Polymer, Vol.44, No.4, 1203-1210, 2003
Development and relaxation of orientation in sheared concentrated lyotropic solutions of hydroxypropylcellulose in m-cresol
Shear-induced orientation and the relaxation of orientation after the cessation of shear in 45 and 50 wt% solutions of cholesteric hydroxypropylcellulose (HPC) in m-cresol have been studied in situ by infrared spectroscopy and polarised microscopy. The shearing experiments were conducted at 30-80 degreesC at shear rates of 1-300 s(-1), which covered the director tumbling, wagging and a small part of the steady-state shear rate regimes. The steady-state order parameter was proportional to the shear rate and the proportionality constant increased with increasing HPC concentration and decreasing temperature. The concentrated solutions studied showed steady-state alignment even in the tumbling regime. Three different shear-rate regions with different behaviours of the solutions after the cessation of shear were found in these concentrated HPC solutions. At low shear rates (1-5 s(-1), referring to the 50% HPC solution) the polymer remained isotropic during shear but became gradually more oriented a few minutes after the cessation of shear, an observation that was substantiated by polarized microscopy. The order parameter reached a final plateau value and stayed constant at this level for long periods of time (similar to24 h). At intermediate shear rates (from 5 to 50 s(-1) for the 50% HPC solution), a detectable order parameter was recorded at steady shear and, after the cessation of shear, the structure returned to an almost isotropic state within a few minutes, after which the orientation gradually started to increase to approach a plateau value after about 150 min. At even higher shear rates (similar to100 s(-1) for to the 50% HPC solution), the initial steady shear order parameter relaxed to an almost isotropic state and remained constant at this level for time periods extending up to 24 h.