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The applicability of azopolymers in optical storage can be extended through the use of nanostructured films produced with the Langmuir-Blodgett (LB) technique, but the film properties need to be optimized since these polymers generally do not form stable Langmuir films to be transferred onto solid substrates. Here, photoinduced birefringence was investigated for mixed Langmuir-Blodgett films from the homopolymers 4-[N-ethyl-N-(2-methacryloxyethyl)]-4'-nitroazobenzene (HPDR1-MA) and poly(dodecylmethacrylate) (HPDod-MA). The interactions between these polymers were studied in Langmuir and LB films. Surface pressure-area isotherms pointed to molecular-level interactions for proportions of 51 mf%, 41 mf% and 31 mf% of HPDR1-MA. Phase segregation was not apparent in the BAM images, in which the morphology of the blend film was clearly different from that of the Langmuir films of neat homopolymers. Through PM-IRRAS, we noted that the interaction between the azopolymer and HPDod-MA affected the orientation of carbonyl groups. Strong interactions for the mixture with 41 mf% of poly(dodecylmethacrylate) led to stable Langmuir films that were transferred onto solid supports as LB films. The photoinduced birefringence of 101-layer mixed LB films show features that make these films useful for optical storage, with the advantage of short writing times in comparison to other azopolymer films., (Copyright © 2010 Elsevier Inc. All rights reserved.)

The influence of the co-surfactant on physicochemical properties of w/o soybean oil microemulsions (MEs) has been studied. In spite of the similarity in phase diagrams, the MEs display remarkable differences when examined by electrical conductivity, dynamic light scattering (DLS), small angle X-ray scattering (SAXS) and linear voltammetry. When different short-chain alcohols were employed as co-surfactants, together with sodium dodecyl sulfate (SDS) as surfactant, the DLS results indicated the systems to be monodisperse. Both the electrical conductivity of the MEs and the hydrodynamic radii of the droplets (R(H)) increased with water content while R(H) diminished as temperature increased, no aggregation or percolation of the droplets being observed. In comparison to w/o MEs prepared with 3-methyl-1-butanol, those prepared with 1-pentanol presented higher electrical conductivity and larger limiting currents at a Pt ultramicroelectrode for oxidation of the water occluded into the particles. Finally, from the electrochemical viewpoint the use of 1-pentanol is recommended, no advantage being gained by using any of the other tested alcohols.

A morphological analysis is presented for Langmuir films of the diazo dyes Sudan 4 (S4), Sudan 3 (S3), and Sudan red (SR), using Brewster angle microscopy. Stable nonmonomolecular structures are formed at the air-water interface denoted as a plateau in the pressure-area isotherms. Monolayer domains are evident by the contrastless image even before the pressure onset, which grow in size until it reached a condensed monolayer. This behavior resembles that of Langmuir films from simple aromatic fatty acids. Films from all the azo dyes display similar features, according to the surface potential isotherms and in situ polarized UV/vis spectroscopy except for the larger area per molecule occupied by S4 and SR. This is attributed to the presence of CH(3) groups that cause steric hindrance modifying the organization of diazo dye molecules at the air-water interface. UV/vis polarized absorption spectroscopy showed preferential orientation of S4 and S3 on the water surface, while SR molecules lie isotropically. For these three diazo dyes, film absorption was negligible at very large areas per molecule, becoming nonzero only at a critical area coinciding with the onset of surface potential. The critical area is ascribed to the formation of a H-bonded network between water molecules and diazo dye headgroups.

In situ UV-vis absorbance measurements are used to investigate aggregation in Langmuir films from the azopolymer poly[4'-[[2-(methacryloyloxy)-ethyl]ethylamino]-2-chloro-4-nitroazobenzene] (HPDR13), a methacrylate derivative of DR13. The level of aggregation in a Langmuir film is intermediate between that of HPDR13 in chloroform solution and in a deposited LB film, as expected. Absorption is negligible at large areas per monomer, and starts to increase at a critical area that is the same as the one obtained in surface potential isotherms, being close to twice the area per monomer for a condensed film. This indicates that the onset for light absorption coincides with a critical packing density where monolayer structuring occurs and there is a sharp change in the effective dielectric constant of the film/water interface. Consistent with a featureless pressure-area isotherm for HPDR13, denoting no significant molecular rearrangement upon film compression, the UV-vis spectra did not vary with the surface pressure. The intensity of absorbed light increased, though, as the film was compressed owing to a higher density of chromophores. At higher subphase temperatures, larger flexibility of HPDR13 chains led to a more compact arrangement, causing the area per monomer to decrease and the absorbed light to increase-with approximately opposite trends.