THERMAL-HISTORY-DEPENDENT TRANSITION IN PRESSED PELLETS OF CLO4(-)-DOPED POLY(3-METHYLTHIOPHENE)

Electron-spin-resonance and dc conductivity data show a thermal-history-dependent transition at 240 K in pressed pellets of ClO4--doped poly(3-methylthiophene) (P3MT). We discuss the possibility of this transition to be a Peierls transition from a room-temperature-metallic to a charge-density-wave state driven by anions ordering at this temperature. Below 100 K, dc conductivity shows a change from linear to exponential decay. Nonlinear conductivity has also been observed in this system for very low electric fields.

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.

In vitro evaluation of the effectiveness of acidic fluoride dentifrices

This study evaluated the effectiveness of acidic low-fluoride dentifrices compared to conventional neutral dentifrices. Enamel blocks were submitted to pH cycling and treatment with slurries of dentifrices containing 0, 275, 412, 550 and 1,100 mu g F/g (pH 4.5 or 7.0), and also a commercial dentifrice (1,100 mu g F/g) and a commercial children's dentifrice (500 mu g F/ g). Variations in surface microhardness and in the mineral content in enamel after pH cycling were calculated. Enamel blocks treated with acidic dentifrices exhibited less mineral loss compared to neutral dentifrices (ANOVA; p < 0.05). The acidic dentifrices with 412 and 550 mu g F/g had the same effectiveness as the neutral 1,100-mu g F/g dentifrice and commercial 1,100-mu g F/g dentifrice. Copyright (c) 2007 S. Karger AG, Basel

Adsorption processes in layer-by-layer films of poly(o-methoxyaniline): the role of aggregation

In this work we investigate the effect from the solution concentration on aggregation in layer-by-layer (LBL) films of poly(omethoxyaniline) (POMA) alternated with poly(vinyl sulfonic acid). Films are adsorbed on hydrophilized glass substrates and characterized with UV-Vis spectroscopy and atomic force microscopy. The formation of aggregates is favored in more concentrated solutions, leading to an increase in the diameter of the domains. This is caused by stronger polymer-polymer interactions under high concentrations. The size of POMA aggregates in solution is estimated to be larger than in LBL films, which is surprising because one should expect aggregates from solution to coalesce into larger aggregates in the deposited films. This unexpected result may be explained by a swelling effect of aggregates in the aqueous POMA solutions, consistent with other reports in the literature which consider the aggregates in solution to be made up of smaller aggregates. Upon adsorption on a solid substrate to form the LBL film, a molecular reorganization probably takes place, resulting in smaller aggregates. It is also found that the size distribution of the POMA domains in the LBL films is determined by the concentration of the solution. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Electrical percolation during gelation of lithium doped siloxane-poly(oxyethylene) hybrids

Gelation mechanisms of lithium-doped Siloxane-Poly(oxyethylene) (PEO) hybrids containing polymer of two different molecular weight (500 and 1900 g/mol) were investigated through the evolution of the electrical properties during the solgel transition. The results of electrical measurements, performed by in-situ complex impedance spectroscopy, were correlated with the coordination and the dynamical properties of the lithium ions during the process as shown by Li-7 NMR measurements. For both hybrids sols, a decrease of the conductivity is observed at the initial gelation stage, due to the existence of an inverted percolation process consisting of the progressive separation of solvent molecules containing conducting species in isolated islands during the solid network formation. An increase of conductivity occurs at more advanced stages of gelation and aging, attributed to the increasing connectivity between PEO chains promoted by the formation of crosslinks of siloxane particles at their extremities, favoring hopping motions of lithium ions along the chains.

Increasing the dielectric breakdown strength of poly(ethylene terephthalate) films using a coated polyaniline layer

The dielectric strength of films made from poly(ethylene terephthalate) (PET) coated with a thin layer of polyaniline (PANI) was studied. The PANI layer was deposited on the PET films by the 'in situ' chemical polymerization method. The PANI layer of the PANI/PET films was undoped in NH4OH 0.1 M solution and re-doped with aqueous HCl solution under different pH values varying from 1 to 10. Electric breakdown measurements were performed by applying a voltage ramp and the results showed a dependence of the dielectric strength on the pH of the doping solution due to the changes in the electrical conductivity of the PANI layer. The dielectric strength of PET/PANI films treated under higher pH conditions showed an electric strength about 30% larger than the PET films, since it leads to a non-conductive PANI layer.

H-bonding in entrapped water in poly(o-methoxyaniline): Results from a differential scanning calorimetry study

Differential scanning calorimetry (DSC) was used to investigate entrapped water in poly(o-methoxyaniline) (POMA) in powder form. Two endothermic peaks were attributed to removal of water molecules that were adsorbed with distinct energies. By obtaining thermograms at various heating rates, we succeeded in applying Kissinger's approaches to estimate activation energies for the water adsorbed. The values obtained were ca. 25 and 53 kJ/mol, which correspond to H-bonding interactions, probably at the amine and imine centers of POMA, respectively. (C) 2005 Elsevier B.V. All rights reserved.