We have investigated the changes in the
molecular conformation, morphology, and
conductivity of polyaniline as it transforms from the insulating
emeraldine base (PANI-EB) to the
conducting emeraldine salt (PANI-ES) in solutions of
hexafluoro-2-propanol (HFIP) and in films processed
from the same solvent. Since both PANI-EB and PANI-ES
dissolve in this single solvent, we are able to
observe for the first time conformational changes as a function of the
molar doping level, y. HFIP both
solvates and complexes PANI-EB (i.e., y = 0) which
promotes a disruption in secondary interactions
between chains and allows individual polyaniline chains to adopt a more
expanded molecular conformation.
As PANI-EB is fully doped to PANI-ES (i.e., y =
0.50), a decrease in the GPC retention time and an
increase in [η] argues in favor of an expanded chain conformation
in HFIP. When the solvent is removed
(under very mild conditions) from PANI-ES, the expanded molecular
conformation is retained in the
solid state, based on the strong absorption of the UV−vis/near-IR
free carrier tail at 2500 nm and good
room temperature conductivity. The results in this study indicate
that the HFIP solvent can be used to
process PANI-EB and PANI-ES with diversified dopant counteranions; in
some cases, enhanced optical,
conductivity, and morphology properties result from the use of this
solvent.
The transformation variant of the fcc to fct transformation in FePt thin films was tailored by controlling the stresses in the thin films, thereby allowing selection of in- or out-of-plane c-axis orientation. FePt thin films were deposited at ambient temperature on several substrates with differing coefficients of thermal expansion relative to the FePt, which generated thermal stresses during the ordering heat treatment. X-ray diffraction analysis revealed preferential out-of-plane c-axis orientation for FePt films deposited on substrates with a similar coefficients of thermal expansion, and random orientation for FePt films deposited on substrates with a very low coefficient of thermal expansion, which is consistent with theoretical analysis when considering residual stresses.
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