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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
191

Mensuração da biomassa e construção de modelos para construção de equações de biomassa / Biomass measurement and models selection for biomass equations

Vismara, Edgar de Souza 07 May 2009 (has links)
O interesse pela quantificação da biomassa florestal vem crescendo muito nos últimos anos, sendo este crescimento relacionado diretamente ao potencial que as florestas tem em acumular carbono atmosférico na sua biomassa. A biomassa florestal pode ser acessada diretamente, por meio de inventário, ou através de modelos empíricos de predição. A construção de modelos de predição de biomassa envolve a mensuração das variáveis e o ajuste e seleção de modelos estatísticos. A partir de uma amostra destrutiva de de 200 indivíduos de dez essências florestais distintas advindos da região de Linhares, ES., foram construídos modelos de predição empíricos de biomassa aérea visando futuro uso em projetos de reflorestamento. O processo de construção dos modelos consistiu de uma análise das técnicas de obtenção dos dados e de ajuste dos modelos, bem como de uma análise dos processos de seleção destes a partir do critério de Informação de Akaike (AIC). No processo de obtenção dos dados foram testadas a técnica volumétrica e a técnica gravimétrica, a partir da coleta de cinco discos de madeira por árvore, em posições distintas no lenho. Na técnica gravimétrica, estudou-se diferentes técnicas de composição do teor de umidade dos discos para determinação da biomassa, concluindo-se como a melhor a que utiliza a média aritmética dos discos da base, meio e topo. Na técnica volumétrica, estudou-se diferentes técnicas de composição da densidade do tronco com base nas densidades básicas dos discos, concluindo-se que em termos de densidade do tronco, a média aritmética das densidades básicas dos cinco discos se mostrou como melhor técnica. Entretanto, quando se multiplica a densidade do tronco pelo volume deste para obtenção da biomassa, a utilização da densidade básica do disco do meio se mostrou superior a todas as técnicas. A utilização de uma densidade básica média da espécie para determinação da biomassa, via técnica volumétrica, se apresentou como uma abordagem inferior a qualquer técnica que utiliza informação da densidade do tronco das árvores individualmente. Por fim, sete modelos de predição de biomassa aérea de árvores considerando seus diferentes compartimentos foram ajustados, a partir das funções de Spurr e Schumacher-Hall, com e sem a inclusão da altura como variável preditora. Destes modelos, quatro eram gaussianos e três eram lognormais. Estes mesmos sete modelos foram ajustados incluindo a medida de penetração como variável preditora, totalizando quatorze modelos testados. O modelo de Schumacher-Hall se mostrou, de maneira geral, superior ao modelo de Spurr. A altura só se mostrou efetiva na explicação da biomassa das árvores quando em conjunto com a medida de penetração. Os modelos selecionados foram do grupo que incluíram a medida de penetração no lenho como variável preditora e , exceto o modelo de predição da biomassa de folhas, todos se mostraram adequados para aplicação na predição da biomassa aérea em áreas de reflorestamento. / Forest biomass measurement implies a destructive procedure, thus forest inventories and biomass surveys apply indirect procedure for the determination of biomass of the different components of the forest (wood, branches, leaves, roots, etc.). The usual approch consists in taking a destructive sample for the measurment of trees attributes and an empirical relationship is established between the biomass and other attributes that can be directly measured on standing trees, e.g., stem diameter and tree height. The biomass determination of felled trees can be achived by two techniques: the gravimetric technique, that weights the components in the field and take a sample for the determination of water content in the laboratory; and the volumetric technique, that determines the volume of the component in the field and take a sample for the determination of the wood specific gravity (wood basic density) in the laboratory. The gravimetric technique applies to all components of the trees, while the volumetric technique is usually restricted to the stem and large branches. In this study, these two techniques are studied in a sample fo 200 trees of 10 different species from the region of Linhares, ES. In each tree, 5 cross-sections of the stem were taken to investigate the best procedure for the determination of water content in gravimetric technique and for determination of the wood specific gravity in the volumetric technique. Also, Akaike Information Criterion (AIC) was used to compare different statistical models for the prediction o tree biomass. For the stem water content determination, the best procedure as the aritmetic mean of the water content from the cross-sections in the base, middle and top of the stem. In the determination of wood specific gravity, the best procedure was the aritmetic mean of all five cross-sections discs of the stem, however, for the determination of the biomass, i.e., the product of stem volume and wood specific gravity, the best procedure was the use of the middle stem cross-section disc wood specific gravity. The use of an average wood specific gravity by species showed worse results than any procedure that used information of wood specific gravity at individual tree level. Seven models, as variations of Spurr and Schumacher-Hall volume equation models, were tested for the different tree components: wood (stem and large branches), little branches, leaves and total biomass. In general, Schumacher-Hall models were better than Spurr based models, and models that included only diameter (DBH) information performed better than models with diameter and height measurements. When a measure of penetration in the wood, as a surrogate of wood density, was added to the models, the models with the three variables: diameter, height and penetration, became the best models.
192

Caracterização de respostas morfológicas e fisiológicas de plantas de soja submetidas a estresse hídrico / Morphological and physiological characterization of soybean plants under water stress

Felisberto, Guilherme 20 January 2016 (has links)
A cultura de soja (Glycine max (L.) Merrill) é muito importante mundialmente em função de seu uso na alimentação animal, como principal fonte de proteína e óleo, além de constituir a matéria prima básica para diversos setores da indústria. Sabe-se que a produtividade potencial de uma cultura é determinada por fatores genéticos e pelos seguintes atributos do ambiente de produção: temperatura, radiação solar, dióxido de carbono e fotoperíodo, sem restrição de água, nutrientes, plantas daninhas, pragas e doenças. A disponibilidade hídrica afeta o crescimento e desenvolvimento da cultura de soja, especialmente durante o período reprodutivo, fase de elevada atividade fisiológica. A deficiência hídrica é o principal fator limitante da produção mundial da cultura, que em sua maioria é cultivada em sistema de sequeiro em áreas com consideráveis riscos de ocorrência de deficit hídrico ao longo do ciclo da cultura. As plantas, ao longo do tempo, desenvolveram mecanismos para tolerar e/ou evitar os efeitos negativos desse estresse. O presente estudo teve como objetivo caracterizar esses mecanismos de tolerância associando-os ao potencial matricial do solo em processo de secagem. Foi avaliado a umidade gravimétrica e potencial matricial do solo, conteúdo relativo de água na folha, potencial hídrico foliar, prolina e caracteres relacionados à produção de plantas de soja, durante o período de enchimento de grãos, submetidas a três, seis, nove e doze dias sem irrigação, comparados com o controle irrigado diariamente. De acordo com o observado, os mecanismos de tolerância da soja à deficiência hídrica foram satisfatórios para a manutenção do conteúdo relativo de água e potencial hídrico foliar em níveis adequados até o valor de potencial matricial de água no solo de -0,8 atm, tendo a prolina papel importante nesse mecanismo. As avaliações hídricas, conteúdo relativo de água e potencial foliar se mostraram relacionados com a manutenção da produtividade de soja sob situação de deficiência hídrica, mostrando-se adequados para o estudo de tolerância de cultivares de soja à restrição hídrica. / Soybean crop (Glycine max (L.) Merrill) is very important worldwide because it is used in animal feeding, a source of protein and oil, and also raw material for many manufactured goods. It is known that a crop potential yield is determined by genetic factors and by the following production environment characteristics: temperature, solar radiation, carbon dioxide, photoperiod, water availability, nutrients, weeds, pests and diseases. Water availability affects soybean growth and development especially during the reproductive phase which has high physiological activity. Water deficit is a key factor on world`s soybean production which is generally grown in dry land systems with considerable high risks of water deficit along soybean crop season. Plants have developed mechanisms over time to tolerate and/or avoid negative effects of this kind of stress. The present study had as the main goal to characterize these mechanisms of tolerance associating them with soil matric potential of a soil in a drying process. It was assessed the gravimetrical humidity and soil matric potential, leaf relative water content, leaf water potential, proline and yield component of plants under three, six, nine and twelve days without irrigation during grain filling phase. In accordance with the observed, soybean water deficit tolerance mechanisms were enough to maintain leaf relative water content and leaf water potential at acceptable levels until soil matric potential were around -0.8 atm, which proline was a key factor in this mechanism. Leaf relative water content and leaf water potential showed to be related in maintaining soybean yield under water deficit and they may be used in studies of soybean tolerant cultivars to water restriction.
193

Desenvolvimento de uma sonda TDR helicoidal para uso em conjunto com o ensaio CPT / Developing a coil TDR probe to use together with the CPT test

Guerrero Doria, Katerin 21 August 2015 (has links)
A reflectometria no domínio do tempo permite estimar o teor de umidade de um meio através da sua correlação com a constante dielétrica. Uma sonda helicoidal TDR, que pode ser cravada em conjunto outros ensaios de penetração in situ para a estimativa do teor de umidade em diversas profundidades, tem aplicação interessante para a investigação geotécnica do subsolo. No presente trabalho, uma sonda TDR foi adaptada e utilizada em conjunto ao ensaio CPT para caracterização de um perfil de solo arenoso não saturado que ocorre na região de Bauru (SP). A calibração dessa sonda foi feita em laboratório especificamente para esse solo. As equações de calibração que mostraram os melhores resultados foram definidas correlacionando a constante dielétrica, condutividade elétrica aparente e a massa específica seca com o teor de umidade. Com o intuito de melhorar a acurácia na determinação do teor de umidade em campo e eliminar possíveis interferências no registro da onda eletromagnética, foram efetuadas modificações em algumas características do projeto original dessa sonda. Tais modificações consistiram em separar os eletrodos condutores e as partes metálicas da sonda, e eliminar o cabo coaxial de extensão, conectando a sonda diretamente a um cabo coaxial de 12 m de comprimento. Tais mudanças levaram a uma melhoria significativa na determinação do perfil de teor de umidade do local estudado. Os valores de teor de umidade de campo determinados usando o TDR ao longo de 8 m de profundidade foram comparados com os valores de referência obtidos de amostras deformadas retiradas com trado mecânico. O erro médio na estimativa do perfil de teor de umidade gravimétrico utilizando a sonda TDR helicoidal foi de 1.61%, na última campanha de ensaios realizados. Os resultados dessa pesquisa indicam que esta ferramenta é adequada para estimar do perfil de teor de umidade para uso em conjunto com o ensaio CPT. / The time domain reflectometry allows estimating the moisture content of a medium by means of its correlation with the dielectric constant. A coil TDR probe, which can be driven into the ground together with others in situ penetration tests, can be used to estimate the moisture content at different depths. It is an interesting approach for geotechnical site characterization. In this work, a coil TDR probe was adapted and used in combination with the CPT test for the site characterization of an unsaturated sandy soil profile which occurs in the region of Bauru (SP). The probe calibration was performed in laboratory specifically for that soil. The calibration equation, which presented the best results, were defined correlating the dielectric constant, electrical conductivity and dry density with the moisture content. In order to improve the accuracy for determining the water content in the field and to eliminate possible interference on the electromagnetic wave registration, modifications were made in some characteristics of the original design of this probe. Such modifications consisted in separating the conductive electrodes from the metal parts of the probe, and eliminating the coaxial extension cable, connecting the probe directly to a coaxial cable 12 m long. Such changes have led to a significant improvement in the determination of the moisture content profile of the studied site. The moisture content values determined in situ by using the TDR along 8 m depth were compared with reference values obtained from disturbed soil samples collected using mechanical augers. The root mean square error of the gravimetric water content profile using the TDR coil probe was 1.61% in the last test campaign. The results of this research indicate that this tool is suitable to estimate the gravimetric moisture content together with the CPT test.
194

Caracterização de respostas morfológicas e fisiológicas de plantas de soja submetidas a estresse hídrico / Morphological and physiological characterization of soybean plants under water stress

Guilherme Felisberto 20 January 2016 (has links)
A cultura de soja (Glycine max (L.) Merrill) é muito importante mundialmente em função de seu uso na alimentação animal, como principal fonte de proteína e óleo, além de constituir a matéria prima básica para diversos setores da indústria. Sabe-se que a produtividade potencial de uma cultura é determinada por fatores genéticos e pelos seguintes atributos do ambiente de produção: temperatura, radiação solar, dióxido de carbono e fotoperíodo, sem restrição de água, nutrientes, plantas daninhas, pragas e doenças. A disponibilidade hídrica afeta o crescimento e desenvolvimento da cultura de soja, especialmente durante o período reprodutivo, fase de elevada atividade fisiológica. A deficiência hídrica é o principal fator limitante da produção mundial da cultura, que em sua maioria é cultivada em sistema de sequeiro em áreas com consideráveis riscos de ocorrência de deficit hídrico ao longo do ciclo da cultura. As plantas, ao longo do tempo, desenvolveram mecanismos para tolerar e/ou evitar os efeitos negativos desse estresse. O presente estudo teve como objetivo caracterizar esses mecanismos de tolerância associando-os ao potencial matricial do solo em processo de secagem. Foi avaliado a umidade gravimétrica e potencial matricial do solo, conteúdo relativo de água na folha, potencial hídrico foliar, prolina e caracteres relacionados à produção de plantas de soja, durante o período de enchimento de grãos, submetidas a três, seis, nove e doze dias sem irrigação, comparados com o controle irrigado diariamente. De acordo com o observado, os mecanismos de tolerância da soja à deficiência hídrica foram satisfatórios para a manutenção do conteúdo relativo de água e potencial hídrico foliar em níveis adequados até o valor de potencial matricial de água no solo de -0,8 atm, tendo a prolina papel importante nesse mecanismo. As avaliações hídricas, conteúdo relativo de água e potencial foliar se mostraram relacionados com a manutenção da produtividade de soja sob situação de deficiência hídrica, mostrando-se adequados para o estudo de tolerância de cultivares de soja à restrição hídrica. / Soybean crop (Glycine max (L.) Merrill) is very important worldwide because it is used in animal feeding, a source of protein and oil, and also raw material for many manufactured goods. It is known that a crop potential yield is determined by genetic factors and by the following production environment characteristics: temperature, solar radiation, carbon dioxide, photoperiod, water availability, nutrients, weeds, pests and diseases. Water availability affects soybean growth and development especially during the reproductive phase which has high physiological activity. Water deficit is a key factor on world`s soybean production which is generally grown in dry land systems with considerable high risks of water deficit along soybean crop season. Plants have developed mechanisms over time to tolerate and/or avoid negative effects of this kind of stress. The present study had as the main goal to characterize these mechanisms of tolerance associating them with soil matric potential of a soil in a drying process. It was assessed the gravimetrical humidity and soil matric potential, leaf relative water content, leaf water potential, proline and yield component of plants under three, six, nine and twelve days without irrigation during grain filling phase. In accordance with the observed, soybean water deficit tolerance mechanisms were enough to maintain leaf relative water content and leaf water potential at acceptable levels until soil matric potential were around -0.8 atm, which proline was a key factor in this mechanism. Leaf relative water content and leaf water potential showed to be related in maintaining soybean yield under water deficit and they may be used in studies of soybean tolerant cultivars to water restriction.
195

Water and Heat Transport in Road Structures : Development of Mechanistic Models

Hansson, Klas January 2005 (has links)
<p>The coupled transport of water and heat, involving freezing and thawing, in the road structure and its immediate environment is important to consider for optimal design and maintenance of roads and when assessing solute transport, of e.g. de-icing salt, from roads. The objective of this study was to develop mechanistic models, and measurement techniques, suitable to describe and understand water flow and heat flux in road structures exposed to a cold climate. </p><p>Freezing and thawing was accounted for by implementing new routines in two numerical models (HYDRUS1D/2D). The sensitivity of the model output to changes in parameter values and operational hydrological data was investigated by uncertainty and sensitivity analyses. The effect of rainfall event characteristics and asphalt fractures on the subsurface flow pattern was investigated by scenario modelling. The performance of water content reflectometers (WCR), measuring water content, was evaluated using measurements in two road structure materials. A numerical model was used to simulate WCR sensor response. The freezing/thawing routines were stable and provided results in agreement with laboratory measurements. Frost depth, thawing period, and freezing-induced water redistribution in a model road was greatly affected by groundwater level and type of subgrade. The simulated subsurface flow patterns corresponded well with published field observations. A new method was successful in enabling the application of time domain reflectometer (TDR) calibration equations to WCR output. The observed distortion in sampling volume for one of the road materials could be explained by the WCR sensor numerical model. Soil physical, hydrological, and hydraulic modules proved successful in simulating the coupled transport of water and heat in and on the road structure. It was demonstrated in this thesis that numerical models can improve the interpretation and explanation of measurements. The HYDRUS model was an accurate and pedagogical tool, clearly useful in road design and management.</p>
196

Improving soil water determination in spatially variable field using fiber optic technology and Bayesian decision theory

Sayde, Chadi 22 March 2012 (has links)
Achieving and maintaining sustainability in irrigated agriculture production in the era of rapidly increasing stress on our natural resources require, among other essential actions, optimum control and management of the applied water. Thus, a significant upgrade of the currently available soil water monitoring technologies is needed. The primary goal of this work was to reduce the uncertainties of spatially variable soil water in the field. Two approaches are suggested: 1) The Bayesian decision model that implicitly accounts for spatial variability at minimal cost based on limited field data, and 2) The Actively Heated Fiber Optic (AHFO) method that explicitly accounts for spatial variability with high sampling density at relatively low cost per measurement point. The Bayesian decision model uses an algorithm to integrate information embodied in independent estimates of soil water depletion to derive a posterior estimation of soil water status that has the potential to reduce the risk of costly errors in irrigation scheduling decisions. The sources of information are obtained from an ET based water balance model, soil water measurements, and expert opinion. The algorithm was tested in a numerical example based on a field experiment where soil water depletion measurements were made at 43 sites in an agricultural field under center pivot irrigation. The results showed that the estimates of the average soil water depletion in the field obtained from the posterior distributions of soil water depletion proved to outperform simple averaging of n soil water depletion measurements, up to n = 35 measurements. For n< 3, the model also provided a 39% average reduction in risk of error derived from non-representative measurements. The AHFO method observes the heating and cooling of a buried fiber optic (FO) cable through the course of a pulse application of energy as monitored by a distributed temperature sensing (DTS) system to reveal soil water content simultaneously at sub-meter scale along the FO cable that can potentially exceeds kilometers in length. A new and simple interpretation of heat data that takes advantage of the characteristics of FO temperature measurements is presented. The results demonstrate the feasibility of AHFO method application to obtain <0.05 m³m⁻³ error distributed measurements of soil water content under laboratory controlled conditions. The AHFO method was then tested under field conditions using 750 m of FO cables buried at 30, 60, and 90 cm depths in agricultural field. The calibration curve relating soil water content to the thermal response of the soil to a heat pulse was developed in the lab. It was successively applied to the 30 and 60 cm depths cables, while the 90 cm depth cable illustrated the challenges of soil heterogeneity for this technique. The method was used to map with high spatial (1m) and temporal (1hr) resolution the spatial variability of soil water content and fluxes induced by the non-uniformity of water application at the surface. / Graduation date: 2012
197

Water and Heat Transport in Road Structures : Development of Mechanistic Models

Hansson, Klas January 2005 (has links)
The coupled transport of water and heat, involving freezing and thawing, in the road structure and its immediate environment is important to consider for optimal design and maintenance of roads and when assessing solute transport, of e.g. de-icing salt, from roads. The objective of this study was to develop mechanistic models, and measurement techniques, suitable to describe and understand water flow and heat flux in road structures exposed to a cold climate. Freezing and thawing was accounted for by implementing new routines in two numerical models (HYDRUS1D/2D). The sensitivity of the model output to changes in parameter values and operational hydrological data was investigated by uncertainty and sensitivity analyses. The effect of rainfall event characteristics and asphalt fractures on the subsurface flow pattern was investigated by scenario modelling. The performance of water content reflectometers (WCR), measuring water content, was evaluated using measurements in two road structure materials. A numerical model was used to simulate WCR sensor response. The freezing/thawing routines were stable and provided results in agreement with laboratory measurements. Frost depth, thawing period, and freezing-induced water redistribution in a model road was greatly affected by groundwater level and type of subgrade. The simulated subsurface flow patterns corresponded well with published field observations. A new method was successful in enabling the application of time domain reflectometer (TDR) calibration equations to WCR output. The observed distortion in sampling volume for one of the road materials could be explained by the WCR sensor numerical model. Soil physical, hydrological, and hydraulic modules proved successful in simulating the coupled transport of water and heat in and on the road structure. It was demonstrated in this thesis that numerical models can improve the interpretation and explanation of measurements. The HYDRUS model was an accurate and pedagogical tool, clearly useful in road design and management.
198

Experimental Study on the Engineering Properties of Gelfill

Abdul-Hussain, Najlaa 29 March 2011 (has links)
Gelfill (GF) is made of tailings, water, binder and chemical additives (Fillset, sodium silicate gel). The components of GF are combined and mixed on the surface and transported (by gravity and/or pumping) to the underground mine workings, where the GF can be used for both underground mine support and tailings storage. Thermal (T), hydraulic (H), and mechanical (M) properties are important performance criteria of GF. The understanding of these engineering properties and their evolution with time are still limited due to the fact that GF is a new cemented backfill material. In this thesis, the evolution of the thermal, hydraulic, mechanical, and microstructural properties of small GF samples are determined. Various binder contents of Portland cement type I (PCI) are used. The GF is cured for 3, 7, 28, 90, and 120 days. It is found that the thermal, hydraulic and mechanical properties are time-dependent or affected by the degree of binder hydration index. Furthermore, a relationship is found between the compressive strength and the saturated hydraulic conductivity of the GF samples. The unsaturated hydraulic properties of GF samples have also been investigated. The outcomes show that unsaturated hydraulic conductivity is influenced by the degree of binder hydration index and binder content, especially at low suction ranges. Simple functions are proposed to predict the evolution of air-entry values (AEVs), residual water content, and fitting parameters from the van Genuchten model with the degree of hydration index (α). Furthermore, two columns are built to simulate the coupled thermo-hydro-mechanical (THM) behaviour of GF under drained and undrained conditions. The obtained results from the GF columns are compared with the small samples. It is observed that the mechanical properties, hydraulic properties (suction and water content), and temperature development are strongly coupled. The magnitude of these THM coupling factors is affected by the size of the GF. The findings also show that the mechanical, hydraulic and thermal properties of the GF columns are different from samples cured in plastic moulds.
199

Experimental Study on the Engineering Properties of Gelfill

Abdul-Hussain, Najlaa 29 March 2011 (has links)
Gelfill (GF) is made of tailings, water, binder and chemical additives (Fillset, sodium silicate gel). The components of GF are combined and mixed on the surface and transported (by gravity and/or pumping) to the underground mine workings, where the GF can be used for both underground mine support and tailings storage. Thermal (T), hydraulic (H), and mechanical (M) properties are important performance criteria of GF. The understanding of these engineering properties and their evolution with time are still limited due to the fact that GF is a new cemented backfill material. In this thesis, the evolution of the thermal, hydraulic, mechanical, and microstructural properties of small GF samples are determined. Various binder contents of Portland cement type I (PCI) are used. The GF is cured for 3, 7, 28, 90, and 120 days. It is found that the thermal, hydraulic and mechanical properties are time-dependent or affected by the degree of binder hydration index. Furthermore, a relationship is found between the compressive strength and the saturated hydraulic conductivity of the GF samples. The unsaturated hydraulic properties of GF samples have also been investigated. The outcomes show that unsaturated hydraulic conductivity is influenced by the degree of binder hydration index and binder content, especially at low suction ranges. Simple functions are proposed to predict the evolution of air-entry values (AEVs), residual water content, and fitting parameters from the van Genuchten model with the degree of hydration index (α). Furthermore, two columns are built to simulate the coupled thermo-hydro-mechanical (THM) behaviour of GF under drained and undrained conditions. The obtained results from the GF columns are compared with the small samples. It is observed that the mechanical properties, hydraulic properties (suction and water content), and temperature development are strongly coupled. The magnitude of these THM coupling factors is affected by the size of the GF. The findings also show that the mechanical, hydraulic and thermal properties of the GF columns are different from samples cured in plastic moulds.
200

In-Situ Ethylene Polymerization with Organoclay-Supported Metallocenes for the Preparation of Polyethylene-Clay Nanocomposites

Maneshi, Abolfazl January 2010 (has links)
In-situ polymerization is one of the most efficient methods for production of polymer clay nanocomposites. In-situ polymerization of olefins using coordination catalysts is a type of heterogeneous polymerization. In order to achieve acceptable clay nanolayer dispersion in the polyolefin matrix, the clay layer exfoliation and particle break up during the polymerization are essential requirements. A literature review on polyolefin/clay nanocomposite is given in Chapter 2. In Chapter 3, we present a new mathematical model, which is as an extension of the multigrain model (MGM), to describe the intercalative polymerization and expansion of clay interlayer spaces during polymerization using clay-supported metallocenes. The results from the model show that, under the studied conditions, mass transfer is not a strong factor controlling clay exfoliation and particle break up. If the polymerization active sites are supported uniformly on all clay surfaces, effective exfoliation will be achieved after a relative short polymerization time. In practice, obtaining good dispersion of clay nanolayers with uniform properties requires that the active sites be exclusively located on the clay nanolayer surfaces, and not extracted by the solvent to form a homogeneous solution. Factors favouring active site extraction would result in nanocomposites with poor properties. In addition, high polymerization activities, stable polymerization runs, and ease of supporting are other criteria for a successful in-situ polymerization. For this purpose we established a catalyst supporting method by which most of these requirements were met. In this method, the water content on the clay surface, which is considered as poison for the metallocene catalyst, was used to produce MAO upon reaction with trimethylaluminum (TMA). Using this method, polymerization was highly active in absence of MAO cocatalyst, knowing that MAO cocatalyst promotes active site extraction from the clay surface and results in poor powder morphology. Chapter 4 describes the development of this supporting methodology. Chapter 4 also investigates the effect of the organic modification type existing on the clay surface on the success of catalyst supporting and in-situ polymerization. We found that using the proposed supporting procedure, only tertiary ammonium type modification enhanced the in-situ polymerization, whereas the quaternary ammonium worsened the catalyst supporting efficiency and led to catalyst with poor or no polymerization activity. It is suggested that, in addition to enhancing clay surface-organic solvent compatibility (which facilitates catalyst supporting), the tertiary ammonium cation reacts with the in-situ produced MAO and increases the stability of the cocatalyst bonded to the clay surface. The effect of different polymerization conditions on the polymerization behavior and nanocomposite structural properties, such as catalyst loading during supporting, polymerization temperature and triisobutylaluminum (TIBA) concentration, were studied in Chapter 5. It was found that TIBA acts merely as scavenger. High polymerization activities were obtained with low Al/Zr ratios (Al from TIBA) and increased Al concentration decreased the polymerization activity and also the quality of powder morphology. Catalyst loading in the supporting step showed to have an important role in determining the final properties. The clay particles with higher catalyst loading resulted in better exfoliation and powder morphologies The effect of solvent type during catalyst supporting and polymerization was studied in Chapter 6. It was shown that catalyst supporting in n-hexane resulted in polymerizations with higher activities and polymers with higher molecular weight were produced. Polymerization with catalyst supported in hexane showed different ethylene uptake profiles, suggesting different mechanism of exfoliation. It is suggested that using this catalyst, the clay is mostly exfoliated before polymerization started. Similar to the original clay, the catalyst supporting efficiency on the organically modified clay was close to 100 percent. However, comparing the polymerization activities of these catalysts to those that were supported directly in the reactor just before the polymerization (in-reactor, or in-situ, supported catalysts) shows that a considerable fraction of the active sites are deactivated during the prolonged contact between catalyst and clay support surface. In Chapter 5, it was shown that the in-reactor supported catalyst had considerably higher polymerization activities, up to 40 percent of that of the homogeneous catalyst. Nanocomposites made with in-reactor supported catalysts had powder morphology and nanaolayer dispersion comparable to those made with clay-supported catalysts.

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