Diploma thesis deals with the methodology of preparation of Alit – the main clinker mineral. The content of this work involves design and optimization of the methodology of preparation of pure Alit polymorphs, analysis of their properties by available analytical methods and evaluation of the change of crystallinity in the process of preparation of these polymorphs by XRD-analysis.

The effect of the sulfates and alkalis on the durability of Portland cement systems was investigated through a series of cube and prism mixes. Durability was assessed using expansion of mortar prisms and the compressive strength of mortar cubes. The study covered a large range of both alkali and sulfate contents using 5 different Portland cements. The alkali contents ranged from 0.27 to 3.8%, the sulfate content (as SO3) ranged from 2.54 to 5%. Doping was done using Terra Alba gypsum and potassium hydroxide. In addition to physical measurements, SEM, XRD, chemical analysis and heat of hydration calorimetry were used for further analysis. Mixing, curing and testing were done at room temperature. The results show that sulfate contents up to the levels used in this study, at low alkali contents and ambient temperature curing, did not adversely affect durability of Portland cement mortars up to 360 days. A correlation was established between expansion and ettringite formation. Increasing the alkali content always resulted in loss of compressive strength, and in some cases, excessive expansion. Excessive expansion was only experienced at the 3.8% level. Alkali levels of up to 2% and sulfate levels of 5% did not result in excessive expansion at room temperature-cure up to the ages reported here. The effect of alkali depended on thecement mineralogical composition, especially C3S content. The addition of alkalis seems to impact the nature of the microstructure and the nature of other hydration products. The addition of sulfates seems to counteract the effect of alkalis, especially on the loss of compressive strength. However, these sulfates may result in other problems as they may be available at any time to form ettringite which may, under certain conditions, result in excessive expansion. It was concluded that sulfate levels on the order of 3-3.6%, did not pose any major durability drawbacks under normal curing temperatures and low alkali contents (<1%). Alkali levels above 1% will adversely affect the durability of Portland cement systems.

Since the energy crisis in 1970’s, research on low energy cements with low CO2-emissions has been increasing. Numerous solutions have been investigated, and the goal of this original research is to create a viable hybrid cement with the components of both Ordinary Portland cement (OPC) and calcium sulfoaluminate cement (CSAC), by forming a material that contains both alite and calcium sulfoaluminate clinker phases. Furthermore, this research focuses on keeping the cost of this material reasonable by reducing aluminum requirements through its substitution with iron. The aim of this work would produce a cement that can use large amounts of red mud, which is a plentiful waste material, in place of bauxite known as an expensive raw material. Modified Bogue equations were established and tested to formulate this novel cement with different amounts of ferrite, from 5% to 45% by weight. This was followed by the production of cement from reagent chemicals, and from industrial by-products as feedstocks (fly ash, red mud and slag). Hydration processes, as well as the mechanical properties, of these clinker compositions were studied, along with the addition of gypsum and the impact of a ferric iron complexing additive triisopropanolamine (TIPA). To summarize this research, the influence of the addition of 5-45% by weight of ferrite phase, was examined with the goal of introducing as much red mud as possible in the process without negatively attenuate the cement properties. Based on this PhD dissertation, the production of high-iron alite-calcium sulfoaluminate-ferrite cements was proven possible from the two sources of raw materials. The hydration processes and the mechanical properties seemed negatively affected by the addition of ferrite, as this phase was not hydrated entirely, even after 6 months of curing. The usage of TIPA counteracted this decline in strength by improving the ferrite hydration and increasing the optimum amount of gypsum required in each composition. The mechanical data were equivalent to OPC strengths for some compositions with 25% ferrite. This preliminary work constitutes the first research phase of this novel cement and requires additional research for its improvement. Topics for additional research are identified in this dissertation.

The influence of tricalcium silicate content of cement on concrete durability has long been a topic of discussion in the literature. The objective of this investigation was to determine whether increasing tricalcium silicate content of cement has a negative effect on concrete sulfate durability. Several mill certificates were reviewed to select cements with similar tricalcium aluminate content and variable tricalcium silicate contents. Cements selected for this study were randomly labeled as cements C, D, D2, E, and P. The following properties were assessed for the as-received cements: Blaine fineness, particle size distribution, chemical oxide content, and mineralogical content. Three different methods were employed to determine the mineralogical composition of the as-received cements: Bogue calculation, internal standard method, and Rietveld refinement analysis. Despite the attempt to select cements with similar composition, it was determined that the as-received cements had compositional differences other than their C3S content. These cements had a variable tricalcium aluminate and alkali content, as well as differences in the amount and form of calcium sulfates. In order to eliminate these variances, doped cements were prepared by increasing the C3S content of the as received cements to 69 % by Bogue calculation. Durability of as-received cements and doped cements was assessed through several measurements including length change, compressive strength, and phase transformation in sodium sulfate solution. For as-received cements, compressive strength of mortar cubes stored in saturated lime solution was evaluated as well. Semiquantitative x-ray diffraction analysis and scanning electron microscopy observations were performed on mortar bars to evaluate the relative amounts and morphology of the hydrated phases. It was concluded at the end of this study that cements with high tricalcium silicate content generally have poor durability in sodium sulfate environment. All the cements experienced higher expansion with increased C3S content. High C3S content combinedwith high C3A content was particularly detrimental to mortar resistance to sodium sulfate attack.

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

Diploma thesis deals with laboratory preparation of the main clinker mineral - alit. The theoretical part summarizes the existing knowledge and the practical part deals with the methodology of preparation of the alite. The main goal was to prepare and study the monoclinic phases of alite, another goal was to optimize the triclinic alite.

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

Portland clinker is thanks to its large-scale production a continuously studied topic. Clinker, or Portland cement, is used for construction purposes, or for insulation and special applications. One of these special applications could be shielding of different types of radiation by making use of the content of barium ions. The present master’s thesis examines the influence of barium oxide on the formation and properties of Portland clinker, which could be, by incorporation of barium ions into the system, used as a binder for buildings resistant to various types of radiation. Barium sulfate and barium carbonate were added to the raw meal in order to prepare clinkers with different content of barium oxide. The effect of barium on the formation of clinker phases was studied (by XRD – Rietveld analysis and by the microscopic point integration), as well as the effects on the variations of temperature of the phase formation (TG-DTA) and the rate of alite formation under isothermal conditions. Furthermore, the ability of barium to become a part of clinker minerals was studied by SEM with EDS, and the solubility of barium phases by ICP-OES. The hydration of clinker minerals containing barium was studied by isothermal calorimetry.