Apparent Breakdown of the Stress-Optic Rule in Rigid-Rod Suspensions: A Stress-Partitioning Interpretation

Abstract

A fundamental problem in the field of anisotropic macromolecular materials concerns how the flow-induced orientational order connects microscopic structure to macroscopic rheological stress and optical anisotropy. This study considered cellulose nanocrystal suspensions as rigid-rod model systems for the purpose of isolating orientational effects from chain stretching. Simultaneous rheo-optical measurements of birefringence, orientation angle, and shear stress were combined with a Fokker-Planck orientation model and stress decomposition. Our results show that, at low values of the Peclet number, birefringence and total stress exhibit proportionality similar to the stress-optic rule. However, the concentration dependence indicates that this proportionality reflects stress partitioning rather than a unique material coefficient. With increasing flow strength, orientational saturation is accompanied by a reduced relative Brownian stress contribution and a corresponding change in the total stress-based relation. Referencing the optical response to an estimated Brownian stress contribution yields a substantially more unified response across concentrations and flow conditions, supporting a stress-partitioning interpretation of apparent stress-optic rule breakdown.