Issue 8, 2022

Physical aging in aqueous nematic gels of a swelling nanoclay: sol (phase) to gel (state) transition

Abstract

Aqueous dispersions of geometrically anisometric, nano-sized sodium-montmorillonite (Na–Mt) display a sol–gel transition at very low solids concentrations. The microstructure of the gel formed at very low ionic strengths is considered electrostatically repulsive with a nematic character, and the gel state at ionic strengths where Debye length is of the order of particle size is conjectured to be free of physical aging. We investigated the nature of osmotically prepared Na–Mt dispersions at low ionic strength (∼10−5 M), below and above the gel point. The sol phase exhibited very low yield stress compared to the gel state, without any sign of physical aging, thus behaving as an equilibrium state. In contrast, the gel exhibited signatures of physical aging, that is, an evolving microstructure that consolidated with time when left undisturbed thus behaving as out of equilibrium state. The physical aging behaviour became more pronounced at Na–Mt concentrations far above the gel point. A critical shear rate existed, below which no stable flows were possible in the gel state representing the microstructural reorganization timescale. Overall, Na–Mt dispersions in the gel state behave like systems that were out of equilibrium with an ever-evolving microstructure, in opposition to the assumption that low ionic strength Na–Mt gels are in an equilibrium phase. The possible origin of physical aging, such as the reversible orientation of Brownian anisotropic particles, stiffening of an existing microstructure, or reorganization of microstructure towards minimal energy configuration is discussed in detail.

Graphical abstract: Physical aging in aqueous nematic gels of a swelling nanoclay: sol (phase) to gel (state) transition

Supplementary files

Article information

Article type
Paper
Submitted
25 Jul 2021
Accepted
04 Oct 2021
First published
04 Oct 2021

Phys. Chem. Chem. Phys., 2022,24, 4703-4714

Physical aging in aqueous nematic gels of a swelling nanoclay: sol (phase) to gel (state) transition

M. Shoaib, N. Molaei and E. R. Bobicki, Phys. Chem. Chem. Phys., 2022, 24, 4703 DOI: 10.1039/D1CP03399A

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