Synthesis of azopolymers with controlled structure and photoinduced birefringence in their LB films

The molecular architecture of azopolymers may be controlled via chemical synthesis and with selection of a suitable film-forming method, which is important for improving their properties for practical uses. Here we address the main challenge of combining the photoinduced birefringence features of azopolymers with the higher thermal and mechanical stabilities of poly(methyl methacrylate) (PMMA) using Atom Transfer Radical Polymerization (ATRP) to synthesize diblock- and triblock-copolymers of an azomonomer and the monomer methyl methacrylate. Langmuir-Blodgett (LB) films made with the copolymers mixed with cadmium stearate displayed essentially the same optically induced birefringence characteristics, in terms of maximum and residual birefringence and time for writing, as the mixed LB films with the homopolymer poly[4-(N-ethyl-N-(2-methacryloxyethyl))amino-2`-chloro-4`-nitroazobenzene] (HPDR13), also synthesized via ATRP. In fact, the controlled architecture of HPDR13 chains led to Langmuir films that could be more closely packed and reach higher collapse pressures than the corresponding films obtained with HPDR13-conv synthesized via conventional radicalar polymerization. This allowed LB films to be fabricated from neat HPDR13, which was not possible with HPDR13-conv. The enhanced organization in the LB films produced with controlled azopolymer chains, however, led to a smaller free volume available for isomerization of the azochromophores, thus yielding a lower photoinduced birefringence than in the HPDR13-conv films. The combination of ATRP synthesis and LB technology is then promising to obtain optical storage in films with improved thermal and mechanical processabilities, though a further degree of control must be sought to exploit film organization while maintaining the necessary free volume in the films. (C) 2008 Elsevier Ltd. All rights reserved.

Determination of the photoinduced birefringence and of the refractive index by Brewster method of epoxy resin doped with CdS

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Temperature dependence of photoinduced birefringence in mixed Langmuir-Blodgett (LB) films of azobenzene-containing polymers

The temperature dependence of photoinduced birefringence was investigated for mixed Langmuir-Blodgett (LB) films from the homopolymer poly[4'-[[2-(methacryloyloxy)ethyl]ethyl-amino]-2-chloro-4-nitroazobenzene] (HPDR13) and cadmium stearate (Cdst) and from the copolymer 4-[N-ethyl-N-(2-hydroxyethyl)]amino-2'-chloro-4'-nitroazobenzene (MMA-DR13) and CdSt. Birefringence was achieved by impinging a linearly polarized light on the LB films. The maximum birefringence achieved decreased with temperature as thermal relaxation of the chromophores was facilitated. The buildup curves for birefringence were fitted with biexponential functions representing distinctly different mechanisms with time constants. The first, fast process is thermally activated and may be represented by an Arrhenius process. The decay of birefringence after switching off the laser source was described by a Kohlraush-Williams-Watts (KWW) function, consistent with a distribution of relaxation times for the polymer system. Activation energies were obtained from Arrhenius plots of the rate constant of the exponential functions and KWW function, which showed that the buildup of birefringence was very similar for the two polymer systems. The decay, however, was slower for the LB film from MMA-DR13/CdSt. (C) 2002 Published by Elsevier B.V. Ltd.

Temperature dependence of photoinduced birefringence in polystyrene doped with Disperse Red-1

A theoretical model on the basis of the free-volume concept is presented explaining the temperature dependence of photoinduced birefringence in polystyrene films that contain Disperse Red-1. Birefringence increases with temperature up to 180 K as the free volume for isomerization increases, and then decreases as thermally activated processes dominate. The fast process of birefringence decay has a time constant that increases with temperature at low temperatures, due to the change kin photoisomerization.

Influence from the free volume on the photoinduced birefringence in azocompound-containing polymers

The photoinduced birefringence is analyzed in a guest-host azobenzene-containing polymer in the temperature range from 20 to 330 K. An anomalous behavior arises in the low-temperature range, suggesting strong influence from the free volume for the chromophores in the polymer. This influence is so strong that quenched samples have a photoinduced signal ca. 5 times greater than the annealed ones at room temperature. An extended free volume model is presented based on two assumptions about thermal fluctuations in the cavities and their size distribution. This model, which is an extension of the model by Mita et al., can explain the main features of the photoinduced birefringence as a function of time, temperature, and initial free volume state. To account for the influence of free volume on the photoorientation, the detailed reorientation model by Sekkat's was used. We show that Sekkat's model leads to an exponential behavior at small orientation regimes, which simplifies the mathematical treatment and allows the mean free volume to be obtained from the data fitting.

Influence of ionic interactions on the photoinduced Birefringence of poly[1-[4-(3-carboxy-4 hydroxyphenylazo) benzene sulfonamido]-1 2-ethanediyl, sodium salt] films

Electrostatic interactions govern most properties of polyelectrolyte films, as in the photoinduced bire-fringence 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 hydroxypheny-lazo) 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 PAH or PAZO.

Photoinduced birefringence at low temperatures in Langmuir-Blodgett films of azobenzene-functionalized copolymers

The temperature dependence has been investigated for the photoinduced birefringence in Langmuir-Blodgett (LB) films from the azocopolymer 4-[N- ethyl -N-(2-hydroxyethyl)] amino-2'-chloro-4'-nitroazobenzene (MMA-DR13) mixed with cadmium stearate. The buildup and relaxation of the birefringence in the range from 20 to 296 K were fitted with a Kohlrausch-Williams-Watts (KWW) function, with a beta-value of 0.78-0.98 for the build-up and 0.18-0.27 for the decay. This is consistent with a distribution of time constants for the kinetics of the birefringence processes. The maximum birefringence increased with increasing temperature up to 120 K because the free volume fluctuation also increased with temperature. Above 120 K, the birefringence decreased with temperature as thermal diffusion dominates. In the latter range of temperature, an Arrhenius behavior is inferred for both build-up and decay of birefringence. In each case two activation energies were obtained: 0.8 and 5 kJ/mol for the build-up and 10 and 30 kJ/mol for the decay. The energies for the build-up are much lower than those associated with motion of the polymer chain, which means that the dynamics is governed by the orientation of the chromophores. For the decay, local motion of lateral groups of the polymer chains becomes important as the activation energies are within the range of gamma-relaxation energies. (C) 2003 Elsevier B.V. B.V. All rights reserved.

Kinetics of photoinduced birefringence in the guest-host system of poly(methyl methacrylate) doped with azobenzene-containing crown ethers

The kinetics of the buildup and decay of photoinduced birefringence was examined in a series of host-guest systems: azobenzene-containing crown ethers, differing in the size of the crowns, dissolved in a poly (methyl methacrylate) matrix. In all samples, the kinetics of the buildup of the birefringence was reasonably described by a sum of two exponential functions, the time constants being inversely proportional to the intensity of the pumping light and the magnitudes of the signals at the saturation level depending on the pumping light intensity and sample thickness. The dark decays were best described by the stretched exponential function, with the characteristic parameters (time constant and stretch coefficient) being practically independent of the type of crown ether. The time constants of the signal decay were orders of magnitude shorter than the respective constants of the dark isomerization of the azo crown ethers, thus indicating that the process controlling the decay was a relaxation of the polymer matrix and/or a rearrangement of the flexible parts of the crowns. (C) 2007 Wiley Periodicals, Inc.

Study of photoinduced birefringence vs As content in thin GeAsS films

Thin films of GeAsS glass are prepared by e-beam evaporation technique. Photoinduced birefringence (PIB) is studied as function of the As content with concentrations ranging from 10% to 40%. Raman spectroscopy is used as additional tool to explain the corresponding changes undergone by the material system. The breakdown of homopolar bonds is suggested as a possible mechanism of photo induced structural changes leading to the creation of the PIB.

Photoinduced phenomena in layer-by-layer films of poly(allylamine hydrochloride) and Brilliant Yellow azodye

The nanoscale interactions between adjacent layers of layer-by-layer (LBL) films from poly(allylamine hydrochloride) (PAH) and azodye Brilliant Yellow (BY) have been investigated, with the films employed for optical storage and the formation of surface-relief gratings. Using Fourier transform infrared spectroscopy, we identified interactions involving SO3- groups from BY and NH3+ groups from PAH. These electrostatic interactions were responsible for the slow kinetics of writing in the optical storage experiments, due to a tendency to hinder photoisomerization and the subsequent reorientation of the azochromophores. The photoinduced birefringence did not saturate after one hour of exposure to the writing laser, whereas in azopolymer films, saturation is normally reached within a few minutes. on the other hand, the presence of such interactions prevented thermal relaxation of the chromophores after the writing laser was switched off, leading to a very stable written pattern. Moreover, the nanoscale interactions promoted mass transport for photoinscription of surface-relief gratings on PAH/BY LBL films, with the azochromophores being able to drag the inert PAH chains when undergoing the trans-cis-trans photoisomerization cycles. A low level of chromophore degradation was involved in the SRG photoinscription, which was confirmed with micro-Raman and fluorescence spectroscopies.

Determination of photoinduced and intrinsic birefringences in PMMA/DR13 guest-host film

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Long-Term Stability at High Temperatures for Birefringence in PAZO/PAH Layer-by-Layer Films

Optical memories with long-term stability at high temperatures have long been pursued in azopolymers with photoinduced birefringence. In this study, we show that the residual birefringence in layer-by-layer (LbL) films made with poly[1-[4-(3-carboxy-4 hydroxyphenylazo)benzene sulfonamido]-1,2-ethanediyl, sodium salt] (PAZO) alternated with poly(allylamine hydrochloride) (PAH) can be tuned by varying the extent of electrostatic interactions with film fabrication at different pHs for PAH. The dynamics of both writing and relaxation processes could be explained with a two-stage mechanism involving the orientation of the chromophores per se and the chain movement. Upon calculating the activation energies for these processes, we demonstrate semiquantitatively that reduced electrostatic interactions in films prepared at higher pH, for which PAH is less charged, are responsible for the longer stability at high temperatures. This is attributed to orientation of PAZO chromophores via cooperative aggregation, where the presence of counterions hindered relaxation.

Investigations on birefringence effects in polymer optical fiber Bragg gratings

Step-index polymer optical fiber Bragg gratings (POFBGs) and microstructured polymer optical fiber Bragg gratings (mPOFBGs) present several attractive features, especially for sensing purposes. In comparison to FBGs written in silica fibers, they are more sensitive to temperature and pressure because of the larger thermo-optic coefficient and smaller Young's modulus of polymer materials. (M)POFBGs are most often photowritten in poly(methylmethacrylate) (PMMA) materials using a continuous-wave 325 nm HeCd laser. For the first time to the best of our knowledge, we study photoinduced birefringence effects in (m)POFBGs. To achieve this, highly reflective gratings were inscribed with the phase mask technique. They were then monitored in transmission with polarized light. For this, (m)POF sections a few cm in length containing the gratings were glued to angled silica fibers. Polarization dependent loss (PDL) and differential group delay (DGD) were computed from the Jones matrix eigenanalysis using an optical vector analyser. Maximum values exceeding several dB and a few picoseconds were obtained for the PDL and DGD, respectively. The response to lateral force was finally investigated. As it induces birefringence in addition to the photo-induced one, an increase of the PDL and DGD values were noticed. © 2014 Copyright SPIE.

Fast dynamics in the optical storage with Langmuir-Blodgett films of a diazocrown ether molecule

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Optical, electrical, and thermochromic properties of polyazothiophene Langmuir-Blodgett films

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)