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.

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%).

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The diploma thesis deals with the heterogeneous technique of preparation of grafted polypropylene g maleic anhydride (PP-g-MAH). The knowledge of the course of the reaction and its impact on the PP grafting process are summarized in the theoretical part. The preparation of the grafted PP was carried out in a fluidized polymerization reactor at 115 °C, speed of mixing 210 rpm, reaction time 60 min and pressure 6 bar. The amount of grafted MAH was monitored by using a MAH concentration 3 and 5 wt% and an initiator concentration 0.25; 0.5; 1; and 1.5 wt%. Modification efficiency was compared by using 3 types of PP with different particle morphology and specific surface area. By creating the theoretical model, the maximum surface concentration of MAH was calculated and compared with experimental data. Characterization of PP materials was performed by Electron Scanning Microscopy (SEM), Differential Scanning Calorimetry (DSC) and particle surface analysis by BET. Quantitative analysis of grafted MAH was determined by FTIR spectroscopy and acid-base titration.

Porous ceramic materials are an interesting group of materials due to a wide range of physical properties, low density, and good permeability. Production of a monolith with a shape stability that would also have a high specific surface area and high porosity is a common problem with porous ceramics. The goal of this work was to maintain the high specific surface area and to produce a monolith with a shape stability. Two forms of porous silica nanofibers (as prepared and milled) were used and partially sintered using the Spark Plasma Sintering method (SPS). Different sintering times and temperatures for SPS were tested. The findings revealed that the best SPS conditions were as follows: temperature: 600 °C, sintering time: 5 minutes, pressure: 3 MPa, and the heating rate: 144 °C/min. These sintering conditions resulted in a stable silica based machinable monolith made from fibers or milled fibers. The monoliths have the specific surface area of up to 470 m^2/g and porosity of 72 %, or the specific surface area of up to 422 m^2/g and porosity of 69 % for as prepared fibers and milled fibers, respectively.

Yes / This paper aims to evaluate the influence of surface area and amount of nano silica (NS) on the performance of concrete with different water/binder (w/b) ratios. For this purpose, 63 different mixes were produced using three NS having three differentsurface areas (52, 250 and 500 m2/g) and w/b ratios (0.4, 0.5 and 0.6). Compressive strengths , workability, water absorption and the microstrcture of concrete mixtures were measured and analysed. and the optimum ratio for each type was determined. The results indicated that the performance of NS particles in concrete is significantly dependent on its amount and surface area as well as w/b ratio. As the w/b ratio increased, a better performance was observed for all types of NS used, whilst NS having 250m2/g surface area was found to be the most effective. The optimum amount of NS ranged from 2 to 5%, depending on NS surface area. / The full-text of this article will be released for public view at the end of the publisher embargo on 15 May 2020.

Les poudres d'aluminium sont depuis longtemps utilisées comme additifs dans de nombreuses formulations pour la pyrotechnie ou les propergols. Introduites en quantité relativement faible dans les propergols des fusées, elles permettent d'accroître significativement les vitesses de combustion. Cependant, les mécanismes à l'origine de cette meilleure réactivité restent encore mal compris et vont bien au-delà d'une simple explication en terme d'augmentation de l'état de division. Au cours de cette thèse nous avons élaboré des poudres d'aluminium par broyage à haute énergie, technique mécanique peu couteuse qui pourrait être une alternative aux procédés de fabrication actuels. Nous montrons que cette méthode permet l'obtention de particules micrométriques ou nanométriques suivant les conditions de broyage. Les particules sont polycristallines et présentent une morphologie en plaquette. Les poudres nanométriques obtenues présentent une réactivité comparable voire même supérieure aux nanopoudres sphériques actuellement élaborées par électro-explosion de fil ou voie plasma. Nous montrons que cette bonne réactivité est lié à la morphologie des particules ainsi qu'à la microstructure de la couche d'alumine native qui passive l'aluminium. / Aluminium nanopowders have been using for a long time as additives in many formulations for propergol or in pyrotechnics. Introduced in small quantity in rocket propergol they allow to increase the combustion rate. However, the reactivity of aluminium particles is not really understood and not just linked to the size reduction effect. All along this study, we have elaborated aluminium powders using high energy mechanical milling, a mechanical technique with a low cost which could be an alternative process of powders fabrication. We prove that this method allows elaboration of micro and nano-particles as a function of the mechanical parameters. The particles are polycristallines with flake morphology. The obtained nanopowders have a similar reactivity, or better than spherical nanopowders obtained by wire electrical explosion or plasma. We proove that this good reactivity is linked to the particles morphology, as well as also to the microstructure of the native alumina core shell.

The pore saturation of natural gas hydrate in sediments is a key parameter for estimating hydrate resources in a reservoir. For a better understanding of gas hydrate distribution, the experimental study of the pore saturation of methane hydrate in sediments from a hydrate reservoir in the Eastern Nankai Trough have been carried out. In total, eleven samples, comprising sand, silty sand, silt, and representative of the main sediment types identified in the Eastern Nankai trough, were tested. The results obtained clearly indicate a particle size and clay content dependent trend: almost 100% of pores were saturated with methane hydrate in sand when little silt and clay were present, decreasing to ~ 13% in silty sand (sand 54%, silt 41% and clay 5%), and ~ 4% in clayey silt. These results are generally consistent with NMR logging results for high-saturation samples, but somewhat different for samples with medium or low saturation levels.