A highly sensitive rheodielectric experimental setup
was used to
investigate the macroscopic alignment of symmetric poly(styrene-b-1,4-isoprene) (SI) diblock copolymers under large-amplitude
oscillatory shear (LAOS). The dielectric normal-mode of the 1,4-cis-polyisoprene chains in the diblock copolymer was chosen
to probe in situ the macroscopic orientation process.
It was shown that the development of the overall orientation of the
lamellar microstructure can be followed in situ using
the time progression of the dielectric loss modulus ε″(t). The dielectric loss ε″(t) correlates directly with the nonlinear mechanical response I
3/1(t) of the sample as determined
via Fourier transform rheology (FT-rheology). In addition to these
two dynamic methods, small-angle X-ray scattering was used to ascertain
the degree and type of the macroscopic orientation as a function of
the applied shear conditions. Evidence presented here showed that
a decrease in ε″(t) relative to the
initial value of ε″(t = 0 s) for a macroscopically
isotropic sample melt was indicative of a macroscopic parallel orientation
while an increase in ε″(t) corresponded
to an overall perpendicular alignment. These phenomena are explained
on a molecular level by the anisotropic diffusion of the confined
polymer chains, resulting in a higher mobility of the dielectrically
active end-to-end vector parallel to the interface, which can be detected
via dielectric spectroscopy.