Physical and chemical kinetics of structural build-up of cement suspensions

Abstract : The structural build-up of fresh cement-based materials has a great impact on their structural performance after casting. Accordingly, the mixture design should be tailored to adapt the kinetics of build-up given the application on hand. The rate of structural build-up of cement-based suspensions at rest is a complex phenomenon affected by both physical and chemical structuration processes. The structuration kinetics are strongly dependent on the mixture’s composition, testing parameters, as well as the shear history. Accurate measurements of build-up rely on the efficiency of the applied pre-shear regime to achieve an initial well-dispersed state as well as the applied stress during the liquid-solid transition. Studying the physical and chemical mechanisms of build-up of cement suspensions at rest can enhance the fundamental understanding of this phenomenon. This can, therefore, allow a better control of the rheological and time-dependent properties of cement-based materials. The research focused on the use of dynamic rheology in investigating the kinetics of structural build-up of fresh cement pastes. The research program was conducted in three different phases. The first phase was devoted to evaluating the dispersing efficiency of various disruptive shear techniques. The investigated shearing profiles included rotational, oscillatory, and combination of both. The initial and final states of suspension’s structure, before and after disruption, were determined by applying a small-amplitude oscillatory shear (SAOS). The difference between the viscoelastic values before and after disruption was used to express the degree of dispersion. An efficient technique to disperse concentrated cement suspensions was developed. The second phase aimed to establish a rheometric approach to dissociate and monitor the individual physical and chemical mechanisms of build-up of cement paste. In this regard, the non-destructive dynamic rheometry was used to investigate the evolutions of both storage modulus and phase angle of inert calcium carbonate and cement suspensions. Two independent build-up indices were proposed. The structural build-up of various cement suspensions made with different cement contents, silica fume replacement percentages, and high-range water reducer dosages was evaluated using the proposed indices. These indices were then compared to the well-known thixotropic index (Athix.). Furthermore, the proposed indices were correlated to the decay in lateral pressure determined for various cement pastes cast in a pressure column. The proposed pre-shearing protocol and build-up indices (phases 1 and 2) were then used to investigate the effect of mixture’s parameters on the kinetics of structural build-up in phase 3. The investigated mixture’s parameters included cement content and fineness, alkali sulfate content, and temperature of cement suspension. Zeta potential, calorimetric, spectrometric measurements were performed to explore the corresponding microstructural changes in cement suspensions, such as inter-particle cohesion, rate of Brownian flocculation, and nucleation rate. A model linking the build-up indices and the microstructural characteristics was developed to predict the build-up behaviour of cement-based suspensions The obtained results showed that oscillatory shear may have a greater effect on dispersing concentrated cement suspension than the rotational shear. Furthermore, the increase in induced shear strain was found to enhance the breakdown of suspension’s structure until a critical point, after which thickening effects dominate. An effective dispersing method is then proposed. This consists of applying a rotational shear around the transitional value between the linear and non-linear variations of the apparent viscosity with shear rate, followed by an oscillatory shear at the crossover shear strain and high angular frequency of 100 rad/s. Investigating the evolutions of viscoelastic properties of inert calcite-based and cement suspensions and allowed establishing two independent build-up indices. The first one (the percolation time) can represent the rest time needed to form the elastic network. On the other hand, the second one (rigidification rate) can describe the increase in stress-bearing capacity of formed network due to cement hydration. In addition, results showed that combining the percolation time and the rigidification rate can provide deeper insight into the structuration process of cement suspensions. Furthermore, these indices were found to be well-correlated to the decay in the lateral pressure of cement suspensions. The variations of proposed build-up indices with mixture’s parameters showed that the percolation time is most likely controlled by the frequency of Brownian collisions, distance between dispersed particles, and intensity of cohesion between cement particles. On the other hand, a higher rigidification rate can be secured by increasing the number of contact points per unit volume of paste, nucleation rate of cement hydrates, and intensity of inter-particle cohesion.

Dette publique, développement monétaire international et demande de monnaie : une analyse à partir des tests de cointégration et du modèle à correction d'erreurs

Résumé : Ce document examine l'effet de la dette publique et du développement monétaire étranger (taux de change et taux d'intérêt étranger) sur la demande de monnaie de long-terme. Le déficit budgétaire est utilisé comme mesure de la dette publique. Cette étude est menée sur cinq pays industrialisés: le Canada, les États-Unis, l'Allemagne, le Royaume-Uni et la France. Le modèle multivarié de cointégration de Johansen & Juselius (1990) est utilisé pour établir le lien entre ces trois variables et la demande de monnaie. Ce modèle examine indirectement deux effets: les effets du déficit budgétaire sur le taux d'intérêt et du développement monétaire étranger sur le taux d'intérêt, à travers la demande de monnaie. L'évidence d'une relation de cointégration entre la demande de monnaie et les dites variables est vérifiée pour la plupart de ces pays. Le test d'exclusion des variables de la relation de long-terme nous révèle que toutes ces variables entrent de façon significative dans la relation de cointégration. Ces résultats suggèrent donc aux autorités monétaires, l'importance de tenir compte à la fois du déficit bugétaire et du développement monétaire étranger dans la formulation de la politique monétaire.||Abstract : This paper examines the impact of both public debt and foreign monetary developments (exchange rate and interest rate) on the long-run money demand. The budget déficit is used as a measure of public debt. Five industrial countries are considered, Canada, the United States, Germany, the United Kingdom and France. The multivariate cointegration model of Johansen & Juselius (1990) is used to establish the relationship between this tree variables and the money demand. This model indirectly examines two effects, the effect of budget déficits on interest rates and the effect of foreign monetary developments on the interest rates, both through money demand. Evidence of long-run relationship between the money demand and the defined variables are found for almost every country. The long-run exclusion test shows that ail these variables significantly enter into the cointegration relation. This suggests that, in formulating monetary policies, policy makers should take into account the influence of both budget déficit and foreign monetary developments on the money demand.