Journal of Colloid and Interface Science, Vol.295, No.2, 445-456, 2006
Electrooptics of beta-FeOOH particle in aqueous media - 2. Field-strength dependence of decay and steady-state birefringence, and the hydrodynamic and electrooptic properties
Steady-state and decay birefringence, expressed in terms of the optical phase retardation per cell length delta/d, was measured on beta-FeOOH in aqueous ionic media at 633 nm and at 25 degrees C by an electric square-pulse technique over a wide range of field strength E to ca. 6 kV/cm. The field-strength dependence of both delta/d and field-free rotational relaxation time tau was determined at the sample concentrations between 0.0011 and 0.055 g/L and in the 0.02-2.0 mM NaCl concentration range. Extrapolation of both delta/d and tau values to infinitely high fields (E-2-> infinity) could yield birefringence- and weight-average quantities, respectively. Observed tau values were decreased at weak fields but leveled off to ca. 0.3 ms at very high fields due to a slight polydispersity regarding the length and volume. of particles. The weight-average relaxation time (tau)(w) was calculated with Perrin's expressions theoretically from the length, width, and volume of beta-FeOOH particles estimated in the dried state from electron micrograph. These quantities were variously averaged. The size distribution was discussed in terms of observed discrete histogram and theoretical (Weibull and Lansing-Kraemer) distribution functions. The sign of observed delta/d value was always positive. The infinitely highfield (delta/d)infinity values and the reduced optical anisotropy factor A-In were evaluated by fitting to theoretical orientation functions. The intrinsic 0 birefringence (n(3) - n(1)) could be estimated with the mean refractive index n(p) reported in the literature. For the spindle-shaped particle with an axial ratio of ca. 4, the sign of Delta g/n is always positive, whereas the quantity (n(3) - n(1)) was either negative (n(p) > 2.35) or positive (n(p) < 2.05) in sign or nearly zero (ca. n(p) = 2.26), depending critically on the np values. (c) 2005 Elsevier Inc. All rights reserved.
Keywords:beta-FeOOH in NaCl solution;particle size distribution;electric birefringence decay;rotational relaxation time;steady-state birefringence;optical anisotropy factors