0000000000479309
AUTHOR
Jean-claude Mutin
Electronic microdiffraction study of structural modifications resulting from the dehydration of gypsum. Prediction of the microstructure of resulting pseudomorphs
Abstract Endothermic decomposition reactions (solid 1→solid 2+gas) generally affect only part of the inter-atomic bonds of the solid 1 structure. In consequence, the morphology and external dimensions of particles remain unchanged (the particles of solid 2 are referred to as pseudomorphs of those of solid 1). The gas release normally leads to a decrease of the molar volume of the precursor solid, resulting in cracking and formation of intra-particle porosity. This work deals with such a reaction: the dehydration of gypsum into sub-hydrated and anhydrous phases. Ultrathin (010) gypsum cleaved plates have been dehydrated under controlled conditions and studied by electron microdiffraction. Al…
Identification des phases sous-hydratées du sulfate de calcium
L'utilisation de moyens et de procedures experimentales adaptees a permis d’identifier chimiquement et structuralement deux formes sous-hydratees de sulfate de calcium : CaSO 4 , 0,5 H 2 O et CaSO 4 , 0,6 H 2 O.Avec l’hanhydrite soluble - γ-CaSO 4 - a laquelle elles s'apparentent structuralement ce sont les trois phases distinctes entrant dans la constitution du plâtre.
Physico-chemical parameters determining hydration and particle interactions during the setting of silicate cements
Abstract Hydration of tricalcium silicate (Ca 3 SiO 5 ), the pure phase used as a model of the portland cements, is the chemical process leading to the formation of hydrates, while setting is a definite time event corresponding to the change of the paste from the soft to the hard state. Setting results from interactions between anhydrous or very partially hydrated particles. The analysis of these interactions leads to the identification of two fundamental steps: the coagulation of cement grains during the first minutes following the mixing and the rigidification of the coagulated structure which arises simultaneously with the acceleration of the calcium silicate hydrates (CSH) formation. …
Influence de l'atmosphère gazeuse sur la cinétique de formation du titanate de baryum par réaction solide-solide
International audience; Les études consacrées à la synthèse, par réaction solide-solide, du titanate de baryum (BaTiO3) ont montré l'importance des propriétés physicochimiques des solides initiaux (BaCO3 et TiO2) sur les propriétés du titanate obtenu. Lors de l'élaboration de céramiques diélectriques, il est en effet nécessaire d'éviter la formation de phases intermédiaires (Ba2TiO4, BaTi4O9, ...) qui nuisent à leurs propriétés diélectriques. La présence de ces phases peut être liée à une maîtrise imparfaite des nombreux paramètres influant sur la cinétique de la réaction. Le rôle de deux de ces paramètres : les traitements mécaniques et la nature de l'atmosphère gazeuse, fait l'objet de ce…
Irreversible modifications of the porous microstructure of soluble anhydrite β-CaSO4 induced by hydration-dehydration cycles
26 pages; The internal surface area of hexagonal (soluble) primary anhydrite CaSO4 produced by dehydration of gypsum decreases by about 70 % when the anhydrite is successively subjected to rehydration and dehydration at room temperature in humid air and in vacuum respectively. In the rehydration step, the hemihydrate is formed; its dehydration yields secondary anhydrite. Additional hydration-dehydration cycles in the same conditions have a much smaller effect. The first cycle also brings about a modification of the t-plot, which reveals that the micropores of primary anhydrite are irreversibly healed. Mercury intrusion porosimetry shows that the primary dehydration of gypsum also generates …
Theory of mercury intrusion in a distribution of unconnected wedge-shaped slits
Effective mercury intrusion in a wedge-shaped slit is gradual, the intruded depth increasing with applied pressure. The Washburn equation must be modified accordingly. It relates the distance, e, separating the three-phase contact lines on the wedge faces to the hydrostatic pressure, P, wedge half-opening angle alpha, mercury surface tension gamma, and contact angle theta: e=(-2gamma/P)cos(theta-alpha) if theta-alpha>pi2. The equations relating the volume of mercury in a single slit to hydrostatic pressure are established. The total volume of mercury V(Hg)(tot)(E(0),e) intruded in a set of unconnected isomorphous slits (same alpha value) with opening width, E, distributed over interval [E(0…
La mesure directe des forces de liaison entre les hydrates appliquée à la prise de plâtre
Le phenomene de prise est un phenomene general, observable sur tous les liants mineraux, ciments siliceux, alumineux... et le plâtre. S'il existe des lois gouvernant la prise, elles doivent s'appliquer a tous ces liants. Aussi, il peut etre justifie de prendre tel ou tel liant pour modele si cela peut simplifier la premiere approche. Ici, l'objectif est de mesurer les forces entre les grains de silicate de calcium hydrate (phase C-S-H) qui est l'hydrate le plus caracteristique des ciments courants. Ces grains sont extremement petits et il a ete choisi de mettre au point les methodes travaillant sur le plâtre qui s'hydrate sous forme de gypse en formant des cristaux de 10 a 100 fois plus gro…
Influence des contraintes sur les propriétés élastiques de surface du gypse sondées par microscopie à force atomique
Resume La modulation de force en microscopie a force atomique (AFM) permet de cartographier les inhomogeneites des proprietes elastiques de surface. L'influence des contraintes laterales sur l'elasticite de surface a pu etre mise en evidence par modulation de force. L'etude a porte sur la face (010) du gypse. Au niveau atomique, les images topographiques different de celles sondant l'elasticite de surface. Au niveau microscopique, les images d'elasticite dependent des contraintes exercees sur le cristal. Sans contrainte, la surface presente une elasticite uniforme. Cependant, les contraintes laterales revelent des phenomenes de glissement, de cisaillement et de nœuds d'elasticite.
Microstructural modifications resulting from the dehydration of gypsum
Various faces of dehydrated gypsum-cleaved blocks and single crystals have been investigated using optical microscopy, SEM, and TEM. The orientation of the cracks with respect to the initial gypsum structure and the Miller indices of all possible crack planes have been determined. These crack planes have been found to be few and to correspond to planes of high atomic density in the initial and final structures, therefore characterised by a low surface tension. These observations allow us to propose cracking criteria based on general concepts of crystal growth. The cracks' dimensions measured on different faces of the pseudomorph are distributed over several orders of magnitude and seems to …
Reactivity of gypsum faces according to the relative humidity by scanning force microscopy
Abstract This article reports the experimental observation of the stability of the different faces of calcium sulphate dihydrate (gypsum CaSO 4 .2H 2 O) according to the relative humidity. Scanning Force Microscopy experiments were carried out with a view to discerning the topography of the surfaces, the chemical compositional domains, and in an attempt to evaluate the friction and viscoelastic properties of the surface. Our results indicate that the (010) face of gypsum is hydrophilic and very reactive contrary to the less hydrophilic (120) and (101) faces which remain stable depending on the relative humidity. It is clear from our results that a precipitation like process can be induced b…
Hydration of calcium sulfate hemihydrate (CaSO4·H2O) into gypsum (CaSO4·2H2O). The influence of the sodium poly(acrylate)/surface interaction and molecular weight
Abstract The retarding influence of sodium poly(acrylate) (PANa) on the hydration of calcium sulfate hemihydrate (CaSO 4 · 1 2 H 2 O) was investigated. This study reports the influence of sodium poly(acrylate) on hemihydrate dissolution, on homogenous and heterogeneous gypsum (CaSO 4 ·2H 2 O) nucleation as well as on gypsum growth. It is shown that adsorption of PANa does not hinder the dissolution of hemihydrate in the present experimental conditions. The specific interaction of PANa with gypsum can explain the oriented growth of gypsum crystal. The gypsum growth is slowed down but cannot be blocked by the adsorption of PANa. On the other hand, PANa can block the heterogeneous and homogeno…
Dynamic mode rheology of cement and tricalcium silicate pastes from mixing to setting
Dynamic mode rheometry was used to study the evolution of the structure of cement and pure tricalcium silicate pastes from mixing up to setting and even after setting, together with the nature of the forces responsible for the mechanical properties of the pastes. A special mixer-type tool was used to study rheology during the very first minutes following the end of mixing, which are out of reach with classical tools. Both kinds of pastes have the same behavior. It was found that the main evolution of the structure of the pastes occurs during the very first minutes following the end of mixing, while there is no change in interparticular forces up to setting and even a few hours later. Settin…
Correlating surface forces with surface reactivity of gypsum crystals by atomic force microscopy. Comparison with rheological properties of plaster
Abstract Atomic Force Microscopy (AFM) was used to image the surface reactivity as well as to characterize quantitatively the surface forces between two gypsum (CaSO 4 , 2H 2 O) crystals. Measurements on different crystal faces, which vary in morphology, structure, hydrophilicity, surface charge, were performed in both air and ionic solutions. In ionic solutions, varying the experimental parameters, the ionic nature and the concentration as well as the duration of the contact leads to the conclusion that the adhesion occurs whatever the orientation of faces. Nevertheless, the magnitude of the adhesion of a physical nature (Van der Waals and ionic correlation) depends on the surface charge d…
Studies on mechanism and physico-chemical parameters at the origin of the cement setting. I. The fundamental processes involved during the cement setting
Abstract The mechanical evolution and the structure of the cement paste have been analysed in relation with the chemical evolution of the system. The setting process can be described as following two fundamental steps: the coagulation of cement grains during the first minutes following the mixing, and the rigidification of the coagulated structure which arises simultaneously with the acceleration of the hydrates formation During the coagulation step, the structure formed is proved to be mechanically reversible. The rigidification of the coagulated structure is provided by the hydrates formation in the contact zone. The increase of the paste cohesion at this stage is proportional to the quan…
Studies on mechanism and physico-chemical parameters at the origin of the cement setting II. Physico-chemical parameters determining the coagulation process
The physico-chemical parameters determining the coagulation of cements grains previously identified as the first fundamental process of cement setting have been investigated in diluted suspensions using an adapted granulometric method. The analysis of the influence of the ionic concentration in solution on the coagulation reveals that calcium concentration is the parameter which determines the particle interactions. There exists a minimum critical concentration of calcium ions in solution which is required to occur the coagulation of cement particles and a dispersive effect appears for very high concentrations. The results are discussed in relation with DLVO theory and specific interactions.
Electrokinetic Properties which Control the Coagulation of Silicate Cement Suspensions during Early Age Hydration
The coagulation of cement particles during early age hydration has been previously identified as the first step of the setting and hardening of cement pastes. By hydrating Ca3SiO5and a silicate-rich clinker under controlled conditions, a correlation between the coagulation of the suspensions and the electrokinetic properties of particles is established. The zeta potential, and hence the surface charge, of particles in suspension depends on the calcium content of the medium. At low concentrations of Ca2+, the zeta potential of Ca3SiO5particles, calcium silicate hydrate (C–S–H), and clinker is negative (<−30 mV) and the suspensions are well dispersed. A strong coagulation occurs at intermedia…