Les composites à matrice céramique ont initialement été développés pour des applications aérospatiales, aéronautiques militaires ou énergétiques en raison de leurs bonnes propriétés à haute température. Ils sont généralement fabriqués par le procédé CVI (Chemical Vapour Infiltration). Un nouveau procédé hybride combinant l’imprégnation de poudre au sein de préformes, suivie de la CVI Réactive(RCVI), est proposé afin de réduire les temps de production. Cette voie est basé sur l’adaptation du procédé RCVD à l’infiltration en milieu poreux. En RCVD, l’absence d’une partie des éléments du dépôt de carbure dans la phase gazeuse implique une consommation/conversion du substrat solide. Dans cette étude, la croissance et la consommation associée ont été étudiées en fonction de divers paramètres dans le système chimique Ti-H-Cl-C. Cette étude est accompagnée d’analyses (DRX, XPS, IRTF) des produits issus de la réaction chimique de formation du TiC. Ensuite, la conversion partielle d’une poudre de carbone submicronique enTiC et la consolidation des zones compactes de poudre par l’infiltration RCVI utilisant le mélange gazeux H2/TiCl4 a été étudiée. La porosité résiduelle et la teneur en TiC ont été mesurées par analyse d’image à différentes distance de la surface des matériaux. Selon la température, plusieurs centaines de micromètres infiltrés ont été obtenus. Finalement, les résultats ont été transposés à l’infiltration RCVI de préformes type CMC. Malgré une teneur minimale de 25% de TiC dans l’ensemble de la préforme, les résultats montrent une mauvaise homogénéité d’infiltration et une mauvaise cohésion des blocs de poudre consolidés avecles fibres de leurs environnements. / Ceramic matrix composites were originally developed for aerospace,military aeronautics or energyapplications thanks to their good properties at high temperature. They are generally made by ChemicalVapor Infiltration (CVI). A new short hybrid process combining fiber preforms lurry impregnation ofceramic powders with an innovative Reactive CVI (RCVI) route is proposed to reduce the productiontime. This route is based on the combination of Reactive Chemical Vapour Deposition (RCVD), whichis often used to deposit coatings on fibres, with the Chemical Vapor Infiltration (CVI).In RCVD, the absence of one element of the deposited carbide in the initial gas phase involves theconsumption/conversion of the solid substrate. In this work, the RCVD growth and the associatedconsumption were studied with different parameters in the Ti-H-Cl-C chemical system. The study hasbeen completed with the chemical products analysis, combining XRD, XPS and FTIR. Then, the partialconversion of sub-micrometer carbon powders into titaniumcarbide and the consolidation of greenbodies by RCVI from H2/TiCl4 gaseous infiltration were studied. The residual porosity and the final TiCcontent were measured in the bulk of the infiltrated powders by image analysis from scanning electronmicroscopy. Depending on temperature, few hundred micrometers-depth infiltrations are obtained.Finally, the results have been transposed to the RCVI into CMC-type preforms. Despite aminimalTiC content of 25% in the overall preform, the results shown a bad homogeneity of the infiltration anda poor cohesion of fibres with RCVI consolidated powder of their environment.

Ice based Cool Thermal Energy Storage (CTES) systems have attracted much attention during last few decades. The reasons are mainly of economical and environmental nature. Compared to conventional refrigeration and air-conditioning systems without cool thermal energy storage, implementation of CTES will increase environmental standards and overall efficiency of the energy systems as it contributes to the phase-out of synthetic refrigerants and reduces peak loads in electricity grids. For the application of a cool thermal energy storages in refrigeration installations and HVAC systems in industry and building sector, it is necessary to have appropriate design tools in order to sufficiently accurate predict their performance. In this thesis theoretical and experimental investigations of two ice based cool thermal energy storage systems, namely static, indirect, external melt, ice-on-coil, i.e. ice bank system and dynamic, ice slurry cool thermal energy storage system are carried out. An ice bank storage technology for cooling purposes is known for a long time. The main drawbacks which are hindering its wider use are the system complexity, high first costs, system efficiency which is highly dependant on design, control and monitoring of the system, etc. On the other hand, ice slurry technology was not well studied until recently, while in the current scientific literature there are still differences between results and conclusions reported by different investigators. The aim of the present thesis is to extend the knowledge in the field of ice based CTES systems, thereby contributing in the development and wider utilization of those systems. In the first part of the thesis a computer application, named “BankaLeda” is presented. It enables simulation of an ice bank system performance. In order to verify developed simulation model an experimental evaluation has been performed. Field measurements have been conducted on a two module silo which was installed as a part of the refrigeration system in dairy and cheese factory “Antun Bohnec” in the city of Ludbreg in Croatia. Experimental findings were compared to the simulation model. The software „BankaLeda“ presents a strong optimization tool for designers and engineers in the field by providing a high degree of freedom in defining particular system design and operating parameters. It offers a basis for assessment and testing of a new energy efficient system arrangements and measures. Besides it will give decisionmakers the ability to test potential solutions in the process of CTES system design. In the second part of the thesis ice slurry pressure drop and heat transfer in horizontal straight tubes have been experimentally investigated. In particular a mixture of 10.3 % of ethanol and water with an initial freezing point of -4.4 °C was considered. It was found that the behaviour of ice slurry flow is changing with time and that ice slurry pressure drop is generally higher than for single phase flow. However for ice concentrations of 15 % and higher, for certain velocities ice slurry pressure drop is found to be of a similar value as for single phase fluid. Moreover, if ice slurry is to be used as a energy transport media it is recommended to keep the ice mass fraction at a level of 20 %. With tube geometry and thermophysical properties of a carrier fluid the heat transfer of ice slurry is generally a function of ice mass fraction and velocity. The imposed heat flux has no or has just minor influence on the heat transfer coefficient. Up to ice mass fraction between 10-15 % the mean heat transfer coefficient shows only slight (laminar flow) or no increase (turbulent flow) in comparison to single phase flow. Beyond that ice mass fraction the heat transfer coefficient is increasing significantly. The test data for pressure drop and heat transfer in laminar and turbulent regime was compared to several correlations from the literature. A new correlations for ice slurry pressure drop and heat transfer in the laminar flow regime, for 10.3 % ethanol and water mixture, were derived based on the present experimental data. The correlation for pressure drop predicts 82 % of the experimental data with ±15 % accuracy, while the correlation for heat transfer predicts 75 % of the data with the same accuracy. In order to investigate advantages and disadvantages of a dynamic, ice slurry system over a static, indirect, external melt, ice-on-coil CTES system and to assess their differences from economical aspects, a theoretical simulation model of an ice slurry CTES have been developed. It was found that the ice slurry based CTES systems posses higher economic and energy saving potential than static type systems. In the best case scenario the total energy consumption of dynamic CTES system was found to be approximately 25 % lower than for a static CTES system. / QC 20100715

In analytical chemistry the main goal is normally to determine the identity and/or concentration of one or more species in a sample. The samples analyzed are often natural samples, containing numerous different species in a complex matrix and the choice of technique for multi-elemental detection is in general inductively coupled plasma spectrometry. The chemical forms of an element can affect many of its characteristics e.g. toxicity, which makes speciation analysis important. Therefore, determination of the identity and quantity of an element is still important, but for many applications measurements of total element concentration provides insufficient information. To be able to perform speciation analysis, separation, identification and/or characterization of the various forms of elements in the sample has to be accomplished. Speciation analysis has been employed in a wide range of disciplines, including for example environmental science, biology and clinical chemistry. This thesis describes work to improve and understand the elemental speciation analysis with liquid chromatography coupled to plasma spectrometry and also highlights the importance and potential of the synergy between atomic spectrometry and molecular mass spectrometry. The combination of the matrix tolerant, robust and very sensitive plasma spectrometry used together with molecular mass spectrometry, which provides structural information and the possibility to identify unknown species, is demonstrated to be a very powerful tool for speciation analysis. In this thesis methods are developed for on-line sample clean-up and pre-concentration coupled to liquid chromatography and plasma spectrometry, which makes handling of small sample volumes easier and also decreases the risk of contamination. The problems associated with organic modifiers in plasma spectrometry are also addressed. Applications of speciation analysis are exemplified by analysis of aluminium-chelated siderophores in field-soil solutions and organic phosphorous species in aquatic sediments. The possibility to analyze un-dissolved samples as slurries with minimal sample preparation is also discussed.

L’objectif de ce travail consiste en l'étude expérimentale et la modélisation du comportement thermo-hydraulique d'un fluide frigoporteur diphasique (FFD) particulier : le coulis de paraffine, en écoulement dans un canal rectangulaire simulant un échangeur à plaques. Les coulis de paraffine sont constitués de particules millimétriques de paraffine, stabilisées dans une matrice poreuse el mises en suspension dans de l'eau. Les particules de paraffines sont composées de 75% en masse de Norpar®15 et de 25% de polymère tri-block qui sert à gélifier la paraffine. Les résultats expérimentaux issus de bilans sur les veines d'essai de l'installation développée el mise en place au Centre de Thermique de Lyon (CETHIL), mettent en évidence une intensification importante du coefficient d'échange thermique, due a la présence des particules dans le fluide porteur. Pour un écoulement laminaire du coulis de paraffine dans le canal de refroidissement, une multiplication moyenne par 1 ,25 à 1 ,5 du coefficient d'échange global par rapport au fluide monophasique a été enregistrée pour des fractions massiques en particules de 6 à 12 %. Par régression linéaire des résultats expérimentaux, des corrélations pour le calcul des nombres de Nusselt local et moyen sont proposées. Une approche théorique basée sur le modèle de mélanges (Mixture Mode!) a été élaborée pour étudier le comportement hydraulique et thermique du fluide frigoporteur diphasique FFD pendant son refroidissement en écoulement laminaire dans un canal rectangulaire. L'évolution des valeurs expérimentales et théoriques pour la température moyenne du fluide et le coemcien1 d'échange thermique paroi - fluide montrent qu'ils sont en bon accord. Le modèle peut être considéré comme satisfaisant car les écarts entre résultats théoriques et expérimentaux n'excèdent jamais 14 %. / This work concerns the experimental investigation and modelling of the thermo hydraulic behaviour of a new Iwo-phase secondary refrigerant, the paraffin slurry, flowing through a rectangular channel of a heat plate exchanger type. The paraffin slurries are made of millimetric bullets of paraffin, stabilized in an organic porous polymeric matrix, in suspension in water serving as a carrying fluid. The paraffin particles used contain 75% of paraffin called NORPAR®15 and 25% of a tri-block polymer of styrene with High Molecular Weight (HMW). The experimental results generated by the heat balances on the test sections of the experimental setup built in the Thermal Center of Lyon (CETHIL), highlight an important increase of the heat transfer coefficient, due to the particles presence in the carrying fluid. For a laminar flow of the paraffin slurry in the cold channel, an average multiplication by 1 .25 to 1.5 of the global heat transfer coefficient compared to the single-phase fluid was recorded for particles mass fractions of 6 to 12%. By regression of the experimental results, correlations for the local and average Nusselt number calculation for the laminar flows are proposed. The particularity of the presented correlations is their validity in the case of a pure fluid as we\l as for a two-phase fluid containing so\id particles. A model for the hydraulic and thermal behaviours studies of a Iwo-phase secondary refrigerant fluid during its cooling in laminar flow through a rectangular channel was developed it is based on the mixture model and to king the slip velocity into account. The evolution of the experimental and theoretical values for the fluid average temperature, the heat flow which crosses the walls and the heat transfer coefficient between the wall and fluid shows good agreement and the model is satisfactory since the variations never exceed 14%.

Cette thèse présente une étude expérimentale visant à caractériser les propriétés hydrauliquesd'écoulements à surface libre de fluides complexes: fluides viscoplastiques et mélangesfluides viscoplastiques-grains. Ce travail est motivé par la nécessité d'améliorer lesconnaissances sur les propriétés des écoulements de laves torrentielles, dans un contexte deprotection contre les risques naturels en montagne. Nous avons développé un dispositif delaboratoire original, un canal à fond mobile, permettant de générer des coulées gravitaires quisont globalement stationnaires dans le référentiel du laboratoire. Les coulées présentent unfront très raide, suivi à l'amont d'une zone d'épaisseur uniforme. Les fluides viscoplastiquesutilisés (carbopol et kaolin) ont été choisis de manière à modéliser la matrice des couléesboueuses naturelles en prenant en compte les critères de similitude adaptés. Ces fluidessuivent une loi de comportement de Herschel-Bulkley, et leurs propriétés rhéologiques ont étédéterminées au moyen d'un rhéomètre de laboratoire en accordant un soin particulier àl'établissement des incertitudes associées. Nous présentons des mesures précises de l'évolutionde l'épaisseur des coulées dans la zone uniforme en fonction de la vitesse du fond du canal etde la pente. Ces résultats sont comparés à des prédictions théoriques correspondant à unécoulement permanent et uniforme d'un fluide de Herschel-Bulkley, et nous montrons quel'accord est satisfaisant moyennant les incertitudes sur les mesures rhéologiques. Nous avonségalement analysé la forme du front des coulées et, là-aussi, l'accord avec des modèleshydrauliques (modèles de type Saint-Venant) est bon. Ces deux études permettent de validerles prédictions hydrauliques obtenues à partir de lois de comportement mesurées aurhéomètre. Enfin, dans une dernière partie, nous présentons une étude préliminaire de ladynamique de particules rigides isolées placées au sein de la coulée, en nous intéressant auxvitesses longitudinales et aux vitesses de chute pour différentes tailles et différentes densitésde particules. / This thesis presents an experimental study dedicated to characterise the hydraulic propertiesof free surface flows of complex fluids : viscoplastic fluids and mixtures made of viscoplasticfluids and grains. This study is motivated by the need to improve knowledge on properties ofthe flow of debris flows in a context of protection against natural hazards in the mountains.We have developed an original laboratory device - a channel with a mobile bottom - togenerate gravitary flows that are globally stationary in the laboratory frame. The flows have avery steep front followed upstream by a zone of uniform thickness. Viscoplastic fluids used(carbopol and kaolin) were selected so to model the matrix of natural mud flows, taking intoaccount the criteria of similarity adapted. These fluids follow a behavior law of Herschel-Bulkley, and their rheological properties were determined using a laboratory rheometer byproviding a particular care to the establishment of the associated uncertainties. We presentaccurate measurements of the evolution of the thickness of the flow in the uniform zone withthe the velocity speed of channel belt. These results are compared with theoretical predictionscorresponding to a steady uniform flow of a fluid of Herschel-Bulkley, and we show that theagreement is satisfactory through the uncertainties on the rheological measurements. We alsoanalyzed the shape of front, and here too, the agreement with hydraulic models (models likeSaint-Venant) is good. Both of the studies allowed to validate the hydraulic predictionsobtained from behavior laws measured with the rheometer. Finally, in a last section, wepresent a Preliminary study about the dynamics of isolated rigid particles placed in the flow,by paying attention to longitudinal velocities and falling velocities for different particle sizesand densities.

The analysis of adhesion mechanisms between mortar lining and porous substrates has been the target of innumerous researchers due to its importance in ensuring system performance. Based on the theoretical reference of the topic, this work of experimental nature aimed to analyze the influence of the superficial topography of ceramic blocks in bonding slurry mortars and their relationship with the set of characteristics of fine aggregates that make up slurry mortars. Initially, the substrates and component materials of the mortars were characterized according to the Brazilian Association of Technical Standards; afterwards, characterization tests of fresh and hardened mortars were carried out. In the testing phase, the blocks received the slurry mortars. The experimental variables studied were: three types of ceramic blocks (ceramic sealing block with smooth surfaces, ceramic sealing block with horizontal grooved surfaces, and ceramic sealing block with vertical grooved surfaces); and two types of slurry mortars (one was prepared with coarse sand and the other with medium sand). Thus, six interfaces were evaluated through aspects of bonding strength and permeability and absorption by the pipe method. In order to observe the extent of adhesion and involvement of the grains of sand through the paste of the slurry mortars, interface analyses were conducted through observation by magnifying glass and petrographic microscope. The characteristics of the sands that influence the performance of fresh and hardened slurry mortars were analyzed, with emphasis on the textural parameters of the sands, which were evaluated with the aid of petrographic analysis. Results showed that there is direct correlation between the extent of adhesion provided by the grooves of the blocks, and bond tensile strength, made possible by the fluid nature of the slurry mortar. Therefore, this indicates the strong influence of the type of ceramic block on results of bond strength. On the other hand, the study of the characteristics of the sands, represented mainly by the granulometric composition, density, unitary mass, void content, degrees of roundness and sphericity, and mineralogy, proved to be useful in order to understand the role of the fine aggregates in the performance of the slurry mortar. Additionally, we observed that the tensile bonding strength was higher for the slurry mortars with coarse sand than with medium sand, when comparing the same type of block, although the tests have pointed to non-significant differences. This fact can be explained by the small difference between some of the characteristics of the sand used; however, the coarse sand studied seems to provide greater integration of the grains involved by the mortar paste, which was indicated by the degree of roundness. Moreover, it was also possible to observe direct relations in achieving results when comparing the permeability and absorption by the pipe method with the initial rate of absorption test (IRA) and extended IRA test. The final observation is that the basic treatment using slurry mortar can provide several benefits: increased roughness of the base, increased tensile bonding strength, adjustment of the suction capacity. This way, it was possible to homogenize the absorption of water by the substrate, thus avoiding different screeding times and performance for the lining layer. Thus, the treatment of the base with the use of slurry mortar can increase the performance and durability of the mortar lining. / A análise dos mecanismos de aderência entre argamassas de revestimento e substratos porosos tem sido alvo de muitos pesquisadores, devido à importância que tem para garantir o desempenho do sistema. Com base no referencial teórico sobre o tema, este trabalho de natureza experimental teve como objetivo principal analisar a influência da topografia superficial de blocos cerâmicos na aderência de argamassas de chapisco e a sua relação, ainda, com o conjunto de características dos agregados miúdos que compõem as argamassas de chapisco. Inicialmente, os substratos e os materiais componentes das argamassas foram caracterizados através do grupo de normas da Associação Brasileira de Normas Técnicas; na sequência, foram realizados ensaios de caracterização das argamassas nos estados fresco e endurecido. Na fase de testes, os blocos receberam as argamassas de chapisco. As variáveis experimentais estudadas foram: três tipos de blocos cerâmicos (bloco cerâmico de vedação com faces lisas, bloco cerâmico de vedação com faces ranhuradas horizontais, e bloco cerâmico de vedação com faces ranhuradas verticais); e dois tipos de argamassas de chapisco (uma elaborada com areia grossa e outra com areia média). Dessa forma, surgiram seis interfaces que foram avaliadas através de aspectos relacionados à resistência de aderência à tração e à permeabilidade e absorção pelo método do cachimbo. Na intenção de observar a extensão de aderência e o envolvimento dos grãos de areia pela pasta das argamassas de chapisco, foram feitas análises da interface através da observação por lupa estereoscópica e microscópio petrográfico. Foram pesquisadas as características das areias que influem no desempenho das argamassas de chapisco em seu estado fresco e endurecido, com ênfase nos parâmetros texturais das areias, avaliados com auxílio da análise petrográfica. Os resultados mostraram que há correlação direta entre a extensão de aderência, proporcionada pelas ranhuras dos blocos cerâmicos e a resistência de aderência à tração, possibilitada pela natureza fluida da argamassa de chapisco, indicando, assim, a forte influência do tipo de bloco cerâmico nos resultados de aderência à tração. De outro lado, o estudo das características das areias, representadas, principalmente, pela composição granulométrica, massa específica, massa unitária, índice de vazios, graus de arredondamento e esfericidade e mineralogia revelou-se útil no sentido de compreender o papel dos agregados miúdos perante o desempenho das argamassas de chapisco. Notou-se que a resistência de aderência à tração foi maior para as argamassas de chapisco com areia grossa do que com areia média, quando se compara um mesmo tipo de bloco, embora os testes tenham apontado diferenças não significativas. Esse fato pode ser explicado pela pouca diferença entre algumas das características das areias utilizadas; porém, a areia grossa estudada parece proporcionar um maior entrosamento dos grãos envolvidos pela pasta da argamassa, indicado pelo grau de arredondamento. Foram observadas, ainda, relações diretas na obtenção de resultados quando se compara a permeabilidade e absorção pelo método do cachimbo com o ensaio do índice de absorção inicial de água (AAI) e AAI estendido. A constatação final é de que o tratamento de base através do emprego de chapisco pode proporcionar vários benefícios: aumento da rugosidade da base, aumento da resistência de aderência à tração e regulagem da capacidade de sucção. Possibilitando, com isso, homogeneizar a absorção de água por parte do substrato, evitando diferentes tempos de sarrafeamento e desempeno para a camada de revestimento. Assim, o tratamento da base com uso do chapisco pode aumentar o desempenho e a durabilidade dos revestimentos de argamassa.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The managedment of the pig manure, in the slurry or solid form (deep bedding), and how it is applied to the soil, in the surface or incorporated, must affect the dynamics of the C and the N in the soil. The objectives of this work were: 1) to evaluate the dynamics of the C and the N in soil and to evaluate the N supply to maize which were applied pig manure in the slurry and solid form, in no-tillage and minimum tillage system; and 2) to use the STICS model (BRISSON et al., 1998) to simulate the dynamics of N and water in the soil-plant system with the use of pig slurry in maize under no-tillage system. To reach the first objective, three experiments were realized. Two of them in the field conditions, during the period of 2002/03 in the Experimental Area of the UFSM/RS Soil Department in a typic Hapludult and one of them in laboratory conditions. The treatments consisted in the application or no application of pig manure in the slurry and solid form (deep bedding) on the crop oats residues with and without incorporation to the soil in the maize. Aiming to reach the second objective, a data set generated in the Experimental Area of the UFSM Soil Department during the period of 1998 to 2002, involving the N dynamics in the soil-plant system, with the use of pig slurry in notillage system was used. The gotten results had indicated that the N losses by NH3 volatilization were higher with the application of pig slurry than with the application of solid manure and that these losses decrease with the incorporation of the manure to the soil. The amounts of mineral N in the soil layer of 0-90 cm did not differ between the treatments with and without incorporation of the manure in spite of the lost N amount by volatilization has been higher in the treatment without incorporation. The incorporation of the manure to the soil did not increase the straw C decomposition and nor the N immobilization. The presence of the oats straw stimulated the immobilization of the ammoniacal N applied with the pig slurry. The solid manure presented low nitrogenous fertilizing otential to the maize when compared to the pig slurry in terms of the low mineralization rate of the organic N, present in the deep bedding. The N-N2O emission increased with the application of the pig slurry on the oats straw in relation to the system with straw and without pig slurry. The pig slurry ammoniacal 15N recovery by the maize in physiological maturation stage was only 14.9%. In the same period, only 49.2% of the ammoniacal 15N applied with the slurry pig slurry were recuperated in the soil and the plant (aerial part + roots), indicating that more than a half of the ammoniacal N applied with the pig slurry was lost through the volatilization, lixiviation and denitrification processes. The STICS model underestimates the amount of N lost by ammonia volatilization after the pig slurry application. The use of a factor in STICS to express the N losses by ammonia volatilization provided an improvement in the simulations of the N dynamics in the soil. The water dynamics in the soil layer of 0 - 60 cm was simulated by STICS with an error lower than 13.5%. These work results showed that the STICS reparametred model presents potential to be used in subtropical weather conditions in the simulation of the N and water dynamics in no-tillage system with the use of pig manure. / A forma como os dejetos de suínos são manejados, se na forma líquida ou sólida (cama sobreposta), e o modo de aplicação dos mesmos no solo, se na superfície ou incorporados, devem afetar a dinâmica do C e do N no solo. Os objetivos deste trabalho foram: 1) avaliar a dinâmica do C e do N no solo e o fornecimento de N ao milho com uso de dejetos de suínos na forma líquida e sólida, em sistema plantio direto e preparo reduzido do solo; e 2) utilizar o modelo STICS (BRISSON et al., 1998) para simular a dinâmica do N e da água no sistema solo-planta com o uso de dejetos líquidos de suínos em sistema plantio direto de milho. Para atingir o primeiro objetivo, foram realizados três experimentos, sendo dois em condições de campo, no período de 2002/03 na área Experimental do Departamento de Solos da UFSM/RS, em solo Argissolo Vermelho distrófico arênico, e um em condições de laboratório. Os tratamentos consistiram da aplicação ou não de dejetos de suínos na forma líquida e sólida (cama sobreposta), sobre os resíduos culturais de aveia com e sem incorporação ao solo, na cultura do milho. Com vistas ao alcance do segundo objetivo, foi utilizado um conjunto de dados gerados na área Experimental do Departamento de Solos da UFSM no período de 1998 a 2002 envolvendo a dinâmica do N no sistema solo-planta com o uso de dejetos líquidos de suínos em sistema plantio direto. Os resultados obtidos indicaram que as perdas de N por volatilização de NH3 foram maiores com a aplicação de dejetos líquidos de suínos do que com a aplicação de dejetos sólidos e que essas perdas diminuíram com a incorporação dos dejetos ao solo. As quantidades de N mineral na camada de 0-90 cm do solo não diferiram entre os tratamentos com e sem incorporação dos dejetos apesar da quantidade de N perdida por volatilização ter sido maior no tratamento sem incorporação. A incorporação dos dejetos ao solo não aumentou a decomposição do C da palha e nem a imobilização de N. A presença da palha de aveia estimulou a imobilização do N amoniacal aplicado com os dejetos de suínos. Os dejetos sólidos apresentaram baixo potencial fertilizante nitrogenado ao milho, comparado aos dejetos líquidos, em função da baixa taxa de mineralização do N orgânico presente na cama sobreposta. A emissão de N-N2O aumentou com a aplicação dos dejetos líquidos sobre a palha de aveia em relação ao sistema com palha e sem dejetos. A recuperação do 15N amonical dos dejetos líquidos pelo milho no estádio de maturação fisiológica foi de apenas 14,9%. Nesse mesmo período, apenas 49,2% do 15N amoniacal aplicado com os dejetos líquidos de suínos foram recuperados no solo e na planta (parte aérea + raízes), indicando que mais da metade do N amoniacal aplicado com os dejetos foi perdido através dos processos de volatilização, lixiviação e desnitrificação. O modelo STICS subestimou a quantidade de N perdida por volatilização de amônia, após a aplicação dos dejetos de suínos. O uso de um fator em STICS para expressar a perdas de N por volatilização de amônia proporcionou uma melhora nas simulações da dinâmica do N no solo. A dinâmica da água na camada 0 60 cm do solo foi simulada por STICS com um erro inferior a 13,5%. Os resultados desse estudo evidenciaram que o modelo STICS reparametrado apresenta potencial para ser utilizado em condições de clima subtropical na simulação da dinâmica do N e da água em sistema plantio direto com o uso de dejetos de suínos.

Made available in DSpace on 2016-12-08T15:50:04Z (GMT). No. of bitstreams: 1 PGMS14DA022.pdf: 1661890 bytes, checksum: 3147ca0fadcd842b04a10dab73754a64 (MD5) Previous issue date: 2014-05-16 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The total content of phosphorus (P) is distributed in the soil forms with different degrees of lability, being the distribution of the forms affected by type soils and soil manegement. The work consisted of three studies, being that the first study quantified the stock of the forms of inorganic and organic P in the surface horizon and in 42 profiles soil of six orders in the Santa Catarina State. After collection, the samples were subjected to chemical fractionation of P Hedley. The soils most weathered had higher stock of P total, while the soils less weathered showed higher levels of labile organic P. In the second study was conducted fractionation analysis of P and P nuclear magnetic resonance (NMR) in soil agroecosystems with high organic matter content. The areas were evaluated in apple orchard, native grass and pine plantation. The results of chemical fractionation and NMR of P, showed that the conversion of natural ecosystems to areas cultivated altered the distribution of P forms in soil, where the fractions organic were reduced in culture without the addition of phosphate fertilizer systems. The third study involved the assessment of forms of P in soils with different clay contents that subjected the applications of liquid swine manure. Soil samples were collected in three regions of Santa Catarina State and subjected to chemical fractionation of P. The results showed that the addition of liquid swine manure for long term increased the content of all forms of P evaluated by fractionation, mainly in inorganic forms, with more accumulated in the topsoil. In soils with sandy texture there accumulation of labile P, and in soils clay there accumulation the of forms lower lability / O conteúdo total de fósforo (P) do solo é distribuido em formas com diferentes graus de labilidade. A distribuição das formas de P podem ser afetadas pelo tipo de solo e o manejo adotado durante seu uso. O trabalho foi composto de três estudos. O primeiro estudo quantificou o estoque das formas de P inorgânicas e orgânicas no horizonte superficial e nos perfis de 42 solos de seis ordens no Estado de Santa Catarina (SC). Após a coleta, as amostras foram submetidas ao fracionamento químico de P de Hedley. No segundo estudo foi realizado o fracionamento químico de P e análise de ressonância magnética nuclear de P (RMN) em amostras de solo de áreas de pomar de maçieira, campo nativo e florestamento de pinus com alto teor de matéria orgânica. O terceiro estudo consistiu na avaliação das formas de P em solos com diferentes teores de argila que foram submetidos a aplicações de dejetos líquidos de suínos. As amostras de solo foram coletadas em três regiões do Estado de SC e submetidas ao fracionamento químico de P. No estudo 1 os solos mais intemperizados apresentaram maiores estoque de P total enquanto os solos menos intemperizados apresentaram maiores teores de P lábil e P orgânico. No segundo estudo os resultados do fracionamento químico e RMN de P mostraram que a conversão de ecossistemas naturais em áreas cultivadas alterou a distribuição das formas de P no solo, onde as frações orgânicas foram reduzidas em sistemas de cultivo sem a adição de fertilizantes fosfatados. Os resultados do terceiro estudo mostraram que a adição de dejetos líquidos de suínos por longo prazo aumentou o teor em todas as formas de P avaliadas pelo fracionamento, principalmente em formas inorgânicas, sendo mais acumulado na camada superficial do solo. Nos solos com textura arenosa houve acúmulo de P principalmente nas frações lábeis e em solos de textura argilosa houve acúmulo de P principalmente em formas de menor labilidade

[pt] A pasta de gelo é uma mistura de água e um aditivo, com finas partículas de gelo, apresentando uma alta densidade de energia térmica. O principal motivo de sua utilização deve-se à combinação do aproveitamento do calor latente na mudança de fase com capacidade de ser bombeado. O presente trabalho trata do estudo experimental sobre a transfe rência de calor e queda de pressão, com mudança de fase, utilizando uma mistura de propileno glicol - água com 13,8% de concentração em peso, num trocador de calor de placas com arranjo em U para 16 placas. Realizaram-se testes de troca de calor com escoamento em paralelo e contra-corrente, para duas condições de fração mássica de gelo e números de Reynolds para a pasta de gelo entre 150 e 425, com diferentes condições de carga térmica. Dos testes foram observados aumentos de até 25% no coeficiente global de troca calor, ao se incrementar a vazão e, conseqüentemente, o número de Reynolds da pasta de gelo. Com o aumento da fração de gelo melhora-se a capacidade de resfriamento, diminuindo o número de Nusselt da pasta de gelo. O coeficiente global de troca, porém, começa a diminuir. Na literatura esta relação ainda não está bem definida. Alguns autores relatam ganhos, perdas ou indiferença no coeficiente global. Resultados do coeficiente global e do número de Nusselt, nos modos paralelo e contra-corrente, não apresentaram grande diferença. A capacidade de resfriamento em contra-corrente foi maior, apresentando valores de efetividade cerca 10% acima dos resultados observados no modo paralelo. Os fatores de atrito encontrados variaram entre 0,030 a 0,085, o que concorda com os resultados apresentados por outros pesquisadores. Como era de se esperar, o fator de atrito diminui com o aumento da vazão mássica e de maneira inversa com o aumento da fração de gelo. / [en] Ice slurry is an aqueous solution from which ice crystals are formed. These crystals possess high energy density, in the form of latent heat. Furthermore, the fact of being a slurry makes it an excellent energy carrier, for it can be easily pumped. The present work presents an experimental procedure to assess the heat transfer and the pressure loss, with phase change, using a mixture of propyleneglycol and water, 13.8% weight, in a U-plate heat exchanger with 16 plates. Tests were carried out for both parallel and counter-flow configurations of the heat exchanger, for two different mass fractions of ice and with Reynolds numbers between 150 and 425 for the slurry. Different thermal loads were considered. The experiments showed increases of up to 25% in the overall heat transfer coeficiente when the slurry flow is increased, with consequent increase in the Reynolds number. By increasing the ice fraction the cooling capacity is improved, reducing the Nusselt number. In the literature, this relationship is not clearly defined, as some authors show gains in the heat exchange coefficient, losses, and some others did not observe any influence on this parameter. Regarding the heat Exchange configuration, i.e., parallel or counter-flow, neither the heat exchange coefficient, nor the Nusselt number suffered major influence. The effectiveness is up to 10% higher for the counter-flow configuration in comparison with the parallel configuration. The figures found for the friction coefficient, between 0,030 and 0,085, are in good agreement with the literature. As expected, the friction coefficient decreases when the mass flow is increased, and increases when the ice fraction is increased.

Marine clay deposits are characterized by very soft to soft consistencies (undrained strength 1-50 kPa), presence of saline pore solution and low-swelling clays. Besides, loss of metastable structure on disturbance, poor undrained strengths of soft clays is contributed by high water contents. Presence of saline pore solution and low-swelling clays (illite, chlorite, kaolinite) play an important role in developing metastable structure of soil sediments deposited in marine environment. The pore solution salinity regulates the “physico-chemical (A - R) stress” that in turn has significant bearing on development of the metastable structure. Metastable structure refers to edge-face, edge-edge associations in card-house arrangement of platy/elongate particles that develop during deposition. Loss of metastable structure of soft marine clays upon disturbance leads to excessive settlements and slope failures. Besides A - R forces, metastable structure of marine clays is contributed by cementation bonds, thixotropic hardening, ion leaching, formation or addition of dispersing agents and chemical weathering. Secondary compression also causes bonding of micro-structural units that increase stiffness and strength of the metastable structure. Review of literature brings out that majority of studies examining the role of physico-chemical factors on the engineering behavior of marine clays have focused on illite rich sediments. However, non-swelling clay, namely, kaolinite is also encountered in marine deposits (example, Pusan clay, Singapore clay, Sarapui soft clays). Kaolinites differ from illites in being 1:1 mineral (unit layer comprises of 1 silica sheet bonded to 1 gibbsite sheet) and having strong hydrogen bonding between unit layers. Consequently, kaolinite particles are thick (0.3 to 3 ìm thickness) with low surface area (10 to 20 m2/g). Also the hydrogen bonding between unit layers do not allow them to separate on hydration. Combination of very low isomorphous substitution (Al for Si 1 in 400), low cation exchange capacity (3 meq/100g), and low surface area, lead to negligible development of diffuse double layer repulsion forces between kaolinite particles. Strong positive edge (developed on broken bonds at particle edges from adsorption of hydrogen ions) negative face attraction between kaolinite particles, encourages flocculation of particles at range of water contents. It was therefore considered of interest to examine the engineering response of kaolinites to changes in pore solution salinity from leaching effects. The focus of the thesis is hence to gain better understanding of physico-chemical (pore solution salinity, A - R forces) and mechanical (secondary compression, loss of overburden) factors towards development of metastable structure of kaolinite clays deposited in synthetic seawater environments in the context of their compressibility and undrained strength characteristics. Laboratory experiments are performed with kaolinites that are slurry consolidated in conventional consolidometers in saline and synthetic seawater solutions. The metastable structure developed by consolidated specimens is relevant to alluvial marine sediments that contain kaolinite (example, Pusan clay, Singapore clay, Sarapui soft clays). The structure of the thesis is as follows: Chapter 1 gives an introduction to the thesis. Chapter 2 provides a detailed review of literature on the role of chemical factors (pore solution composition, A - R forces, osmotic suction) and mechanical processes (secondary compression and overconsolidation) in developing metastable structure of kaolinite specimens subjected to slurry consolidation and the consequent influence of metastable structure on compression, undrained strength and sensitivity characteristics of clay specimens. The Chapter also defines the scope and objectives of the study. Chapter 3 details the experimental program undertaken to bring out the role of chemical factors and mechanical processes in influencing the 1-dimensional compression and undrained strength characteristics of slurry consolidated kaolinites prepared in saline medium. Chapter 4 delineates the role of chloride salt solutions (sodium, magnesium and calcium) and synthetic seawater solution in contributing to the metastable structure developed by slurry consolidated kaolinites at various vertical effective stress (óv’) and the consequent influence of metastable structure on 1-dimensional compression, undrained strength and sensitivity characteristics of the clay. Chapter 5 examines influence of secondary compression on metastable structure developed by kaolinites that were slurry consolidated in 24.53 g/L sodium chloride and synthetic seawater solutions and the consequence of the developed metastable structure on undrained strength and sensitivity. The chapter also examines the consequences of secondary compression experienced by soft overconsolidated kaolinites on their undrained strength and sensitivity characteristics. Chapter 6 examines the relative influence of differential osmotic stress and electrochemical stress on the consolidation behaviour of kaolinite specimens that are slurry consolidated in sodium chloride solutions. The osmotic efficiencies (á) of kaolinite were obtained using the Fritz-Marine Membrane Model. Chapter 7 summarizes the major conclusions of the thesis.