Superposition of Oscillations on Steady Shear Flow as a Technique for Investigating the Structure of Associative Polymers

Abstract

The viscoelastic properties over a range of steady shear conditions of an alkali-swellable associative polymer have been determined using the technique of superposition of oscillations upon steady shear flow, thus enabling the structure of the polymer to be investigated. The associative polymer studied consists of a backbone of methacrylic acid and ethyl acrylate to which is attached macromolecules containing C 20 hydrophobes via an ethylene oxide−isocyanate linkage. A 1 wt % solution with its pH adjusted to 9.5 was used. At high pHs, the polymer solubilizes to form a network of both intra- and intermolecular associating hydrophobic junctions. The solution shows a non-power-law shear-thinning behavior: the viscosity flow curve, when plotted against shear stress, shows two distinct regions where network rupture is prominent, at stress of 2 Pa and between 40 and 50 Pa. By superimposing small amplitude oscillations on to shear flow at constant stresses, the network structure of the polymer is unperturbed and linear viscoelastic properties of the polymer under the applied stress conditions can be obtained. At an applied stress of 2 Pa and above, both the storage and loss moduli of the polymer are greatly reduced at low frequencies, with the G ‘ approaching second-order behavior and η‘ tending toward constant values. By analogy to Maxwell relaxation time, an estimate of the relaxation time of the associative polymer at different stress conditions can be made. The results show that the relaxation time is reduced by up to 4 orders of magnitude as the stress is increased from 1 to 60 Pa, while a much smaller decrease in viscosity is observed. At sufficiently high frequencies, both the storage and loss moduli show an increase above their linear viscoelastic values as the strain amplitude is increased. This behavior is believed to be dependent on the relaxation time of the polymer which is a function of the state of network disruption. Thus the technique may prove to be a powerful tool for probing the structure of network polymer in solution.