Vk. Gupta et al., DYNAMICS OF SHEAR ALIGNMENT IN A LAMELLAR DIBLOCK COPOLYMER - INTERPLAY OF FREQUENCY, STRAIN AMPLITUDE, AND TEMPERATURE, Macromolecules, 29(3), 1996, pp. 875-884
Rheo-optical methods are used to examine the combined effect of shear
frequency, strain amplitude, and temperature on the direction and kine
tics of flow-induced alignment in lamellar block copolymers. The devel
opment of shear-induced alignment in a nearly symmetric polystyrene-po
lyisoprene diblock (ODT similar or equal to 164 degrees C) is recorded
in real time using flow birefringence as a probe of the transient lam
ellar orientation distribution. As alignment progresses during large a
mplitude oscillatory shearing, the birefringence shows an initial ''fa
st'' and a later ''slow'' change. While increasing strain amplitude (g
amma(0)) generally speeds both the fast and the slow processes, below
a critical gamma(0) the slow process is not observed and a well-aligne
d state is not achieved. The transient birefringence observed at a par
ticular frequency and temperature, but different strain amplitudes, ca
n be partially superposed by scaling time with gamma(0)(n(omega)). How
ever, the ''fast'' and ''slow'' processes require different values of
n(omega). Estimates of n(omega) show that effects of strain are highly
nonlinear and stronger than the simple rescaling of time in terms of
either cumulative strain (similar to t gamma(0)) or cumulative flow en
ergy (similar to t gamma(0)(2)). The effect of temperature enters most
strongly through the shift of time scale of molecular relaxations (al
pha(T)).