The current study focuses on the effects of the molecular weight on the mechanical behavior of agarose gels. The small strain rheology and large strain deformation/failure behavior of three different molecular weight agarose gels have been examined, with the results expressed in term of molar concentration. For small deformation strains, the gelation temperature at low concentrations and the critical concentration for gel formation are strongly affected by the molecular weight. In addition, the elasticity of the network is also very sensitive to this parameter. It has been demonstrated that the experimental gelation cure curves can be superimposed on a universal gelation master curve, independent of the cure time. This would indicate self-similarity of the network at different scales, irrespective of concentration. A relationship between the elastic modulus and the molecular weight has been extracted from these results, where the molecular weight dependence exhibits a power law exponent of 2.42. For large deformation strains, the Poisson ratio has been estimated to be 0.5 for each of the agarose types examined, which indicates that these gels are incompressible. The strain at failure is largely dependent on the molecular weight, and is essentially independent of the biopolymer concentration. This result highlights the fact that the strain at failure is sensitive to the connectivity distances in the gel network. However, the failure stress and Young's modulus of agarose gels show a dependence on both concentration and molecular weight. The observations regarding Young's modulus are in good agreement with those found for small deformation strain rheology for the shear modulus. One of the primary advantages of using the lowest molecular weight agarose is that higher molar concentrations can be reached (more molecules per unit volume). However, the mechanical response of agarose gels is very sensitive to the molecular weight at fixed molar concentration, and if the present results are extrapolated to very low molecular weight, it can be suggested that below a limiting molecular weight a percolating network will not be formed, as suggested by the Cascade model (Carbohydr. Polym. 1994, 23, 247-251). This speculation is based on the influence of the "connectivity" at long distances, which influences the strain at failure (when the strain at failure is zero, the system is not connective).

The flow anisotropy of a concentrated colloidal suspension at the jamming transition is studied. It is shown that the use of rough spherical particles reduces the hydrodynamic lubrication forces between adjacent colloids and makes possible the study of the stress tensor anisotropy. At low shear rates, the suspension exerts an attractive force between two opposite surfaces, whereas at higher shear rates it becomes dilatant. Direct confocal microscopy observation of the particles organization reveal that crystallites form at high shear rate.

We study the stress response to a steady imposed shear rate in a concentrated suspension of colloidal particles. We show that, in a small range of concentrations and shear rates, stress exhibits giant fluctuations. The amplitude of these fluctuations obeys a power-law behavior, up to the apparition of a new branch of flow, leading to an excess of high amplitude fluctuations which exhibit a well-defined periodicity.

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Developing functional concrete mixtures with less ordinary portland cement (OPC) has been one of the key objectives of the 21st century sustainability movement. While the supplies of many alternatives to OPC (such as fly ash or slag) may be limited, those of limestone and silica powders produced by crushing rocks seem virtually endless. The present study examines the chemical and physical influences of these powders on the rheology, hydration, and setting of cement-based materials via experiments and three-dimensional microstructural modeling. It is shown that both limestone and silica particle surfaces are active templates (sites) for the nucleation and growth of cement hydration products, while the limestone itself is also somewhat soluble, leading to the formation of carboaluminate hydration products. Because the filler particles are incorporated as active members of the percolated backbone that constitutes initial setting of a cement-based system, replacements of up to 50 % of the OPC by either of these powders on a volumetric basis have minimal impact on the initial setting time, and even a paste with only 5 % OPC and 95 % limestone powder by volume achieves initial set within 24 h. While their influence on setting is similar, the limestone and silica powders produce pastes with quite different rheological properties, when substituted at the same volume level. When proceeding from setting to later age strength development, one must also consider the dilution of the system due to cement removal, along with the solubility/reactivity of the filler. However, for applications where controlled (prompt) setting is more critical than developing high strengths, such as mortar tile adhesives, grouts, and renderings, significant levels of these powder replacements for cement can serve as sustainable, functional alternatives to the oft-employed 100 % OPC products.

Résumé -Coagulation, rhéofluidification et rhéoépaississement dans les coulis de ciment -Le comportement rhéologique des coulis de ciment peut se décliner en plusieurs comportements élémentaires : -la formation rapide d'un gel faible au repos ; -l'effondrement de ce gel sous une contrainte critique directement liée à l'intensité des forces interparticulaires ; -la destruction progressive des fragments de ce gel sous cisaillement modéré, avec un comportement d'autant plus rhéofluidifiant que la taille des grains élémentaires est faible ; -la reformation, d'abord transitoire puis continue, à fort gradient de vitesse, de structures résistant au cisaillement, probablement sous forme de chaînes de grains au contact avec, sur le plan rhéologique, l'apparition d'un rhéoépaississement ; -éventuellement, le blocage de l'écoulement. Nous démontrons les mécanismes de passage d'un état au suivant. Nous montrons comment l'addition d'agents dispersants favorise l'état rhéoépaississant au détriment de l'état rhéofluidifiant et comment le contrôle de l'état de surface des grains et du frottement intergranulaire permet de limiter le rhéoépaississement et les risques de blocage. Abstract -Gelation, Shear-Thinning and Shear-Thickening in Cement Slurries