structure of the enamel of deciduous teeth and determine in which ways this tissue actually differs from the enamel of permanent teeth. Comparison of these substrates under different aspects is fundamental to establish preventive and restorative protocols, as well as materials and techniques that are specific and effective for deciduous and permanent teeth. Therefore, the aim of the present in vitro study was to perform a comparative analysis of the enamel of deciduous and permanent teeth by evaluating its physical and chemical properties. Chemical analysis comprised enamel surface mapping by Energy Dispersive X-ray Microfluorescence (&mu;FRX) (n=10) and Fourier Transform Infrared Spectroscopy (FTIR) (n=10). For the physical analysis, Permeability (n=12), Microhardness (n=12), Radiodensity (n=10) and Ultimate Tensile Strength (n=15) tests were performed. Data distribution and homogeneity were analyzed. In the &mu;FRX and FTIR data distribution was not normal and the Mann-Whitney non-parametric test was used for statistical analysis. For the other tests, data distribution was normal and homogenous. Thus, one-way analysis of variance (type of substrate) was used for the Permeability; twoway analysis of variance (type of substrate and depth) was used for the Microtensile Bond Strength test (p<0.05); data from Radiodensity and Microhardness test were analyzed using the Students t-test. Considering the limitations of an in vitro investigation, the findings revealed that with respect to the physical properties, the enamel of deciduous teeth presented greater permeability and radiodensity and lower ultimate bond strength and microhardness of substrate when compared with the enamel of permanent teeth. Regarding the chemical properties, the amount of calcium, phosphorus and Ca/P (wt%) as well as the amount of carbonate and water was similar for both types of substrates evaluated. 22 Therefore, the enamel of deciduous teeth presented different physical properties compared to the permanent teeth, despite the similarity in chemical properties analyzed.

O presente estudo teve por objetivo determinar as propriedades tecnológicas da madeira de paricá, obtida de árvores de Schizolobium amazonicum Huber ex Ducke aos 14 anos provenientes de duas diferentes áreas de florestas plantadas no estado de Rondônia. Foi amostrado a campo um total de oito árvores, sendo quatro de cada um dos plantios, nos municípios de Rolim de Moura e Parecis. De cada árvore foram obtidas duas toras subsequentes com comprimento de 2,0 m, definidas após a extração de discos removidos ao longo de três posições longitudinais, que foram empregados na determinação da variação radial das características de fibras e vasos e composição química da madeira, e na variação longitudinal da densidade básica e na massa específica aparente, esta última por meio da densitometria de raios x. Da primeira tora foi determinado o rendimento em laminação e das lâminas geradas, produzidos painéis compensados que foram avaliados quanto ao desempenho físico-mecânico. Da segunda tora amostrada, foram confeccionados corpos de prova das porções próximas à medula e casca para a caracterização mecânica da madeira sólida. Os resultados obtidos mostraram que tanto o comprimento das fibras como a espessura de parede celular tenderam a um aumento gradativo, com estabilização na posição a 75% do raio em ambos os plantios amostrados. Ao longo da distância radial a madeira proveniente da área de solo de textura argilosa (Rolim de Moura) tendeu sempre a apresentar valores mais elevados de diâmetro de vasos e área ocupada em relação à madeira da área de solo de textura média e de maior compactação (Parecis), resultando em efeito da proveniência. O teor de cinzas diferiu-se entre as duas áreas, sendo maior na madeira proveniente de Parecis. A densidade básica e massa específica aparente não sofreram influência da proveniência, e mostraram tendência de redução ao longo da porção longitudinal avaliada. Houve influência somente da posição radial nas propriedades mecânicas da madeira, com a maior diferença para o MOE em flexão estática. O rendimento efetivo da laminação das toras foi próximo de 72%, e as propriedades mecânicas dos painéis compensados produzidos tornam os mesmos aptos para aplicação estrutural e naval, segundo normatização relativa a este tipo de produto. Tomando-se por base a variação radial dos parâmetros de comprimento e espessura de parede das fibras, já se observa a presença de madeira adulta no S. amazonicum aos 14 anos nas condições de crescimento avaliadas. Embora os coeficientes indicativos de qualidade das fibras comprovem o potencial da espécie na produção de polpa e papel na idade considerada, o elevado teor de extrativos deve ser considerado nos programas de melhoramento genético. Com exceção da resistência ao cisalhamento, a madeira de paricá aos 14 anos apresentou um incremento nos valores de propriedades mecânicas em relação a outros estudos com esta espécie, principalmente no que se refere à rigidez de sua madeira ao esforço de flexão estática. O rendimento encontrado na laminação e as propriedades dos painéis confirmam a aptidão da espécie na manufatura de compensados. / This research aimed to determine the technological properties of the paricá wood obtained from Schizolobium amazonicum Huber ex Ducke trees at age 14 from two different areas of planted forests in Rondônia, Brasil. It was sampled in field a total of eight trees, being four of each one of the plantations in the cities of Rolim de Moura and Parecis. Two subsequent logs with a length of 2.0 m were obtained from each tree defined after the extraction of the disks removed along of three longitudinal positions, which were used for determining the radial variation characteristics of the fibers and vessels and chemical composition of the wood, in the longitudinal variation of the basic density and in the apparent specific mass, being this one by an x-ray densitometry. The first log was determined the yield generated in the peeling process and veneers, producing plywood panels that were evaluated for physical and mechanical performance. From the second log sampled, test pieces of the portions near the cord and bark were made for the mechanical characterization of the solid wood. The obtained results show that both the length of the fiber as the cell wall thickness tended to a gradual increase with stabilization at 75% from the radius in both sampled plantations. Along the radial distance, the wood from the clay ground area (Rolim de Moura) has always tended to show higher values of diameter of vessels and occupied area in relation to the wood ground area of medium texture and higher compaction (Parecis), resulting in effect of the origin. The ash content was granted in two areas, being higher in the wood from Parecis. The density and specific gravity were not affected by the origin of wood, and tended to decrease along the longitudinal portion. There was only influence of the radial position on the mechanical properties of wood, only, with the biggest difference for the MOE in bending. The actual yield of the logs lamination was around 72%, and the mechanical properties of plywood produced make them them suitable for structural and marine applications, according to standardization concerning this type of product. Based on the radial variation of the parameters of length and wall thickness of the fibers, it is observed the presence of mature wood in S. amazonicum at age 14 in the evaluated growing conditions. Though the indicative coefficients of the quality of the fibers demonstrate the potential of the species in the production of pulp and paper at the age considered, the high content of extractives should be considered in breeding programs. Except for the shear strength wood paricá at age 14 showed an increase in the values of mechanical properties relative to other studies of this species, particularly in regard to the rigidity of its wood to bending stress. The yield found in the lamination and properties of panels confirm the suitability of the species in the manufacturing of plywood.

Este trabalho teve como objetivo avaliar o efeito de atributos físicos e químicos do solo na qualidade da madeira, estabelecendo correlações com as variáveis do processo de polpação celulósica. Para tanto, foram selecionadas cinco áreas no planalto ocidental do Estado de São Paulo, plantadas com um mesmo clone de Eucalyptus grandis Hill Ex Maiden (Coff´s Harbour), com idades variando entre 6,5 e 7,0 anos de idade, pertencentes à Suzano Papel e Celulose. Foram coletadas amostras de solo deformadas para fins de análises físicas e químicas. Amostras não deformadas foram utilizadas para análises físico-hídricas. Em cada uma das cinco áreas, foram demarcadas, aleatoriamente, 3 parcelas com 100 plantas cada. Em cada parcela, foram medidos os diâmetros à altura de 1,3 m (DAP) e a altura de todas as árvores. Os dados foram classificados em quatro classes de DAP e obtidos os DAPs médios de cada classe. Foi coletada uma árvore de cada classe e de cada parcela, mensuradas e estimadas as massas de lenho, casca, folha e galhos. Os troncos de cada árvore foram picados, individualmente, em picador industrial. Uma amostra dos cavacos foi utilizada para a análise de extrativos e componentes da madeira, de acordo com os métodos estabelecidos pela TAPPI e ABTCP. As condições de polpação foram estabelecidas, fixando-se o número kappa em 17 ± 0,5, a temperatura de cozimento em 165 °C, o tempo de elevação da temperatura em 90 minutos, o tempo à máxima temperatura em 60 minutos e a sulfidez do licor de cozimento em 24%. A carga de álcali foi variável e necessária para se atingir o número kappa desejado. Buscou-se descrever as relações entre os atributos do solo, a produtividade e a qualidade da madeira. Os resultados mostraram que os atributos físicos do solo, sobretudo o teor de argila, diretamente relacionado à quantidade de água disponível, foram os que mais afetaram a produtividade e a qualidade da madeira. A densidade básica da madeira não se alterou nas diferentes classes de solo. Por outro lado, aumentou exponencialmente com o volume das árvores, independentemente do solo em que cresceram. O teor de lignina total diminuiu e o de holocelulose aumentou exponencialmente, com o aumento do teor de argila do solo (até cerca de 35 a 40% de argila). O teor de extrativos não foi afetado pelos atributos do solo. Atribuiu-se à compensação entre o aumento do teor de holocelulose e a diminuição do teor de lignina total a não-variação da densidade básica da madeira nos diferentes solos. O rendimento de celulose depurada relacionou-se exponencialmente com o teor de argila do solo. No solo com textura muito argilosa (LVd2), o rendimento foi 6% maior do que no solo de textura arenosa (RQ). / The objective of this work was to evaluate the effect of soil physical and chemical attributes on timber quality, and to establish correlations with cellulose pulping process variables. To achieve this, five areas were selected at the Western Plateau of the State of São Paulo, planted with the same Eucalyptus grandis Hill Ex Maiden (Coff´s Harbour) clone, with ages ranging between 6.5 and 7.0 years, owned by Cia. Suzano Papel e Celulose. Deformed soil samples were collected for physical and chemical analysis purposes. Non-deformed samples were used in the physical and moisture analyses. Three plots containing 100 plants each were demarcated at random in each of the five areas. The diameters at a 1.3 m height (DBH) and heights of all trees were measured for each plot. The data were classified into four DBH classes and the mean DAP values for each class were obtained. One tree was collected from each class and each plot, and its wood, bark, leaf, and branch masses were measured and estimated. The trunks of each tree were individually chopped in a tree chopper. A sample from the chips was used in the analysis of wood extractives and components, according to methods established by TAPPI and ABTCP. The pulping conditions were established by fixing the Kappa number at 17 ± 0.5, cooking temperature at 165 °C, temperature ramp time at 90 minutes, time at maximum temperature at 60 minutes, and cooking liquor sulfidity at 24%. The alkali load was variable and adjusted as needed to reach the desired Kappa number. We sought to describe the relations between soil attributes and wood productivity and quality. The results showed that the soil physical attributes, especially clay content, which is directly related to the amount of available water, affected wood productivity and quality the most. Basic wood density did not change for different soil classes. On the other hand, it increased exponentially with tree volume, regardless of the soil where they were grown. Total lignin content decreased, and holocellulose content exponentially increased as soil clay content increased (until about 35 to 40% clay). The extractives content was not affected by soil attributes. The compensation between the increase in holocellulose content and the decrease in total lignin content was attributed to the lack of basic wood density variation in different soils. Screened cellulose yield exponentially increased with soil clay content. In the very clayey-textured soil (LVd2), yield was 6% higher than in the sandy-textured soil (RQ).

A madeira é um material de grande versatilidade, que atende a demanda de importantes setores da nossa economia. Além de ser uma matéria-prima natural e renovável, o consumo energético envolvido em sua manufatura é bem menor quando comparado com outros materiais de origem mineral. Porém, características intrínsecas da madeira resultam na sua capacidade de troca higroscópica com o ambiente, que se manifesta durante sua vida útil e causa a movimentação dimensional dos produtos. Visando reduzir esse efeito indesejável, o presente estudo buscou melhorar a estabilidade dimensional da madeira de folhosas, a partir da aplicação de tratamentos térmicos adicionais, em madeiras submetidas à secagem ao ar e convencional. As madeiras selecionadas foram as espécies comercialmente conhecidas como Jatobá e Muiracatiara, das quais foram coletadas 5 tábuas radiais e 5 tábuas tangenciais de cada espécie, tanto secas ao ar e como em estufa, escolhidas do estoque de uma indústria de pisos de madeira maciça. Dessas tábuas foram cortadas amostras para a aplicação dos tratamentos térmicos, que consistiram da exposição da madeira a temperaturas de 60°C, 75°C e 90°C por períodos de 24, 48, 72 e 96 horas. Após os tratamentos as amostras foram expostas a um ambiente de baixa umidade relativa (Condicionamento 1) e, após estabilização, foram expostas a um ambiente de alta umidade relativa (Condicionamento 2). Ao final dos tratamentos térmicos e dos condicionamentos foram medidos os teores de umidade e as dimensões das amostras. Os resultados obtidos permitiram verificar que a umidade de equilíbrio da madeira de Jatobá foi menor do que a da Muiracatiara, comportamento similar ao das amostras tangenciais em relação às radiais e da madeira seca em estufa em relação à madeira seca ao ar; mas que essas diferenças não são importantes na industrialização da madeira. Dentre os tratamentos térmicos, o mais eficiente foi a exposição à temperatura de 90ºC, independente do tempo de exposição. Esse tratamento reduziu a higroscopicidade da madeira e a movimentação dimensional decorrente das variações no teor de umidade, sendo que esse efeito foi mais pronunciado na madeira seca em estufa do que na madeira seca ao ar. A principal conclusão é que o tratamento térmico adicional, utilizando temperatura de 90ºC, apresenta potencial para aplicação industrial visando reduzir a movimentação dimensional da madeira e seus derivados. / Lumber is a material of great versatility, which meets the demand of important sectors of our economy. In addition, lumber is a natural and renewable raw material; consuming less energy in its production when compared with other materials of mineral origin. However, hygroscopicity is an intrinsic characteristic of the wood, which remains active during the life cycle and cause dimensional movement of lumber and its products. To reduce this undesirable effect, the present study aimed to improve the dimensional stability of hardwood lumber through the application of additional heat treatments to conventional and air-dried timber. The selected species were those commercially known as Jatobá and Muiracatiara, of which were collected 5 quarter sawn and 5 flat sawn boards of each species, both air dried and kiln dried, chosen from the stock of a flooring mill. These boards were cut to samples for the application of heat treatment, which consist in lumber exposure to temperatures of 60ºC, 75ºC and 90ºC during periods of 24, 48, 72 and 96 hours. After heat treatment the samples were exposed to a dry environment (low relative humidity, Condition 1) and, after to reach equilibrium moisture content, exposed to a wet environment (high relative humidity, Condition 2). Samples dimensions and moisture content were measured after the heat treatment and both two conditioning. The obtained results allowed to verify that equilibrium moisture content of Jatobá lumber was smaller than Muiracatiara lumber, similar behavior found for flat sawn samples compared to quarter sawn and for kiln-dried in relation to air dried lumber; but these differences are not important in lumber industrialization processes. Among the heat treatments, the most effective was the exposure at a temperature of 90°C, regardless of time of exposure. This treatment reduced the wood hygroscopicity and its dimensional movement caused by the variation in its moisture content, and this effect was more pronounced in the kiln dried wood than in air dried wood. The main conclusion is that additional heat treatment, using a temperature of 90°C, have potential for industrial application aiming to reduce the dimensional movement of lumber and its products.

Made available in DSpace on 2016-08-19T12:56:32Z (GMT). No. of bitstreams: 1 GILVAN PEREIRA DE FIGUEREDO.pdf: 11579757 bytes, checksum: dda638ee3ac748c09fb726ca60cc9e98 (MD5) Previous issue date: 2010-03-12 / The State of the Maranhão, Northeast of Brazil, has large occurrences of clays and zeolites. Nevertheless, these materials are not commercially exploited, due to lack of studies on its mineralogical and chemical composition. In this context, the objective this paper has as to study the physico-chemical features, particularly textural and structural properties and surface acidity of some natural clays and zeolites from the State of Maranhão. Thirteen samples of clays and four of zeolites were collected in Governador Edson Lobão, Montes Altos, Barra do Corda, Presidente Dutra, Grajaú, Codó and Carolina. All materials were characterized by X ray diffraction (XRD), X ray fluorescence (XRF), thermal analysis (TGA/DTA/DSC), N2 and n-butylamine adsorption/desorption. The obtained results revealed that the clays are, under a mineralogy view point, constituted by, basically, smectites and kaolinites, being some of these solid composites for 100% of sand and another one for a mixture of minerals of iron and clay, showing diversified chemical compositions and specific areas which varying from 2 m2/g until 85 m2/g. The zeolites showed to be structurally similar with a mixed mineralogical composition, presenting stilbite phases as well as smectite, with quite low specific areas (5 m2/g until 13 m2/g). Zeolites revealed to be more acidic than the clays. However, it should be emphasized that the surface acidity of all clays is also significant, being characterized by strong acid sites. In the particular case of the smectites, mainly of A5 sample, it was verified that the chemical activation, through acid treatment, modified its crystalline structure and increased its specific area for 136,53 m2/g. The adsorption capacity of the acid-activated clays had been more of natural clays and in some cases, these values had been similar to those gotten when using commercial clays. In a general way, this study indicates that the evaluated solids can be applied as adsorbents, as catalysts and as raw materials for refractory and ceramics production. / O Estado do Maranhão, Nordeste do Brasil, possui diversas ocorrências de argilas e de zeólitas. Apesar disso, esses materiais não são explorados comercialmente, devido à falta de estudos sobre sua composição mineralógica e química. Diante disso, este trabalho tem como objetivo estudar as características físico-químicas, especialmente as propriedades texturais e estruturais e acidez superficial de algumas argilas e zeólitas naturais do Estado do Maranhão. Foram coletadas treze amostras de argilas e quatro de zeólitas, nos municípios de Governador Edson Lobão, Montes Altos, Barra do Corda, Presidente Dutra, Grajaú, Codó e Carolina. Os materiais foram caracterizados por DRX, FRX, TGA/DTA/DSC, adsorção/dessorção de N2 e de n-butilamina. Os resultados obtidos revelaram que as argilas são mineralogicamente constituídas por, basicamente, esmectitas e caulinitas, sendo alguns desses sólidos compostos por quase 100% de areia e outro por uma mistura de minerais de ferro e argila, apresentando composições químicas variadas e áreas específicas que vão de 2 a 84 m2/g. As zeólitas são estruturalmente semelhantes, de composição mineralógica mista, apresentado estruturas de estilbita cálcica e esmectita, com áreas específicas bastante baixas (5 m2/g a 13 m2/g). As zeólitas mostraram-se muito mais ácidas do que as argilas. Porém, deve-se ressaltar que a acidez superficial das argilas é também apreciável, possuindo sítios ácidos mais fortes. No caso particular das esmectitas, principalmente da amostra A5, verificou-se que a ativação química, através de tratamento ácido, modificou sua estrutura cristalina e aumentou sua área específica para 136,53 m2/g. A capacidade de adsorção das argilas ativadas foram superiores a das argilas naturais e em alguns casos, esses valores foram semelhantes àqueles obtidos ao empregar argilas comerciais. De um modo geral, este estudo indica que os sólidos avaliados podem ser aplicados tanto como adsorventes e catalisadores quanto como matérias-primas para a produção de material cerâmico e refratário.

Orientador: Katia Tannous / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química / Made available in DSpace on 2018-08-21T03:23:09Z (GMT). No. of bitstreams: 1 Lourenco_JoanaBratz_M.pdf: 4471799 bytes, checksum: b024641bde2dc64cccbbc8f18b82a373 (MD5) Previous issue date: 2012 / Resumo: Este trabalho tem por objetivo estudar o comportamento fluidodinâmico de misturas binárias entre as biomassas madeira de eucalipto (Eucalyptus grandis) e o caroço do fruto do tucumã (Astrocaryum aculeatum), e areia como inerte, visando à aplicação em processos de termoconversão que utilizam a tecnologia de leito fluidizado. Os experimentos foram realizados em uma coluna de acrílico de diâmetro interno de 0,092 m. Os materiais escolhidos pertenceram às categorias A, B e D da classificação de Geldart. Observação: O resumo, na íntegra, poderá ser visualizado no texto completo da tese digital / Abstract: The objective of this study is to analyze the fluid dynamic behavior of binary mixtures between biomasses, eucalyptus wood (Eucalyptus grandis) and tucumã endocarp (Astrocaryum aculeatum), and inert (sand), aiming the application in thermoconversion processes that use the fluidized bed technology. The experiments were carried out in an acrylic column with an internal diameter of 0.092 m. ... Note: The complete abstract is available with the full electronic digital thesis or dissertations / Mestrado / Engenharia de Processos / Mestra em Engenharia Química

Orientador: Katia Tannous / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química / Made available in DSpace on 2018-08-21T11:07:43Z (GMT). No. of bitstreams: 1 Nascimento_VicenteFranco_M.pdf: 7282944 bytes, checksum: fb759d971353c73317d6c0ac1974ee13 (MD5) Previous issue date: 2012 / Resumo: Este trabalho tem como objetivo avaliar o potencial de biomassas amazônicas (ouriço de castanha-do-brasil, ouriço da sapucaia e caroço do fruto do tucumã) visando sua utilização como insumo energético em processos de termoconversão. As caracterizações das propriedades estabelecidas foram: física (diâmetro médio, esfericidade, massa específica real e aparente, e morfologia), química (analises química, elementar e imediata), térmica (Poder Calorífico Superior, Poder Calorífico Inferior e termogravimetria) e um estudo cinético (energia de ativação e fator pré-exponencial) a partir da análise termogravimétrica. As biomassas foram moídas em um moinho de martelo e separadas por peneiramento, onde o intervalo granulométrico escolhido foi de 497-2019 ?m. As partículas foram definidas como irregulares e suas esfericidades foram calculadas mediante as equações de Massarani e Peçanha (1986) e Riley (1941), obtendo as faixas de 0,3-0,8 e 0,6-0,9, respectivamente. As massas específicas, real e aparente, foram determinadas através de picnômetro a gás de Hélio e porosímetro de mercúrio, tendo como resultado valores entre 1424-1479 kg/m3 e entre 678-1115 kg/m3, respectivamente. Na análise morfológica foram encontradas duas estruturas celulares principais relacionadas à rigidez das biomassas, sendo estas: fibras e esclereídes. A análise da composição química apresentou teores de hemicelulose entre 2-3%, de celulose entre 31-58%, e de lignina 36-38%. A composição elementar foi determinada mediante analisador elementar CHN-S, onde se constatou a predominância dos teores de carbono e oxigênio (máx. 48%-47%, respectivamente). A composição imediata foi determinada mediante normas técnicas, obtendo-se: teor de umidade entre 7%-8% (ASTM E871-82), materiais voláteis 79%-86% (ASTM E872-82), cinzas 0,4%-2,0% (ASTM E1755-01) e carbono fixo 13-20% (por diferença). O Poder Calorífico Superior foi determinado pela norma ASTM D240-09 (Sanchez, 2010) e situou-se entre 19-20 MJ/kg. O Poder Calorífico Inferior foi determinado pela equação de Mendeleev resultando em 16 MJ/kg-17 MJ/kg. A partir da análise termogravimétrica das biomassas foram identificadas três regiões de perda de massa: 25-150ºC, atribuída à eliminação de água; 200-420ºC e 430-900ºC, atribuídas à degradação térmica das biomassas. Os principais componentes associados foram hemicelulose e celulose, e lignina, respectivamente. Na análise cinética da reação, a energia de ativação e fator pré-exponencial foram determinados através de dois métodos dinâmicos (Kissinger e Ozawa). A variação destes parâmetros foi mais significativa para o caroço do fruto do tucumã em relação os diâmetros médios, bem como entre as conversões das reações de degradação / Abstract: This study aims to evaluate the potential of Amazonian biomass (woody shell of the Brazil nut, woody shell of the sapucaia and tucumã endocarp) for their use as energy input into thermoconversion processes. The characterizations of the properties were established: physical (mean particle diameter, sphericity, real and apparent density, and morphology), chemical (chemical, ultimate and proximate analysis), thermal (Higher Heating Value, Lower Heating Value, thermogravimetry) and a kinetic study (activation energy, pre-exponential factor) from the thermogravimetric analysis. The biomasses were ground in a hammer mill and separated by sieving, where the particle sizes range 497-2019 microns was chosen. The particles were defined as irregular and its sphericities were calculated by Massarani and Peçanha (1986) and Riley (1941) equations obtaining ranges from 0.3 to 0.8 and 0.6 to 0.9 respectively. The densities (apparent and true) were determined by gas Helium pycnometer and mercury porosimeter resulting 1424-1479 kg/m3 and between 678-1115 kg/m3, respectively. In the morphological analysis, two major cellular structures related to the rigidity of biomass were found: fibers and sclereids. The chemical composition analysis showed that: 2-3% of hemicelluloses content, 31-58% of cellulose content and 36-38% of lignin content. The ultimate analysis was determined by CHN-S elemental analyzer, which it is noticed the predominance of carbon and oxygen (máx.48%-47%, respectively). The proximate analysis was determined by testing standards according: 7%-8% of moisture content (ASTM E871-82), 79%-86% of volatile materials (ASTM E872-82), 0.4%-2.0% of ash (ASTM E1755-01) and 13-20% of fixed carbon (by difference). The Higher Heating Value was determined by ASTM D240-09 (Sanchez, 2010) and obtaining between 19 MJ/kg -20 MJ/kg. The Lower Heating Value was determined by the Mendeleev formula resulting in 16 MJ/kg-17 MJ/kg. From the thermogravimetric analysis of biomass three regions of mass loss were identified: 25°C-150°C attributed to the elimination of water; 200°C-420°C and 430°C-900°C attributed to thermal degradation of biomass corresponded to hemicelluloses and cellulose, and lignin, respectively. In analyzing the reaction kinetics, the activation energy and pre-exponential factor were determined through two dynamic methods (Kissinger and Ozawa). The variation of these parameters was more significant for the tucumã endocarp relating to mean particle diameters as well as conversion of thermal degradation reactions / Mestrado / Engenharia de Processos / Mestre em Engenharia Química

Management-induced degradation of soil chemical and microbial quality is one of the most pressing concerns and a considerable threat to the sustainability of agroecosystems. However, information on this important issue is limited and largely based on short-term studies. A long-term experiment initiated in 1939 at the University of Pretoria provided a unique opportunity to assess the direct and residual effects of manure and inorganic fertilizers on soil chemical properties, microbial components and maize yield in rotation with field pea. Long-term addition of manure resulted in increased total organic C (TOC), total N and available P levels in the soil. Seasonally, these nutrients exhibited variations that appeared to be related to influences of crop rotation. Soil N content in an adjacent native site remained relatively constant but tended to increase in the control and manured plots. Soil microbial biomass C, N and P and microbial populations were affected by previous manure application as well as by crop rotation. Microbial biomass and numbers were generally higher in the manured plots. Manure application also had substantial residual effects and resulted in maize grain yields higher than in the control. Long-term NPK application resulted in decreased TOC and basic cation contents, and lowering of soil pH. The decrease in TOC was greater in single fertilizer treatments whereas basic cation contents and pH declined more in the balanced fertilizer treatments. Soil microbial biomass and numbers were influenced by, and exhibited qualitative changes in response to, long-term fertilization. Crop rotation also exerted effects on chemical and microbial properties of the soil. Maize grain yield showed significant increases in response to balanced fertilizer treatments. Response of maize to simple fertilizer applications was not beneficial in terms of yield returns. These results suggest that judicious use of inorganic fertilizers may, in the long-term, maintain soil quality and productive capacity. A comparison of the effects of residual manure and NPK fertilizers on the content of selected nutrients, microbial properties, C and N inputs, tissue nutrient concentration and crop yield showed differences due to treatments. TOC, total N and available P levels were increased due to residual manure alone or in combination with NPK fertilizers. C and N inputs and tissue P concentration were also generally higher in manured than in the NPK treatment. However, the higher increase in nutrient contents of manured plots was not reflected in microbial properties of the soil. Despite lower nutrient levels, the NPK treatment resulted in relatively greater increases in microbial properties of the soil. The differential responses were largely due to differences in quality and decomposability of organic material. Organic material in the NPK treatment appeared to have a higher decomposition and turnover rate than in other treatments, suggesting that C limitation in soils of low C but good nutrient supply may be compensated by high turnover rates of the available organic materials. The beneficial effect of residual manure on microbial properties and crop yield was decreased by application of supplemental N fertilizer but remained unaffected by application of supplemental K fertilizer. The depressive effect of excess soil P levels on soil microbial properties and crop yield was exacerbated by supplemental N fertilizer and mitigated by supplemental manure and K fertilizer applied to residual P. The decrease in available P levels due to supplemental K application implies that this may serve as a viable alternative to ameliorate soils with excess P levels. / Thesis (PhD (Plant Production and Soil Science))--University of Pretoria, 2003. / Plant Production and Soil Science / unrestricted

Les liquides ioniques sont des composés uniquement constitués d‘ions souvent volumineux, asymétriques et flexibles. Ils possèdent des températures de fusion basses, typiquement au-dessous de 100°C. Ils sont considérés comme des solvants prometteurs pour une chimie durable du fait, notamment, de leur tension de vapeur négligeable. Ils présentent d‘autres propriétés intéressantes : grande stabilité thermique, pression de vapeur quasiment nulle, non-inflammabilité, propriétés modulables par changement de l‘anion ou du cation, etc. Ils sont classiquement organisés par familles, en fonction de la structure chimique de leur cation : imidazolium, pyridinium, pyrrolidinium, etc. Leurs domaines d‘application sont très variés : synthèse, catalyse, séparation et extraction. Cependant, l‘utilisation des liquides ioniques à l‘échelle industrielle est encore limitée par manque de connaissances fondamentales et par l‘absence de données fiables sur leurs propriétés, leur devenir et leur impact environnementaux. La toxicité des liquides ioniques a récemment été démontrée ainsi qu'une résistance à la biodégradation. Dans ce contexte et en vue du développement à grande échelle de l‘utilisation de ces composés, la recherche de liquides ioniques à faible impact environnemental (moins toxiques, facilement biodégradables) devient essentielle. L‘introduction dans les chaînes latérales alkyles des imidazolium et pyridinium de groupements fonctionnels oxygenés, qui peuvent être reconnus par des enzymes (ex. esters, éthers, alcools terminaux), a grandement amélioré leur biodégradabilité. En même temps, il est important de garantir que la présence de ces groupements n‘affecte pas les propriétés physico-chimiques des liquides ioniques requises pour un usage spécifique dans des procédés chimiques. Dans ce projet de doctorat, nous avons sélectionné divers liquides ioniques basés sur les cations imidazolium, pyridinium, pyrrolidinium et ammonium, avec ou sans groupements fonctionnels (alcool/ester/éther) et avec trois types d‘anions, comme cibles d‘étude. L‘objectif était d‘examiner si les modifications de structures peuvent effectivement baisser leur impact environnemental tout en gardant leurs propriétés intéressantes pour des applications industrielles. Dans un premier temps, nous avons étudié plusieurs propriétés physico-chimiques importantes pour des applications ultérieures et/ou indicatrices de leur impact environnemental : les propriétés volumiques, la viscosité, la solubilité de gaz, la solubilité dans l‘eau, le coefficient de partage octanol-eau et le coefficient de diffusion dans l‘eau. Dans un deuxième temps, nous avons étudié leur impact environnemental par la mesure de la toxicité sur quatre microorganismes différents et l‘étude de leur biodégradation en présence de souches pures de bactéries. En complément, nous avons essayé de trouver des modèles basés sur les informations structurales pour estimer certaines propriétés. L‘insertion de groupements oxygénés sur la chaîne alkyle des cations ne change pas significativement les propriétés volumiques ; ni le coefficient de diffusion dans l‘eau. Les propriétés de solvatation des liquides ioniques basés sur des cations imidazolium et ammonium ne sont pas modifiées significativement, mais celles des pyridinium sont réduites, à cause d'une contribution entropique défavorable à l'énergie de Gibbs de solvatation. La présence de groupements oxygénés dans la chaîne alkyle du cation augmente la viscosité d‘un ordre de grandeur comparativement aux liquides ioniques sans groupements oxygénés. Dans le cas de l‘anion octylsulfate la viscosité augmente de deux ordres de grandeur. La présence de groupements oxygénés augmente la biodégradabilité des liquides ioniques. La présence de groupements esters rend les liquides ioniques plus sensibles à l‘ hydrolyse dans les conditions abiotiques et biotiques, toutefois le noyau imidazolium n‘en devient pas biodégradable pour autant. L‘introduction de groupements oxygénés augmente la solubilité dans l‘eau, diminue la valeur du coefficient de partage octanol-eau et entraine une baisse de la toxicité ce qui signifie que ces liquides ioniques présentent un plus faible impact environnemental. / Ionic liquids are the salts composed only by bulky, unsymmetrical and flexible organic cations and inorganic or organic anions. Their melting points are particularly low, usually below 100°C. The ionic liquids present several interesting properties : high thermal stability, low vapor pressure, non-flammability and tunable properties by changing the anion or cation. They are considered as promising high performance fluids with low environmental impact that can be applied in the fields of chemistry, chemical engineering or materials science both in processes (separation, catalysis) or as devices (optical components or lubricants).The application of ionic liquids at an industrial scale is still limited and fundamental information and reliable data on their properties, environmental fate and impact are rare. In this context and for the development of applications in wide scale, the research on ionic liquids with an expected low environmental impact (less toxic, readily biodegradable) is essential. The introduction of oxygenated functional groups – ester, ether or hydroxyl – in the alkyl side chains of imidazolium and pyridinium-based ionic liquids is expected to greatly improve their biodegradability. The effect of the functionalization on the physico-chemical properties of the ionic liquids is important in order to propose efficient, low environmental impact, ionic liquids for different applications and chemical processes. In this work, we have selected different ionic liquids based on the imidazolium, pyridinium, pyrrolidinium and ammonium cations, with or without functional groups (hydroxyl/ester/ether), and with three types of anions. Our objective was to examine if the modification of chemical structures of the ions effectively have lower environmental impact, and if they their interesting properties are remained. We have studied, for all the ionic liquids, several physico-chemical properties considered important to quantify the environmental impact of chemicals : the density, the viscosity, the gas solubility, the aqueous solubility, the octanol-water partition coefficient and the aqueous diffusivity. We have also tested their toxicity towards four different microorganisms and their biodegradation in presence of pure strain of bacteria. Finally, we have tried to develop some empirical and semi-empirical models based on molecular structure information for predicting some of these properties.The introduction of oxygenated groups in the alkyl chains on cations does not change significantly the volumetric properties of ionic liquids, or their diffusion coefficient in water, but increases the viscosity of the pure salts up to one order of magnitude. Carbon dioxide solubilities in ionic liquids are not significantly influenced by the introduction of oxygen functional groups in the cations of the ionic liquids except in the case of the pyridinium based ionic liquids for which the carbon dioxide solubility decreases significantly due to a defavourable entropic contribution to the Gibbs energy of solvation. The modification of the ionic liquids by introducing oxygenated chemical functions makes them more biodegradable. In the case of imidazolium-based ionic liquids, the presence of the ester group makes the cation more susceptible to hydrolysis, the imidazolium ring being still resistant to the degradation. The functionalization of the cation also increases the solubility in water of the resulting ionic liquids and reduces the octanol-water partition coefficient and their toxicity, leading us to conclude that they are more environmental friendly than the non-functionalized ionic liquids.

Management-induced degradation of soil chemical and microbial quality is one of the most pressing concerns and a considerable threat to the sustainability of agroecosystems. However, information on this important issue is limited and largely based on short-term studies. A long-term experiment initiated in 1939 at the University of Pretoria provided a unique opportunity to assess the direct and residual effects of manure and inorganic fertilizers on soil chemical properties, microbial components and maize yield in rotation with field pea. Long-term addition of manure resulted in increased total organic C (TO C), total Nand available P levels in the soil. Seasonally, these nutrients exhibited variations that appeared to be related to influences of crop rotation. Soil N content in an adjacent native site remained relatively constant but tended to increase in the control and manured plots. Soil microbial biomass C, Nand P and microbial populations were affected by previous manure application as well as by crop rotation. Microbial biomass and numbers were generally higher in the manured plots. Manure application also had substantial residual effects and resulted in maize grain yields higher than in the control. Long-term NPK application resulted in decreased TOC and basic cation contents, and lowering of soil pH. The decrease in TOC was greater in single fertilizer treatments whereas basic cation contents and pH declined more in the balanced fertilizer treatments. Soil microbial biomass and numbers were influenced by, and exhibited qualitative changes in response to, long-term fertilization. Crop rotation also exerted effects on chemical and microbial properties of the soil. Maize grain yield showed significant increases in response to balanced fertilizer treatments. Response of maize to simple fertilizer applications was not beneficial in terms of yield returns. These results suggest that judicious use of inorganic fertilizers may, in the long-term, maintain soil quality and productive capacity. A comparison of the effects of residual manure and NPK fertilizers on the content of selected nutrients, microbial properties, C and N inputs, tissue nutrient concentration and crop yield showed differences due to treatments. TOC, total N and available P levels were increased due to residual manure alone or in combination with NPK fertilizers. C and N inputs and tissue P concentration were also generally higher in manured than in the NPK treatment. However, the higher increase in nutrient contents of manured plots was not reflected in microbial properties of the soil. Despite lower nutrient levels, the NPK treatment resulted in relatively greater increases in microbial properties of the soil. The differential responses were largely due to differences in quality and decomposability of organic material. Organic material in the NPK treatment appeared to have a higher decomposition and turnover rate than in other treatments, suggesting that C limitation in soils of low C but good nutrient supply may be compensated by high turnover rates of the available organic materials. The beneficial effect of residual manure on microbial properties and crop yield was decreased by application of supplemental N fertilizer but remained unaffected by application of supplemental K fertilizer. The depressive effect of excess soil P levels on soil microbial properties and crop yield was exacerbated by supplemental N fertilizer and mitigated by supplemental manure and K fertilizer applied to residual P. The decrease in available P levels due to supplemental K application implies that this may serve as a viable alternative to ameliorate soils with excess P levels. / Thesis (PhD)--University of Pretoria, 2010. / Plant Production and Soil Science / unrestricted