ABSTRACT
Electrostatic interactions govern most properties of polyelectrolyte films, as in the photoinduced birefringence of azo-containing polymers. In this paper we report a systematic investigation of optical storage characteristics of cast and layer-by-layer (LbL) films of poly[1 -[4-(3-carboxy-4 hydroxyphenylazo) benzene sulfonamido]-1,2-ethanediyl, sodium salt] (PAZO). Birefringence was photoinduced faster in PAZO cast films prepared at high pHs, with the characteristic writing times decreasing almost linearly with the pH in the range between 4 and 9. This was attributed to an increased free volume for the azochromophores with the enhanced electrostatic repulsion in PAZO charged to a greater extent. In contrast, in LbL films of PAZO alternated with poly(allylamine hydrochloride) (PAH), the electrostatic interactions between the oppositely charged polymers hampered photoisomerization and molecular rearrangement, thus leading to a slower writing kinetics for highly charged
Subject(s)
Benzene/chemistry , Birefringence , Polystyrenes/chemistry , Sodium/chemistry , Electrochemistry/methods , Hydrogen-Ion Concentration , Ions , Kinetics , Light , Models, Chemical , Models, Statistical , Nanotechnology/methods , Photochemistry/methods , Static Electricity , Time FactorsABSTRACT
The phase transition from the non-polar alpha-phase to the polar beta-phase of poly(vinylidene fluoride) (PVDF) has been investigated using micro-Raman spectroscopy, which is advantageous because it is a nondestructive technique. Films of alpha-PVDF were subjected to stretching under controlled rates at 80 degrees C, while the transition to beta-PVDF was monitored by the decrease in the Raman band at 794 cm(-1) characteristic of the alpha-phase, along with the concomitant increase in the 839 cm(-1) band characteristic of the beta-phase. The alpha-->beta transition in our PVDF samples could be achieved even for the sample stretched to twice (2x-stretched) the initial length and it did not depend on the stretching rate in the range between 2.0 and 7.0 mm/min. These conclusions were corroborated by differential scanning calorimetry (DSC) and X-ray diffraction experiments for PVDF samples processed under the same conditions as in the Raman scattering measurements. Poling with negative corona discharge was found to affect the alpha-PVDF morphology, improving the Raman bands related to this crystalline phase. This effect is minimized for films stretched to higher ratios. Significantly, corona-induced effects could not be observed with the other experimental techniques, i.e., X-ray diffraction and infrared spectroscopy.
Subject(s)
Crystallography/methods , Materials Testing/methods , Polyvinyls/analysis , Polyvinyls/chemistry , Spectrum Analysis, Raman/methods , Membranes, Artificial , Phase Transition , Physical Stimulation/methods , Stress, Mechanical , Temperature , Tensile StrengthABSTRACT
The generation of surface anisotropy by photochemical means has been proposed as an attractive method to align liquid crystals. In this paper, we present an experimental study of the alignment induced on a liquid crystal by a polymer film containing azo-dye groups in the side chain. Optical measurements were performed in nematic liquid crystal cells to determine the azimuthal and zenithal anchoring strengths as a function of the irradiation energy and chromophores concentration. It was observed that the director tends to align perpendicular to the polarization direction of the incident light and the orientation process consists essentially of a rotation of the director in the plane parallel to the boundary surfaces. However, the concentration of azo-dye groups in the polymer film must exceed a minimum value to get a macroscopical effect on the liquid crystal alignment. It is shown that the azimuthal anchoring strength can be varied two orders of magnitude by controlling the irradiation energy and azo-dye concentration.