Probing the shear-induced microstructure of a smectite clay aqueous suspensions using rheo-USANS and rheo-SIPLI...

The static microstructure of aqueous sodium-montmorillonite (Na-Mt) suspensions at low ionic strengths (where Particle Size/Debye Length ≈1) exhibits both the particle-particle ordering as well as aggregation with repulsive ordered domains having characteristic optical birefringence and attractive aggregated entities larger than 20 µm resulting in ever-increasing yield stresses also known as physical aging-rejuvenation behavior. We hypothesize that the attractive particle-particle aggregation is the underlying cause behind the physical aging-rejuvenation behavior observed in Na-Mt suspensions with no contribution from structural dynamics driven by repulsive particle-particle ordering or jamming.

We investigate the shear-induced microstructure of aqueous Na-Mt suspensions in the sol and gel state using rheo-ultra-small angle neutron scattering (rheo-USANS) experiments at shear rates of 1, 50, 500, and 2000 s^-1. We also perform rheo-shear-induced polarization light imaging (rheo-SIPLI) experiments to relate ordering with shearing and aging.

Shearing the suspensions at low to moderate shear rates induces particle-particle aggregation and shearing at high shear rates induces the breakage of particle-particle aggregation in the sol and gel states, suggesting the microstructural aggregation in the sol and gel state is shear sensitive and a full rejuvenation or breakage of particle-particle aggregation is only achieved at a minimum critical shear rate. The rheo-SIPLI experiments reveal that the sol and gel state exhibited strong Maltese cross patterns at a shear rate of 1000 s^-1, indicating particle-particle ordering. Post shearing, the gel exhibited temporal evolution of storage modulus without any noticeable influence on the appearance of the Maltese cross pattern indicating physical aging and particle ordering are distinct length scale phenomena in Na-Mt suspensions and the physical aging-rejuvenation behaviour is a feature of particle-particle aggregation as opposed to ordering.