Orientador: João Manuel Marques Cordeiro / Abstract: The energetical and environmental problematic related to the cement production is a very sensitive issue. As every other field, the construction industry must go through drastic change in the design of concrete and cement-based materials. The understanding of the physical and chemical properties of the Portland cement (PC) clinker is important to improve its design. Tricalcium silicate C3S, or alite, is the main phase of PC clinker and has been largely studied since it is the first responsible for the strength development of the cement paste. On the other hand, the development of computational methods at the molecular scale has made possible the modelling of structural, dynamical and energetic properties, sometimes hardly measurable by experimental means. Such methods are relatively new in the field of cement chemistry, but have been increasingly employed over the last 15 years. In this project, density functional theory (DFT), classical molecular dynamics (MD), and ab initio molecular dynamics (AIMD) are employed towards a better understanding of mechanical, thermal, and superficial properties of monoclinic C3S, as well as C3S/water interface features. The present thesis consists of five chapters. The first chapter presents a review of the literature on the chemistry of cement, and more particularly on the hydration process modeling. The various phases which compose the Portland cement clinker are introduced, then the the different polymorphs of C3S are described, in particu... (Complete abstract click electronic access below) / Resumo: A produção de cimento envolve questões energéticas e ambientais muito relevantes. Em função disso, a indústria da construção deve sofrer mudanças radicais na concepção de concreto de materiais cimentícios. A compreensão das propriedades físicas e químicas do clínquer de cimento Portland (PC) é importante para melhorar seu design. O silicato tricálcico (C3S), ou alita, é a fase principal do clínquer de PC e tem sido amplamente estudado uma vez que é o principal responsável pelo desenvolvimento da resistência da pasta de cimento. Por outro lado, o desenvolvimento de métodos de cálculo na escala molecular possibilitou a modelagem de propriedades estruturais, dinâmicas e energéticas, às vezes difícil de medir por meios experimentais. Esses métodos são relativamente novos no campo da química do cimento, mas tem sido cada vez mais empregados nos últimos 15 anos anos. Neste trabalho, a teoria de funcional da densidade (DFT), a dinâmica molecular clássica (MD) e a dinâmica molecular ab initio (AIMD) são utilizadas para permitir uma melhor compreensão das características mecânicas, térmicas e de superfície do C3S monoclinico, bem como propriedades da interface C3S/água. Esta tese consiste em cinco capítulos: O primeiro capítulo apresenta uma revisão da literatura sobre a química dos cimento e, mais particularmente, sobre o processo de hidratação e sua modelagem. Introduzimos as diferentes fases que compõem o clínquer de cimento Portland, em seguida, a estrutura e os diferentes polimor... (Resumo completo, clicar acesso eletrônico abaixo) / Doutor

Ce travail consacré à l’étude des différents paramètres influençant l’hydratation de la phase silicate principale du Ciment Portland Ordinaire (OPC) a été réalisé au Laboratoire Interdisciplinaire Carnot de Bourgogne (ICB). Cette étude s’inscrit dans le cadre du projet « Crystal Growth Control » initié par BASF dans le but de contrôler et de prévoir le mieux possible l’hydratation du Ciment Portland Ordinaire. La dissolution de l’alite, comme celle du C3S pur, est rapide dans l’eau pure. La vitesse diminue avec l’écart à l’équilibre et la concentration en ions aluminates en solution. On observe également une adsorption sur la surface de l’alite de l’aluminium libéré par la dissolution. La germination et la croissance des C-S-H a été étudié d’une part, en présence d’aluminates en solution et d’autre part en présence de sels inorganiques connus pour être des accélérateurs de l’hydratation du ciment Portland Ordinaire. La présence d’aluminium ne modifie pas la germination initiale des C-S-H mais semble participer directement à l’origine de la période dormante du ciment. L’hydratation du C3S dans des solutions salines conduit à former pendant la germination initiale d’autant plus de C-S-H que la solution est concentrée. De plus la morphologie des germes est modifiée. Chaque germe doit contenir plus de matière en occupant moins de surface. La simulation de l’ensemble de la courbe d’avancement de l’hydratation observée dans les solutions de sels de nitrates et d’halogénures de calcium, sodium et potassium à l’aide du modèle de croissance par agrégation de particules cubiques confirme l’anisotropie au cours de la croissance des germes. La vitesse de croissance des C-S-H perpendiculairement à la surface des grains augmente avec la concentration et l’effet est très dépendant de la nature de l’anion. Ce comportement est à rapprocher des séries d’Hofmeister / This work devoted to study various parameters influencing hydration of silicate phase main Ordinary Portland Cement (OPC) was performed at the Laboratoire Interdisciplinaire Carnot de Bourgogne (ICB). This study is part of the project "Crystal Growth Control" initiated by BASF in order to monitor and provide the best as possible the hydration of Ordinary Portland Cement. The dissolution of alite, like the pure C3S one, is fast in pure water. Speed decreases with deviation from equilibrium and the concentration of aluminates ions in solution. There is also an adsorption on the surface of the aluminum which is into the alite and released by dissolution. Germination and growth of C-S-H has been studied on the one hand, in the presence of aluminates ions within the solution and the other, in the presence of inorganic salts known to be accelerators of Ordinary Portland cement hydration. The presence of aluminum does not alter the initial germination of C-S-H but seems directly involved in the origin of the dormant period of cement. The hydration of C3S in salt solutions leads to the formation during the initial germination even more C-S-H that the solution is concentrated. In addition, the morphology of seeds is modified. Each seed must contain more material occupying less space. Simulation of the entire hydration progress curve observed in solutions of salts of nitrates and halides of calcium, sodium and potassium with the growth model based on the cubic particles aggregation confirms the anisotropy in the growth of seeds. The C-S-H perpendicular growth rate to the surface of the grains increases with the salt concentration and the effect is very dependent on the nature of the anion. This behavior is closer to the Hofmeister series

This diploma thesis compares impact of various high-energy grinding technologies on crystallographic and granulometric properties of portland cement. It also observes the influence of the conventional and high-speed grinding technology on the resulting physical and mechanical properties of portland cement, depending on the storage time.