Conselho Nacional de Desenvolvimento Científico e Tecnológico / Soil structure is defined by form and arrangement of soil particles and pores. As a consequence of time increase of no-tillage use the soil structure has been modified by repetition of traffic caused by agricultural operations throughout years, which, in turn, has been identified as compaction implying in lost of soil quality. In this study, the S index sensibility was tested as related to other soil physical properties and was evaluated also the alterations of pore diameters and its implications on saturated hydraulic conductivity and air conductivity caused by soil use. Its was used six Oxisols, classified by brazilian soil classification system as: Latossolo Vermelho eutrófico, Latossolo Vermelho aluminoférrico, Nitossolo Vermelho distrófico, Latossolo Bruno alumínico, Latossolo Vermelho distrófico de textura média, Latossolo Vermelho distrófico de textura argilosa e Latossolo Vermelho distroférrico. The soil uses studied were: a) natural condition represented by native forest or grass field and; b) no-tillage. The S index was not associated to total clay content neither to dispersed clay content. However, for clayey soils the S index had an exponential decreased as the bulk density increased and an exponential increase as organic matter increased. The available water had a log increase with S increase and pre-consolidation pressure reduced exponentially as S index increased. These results imply sensibility to S index to evaluate soil quality of clayey soils. The soil use effects on water and air flow was detected by alterations caused by notillage on increasing bulk density, reducing total porosity, changing pore size distribution with increase in micropores as macropores reduced causing, in turn, reduction on saturated hydraulic conductivity and air conductivity. The high aggregation state of soils under native forest favored to presence of big pores and smaller amount of intermediate pores. In more compacted layer of soils under no-tillage was detected reduction of intermediate pore class and increase in micropores. / A estrutura do solo é definida pela sua condição física, expressa pela dimensão, forma e arranjo das partículas sólidas e dos poros a elas associados. Com o tempo de uso do sistema plantio direto, a estrutura do solo é modificada pela repetitividade das operações agrícolas realizadas ao longo dos anos. A alteração da estrutura pela compactação tem causado perdas na qualidade física dos solos. Neste trabalho, testou-se a sensibilidade do índice S, em relação a algumas propriedades físicas dos solos e avaliaram-se as alterações impostas pelo uso do solo no diâmetro dos poros, na condutividade hidráulica saturada e na condutividade do ar. Os solos avaliados foram: Latossolo Vermelho eutrófico, Latossolo Vermelho aluminoférrico, Nitossolo Vermelho distrófico, Latossolo Bruno alumínico, Latossolo Vermelho distrófico de textura média, Latossolo Vermelho distrófico de textura argilosa e Latossolo Vermelho distroférrico. Os sistemas de uso foram: condição natural, representada pela mata nativa ou campo nativo; e condição de lavoura, sob plantio direto. O índice S não se relacionou com o teor de argila total ou argila dispersa. Para o os solos argilosos e muito argilosos, o índice S apresentou um decréscimo exponencial com o aumento da densidade do solo e um crescimento exponencial com o aumento da matéria orgânica do solo. A água disponível as plantas aumentou de forma logarítmica com o aumento do S enquanto a pressão de préconsolidação reduziu exponencialmente com o aumento do S. Conclui-se que o índice S apresentou sensibilidade para determinar a qualidade física dos solos de textura argilosa e muito argilosa. Quanto ao impacto do uso do solo sobre os fluxos de água e ar, constatou-se que o solo sob cultivo apresentou aumento na densidade e redução na porosidade total, ocorreu alteração na distribuição do diâmetro de poros com aumento da quantidade de poros pequenos em detrimento dos poros maiores, o que provocou a redução da condutividade hidráulica saturada e da condutividade do ar no solo. A alta estruturação do solo na mata nativa favoreceu a presença de poros grandes e menor quantidade de poros de tamanho intermediário. Nas camadas mais compactadas do plantio direto verificou-se a redução da classe de poros de tamanho intermediário e o aumento da quantidade de poros pequenos.

Dans l'industrie du raffinage, les procédés de craquage catalytique permettent la production de carburants à partir de coupes pétrolières lourdes, telles que les distillats sous vides (DSV). Pour optimiser ces procédés, un hydrotraitement préalable est nécessaire. Ces dernières années, les travaux conséquents de R&D ont considérablement amélioré l'activité des catalyseurs d'hydrotraitement. Par conséquent, le transfert de matière interne peut devenir limitant, il doit donc être quantifié.Une méthodologie utilisant la chromatographie inverse liquide a été développée afin de caractériser le transfert de matière dans des supports aluminiques de catalyseur. Le système a ensuite été déployé pour caractériser l'influence de l'adsorption, de la température et des précurseurs de la phase active. Dans des alumines mésoporeuses, le régime de diffusion est moléculaire pour des composés saturés allant des coupes essences au DSV. Ainsi, pour différentes alumines, des valeurs de tortuosité ont été estimées et corrélées aux propriétés texturales (porosité, surface spécifique et distribution en taille des pores). Ces relations montrent que les valeurs de tortuosité obtenues ne sont pas en accord avec un solide homogène vis-à-vis des propriétés de transfert de matière. Il y aurait donc une organisation dans la porosité des alumines.Un test catalytique en réacteur agité a aussi été développé pour étudier le transfert de matière en conditions réactives. L'impact de la taille des grains sur l'hydrodésulfuration d'une molécule synthétisée a été caractérisé et modélisé. Ces résultats ont été comparés aux expériences de chromatographie inverse avec un bon accord / The catalytic cracking has an important role in fuels production from heavy oil cuts like vacuum gas oil (VGO). To optimize these processes, a pre-hydrotreatment is required. The amount of work dealt by the research community in the last years has highly contributed to the enhancement of the catalyst’s activity. Therefore, the internal mass transfer can become the limiting step and it must be quantified.A methodology based on inverse liquid chromatography has been developed to characterize the mass transfer within alumina catalyst supports. The experimental setup was also used to study the influence of several parameters into mass transfer properties such as, adsorption, temperature, and active phase precursors. In mesoporous aluminas, the diffusion regime undertaken by saturated compounds, going from gasoline to VGO is the molecular regime. For different alumina supports, tortuosity values were estimated and correlated to the textural properties (porosity, specific surface area and pore size distribution). These results showed that the aluminas can not be considered as homogeneous supports given the estimated mass transfer properties. Thus, we assume that a hierarchical porous structure might be in cause. A catalytic test promoted in a stirred reactor was also developed to study the mass transfer properties under reactive conditions. The impact of the particle grains size into the hydrodesulphurization of a synthetized molecule was characterized and modeled. A good agreement was found between the data obtained using the inverse chromatography experiments and the catalytic tests

Ce travail de recherche a pour but d’étudier des matériaux cimentaires soumis à des attaques sulfatiques selon trois différentes conditions : attaques sulfatiques externes (ASE), formation différée d’ettringite communément appelée attaque sulfatique interne et l’effect couplé des deux réactions, ainsi que de proposer un mécanisme uniforme pour les dégradations causées par ces réactions. En se basant sur le mécanisme proposé, un model poro-mécanique est proposé pour simuler l’expansion induite par les produits expansifs néoformés pendant la dégradation. Cette étude inclut trois parties : dans la première partie, les dégradations des éprouvettes de pâte de ciment correspondant à deux types de ciments (CEM I et CEM III) et deux dimensions exposées à trois différents types d’attaques sulfatiques (ASE, ASI, et le couplage des deux réactions), sont étudiés et comparés : variations de longueur, de masse, ainsi que des observations visuelles. Les éprouvettes exposées au couplage ASE-ASI montrent la cinétique d’expansion la plus rapide et le degré de dégradation le plus important, comparé aux autres cas. Ensuite, la structure poreuse des pâtes de ciment avant et après les attaques sulfatiques est caractérisée en utilisant différentes techniques : porosimétrie à mercure (MIP), sorption dynamique de vapeur (DVS), porosité accessible à l’eau ou essais de dissolution par traitement thermique. En comparant les variations de la distribution de la taille des pores des pâtes de ciment exposées à différentes conditions, les cristaux néoformés se trouvent précipités à la fois dans les pores capillaires et les pores des C-S-H. En plus de l’évolution de la distribution de la taille des pores pendant l’ASI, un mécanisme de dégradation est proposé : les cristaux néoformés (l’ettringite) sont précipités dans les grands pores, sans provoquer une expansion manifeste, et ils sont ensuite précipités dans les pores capillaires et les pores des C-S-H, ce qui induit un gonflement. Par ailleurs, le volume des pores occupé par les produits de l’ASI sont libérés après des essais de dissolution par traitement thermique, ce qui confirme la formation de produits d’expansion dans cette gamme de pores. Enfin, en se basant sur les résultats expérimentaux montrant que l’ettringite se forme en allant des grands pores vers les plus petits, un model poro-mécanique est proposé pour simuler l’expansion des matériaux cimentaires soumis à des attaques sulfatiques. Le modèle est basé sur la croissance contrôlée en surface et les propriétés physicochimiques pour l’ASE et l’ASI, malgré les différences entre ces deux réactions. Deux constantes indépendantes : ai et ap sont proposées pour représenter la cinétique de l’invasion des cristaux et la déformation. De plus, le modèle peut être couplé avec toutes les théories mécaniques, par exemple : l’élasticité, la plasticité, la théorie de l’endommagement ou autres. Le modèle illustre bien le processus de cristallisation et il prédit l’expansion correspondante à la fois à l’ASE et l’ASI / This work aims to study cement-based materials subjected to sulfate attacks in three different conditions: External Sulfate Attack (ESA), Delayed Ettringite Formation (DEF) and the Coupling effect of both, and to propose the same damage mechanism for all of them. Based on the proposed mechanism, a poromechanical model is established to simulate the expansion induced by expansive crystals during the degradation. The study includes the following three parts. In the first part, the degradation of cement paste specimens with two kinds of cement type (CEM I and CEM III) and two dimensions (2 2 12 cm3 and 11 11 22 cm3) exposed to three sulfate attack conditions (ESA, DEF, and Coupling effect) are studied and compared, including the length variation, mass variations, and observations. The specimens exposed to the coupling effect show the fastest kinetics and the most serious degree of degradation compared to the other cases. Then, the pore structure of cement pastes before and after sulfate attacks is characterized via different techniques: MIP, DVS, water accessible tests and heat-based dissolution tests. By comparing the variation of pore size distribution of cement pastes exposed to different conditions, the generated crystals are found to be precipitated both in capillary and gel pores. In addition to the evolution of pore size distribution during DEF, a damage mechanism is proposed: the generated crystals (ettringite) precipitate in the big pores without inducing an obvious expansion, and then penetrate into capillary and gel pores, which leads to a swelling. Moreover, the pore volume occupied by DEF induced products is released after heat-based dissolutiontests, which further confirms the formation of expansive products in that porerange. Finally, based on the experimental conclusion that ettringite forms through the large to small pores in all cases, a poromechanical model is proposed to simulate the expansion of cement-based materials submitted to sulfate attacks. The model is based on the surface-controlled growth and physicochemical properties both for ESA and DEF, despite the different source of sulfate ions. Two independent constants, ai and ap, are proposed to represent the kinetics of crystal invasion and deformation. Moreover, the model could be coupled with any mechanical theories, e.g. elasticity, plasticity, damage theory or any other. The model well illustrates the crystallization process and well predicts the corresponding expansion both in ESA and DEF

Die vorliegende Arbeit befasst sich mit Untersuchung der gekoppelten Einflüsse ‎von Gasart, Porengröße und Porengrößenverteilung auf die effektive ‎Wärmeleitfähigkeit nicht-durchströmter poröser Materialien (Dämmstoffe). Diese ‎Zusammenhänge sind bisher nur ansatzweise bekannt und für eine spätere ‎praktische Anwendung von zunehmend großer Bedeutung. Um dies zu erreichen ‎wurden 12 verschiedene hoch poröse Materialien (Porosität höher als 70 %) ‎ausgewählt, die unterschiedlichen Porengrößenverteilungen im Makro- Mikro- und ‎Nanobereich haben. Die effektive Wärmeleitfähigkeit wurde hauptsachlich in zwei ‎unterschiedlichen Messverfahren untersucht. Die Messungen erfolgt bei normalem ‎Druck in vier Gas Atmosphären ‎(Kr, Ar, N2 and He) bei Temperaturen bis maximal 900 °C. Kritische Analyse zum ‎jeweiligen Messverfahren und Auswertungsalgorithmus wurden durchgeführt. Ein ‎mathematisches Model basiert auf die Porengrößenverteilung mit Berücksichtigung ‎des Knudsen Effekts wurde entwickelt um die Änderung der effektiven ‎Wärmeleitfähigkeit beim Wechsel der Gas Atmosphäre auszuwerten. Diese führt zu ‎besser Ergebnisse als die ausgewertet Ergebnisse von den vorhandenen Modellen ‎aus der Literatur. ‎ / In the present work, the influences of exchanging the filling gas accompanied with Knudsen effect on effective thermal conductivity were investigated with experiments and physical mathematical modeling. This work is thought to be the first intensive study in this area of the research, which includes twelve different porous insulation materials. Analysis of the huge number of experimental results leaded to new observations regarding various coupling effects. An improved model for predicting the change in effective thermal conductivity due to exchanging the filling gas has been developed with regards to the Knudsen effect based on models for rarefied gases and parallel arrangements models for effective thermal conductivity.

No description available.

This paper deals with the determination of the capillary pore-size distribution (CPSD) and equilibrium moisture content (EMC) of untreated and thermally modified (TM) Norway spruce [Picea abies (L.) Karst.] by means of the pressure plate technique (PPT). Desorption experiments were conducted at very high values of relative humidity (RH) in the range between 99.2% and 100%. The thermal modification of spruce results in an alteration of the CPSD, owing to the formation of intercellular cracks in the middle lamella, as a result of cell-wall compression. The desorption curves for both untreated and TM spruce show an extremely upward bend at 99.97% RH. This step reflects an EMC of 38.1% for untreated spruce and 33.8% for TM spruce. None of the samples shrunk during the PPT measurements. Following desorption experiments at 97.4% RH, all samples shrunk. This step reflects an EMC of 27.9% for untreated spruce and 21.7% for TM spruce.

No description available.