Self-assembled films from WO(3): Electrochromism and lithium ion diffusion

WO(3)/chitosan and WO(3)/chitosan/poly(ethylene oxide) (PEO) films were prepared by the layer-by-layer method. The presence of chitosan enabled PEO to be carried into the self-assembled structure, contributing to an increase in the Li(+) diffusion rate. On the basis of the galvanostatic intermittent titration technique (GITT) and the quadratic logistic equation (QLE), a spectroelectrochemical method was used for determination of the ""optical"" diffusion coefficient (D(op)), enabling analysis of the Li(+) diffusion rate and, consequently, the coloration front rate in these host matrices. The D(op) values within the WO(3)/chitosan/PEO film were significantly higher than those within the WO(3)/chitosan film, mainly for higher values of injected charge. The presence of PEO also ensured larger accessibility to the electroactive sites, in accordance with the method employed here. Hence, this spectroelectrochemical method allowed us to separate the contribution of the diffusion process from the number of accessible electroactive sites in the materials, thereby aiding a better understanding of the useful electrochemical and electrochromic properties of these films for use in electrochromic devices. (C) 2010 Elsevier B.V. All rights reserved.

Synthesis and electrochemical properties of vanadyl phosphate di-hydrate/polyaniline derivatives hybrid films

Vanadyl phosphate and its hybrid compounds have proven to undergo electrochemical intercalation and de-intercalation of lithium ions, which enables its use as cathode material for Li ion rechargeable batteries. In this context, vanadyl phosphate di-hydrate/polyaniline derivatives hybrid films were synthesized via the exfoliation and reconstruction approach in order to evaluate their potential use as cathode in ion lithium batteries. X-ray diffraction patterns indicate that the lamellar structure of the inorganic matrix is maintained, consistent with the topotactic process. In the scanning electron micrographs, hybrid films exhibit rough surface consisting of warped and cracked crystallites, quite different from vanadyl phosphate di-hydrate square platelets crystallites. Electrochemical evaluation using cyclic voltammetry and charge-discharge galvanostatic techniques shows small differences between the charge and the discharge curves, indicating an irreversibility of the hybrid systems. (C) 2009 Elsevier B.V. All rights reserved.

Pt/TiO(2)/poly(vinyl sulfonic acid) Layer-by-Layer Films for Methanol Electrocatalytic Oxidation

One major challenge for the widespread application of direct methanol fuel cells (DMFCs) is to decrease the amount of platinum used in the electrodes, which has motivated a search for novel electrodes containing platinum nanoparticles. In this study, platinum nanoparticles were electrodeposited on layer-by-layer (LbL) films from TiO(2) and poly(vinyl sulfonic) (PVS), by immersing the films into a H(2)PtCl(6) solution and applying a 100 mu A current during different electrode position times. Scanning tunnel microscopy (STM) and atomic force microscopy (AFM) images showed increased platinum particle size and electrode roughness for increasing electrodeposition times. The potentiodynamic profile of the electrodes indicated that oxygen-like species in 0.5 mol L(-1) H(2)SO(4) were formed at less positive potentials for the smallest platinum particles. Electrochemical impedance spectroscopy measurements confirmed the high reactivity for the water dissociation and the large amount of oxygen-like species adsorbed on the smallest platinum nanoparticles. This high oxophilicity of the smallest nanoparticles was responsible for the electrocatalytic activity of Pt-TiO(2)/PVS systems for methanol electrooxidation, according to the Langmuir-Hinshelwood bifunctional mechanism. Significantly, the approach used here combining platinum electrodeposition and LbL matrices allows one to both control the particle size and optimize methanol electrooxidation, being therefore promising for producing membrane-electrode assemblies of DMFCs.

Er(3+)-doped silica-hafnia films for optical waveguides and spherical resonators

In this paper we present some result on sol-gel derived silica-hafnia systems. In particular we focus on fabrication, morphological and spectroscopic assessment of Er(3+)-activated thin films. Two examples of silica-hafnia-derived waveguiding glass ceramics, prepared by top-down and bottom-up techniques are reported, and the main optical properties are discussed. Finally, some properties of activated microspherical resonators, having a silica core, obtained by melting the end of a telecom fiber, coated with an Er(3+)-doped 70SiO(2)-30HfO(2) film, are presented. (C) 2009 Elsevier B.V. All rights reserved.

Time flies with music whatever its emotional valence

The present study used a temporal bisection task to investigate whether music affects time estimation differently from a matched auditory neutral stimulus, and whether the emotional valence of the musical stimuli (i.e., sad vs. happy music) modulates this effect. The results showed that, compared to sine wave control music, music presented in a major (happy) or a minor (sad) key shifted the bisection function toward the right, thus increasing the bisection point value (point of subjective equality). This indicates that the duration of a melody is judged shorter than that of a non-melodic control stimulus, thus confirming that ""time flies"" when we listen to music. Nevertheless, sensitivity to time was similar for all the auditory stimuli. Furthermore, the temporal bisection functions did not differ as a function of musical mode. (C) 2010 Elsevier B.V. All rights reserved.

Determination of mechanical properties of PECVD silicon nitride thin films for tunable MEMS Fabry-Pérot optical filters

This paper reports an investigation on techniques for determining elastic modulus and intrinsic stress gradient in plasma-enhanced chemical vapor deposition (PECVD) silicon nitride thin films. The elastic property of the silicon nitride thin films was determined using the nanoindentation method on silicon nitride/silicon bilayer systems. A simple empirical formula was developed to deconvolute the film elastic modulus. The intrinsic stress gradient in the films was determined by using micrometric cantilever beams, cross-membrane structures and mechanical simulation. The deflections of the silicon nitride thin film cantilever beams and cross-membranes caused by in-thickness stress gradients were measured using optical interference microscopy. Finite-element beam models were built to compute the deflection induced by the stress gradient. Matching the deflection computed under a given gradient with that measured experimentally on fabricated samples allows the stress gradient of the PECVD silicon nitride thin films introduced from the fabrication process to be evaluated.

Characterization of mechanical properties of silicon nitride thin films for MEMS devices by nanoindentation

An experimental investigation of mechanical properties of thin films using nanoindentation was reported. Silicon nitride thin films with different thicknesses were deposited using plasma enhanced chemical vapor deposition (PECVD) on Si substrate. Nanoindentation was used to measure their elastic modulus and hardness. The results indicated that for a film/substrate bilayer system, the measured mechanical properties are significantly affected by the substrate properties. Empirical formulas were proposed for deconvoluting the film properties from the measured bilayer properties.

Immobilisation of electroactive macrocyclic complexes within titania films

The 4-carboxyphenyl-appended macrocyclic ligand trans-6,13-dimethyl-6-((4-carboxybenzyl)amino)-1,4,8,11-tetraazacyclotetradecane-6-amine (HL10) has been synthesised and complexed with Co-III. The mononuclear complexes [Co(HL10)(CN)](2+) and [CoL10(OH)](+) have been prepared and the crystal structures of their perchlorate salts are presented, where the ligand is bound in a pentadentate mode in each case while the 4-carboxybenzyl-substituted pendent amine remains free from the metal. The cyano-bridged dinuclear complex [CoL10-mu-NC-Fe(CN)(5)](2-) was also prepared and chemisorbed on titania-coated ITO conducting glass. The adsorbed complex is electrochemically active and cyclic voltammetry of the modified ITO working electrode in both water and MeCN solution was undertaken with simultaneous optical spectroscopy. This experiment demonstrates that reversible electrochemical oxidation of the Fe-II centre is coupled with rapid changes in the optical absorbance of the film.

Bovine pericardium coated with biopolymeric films as an alternative to prevent calcification: In vitro calcification and cytotoxicity results

Bovine pericardium, for cardiac valve fabrication, was coated with either chitosan or silk fibroin film. In vitro calcification tests of coated and non coated bovine pericardium were performed in simulated body fluid solution in order to investigate potential alternatives to minimize calcification on implanted heart valves. Complementary, morphology was assessed by scanning electron microscopy - SEM; X-ray diffraction (XRD) and infrared spectroscopy (FTIR-ATR) were performed for structural characterization of coatings and biocompatibility of chitosan. Silk fibroin films were assayed by in vitro cytotoxicity and endothelial cell growth tests. Bovine pericardium coated with silk fibroin or chitosan did not present calcification during in vitro calcification tests, indicating that these biopolymeric coatings do not induce bovine pericardium calcification. Chitosan and silk fibroin films were characterized as non cytotoxic and silk fibroin films presented high affinity to endothelial cells. The results indicate that bovine pericardium coated with silk fibroin is a potential candidate for cardiac valve fabrication, since the affinity of silk fibroin to endothelial cells can be explored to induce the tissue endothelization and therefore, increase valve durability by increasing their mechanical resistance and protecting them against calcification. (C) 2010 Elsevier B.V. All rights reserved.