Etude des proprietes microstructurales et rheologiques de suspensions non-aqueuses d'argile
Abstract
Phyllosilicates or layered silicates consist of individual layers with nanometric dimensions. In static fluids without external forces, attractive and repulsive colloidal forces acting between the colloidal layers lead to their self-organization on multiple length scales. Under flow, a wide range of complex rheological behaviors, including shear-thinning behavior and transition from fluid-like to solid-like behavior leading to thixotropic phenomena, is expected from structural evolution. Recently, layered silicates have attracted great interest as nanoscale fillers for reinforcement of polymers (PNCs) motivating the investigation of the structural properties of non-aqueous layered silicate suspensions. At the origin of this study, the linear and nonlinear viscoelastic properties of non-aqueous layered silicate suspensions were observed to depend on flow history. Hence, the ultimate aim of this work was to establish relationships between their rheological behavior and their structural properties. The picture of their inner structure has been achieved using a combination of light scattering techniques and advanced rheometric and microscopy measurements. The flow-induced orientation of the phyllosilicate has been quantified optically using linear dichroism measurements, and mechanically using a newly developed non-destructive method based on two-dimensional small amplitude oscillatory shear flow (2D-SAOS). The spatial distribution at the microscopic scale of the phyllosilicate has been inferred from small angle light scattering (SALS) patterns and directly observed using confocal laser microscopy (CLSM). The combination of these techniques allowed highlighting the microscopic and self-similar nature of non-aqueous phyllosilicate suspensions. The solid-like properties of these suspensions were consequently ascribed to the presence of space-filling networks made of mass fractal clusters. Under flow, the shear-thinning behavior of these suspensions was explained by the shear rate dependency of the microstructure characteristic length scale. By increasing the shearing amplitude, the characteristic length scale of the non-equilibrium microstructures was shown to decrease from high to low plateau values. This structural evolution with the shearing amplitude was attributed to a reversible shear-induced aggregation. Limited structural orientational changes were also observed in the vorticity plane with anisotropy and orientation that developed in the same range of shear rate as the shear-thinning behavior of the suspensions. Upon cessation of flow, the lack of orientational recovery was explicitly shown with the 2D-SAOS experiments, while the lack of structural recovery at the micro-scale was observed in CLSM. The thixotropic behavior of these suspensions is therefore due to local rearrangements at the nano-scale. The non-equilibrium structures were actually shown to persist upon cessation of flow leading to different metastable structures. This work has allowed us to elucidate the effect of the flow history on the linear and nonlinear viscoelastic properties of these suspensions.
- Publication:
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Ph.D. Thesis
- Pub Date:
- 2008
- Bibcode:
- 2008PhDT.......155M