In the first part of this thesis, CaCO3 (calcite) powder ball-milled to micro/nano scale were subjected to isothermal firing in the temperature range of 450-600 ¢XC in an open air furnace in order to study specific-surface area reduction as a result of early-stage sintering/coarsening/coalescence/repacking (denoted as SCCR process) of the fine particles. The surface area and pore size distributions were obtained from the BET and BJH methods, respectively. The H1 type adsorption/desorption hysteresis loop of the type IV isotherm was used as an indicator of cylindrical pore formation upon dry pressing and firing of the powder. The apparent activation energy for the onset SCCR of the dry-pressed calcite powder turned out to be 57.5¡Ó1.0 kJ/mol based on t0.5, i.e. time for 50 % specific surface area reduction. The minimum temperature for such an incipient SCCR process was estimated to be 590K (317¢J) by extrapolating the specific-surface-area reduction rate to null. The mechanism of specific surface area change includes the Brownian motion, coarsening and coalescence/repacking of calcite particles besides sintering via synchronizing diffusion of calcium ion and carbonic acid ion along grain surface and boundary. In the second part of this thesis, pulsed laser ablation on micrometer-sized calcite (type I) powder in liquid H2O (PLAL) was conducted to study the structure and optical property change of calcium carbonate under a dynamic high-temperature. high-pressure aqueous condition. X-ray diffraction (XRD) indicated the fragmented calcite I powder via such a PLAL process change predominantly into a metastable CaCO3 II phase presumably by a displacive type transformation from calcite I and/or nucleated from atom clusters. The refined XRD lattice parameters indicate a significant internal compressive stress (up to 1.5 GPa) was retained for the predominant CaCO3 II nanoparticles having well-developed (013), (010) and (013) faces as revealed by transmission electron microscopy (TEM). Minor calcium carbonate nanoparticles were also identified by TEM to be other high-pressure polymorphs (type III and aragonite), hydrated (monohydrocalcite, ikaite), amorphized (amorphous calcium carbonate), and even decomposed as cubic lime (CaO). Monohydrocalcite occasionally occurred as epitaxial intergrowths within the predominant CaCO3 II matrix. Vibrational spectroscopy (Raman and FTIR) indicated the structure units of the overall nanoparticles by the PLAL process were considerably modified as a combined results of size miniature, protonation and internal compressive stress. The UV-visible absorption results further indicate that the minimum band gap of the colloidal solution was narrowed down to ca. 5 eV and 3 eV for the predominant CaCO3 II and minor accessory phases, respectively, thus shedding light on their potential opto-catalytic applications.

The aim of this research was to determine the effects of the fineness of different mineral additives on loss on ignition, heat of hydration, physical, mechanical and chemical properties of blended cements. For that purpose, portland cement clinker was replaced with granulated blast furnace slag (GBFS), natural pozzolan (NP) and limestone (L) at 6%, 20% and 35% replacement levels. Blended cements containing GBFS and NP were ground to a fineness of 3000, 5000 and 6000 cm2/g. Cements containing L were ground to 3000 cm2/g, 4000 cm2/g and 4500 cm2/g. All of the blended cement types mentioned above were both interground and separately ground to the specified fineness levels. Therefore, a total of 57 different cements were produced. Loss on ignition, heat of hydration, chemical, mechanical and physical analyses were performed on the produced cements. Moreover, the chemical analyses of the cements were obtained for cement particles finer (-45&mu / m) and coarser (+45&mu / m) than 45 &mu / m in order to determine the ingredients of -45 &mu / m, which is known to be more reactive. As a result it was shown that the grindability differences of the cement ingredients affect the properties of blended cements. An increase in the specific surface area increases both the compressive strength and heat of hydration values and adversely affects the loss on ignition values. The results also showed that if the cement particles were ground finer, it was more prone to moisture which resulted in higher loss on ignition values after longer periods.

A series of studies have been carried out to elucidate the sediment effect on the saturation level of methane hydrate in sediments. The specimens tested covered most of the natural sediment types, with various combinations of particle size and mineral composition. The results obtained indicate that particle size and clay contents are the two key factors determining the saturation level of gas hydrate in sediments: the finer the particle size and/or the higher the clay content, the lower the hydrate saturation. The observed particle size effect and clay effect on hydrate saturation can be accredited to the specific surface area of a sediment.

The importance of studying the behaviour and properties of concrete can be highlighted by considering the fact that concrete is the most used man-made material in the world. The very first step in making concrete is its mix design and deciding the type and amount of constitutes used in the production of concrete which should fulfil the requirements of the final product. Mix design models are commonly used for the purpose of proportioning concrete ingredients while anticipating the properties of the final product.  The current document deals with the commonly used principals in mix design models namely particle packing theory and excess water/paste layer theories. The conducted studies includes an investigation on accuracy of particle packing models (Toufar, 4C, CPM) and also tries to address the issue with measurement of specific surface area of particles as an essential input to water/paste layer theories.  It has been observed that the particle packing models can predict the packing density with acceptable margin. However, it should be mentioned that the particle packing models by themselves are not mix design models but should be rather used as a part of a mix design. In addition, it was found that the accuracy of calculating the specific surface area of particles based on their size distribution curve can be further improved by assuming angular platonic solids as uniform shape of aggregate instead of traditional approach of assuming spheres for aggregates’ shape.

Este trabalho visa à quantificação da carbonatação em argamassas de cimento branco em comparação à carbonatação de argamassas de cimento cinza convencional. O estudo experimental foi dividido em 2 fases distintas. Na primeira foram produzidos 12 cimentos pela substituição de 0, 5, 10 e 20% de 3 clínqueres de diferentes procedências por um calcário calcítico. Nesta etapa do trabalho o clínquer e o calcário foram moídos conjuntamente, de forma que não havia controle sobre a granulometria do calcário e do clínquer individualmente. Na segunda fase foram produzidos 21 cimentos, os quais foram constituídos pela adição ao clínquer de 0, 5 10 e 20% do mesmo calcário da primeira fase e de um fíler quartzoso moído de forma a possuir a mesma granulometria do calcário. Nesta etapa os materiais foram previamente moídos, de forma que sua granulometria inicial era controlada, constituindo-se, portanto, 21 cimentos com a mesma finura e 21 argamassas com a mesma relação água/aglomerante. Os resultados dos ensaios de carbonatação, resistência à compressão, porosimetria, termogravimetria, difração de raios-X e análise do pH da solução aquosa dos poros indicam que o calcário tem um efeito potencializador da hidratação das argamassas, com efetivo refinamento da estrutura porosa. Entretanto, a comparação entre os resultados de ambas as fases do estudo mostra que a melhora do desempenho de cimentos acrescidos de calcário não se deve apenas ao efeito de fíler desta adição, mas a uma melhora na eficiência dos cimentos compostos, possivelmente pelo maior moabilidade da mistura clínquer-calcário induzida pelo calcário, isto é, o calcário, quando co-moído com o clínquer, faz com este atinja uma maior superfície específica, aumentando, desta forma, a sua reatividade. Argamassas feitas com cimentos brancos apresentaram menor carbonatação do que argamassas feitas com cimentos cinzas, considerando uma mesma relação água/aglomerante e uma mesma superfície inicial. Os resultados indicam algum tipo de interação química do calcário com a pasta que aumenta a carbonatação, mas este efeito é perceptível para teores elevados de adição. / The present study aims to quantify white cement mortars carbonation when compared to carbonation of conventional gray cement mortars. In the first part of the research, 12 cements were produced by substitution of 0, 5, 10 and 20% of 3 different clinkers by limestone. Clinker and limestone were ground together, so that there was no control over the fineness of limestone and clinker individually. In the second stage of the research 21 cements were produced, which were formed by adding to clinker 0, 5, 10 and 20% of limestone and a crushed quartz filler with the same fineness of limestone. In this second part of the research the materials were first milled, so that their initial particle size was controlled, criating therefore 21 cements with the same finess and 21 mortars with the same water / binder ratio. The test results of carbonation and porosimetry show that limestone has a potentiating effect on mortars hydration with effective refinement of the porous structure. However, the results show that the performance improvement of cement with limestone is not only due to the limestone effect as a filler, but also due to an improvement in the efficiency of blended cements, possibly due to greater efficiency of the clinkers that were milled together with limestone. White cement mortars showed less carbonation than gray cement mortars, assuming the same water / binder ratio and the same initial specific surface. The results show a possible chemical interaction between limestone and the cement paste that eventually increase carbonation depth. This effect was only observable with high addition contents.

Este trabalho visa à quantificação da carbonatação em argamassas de cimento branco em comparação à carbonatação de argamassas de cimento cinza convencional. O estudo experimental foi dividido em 2 fases distintas. Na primeira foram produzidos 12 cimentos pela substituição de 0, 5, 10 e 20% de 3 clínqueres de diferentes procedências por um calcário calcítico. Nesta etapa do trabalho o clínquer e o calcário foram moídos conjuntamente, de forma que não havia controle sobre a granulometria do calcário e do clínquer individualmente. Na segunda fase foram produzidos 21 cimentos, os quais foram constituídos pela adição ao clínquer de 0, 5 10 e 20% do mesmo calcário da primeira fase e de um fíler quartzoso moído de forma a possuir a mesma granulometria do calcário. Nesta etapa os materiais foram previamente moídos, de forma que sua granulometria inicial era controlada, constituindo-se, portanto, 21 cimentos com a mesma finura e 21 argamassas com a mesma relação água/aglomerante. Os resultados dos ensaios de carbonatação, resistência à compressão, porosimetria, termogravimetria, difração de raios-X e análise do pH da solução aquosa dos poros indicam que o calcário tem um efeito potencializador da hidratação das argamassas, com efetivo refinamento da estrutura porosa. Entretanto, a comparação entre os resultados de ambas as fases do estudo mostra que a melhora do desempenho de cimentos acrescidos de calcário não se deve apenas ao efeito de fíler desta adição, mas a uma melhora na eficiência dos cimentos compostos, possivelmente pelo maior moabilidade da mistura clínquer-calcário induzida pelo calcário, isto é, o calcário, quando co-moído com o clínquer, faz com este atinja uma maior superfície específica, aumentando, desta forma, a sua reatividade. Argamassas feitas com cimentos brancos apresentaram menor carbonatação do que argamassas feitas com cimentos cinzas, considerando uma mesma relação água/aglomerante e uma mesma superfície inicial. Os resultados indicam algum tipo de interação química do calcário com a pasta que aumenta a carbonatação, mas este efeito é perceptível para teores elevados de adição. / The present study aims to quantify white cement mortars carbonation when compared to carbonation of conventional gray cement mortars. In the first part of the research, 12 cements were produced by substitution of 0, 5, 10 and 20% of 3 different clinkers by limestone. Clinker and limestone were ground together, so that there was no control over the fineness of limestone and clinker individually. In the second stage of the research 21 cements were produced, which were formed by adding to clinker 0, 5, 10 and 20% of limestone and a crushed quartz filler with the same fineness of limestone. In this second part of the research the materials were first milled, so that their initial particle size was controlled, criating therefore 21 cements with the same finess and 21 mortars with the same water / binder ratio. The test results of carbonation and porosimetry show that limestone has a potentiating effect on mortars hydration with effective refinement of the porous structure. However, the results show that the performance improvement of cement with limestone is not only due to the limestone effect as a filler, but also due to an improvement in the efficiency of blended cements, possibly due to greater efficiency of the clinkers that were milled together with limestone. White cement mortars showed less carbonation than gray cement mortars, assuming the same water / binder ratio and the same initial specific surface. The results show a possible chemical interaction between limestone and the cement paste that eventually increase carbonation depth. This effect was only observable with high addition contents.

La neige est un matériau poreux dont la microstructure change en permanence. L'ensemble de ces transformations, qui prend le nom de ``métamorphisme", est susceptible d'affecter les propriétés thermiques, mécaniques et électromagnétiques de la neige au niveau macroscopique. En particulier, les échanges d'énergie et de matière à l'intérieur du manteau neigeux et entre la neige et l'atmosphère sont fortement influencés par l'évolution au cours du temps de la microstructure de la neige. Une représentation adéquate du métamorphisme dans les modèles de manteau neigeux s'avère donc cruciale. La microstructure d'un matériau poreux peut être raisonnablement décrite en se servant d'un nombre réduit de variables. En effet, la masse volumique, la surface spécifique (SSA) et la distribution de courbure permettent de caractériser la microstructure d'un matériau. Cependant, dans le cas de la neige cette approche n'en est qu'à ses débuts et n'a pas encore été appliquée de façon systématique. Des variables semi-empiriques, difficiles à mesurer et dépourvues de lien direct avec d'autres propriétés physiques, sont encore largement utilisées dans les modèles détaillés de manteau neigeux. Ce travail de thèse s'inscrit dans cette tentative de représenter la microstructure de la neige au cours du temps à l'aide de variables bien définies et mesurables sur le terrain. Parmi ces variables, nous nous sommes attachés notamment à la SSA, qui constitue une grandeur essentielle pour l'étude du manteau neigeux et de son évolution temporelle. Différentes lois d'évolution de la SSA ont été étudiées, à partir de relations empiriques basées sur des ajustements de données expérimentales jusqu'aux modèles physiques qui représentent le flux de la vapeur d'eau entre les grains de neige. Ces lois ont été dans un premier temps testées à l'aide d'un modèle simplifié de manteau neigeux et puis introduites directement dans le modèle SURFEX/ISBA-Crocus. Pour ce faire, la SSA dans Crocus a été transformée en variable prognostique, en remplaçant d'autres variables semi-empiriques préexistantes. Les différentes formulations de l'évolution temporelle de la SSA ont été comparées à des mesures de terrain, acquises lors de deux campagnes à Summit (Groenland) et au Col de Porte (France). Ces mesures ont été effectuées en utilisant de nouvelles techniques optiques et ont permis d'obtenir un riche jeu de données avec une grande résolution verticale. Les résultats montrent que les différentes formulations sont comparables et reproduisent bien les mesures, avec un écart quadratique moyen entre les valeurs de SSA simulées et observées inférieur à 10 m^2/kg. Enfin, nous avons contribué à faire le pont entre la microstructure de la neige et ses propriétés macroscopiques. En particulier, nous nous sommes intéressés au lien entre, d'une part, la SSA et, d'autre part, les propriétés mécaniques et optiques. Dans le premier cas, nous avons investigué la corrélation entre la SSA et la résistance à l'enfoncement mesurée avec un Snow Micro Pen (SMP). Les résultats encore préliminaires semblent indiquer que la SSA peut être dérivée de la masse volumique et de grandeurs micro-mécaniques estimées à partir du signal du SMP avec un modèle statistique. Dans le deuxième cas, nous avons simulé l'albédo de surface à Summit à partir des profils mesurés de masse volumique et de SSA et du contenu en impuretés. Les résultats de cette étude ont démontré que l'albédo spectral peut être correctement simulé à l'aide d'un modèle de transfert radiatif et l'énergie absorbée par le manteau neigeux peut être estimée avec une précision d'environ 1%. / Snow is a porous medium whose microstructure is constantly subjected to morphological transformations. These transformations, which take the name of ``metamorphism", are likely to affect the thermal, mechanical and electromagnetic properties of snow at the macroscopic level. Specifically, the exchange of energy and matter within the snowpack and between the snow and the atmosphere above are strongly impacted by the evolution over time of the snow microstructure. Therefore, an adequate representation of metamorphism in snowpack models is crucial. The microstructure of a porous medium can be reasonably described using a reduced number of variables. Indeed, the density, the specific surface area (SSA) and the curvature distribution are able to characterize the microstructure of such a material. However, in the case of snow this approach is still in its infancy and has not yet been systematically applied. Semi-empirical variables, difficult to measure and not directly linked to other relevant physical properties, are still widely used in so-called detailed snowpack models. This work contributes to the attempt to represent the state of the snow using well-defined and easily measurable microstructural variables. Among these variables, we focused particularly on the SSA, which is a key quantity for the study of snow and its temporal evolution. Different evolution laws of SSA were studied, starting from empirical relationships based on experimental data adjustments to physical models that represent the flow of water vapor between snow grains. These laws were initially tested using a simplified snowpack model and then introduced directly into the SURFEX/ISBA-Crocus snowpack model. To this end, the SSA in Crocus was turned into a prognostic variable, replacing other preexisting semi-empirical variables. The different formulations of the temporal evolution of the SSA were compared with field measurements, acquired during two campaigns at Summit (Greenland) and the Col de Porte (France). These measurements were carried out using new optical techniques and yielded a rich dataset with high vertical resolution. The results show that the different formulations are comparable and reproduce well the observations, with an average root-mean-square deviation value between simulated and measured SSA lower than 10 m^/kg. Finally, we contributed to bridge the gap between snow microstructure and macroscopic properties. In particular, we investigated the link between the SSA on the one hand and the mechanical and optical properties on the other hand. In the first case, we investigated the correlation between the SSA and the penetration resistance measured with a Snow Micro Pen (SMP). The preliminary results suggest that the SSA can be retrieved from the snow density and the micro-mechanical parameters estimated from the SMP signal using a statistical model. In the second case, we simulated the surface albedo at Summit from the measured profiles of density, SSA and impurities within the snowpack. The results of this study showed that the spectral albedo can be simulated successfully using a radiative transfer model and the energy absorbed by the snowpack can be estimated with a good accuracy (about 1%).

Made available in DSpace on 2014-10-09T12:46:24Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:01:24Z (GMT). No. of bitstreams: 1 07540.pdf: 5595475 bytes, checksum: 832f00e3a259330c79b1d3676cd33214 (MD5) / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

Este trabalho visa à quantificação da carbonatação em argamassas de cimento branco em comparação à carbonatação de argamassas de cimento cinza convencional. O estudo experimental foi dividido em 2 fases distintas. Na primeira foram produzidos 12 cimentos pela substituição de 0, 5, 10 e 20% de 3 clínqueres de diferentes procedências por um calcário calcítico. Nesta etapa do trabalho o clínquer e o calcário foram moídos conjuntamente, de forma que não havia controle sobre a granulometria do calcário e do clínquer individualmente. Na segunda fase foram produzidos 21 cimentos, os quais foram constituídos pela adição ao clínquer de 0, 5 10 e 20% do mesmo calcário da primeira fase e de um fíler quartzoso moído de forma a possuir a mesma granulometria do calcário. Nesta etapa os materiais foram previamente moídos, de forma que sua granulometria inicial era controlada, constituindo-se, portanto, 21 cimentos com a mesma finura e 21 argamassas com a mesma relação água/aglomerante. Os resultados dos ensaios de carbonatação, resistência à compressão, porosimetria, termogravimetria, difração de raios-X e análise do pH da solução aquosa dos poros indicam que o calcário tem um efeito potencializador da hidratação das argamassas, com efetivo refinamento da estrutura porosa. Entretanto, a comparação entre os resultados de ambas as fases do estudo mostra que a melhora do desempenho de cimentos acrescidos de calcário não se deve apenas ao efeito de fíler desta adição, mas a uma melhora na eficiência dos cimentos compostos, possivelmente pelo maior moabilidade da mistura clínquer-calcário induzida pelo calcário, isto é, o calcário, quando co-moído com o clínquer, faz com este atinja uma maior superfície específica, aumentando, desta forma, a sua reatividade. Argamassas feitas com cimentos brancos apresentaram menor carbonatação do que argamassas feitas com cimentos cinzas, considerando uma mesma relação água/aglomerante e uma mesma superfície inicial. Os resultados indicam algum tipo de interação química do calcário com a pasta que aumenta a carbonatação, mas este efeito é perceptível para teores elevados de adição. / The present study aims to quantify white cement mortars carbonation when compared to carbonation of conventional gray cement mortars. In the first part of the research, 12 cements were produced by substitution of 0, 5, 10 and 20% of 3 different clinkers by limestone. Clinker and limestone were ground together, so that there was no control over the fineness of limestone and clinker individually. In the second stage of the research 21 cements were produced, which were formed by adding to clinker 0, 5, 10 and 20% of limestone and a crushed quartz filler with the same fineness of limestone. In this second part of the research the materials were first milled, so that their initial particle size was controlled, criating therefore 21 cements with the same finess and 21 mortars with the same water / binder ratio. The test results of carbonation and porosimetry show that limestone has a potentiating effect on mortars hydration with effective refinement of the porous structure. However, the results show that the performance improvement of cement with limestone is not only due to the limestone effect as a filler, but also due to an improvement in the efficiency of blended cements, possibly due to greater efficiency of the clinkers that were milled together with limestone. White cement mortars showed less carbonation than gray cement mortars, assuming the same water / binder ratio and the same initial specific surface. The results show a possible chemical interaction between limestone and the cement paste that eventually increase carbonation depth. This effect was only observable with high addition contents.

Made available in DSpace on 2014-10-09T12:46:24Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:01:24Z (GMT). No. of bitstreams: 1 07540.pdf: 5595475 bytes, checksum: 832f00e3a259330c79b1d3676cd33214 (MD5) / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP