The investigation of alpha -> beta phase transition in poly(vinylidene fluoride) (PVDF)

The phase transition from the non-polar a-phase to the polar beta-phase of poly(vinylidene fluoride) (PVDF) has been investigated using micro-Raman spectroscopy, which is advantageous for being a non-destructive technique. Films of alpha-PVDF were subjected to stretching under controlled rates and at 80 degrees C, the transition to beta-PVDF being monitored by the decrease in the Raman band at 794 cm(-1) characteristic of the a-phase, with the concomitant increase in the 839 cm(-1) band characteristic of the beta-phase. 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, viz. X-ray diffraction and infrared spectroscopy.

Thermal behavior of the maleic anhydride modified poly(3-hydroxybutyrate)

Poly(3-hydroxybutyrate), PHB has been structurally modified through reaction with maleic anhydride, MA. Transesterification reaction was carried out fixing the PHB and MA and besides time and temperature the concentration of the triethylamine (used as catalyst) was changed. Glass transition, melting and crystallization temperature obtained from DSC curves and thermal degradation temperatures obtained from TG traces were used to evaluate the influence of the reaction conditions on the modification of PHB according to factorial design. on the base of the results the optimum conditions are to perform the PHB modification reaction with MA reaction at 110 degrees C for 1 h with 5% v/v triethylamine.

Preconcentration of rutin at a poly glutamic acid modified electrode and its determination by square wave voltammetry

The voltammetric determination of rutin in 0.04 mol l(-1) B-R buffer (pH 4.0) by square wave voltammograms (+0.41 V vs. Ag/AgCl(sat.)) at a poly glutamic acid modified glassy carbon electrode was found to be several orders of magnitude lower than that on a bare glassy carbon electrode. Rutin can be preconcentrated on the films of poly glutamic acid and presented linear relationship from concentration of 7 x 10(-7) to 1 x 10(-5) mol l(-1) in 0.04 mol l(-1) B-R buffer pH 4.0. The method was successfully applied to the determination of rutin in pharmaceutical formulation without any pretreatment.

Fabrication and testing of a poly(vinylidene fluoride) (PVDF) microvalve for gas flow control

A microactuator made from poly(vinylidene fluoride) (PVDF), a piezoelectric polymer, was fabricated to control the gas flow rate through a glass micronozzle. The actuator was formed by gluing together two PVDF sheets with opposite polarization directions. The sheets were covered with thin conducting films on one side, that were then used as electrodes to apply an electric field to move the valve. The actuator has a rectangular shape, 3 mm x 6 mm. The device was incorporated with a micronozzle fabricated by a powder blasting technique. Upon applying a DC voltage across the actuator electrodes, one sheet expands while the other contracts, generating an opening motion. A voltage of +300 V DC was used to open the device by moving the actuator 30 mu m, and a voltage of -200 V DC was used to close the device by moving the actuator 20 mu m lower than the relaxed position. Flow measurements were performed in a low-pressure vacuum system, maintaining the microvalve inlet pressure constant at 266 Pa. Tests carried out with the actuator in the open position and with a pressure ratio (inlet pressure divided by outlet pressure) of 0.5, indicated a flow rate of 0.36 sccm. In the closed position, and with a pressure ratio of 0.2, a flow rate of 0.32 sccm was measured.

ELECTROACTIVE BLENDS OF POLY(VINYLIDENE FLUORIDE) AND POLYANILINE DERIVATIVES

The conditions for processing and doping of blends of poly(o-alkoxyaniline)s and poly(vinylidene fluoride) were investigated. Flexible, free-standing and stretchable films of blends of various compositions were obtained by casting. A low percolation threshold was observed with the onset of conductivity at low polyalkoxyaniline contents (i.e. 5%). Interestingly, these blends displayed electrochromism with colour changes similar to those of the parent conducting polymer, as observed from cyclic voltammetry measurements. This behaviour is seen even for low contents of the conducting polymer, indicating that a continuous conducting pathway, which is capable of exchanging charge, is formed within the insulating matrix.

STUDY OF POLING BEHAVIOR OF BIAXIALLY STRETCHED POLY(VINYLIDENE FLUORIDE) FILMS USING THE CONSTANT-CURRENT CORONA TRIODE

This article reports systematic results of corona poling measurements obtained on biaxially stretched polyvinylidene fluoride films charged in dry air. Charging was performed using the constant current corona triode. The dependence of the poling process on the sample thickness, charging current, and successive charging processes was investigated. Phase transitions from alpha to delta and to beta phases were observed when virgin samples were corona charged. The thermal pulse technique showed that the polarization profiles during charging can be made consistently almost uniform and that the ferroelectric reorientation can be associated with the rising plateau region displayed on potential buildup curves. (C) 1995 American Institute of Physics.

Montmorillonite (MMT) effect on the structure of poly(oxyethylene) (PEO)-MMT nanocomposites and silica-PEO-MMT hybrid materials

In this work we report the effects of incorporation of variable amounts (0.5-25%w/w) of montmorillonite in poly(oxyethylene) based materials in order to decrease the polymer crystallinity. Two different classes of materials were studied: silica-poly(oxyethylene)-montmorillonite hybrids prepared by the sol-gel route and poly(oxyethylene)-montmorillonite nanocomposites prepared by mixing the dry clay or the clay aqueous suspension into the melt poly(oxyethylene). The effects of monternorillonite loading on the poly(oxyethylene) crystallization control and on the nanostructural features were investigated by X-ray powder diffraction, small-angle X-ray scattering and differential scanning calorimetry. Experimental results show that free montmorillonite layers coexist with open aggregates and tactoids in the poly(oxyethylene)-montmorillonite nanocomposites, with different features depending on the filler proportion and preparation route. The intercalation of polymer chains in montmorillonite galleries markedly hinders the crystallization of the poly(oxyethylene) matrix. For hybrids materials the silica phase favors the exfoliation of montmorillonite tactoids, so that samples are predominantly constituted by dispersed platelets. (c) 2006 Elsevier B.V. All rights reserved.

Weak ferromagnetism in poly(3-methylthiophene)(PMTh)

Ferromagnetic behaviour at 300 K has been observed from SQUID experiments in ClO4- doped PMTh, the samples were prepared electrochemically at 25 degreesC in acetonitrile with 0.1M LiClO4 and then partially reduced. Atomic absorption analysis discards magnetic particles contamination. Hysteresis curves were observed for pressed pellets in ail range of temperatures (300K-2K). The remanence at 300 K and pressed at 250 bar was around 8.06x10(-4) emu/g with coercitivity of 130 Oe. The influence of water content in the solvent during the sample synthesis and the pressure is shown. We discuss a model that explains our data in terms of the anisotropic superexchange Dziatoshinski-Moriya interaction giving rise to weak ferromagnetism.

Evidence of room temperature charge-density wave behavior and glass-like states in pressed pellets of lightly doped poly (3-methyl thiophene)

We show room temperature charge-density wave (CDW) characteristics in d.c. and a.c. electric data in pressed pellets of lightly doped poly(3-methylthiophene). The possibility of a Peierls glass is discussed and metastables states are observed. D.C. and A.C. data also show a state with negative differencial resistance.

Room temperature ferromagnetic behavior in pressed pellets of doped poly (3-methylthiophene)

Room temperature ferromagnetic behavior has been observed in pressed pellets of doped poly(3-methylthiophene). In this work we show that thermoremance data taken in two different ways favours the interpretation of data in terms of the Dzialoshinski-Moriya anisotropic superexchange interaction of the polarons via dopant anions giving rise to weak ferromagnetism.

Structure of magnetic poly(oxyethylene)-siloxane nanohybrids doped with Fe-II and Fe-III

Hybrid organic - inorganic nanocomposites doped with Fe-II and Fe-III ions and exhibiting interesting magnetic properties have been obtained by the sol - gel process. The hybrid matrix of these ormosils ( organically modified silicates), classed as di-ureasils and termed U( 2000), is composed of poly( oxyethylene) chains of variable length grafted to siloxane groups by means of urea crosslinkages. Iron perchlorate and iron nitrate were incorporated in the diureasil matrices, leading to compositions within the range 80 greater than or equal to n greater than or equal to 10, n being the molar ratio of ether-type O atoms per cation. The structure of the doped diureasils was investigated by small-angle X-ray scattering (SAXS). For Fe-II-doped samples, SAXS results suggest the existence of a two-level hierarchical structure. The primary level is composed of spatially correlated siloxane clusters embedded in the polymeric matrix and the secondary, coarser level consists of domains where the siloxane clusters are segregated. The structure of Fe-III-doped hybrids is different, revealing the existence of iron oxide based nanoclusters, identified as ferrihydrite by wide-angle X-ray diffraction, dispersed in the hybrid matrix. The magnetic susceptibility of these materials was determined by zero-field-cooling and field-cooling procedures as functions of both temperature and field. The different magnetic features between Fe-II- and Fe-III-doped samples are consistent with the structural differences revealed by SAXS. While Fe-II-doped composites exhibit a paramagnetic Curie-type behaviour, hybrids containing Fe-III ions show thermal and field irreversibilities.

Huge values of room-temperature dielectric constants in pellets of poly(3-methylthiophene)

Room temperature data of impedance and phase angle in pellets of electrochemically synthesized ClO4- doped poly(3-methylthiophene) (P3MT) were analyzed assuming the sample being represented by a parallel resistor-capacitor (RC) circuit or by a series RC circuit. The last assumption proved to be the correct one, and to confirm it we use the sample as the RC component of a resistor-capacitor-inductor series resonator. We discuss the possibility of this RC series behavior to be due to a charge-density wave characteristic also evidenced from the huge values of the low-frequency dielectric constant of the system.

Thermal diffusivity analysis of doped poly(methyl-methacrylate) with electron donor and acceptor molecules

A computer-assisted method for analysing photoacoustic spectra has been developed in the Windows(TM) environment with the use of an easy graphical interface, the computer simulation was carried out with the aim of using the entire expression of the Rosencwaig-Gersho theory, thus permitting multiple applications. The simulation was applied to a system that mimics the electron transfer process in which the concentration of octaethylporphin donor molecules was constant whereas the concentration of duroquinone and 2,3-dichloro-5,6-dicyano-1, l-benzoquinone acceptor molecules varied. The increment of the acceptor concentration influenced the photoacoustic amplitude and phase signals. In the phase signal a significant shift to smaller values was observed, denoting a faster heat generation. The analysis of the photoacoustic signal enabled the determination of the thermal diffusivity, the result obtained through the simulation was about (7 +/- 1) x 10(-7) m(2) s(-1) indicating that changes in the photoacoustic phase signals were due to the electron transfer process rather than changes in the thermal properties of the sample.

Renewable drops electrochemical sensor for sulfide ions detection

The design and characteristics of a novel electrochemical system, which uses a drop as a renewable electroanalytical sensor, are described. This article describes the performance of the electrochemical system, the coupling of the experimental arrangement with flow injection technique and a demonstration of its applicability for the measurement of sulfide. The method is based on renewable drops of ferricyanide ions, buffered by borate. The ferrocyanide ions, product of the reaction between ferricyanide and sulfide ions, are oxidized on a platinum microelectrode and the current measured is related to sulfide concentration. The measurements can be done in continuous or static flow mode. In continuous mode, the detection limit is 5.0 x 10(-5) mol L-1.

Structure and electrical properties of potassium-doped siloxane-poly(oxypropylene) ormolytes

The structure and the ionic conduction properties of siloxane-poly(oxypropylene) (PPO) hybrids doped with different potassium salts (KCF3SO3, KI, KClO4 and KNO2) are reported for two polymer molecular weights (300 and 4000 g/mol), labelled PPO300 and PPO4000, respectively. The doping concentration, related to the concentration of the ether type oxygen of the PPO chain, is the same whatever the salt and verifies [O]/[K] = 20. Ionic room temperature conductivity shows the highest value for the KCF3SO3 doped PPO4000 hybrid (4 x 10(-7)Omega(-1).cm(-1)). The structure of these hybrids was investigated by X-ray powder diffraction (XRPD) and X-ray absorption spectroscopy (EXAFS and XANES) at the potassium K-edge (3607 eV). XRPD results show that the hybrid matrix is always amorphous and the formation of secondary potassium phases is observed for all the samples, except for the KCF3SO3 doped PPO4000 hybrid. EXAFS results evidence a good correlation between the ionic conductivity and the presence of oxygen atoms as first neighbours around potassium.