Solvents effects in the formation and viscoelasticity of DBS organogels

Abstract

The gel behavior of dibenzylidene sorbitol (DBS) in different solvents was studied by rheology, optical microscopy and transmission electron microscopy. It was found that DBS molecules would self-assemble into fibrils with a helical structure, and the fibrillar diameter decreased with increasing solvent polarity. The gel dissolution temperature was extremely sensitive to the DBS concentration and solvent polarity, which could be explained by the Gibbs–Thomson equation through interfacial stress. The phase diagram, which classified the sol, the gel and the cluster regime in different solvents was determined by rheology and optical microscopy. The critical gel concentration was found to increase as the difference in the polar and hydrogen-bonding components of the solubility parameter (Δδ_ph) between the gelator and solvents decreased. Meanwhile, the difference in the critical gel concentration in different solvents could explain the difference in the relaxation exponent and the gel strength at the gel point well. In the stable gel state, the plateau modulus depended on the gelator concentration according to a power-law scaling, G^o_N ∝ c², which was consistent with entanglement theory and independent of the type of solvent. However, the gelator–solvent interaction and its temperature dependence were found to affect the stability of the gel substantially under large amplitude oscillatory shear. The critical strain would increase as Δδ_ph decreased, and showed more evident temperature dependence on solvents with a smaller Δδ_ph.