Molecular simulation of nanocolloid rheology: Viscosity, viscoelasticity, and time-concentration superposition

• Published in: Journal of rheology (New York : 1978) 2020-05, Vol.64 (3), p.529-543
• Main Authors: Sundaravadivelu Devarajan, Dinesh, Nourian, Pouria, McKenna, Gregory B., Khare, Rajesh
• Format: Article
• Language: English
• ISSN: 0148-6055; 1520-8516
• DOI: 10.1122/1.5125142

A particulate molecular model in which the solvent particles are considered explicitly is developed for studying the linear viscoelasticity of nanocolloidal suspensions using molecular dynamics simulations. Nanocolloidal systems of volume fractions ranging from 0.10 to 0.49 are studied. The hydrodynamics in these model systems are governed by interparticle interactions. The volume fraction dependence of the relative zero shear viscosity exhibited by this molecular model is consistent with that reported in the literature experiments and simulations. Over the range of frequencies studied, the relative dynamic viscosity values follow the same qualitative trend as that seen in the literature experiments. The time-concentration superposition (TCS) principle is successfully applied to construct the viscoelastic master curves that span nine decades of frequency in the case of the elastic modulus and more than four decades of frequency in the case of the loss modulus. The TCS principle was observed to fail at high volume fractions that are near the glass transition concentration; this finding is consistent with the literature experimental and simulation observations. The volume fraction dependence of the shift factors used in the construction of the viscoelastic master curves is in good quantitative agreement with that of the viscosity of the nanocolloidal systems. Our results demonstrate that molecular simulations in conjunction with an explicit solvent model can be used to quantitatively represent the viscosity and the viscoelastic properties of nanocolloidal suspensions. Such particulate models will be useful for studying the rheology of systems whose properties are governed by specific chemical interactions.