La politique mondiale de réduction des émissions de gaz à effet serre repose en grande partie sur la recherche de nouvelles solutions pour l’industrie cimentaire qui contribue largement aux émissions de CO2. Parmi ces solutions, l’exploitation de ciments riches en silicate bicalcique, Ca2SiO4, ou bélite, qui est sa dénomination cimentaire, semble intéressante puisque le procédé industriel de fabrication requiert une moindre demande en calcaire et une température de cuisson plus basse que dans le cas des ciments Portland. A ce jour, les freins à une exploitation massive par les cimentiers de la bélite sont l’absence ou la lenteur de la réactivité avec l’eau, qui se traduit par une lente montée en résistance mécanique des ciments bélitiques, et le ‘dusting’ ou éclatement au refroidissement du fait de la transformation allotropique β. Les interprétations de ces phénomènes restent, à ce jour, contradictoires car elles reposent bien souvent sur l’analyse de la bélite dans un clinker, avec toute sa complexité. Aussi, nous avons choisi d’entreprendre une étude fondamentale des propriétés de β-Ca2SiO4. Afin de valoriser notre travail, nous avons essayé d’apporter des explications aux inconvénients majeurs qui bloquent l’exploitation des ciments bélitiques. Nous avons travaillé d’une part avec de la bélite synthétisée par voie chimique, pure ou dopée avec des éléments choisis (phosphore, soufre, bore) et, d’autre part, avec une bélite extraite d’un clinker sulfoalumineux bélitique. Nous nous sommes particulièrement intéressés à la stabilisation du polymorphe haute température β. Cette stabilisation a été étudiée d’un point de vue microstructural et chimique. La phase β est maclée. Les surfaces des grains présentent des défauts (dislocations, joints de macles et joints de grains avec des désorientations) qui sont autant de sites potentiels pour une réaction avec l’eau. Que ce soit la bélite de synthèse ou la bélite extraite d’un clinker, elle réagit rapidement avec l’eau. En revanche, la bélite dans une matrice cimentaire réagit lentement. Nous avons attribué cette caractéristique non pas à la lente hydraulicité de la bélite elle-même mais plutôt à la formation, au cours de l’hydratation du ciment, d’hydrates qui viennent recouvrir les grains de belite et empêcher sa dissolution. Ce travail propose également des solutions pour améliorer l’hydraulicité de la bélite contenue dans une matrice cimentaire. / The global policy for reducing greenhouse gas emissions is largely based on finding new solutions for the cement industry, which contributes significantly to CO2 emissions. Among these solutions, the exploitation of cements rich in dicalcium silicate, Ca2SiO4, or belite, which is its cementitious name, seems interesting since the industrial manufacturing process requires a lower demand for limestone and a lower firing temperature than in the case Portland cements. To date, the obstacles for a massive exploitation of the belite by cement producers are the absence or the slowness of its reactivity with the water, which results in a slow increase in mechanical resistance of the belite rich cements, and the 'dusting', or splitting on cooling due to the β allotropic transformation. The interpretations of these phenomena remain, to date, contradictory because they are often based on the analysis of belite in a clinker, with all its complexity. In this context, we have chosen to undertake a fundamental study on the properties of β-Ca2SiO4. In order to value our work, we have tried to explain the major disadvantages that retard or prevent the exploitation of belite rich cements. On one hand, we worked with chemically synthesized belite, either pure or doped with selected elements (phosphorus, sulfur, boron) and, on the other hand, with a belite extracted from a belite sulfoaluminate clinker. We focused on the stabilization of the high temperature β polymorph. This stabilization has been studied from a microstructural and chemical point of view. The β phase is twinned. The grain surfaces have defects (dislocations, twin joints and grain boundaries with disorientations) which are all potential sites for a reaction with water. Whether belite is synthetic or extracted from a clinker, it reacts quickly with water. In contrast, belite in a cement matrix responds slowly. We have attributed this characteristic not to the slow hydraulicity of the belite itself, but to the formation, during the hydration of the cement, of hydrates which cover the belite grains and prevent their dissolution. This work also proposes solutions to improve the hydraulicity of the belite contained in a cement matrix.

The subject of this doctoral thesis was to elucidate the mechanism of reaction leading to the formation of dicalcium silicate (C2S), its solid solutions and other phosphatic calcium silicate phases using the sol-gel method of synthesis. SiO2 (Tosil A), CaO (calcium nitrate tetra-hydrate) and H3PO4 (as a source of P2O5) were used as starting materials. Series of samples with different content of P2O5 were synthesized. The characterization of Tosil A and samples was based on the following methods: DTA/TGA and EGA, XRD and SEM and EDS analy-ses. It is known, that phosphorous oxide can enter the structure of C2S and possibly form solid solutions and different phosphatic calcium silicate phases in C2SâC3P system. Depending on the P2O5 concentration in mixtures, three distinct phases are formed: larnite (2CaOâSiO2), Ca14,92(PO4)2,35(SiO4)5,65 and 5CaOâSiO2âP2O5, as detected by XRD. Local microanalysis de-monstrated the presence of calcium phosphate epicenters (C3P) containing SiO2, calcium sili-cate (C2S) zones with minimum content of P2O5 and intermediary areas of various phosphatic calcium silicates. The formation of two distinct islets of C2S and C3P is due the affinity of acid oxides (SiO2, P2O5) towards the basic one (CaO) during the sol-gel process. Then, the formation of various phosphatic calcium silicates results from the diffusion of P2O5 and SiO2 towards calcium silicate and calcium phosphate, respectively.

DIPLOMA THESIS IS DEVOTED TO THE STUDY OF PREPARATION OF PURE BELITE CLINKER FOR THE POTENTIAL INCREASE OF KINETICS OF THE HYDRATION PROCESS BY CHEMICAL ACTIVATION. THE THESIS OF THIS WORK IS BASED ON RESEARCH FINDINGS CONCERNING BELITE CLINKER AND RESEARCH AT THE INSTITUTE OF THD. THE THESIS AIMS TO DESIGN COMPOSITION OF THE RAW MEAL BURNING BELITE, FOLLOWING MODIFICATION BY SULPHATE AND POTASSIUM CARBONATE IN ORDER TO POTENTIALLY INCREASE THE REACTIVITY OF THE BURNT BELITE CLINKER AND THE LABORATORY FIRING OF PREPARED SAMPLES. THE LAST STEP WAS TO ASSESS THE MINERALOGICAL COMPOSITION OF BURNED SAMPLES XRD ANALYSIS AND FOLLOWING COMPARISON CELL PARAMETER OF BELITE WITH AND WITHOUT ADDED MODIFYING ADDITIVES.

DIPLOMA THESIS IS FOCUSED ON THE PREPARATION AND PROPERTIE OF BELITE CLINKER. IT IS BASED ON THE STUDY OF SCIENTIFIC ARTICLES DEALING WITH THE ABOVE MENTIONED TOPIC AS WELL AS THE ANALYSIS OF THE BRNO THD INSTITUTE´S RESEARCH RESULTS. AS PART OF MY EXPERIMENTAL WORK, A PROPOSAL OF THE COMPOSITION OF RAW MEAL TO EXTRACT BELITE CLINKER IN THE PRESENCE OF POTASSIUMS CARBONATE AND SULPHATE WAS MADE TO MODIFY RAW MEAL. THE PURPOSE OF MODIFYING RAW MEAL IS A POTENTIAL INCREASE IN BELITE CLINKER REACTIVITY. FURTHER THE EXTRACTION OF BYPASS DUST FROM A LOCAL CEMENT PLANT WAS CONDUCTED. THE EVALUATION OF THIS RESEARCH WAS MADE BY THE X-RAY DIFFRACTION (XRD) ANALYSIS METHOD.