Clinker | EPFL Graph Search

Le clinker est un constituant du ciment, qui résulte de la cuisson à très haute température d'un mélange composé d'environ 80 % de calcaire (CaCO3 qui apporte l'oxyde de calcium, CaO) et de 20 % d'aluminosilicates (essentiellement des argiles : phyllosilicates) qui apportent les oxydes de silicium (SiO2), d'aluminium () et de fer (FeO et ). La « farine » ou le « cru » est formé du mélange de poudre de calcaire et d'argile. La cuisson, ou clinkérisation, se fait à une température d'environ , ce qui explique la forte consommation énergétique de ce processus. La clinkérisation explique en partie la contribution importante des cimenteries aux émissions de gaz à effet de serre. 250px|thumb|Nodules de clinker de ciment habituel après refroidissement Le clinker se présente sous la forme de nodules durs et cristallisés, de teinte grise foncée pour les ciments habituels et verte pour le clinker de ciment blanc. Le clinker pour ciment blanc est un clinker spécial à faible teneur en oxydes de fer et donc à point de fusion plus élevé car les oxydes de fer manquent comme fondant (ou flux) dans le diagramme ternaire CaO – – pour abaisser son point de fusion. Le ciment blanc exige des matières premières (calcaire et argile) ne contenant que très peu d'oxydes de fer. La couleur verte de ce clinker très pur est due aux cations ferreux (Fe) davantage dilués dans la masse de sa matrice cristalline. Il est plus onéreux à produire en raison de sa consommation d'énergie plus élevée. Son usage coûteux le destine surtout aux ciments blancs utilisés pour le rejointoyage des carrelages à l'intérieur des bâtiments (p. ex. les locaux sanitaires) et aux bétons de parement (architectonique). La composition des clinkers gris est représentée par quatre grandes phases cristallines caractéristiques de la chimie du ciment. Elles sont en moyenne les suivantes : Ca3SiO5 : silicate tricalcique (SiO2 – 3 CaO) : 50 à 65 % (alite) ; Ca2SiO4 : silicate bicalcique (SiO2 – 2 CaO) : 15 à 20 % (bélite) ; Ca3Al2O6 : aluminate tricalcique (Al2O3 – 3 CaO) : 5 à 15 % (aluminate) ; Ca4Al2Fe2O10 : ferro-aluminate tétracalcique (Al2O3 – Fe2O3 – 4 CaO) : 5 à 10 % (ferrite).

Impact of water activity on the mineralogy of hydrated cement

Luis Guillermo Baquerizo Ibarra

Cement hydrates and their chemically bound water content are sensitive to changes in relative humidity (RH) and temperature. This may cause specific solid volume changes affecting dimensional properties of hydrated cement paste such as shrinkage, swelling and expansion, and therefore impact the performance and the transport properties of cementitious materials. The present thesis studies the impact of drying conditions on the structure and thermodynamic properties of crystalline cement hydrates in different hydration states (i.e. varying molar water contents). The cement hydrates studied include the most important AFm and AFt phases present in different types of cements. A novel multi method approach, including XRD, TGA, DSC, sorption balance measurements, sorption calorimetry and the hydrate pair ¿ humidity buffer method, was used to derive physico-chemical boundary conditions and the thermodynamic properties of the studied hydrated phases. The stability and hydration states of AFm phases depend on the anion content and the exposure conditions. Some phases such as monosulfoaluminate and hydroxy-AFm are very sensitive to different relative humidities. On the other hand monocarboaluminate and strätlingite present very good volume stability with varying RH. Ettringite shows a strong hysteresis during desorption/adsorption, and the thermodynamic properties associated with its decomposition and reformation were determined. The experimental results were included into a thermodynamic model capable of predicting the response of cementitious systems considering the ¿true¿ crystal water content on the final phase assemblage in two different scenarios: i) during hydration, even at conditions where the amount of water added was insufficient for complete hydration, and ii) during drying and re-wetting processes in already hydrated systems. Our work hence opens the possibility to model the response of various cement materials exposed to different climatic conditions and to engineer cementitious systems with respect to minimizing volume changes in the course of drying, which may positively impact properties like drying shrinkage and total porosity.

EPFL2015

Fe-containing Hydrates and their Fate during Cement Hydration

Belay Zeleke Dilnesa

Thermodynamic modeling is a versatile tool for predicting the chemical composition cement during the hydration of cement. The quality of the thermodynamic modeling depends directly on the quality and completeness of thermodynamic database used. One of the main limitations of modeling the hydration of cement is the lack of thermodynamic data for Fe containing hydrates. In addition, the formation of solid solutions between Fe- and Al-containing hydrates could stabilize mixed solids. However, it is unclear to what extent such solid solution formation occurs. Also experimentally it is very difficult to identify Fe-containing hydrates in hydrating cements by standard analytical techniques as the signals from Fe-containing phases significantly overlap with those from the corresponding Al-containing phases. Thus, in this study, potential Fe-containing hydrates like Fe-hemicarbonate (Fe-Hc), Fe-monocarbonate (Fe-Mc), Fe-monosulphate (Fe-Ms), Fe-Friedel's salt (Fe-Fr), Fe-strätlingite (Fe-St), Fe-katoite (C3FH6 ) and Fe-siliceous hydrogarnet (Fe-Si-Hg) were synthesised at 20, 50 and 80 °C. The solid phases were characterized by X-ray powder diffraction (XRD), Thermogravimetric analysis (TGA), scanning electron microscopy (SEM), vibrational spectroscopy (Raman and Infrared spectroscopy) and Extended X-ray absorption fine structure spectroscopy (EXAFS). The compositions of the liquid phases were analyzed using inductively-coupled plasma optical emission spectrometry and mass spectrometry (ICP-OES and MS). At ambient temperature Fe-Mc, Fe-Ms, Fe-Fr and Fe-Si-Hg were stable, while Fe-Hc, Fe-katoite and Fe-St were metastable. Fe-Mc, Fe-Ms, Fe-Fr and Fe-Si-Hg were stable also at 50 °C, but the Fe-AFm phases were unstable at 80 °C while Fe-Si-Hg were stable up to above 100 °C. The measured composition of the liquid phase was used to calculate the solubility products at 20 and 50 °C and to derive the data for standard conditions (25 °C, 1 atm). The solubility products of Fe-Fr was similar to the solubility product of Al-Fr, while the solubility products of Fe-Mc and Fe-Ms were about 3 log unit lower than that of Al-Mc and Al-Ms indicating that in Fe-Friedel's salt is probably not stable in cements. The very low solubility product of Fe-Si-Hg (5 to 7 log units lower than that of Al-Si-Hg) implies that Fe-Si-Hg could be a stable phase in hydrated cements. Also the mixed Al- and Fe-containing hydrates were synthesized to study the extent of solid solution formation. Both XRD and thermodynamic modelling of the liquid compositions indicated that Al- and Fe-monosulphate and Al- and Fe-Friedel's formed solid solutions with a miscibility gap, while Al- and Fe- monocarbonate existed as two separate hydrates due to their different crystal structure (Al-Mc: monoclinic, Fe-Mc: rhombohedral). The formation of solid solution between Al and Fe-siliceous hydrogarnet seemed probable. To understand to what extent the findings from the synthesised hydrates were relevant for real cements, the speciation of iron was determined in hydrating cement using EXAFS spectroscopy. Identification of Fe-containing hydrates and quantification of their contributions was achieved by combining principal component analysis with iterative target tests, and linear combination. The results show that several Fe species already contributed to the overall Fe K-edge spectra of cement pastes during the first day of hydration. While ferrite was the dominant Fe-containing phase in the unhydrated cement, Fe-hydroxide was detected shortly after starting the hydration process. With time the formation of stable Al/Fe-siliceous hydrogarnet was observed, while the amounts of Fe-hydroxide and ferrite clinker slowly decreased. The latter finding agrees with results from thermodynamic modeling of the hydration process, which predicts formation of stable Al/Fe-siliceous hydrogarnet in cement system. The determination of the solubility products of these hydrates will help to extend the thermodynamic data base of cement minerals and establish whether and to which extent Fe-containing hydrates are stable in fresh and in leached cementitious systems. The results from this study on the Fe speciation in cementitious systems are important for a better understanding of cement-water interactions with a view to the durability of cementitious materials.

EPFL2012