Extensional rheology of elastoviscous aqueous PEO/PEG or DMS Boger fluids and weakly elastic alternatives for investigating viscoelastic flows and instabilities

Abstract

Boger fluids that exhibit a rate-independent shear viscosity (typically ∼ 1 Pa∙s = 1000x water viscosity) and elasticity measurable using torsional rheometers (modulus, relaxation time, or first normal stress difference) are considered as the realization of viscoelastic fluids described by the Oldroyd-B model. However, Boger fluids, conventionally formulated as dilute solutions of high molecular weight (M_w) polymers in relatively high viscosity solvents (or solutions of oligomers or lower M_w polymer), are unsuitable for emulating polymeric fluids used in coating formulations that are lower in viscosity, appear inelastic in torsional shear rheometry, and yet appear prone to viscoelastic instabilities. Therefore, Dontula, Macosko, and Scriven (DMS) (AIChE J, 1998) chose to create an alternative model of elastic fluids by dissolving ultrahigh molecular weight (UHM_w) poly(ethylene oxide) (PEO) in an aqueous solution of its lower M_w analog, often referred to as poly(ethylene glycol) or PEG. Even though numerous studies of printing and coating flow instabilities use this aqueous PEO/PEG or DMS Boger fluids as model viscoelastic fluids, only a few explicitly measured elastic properties, especially using relaxation time, and hardly any characterized extensional rheology. In this contribution, we recreate the DMS Boger fluids to examine their elasticity and extensional rheology response using dripping-onto-substrate (DoS) rheometry that relies on an analysis of capillarity-driven pinching dynamics. Though the aqueous PEG solution is often treated as a viscous and Newtonian solvent, we discover that in DoS rheometry, both the PEG solution and the DMS Boger fluid display power law response followed by elastocapillary, in contradiction with the assumptions and the response expected of the Oldroyd-B model. Furthermore, the solution of entangled PEG chains influences specific viscosity, pinching dynamics, and measured extensional rheology response in striking contrast with Newtonian solvents of the same viscosity. Lastly, we describe the possibility of using dilute, aqueous solutions of UHM_w PEO as model viscoelastic fluids for coating flows, for both elasticity and extensional viscosity can be determined using DoS rheometry. Due to their water-like viscosity, the aqueous PEO solutions appeal as model fluids that have elasticity, emulate Newtonian fluids in the early stages of pinching, and have a relaxation time tunable by changing polymer M_w or concentration.