Structural, electronic, and magnetic entropy contributions of the orbital order-disorder transition in LaMnO(3)

Measurements of X-ray diffraction, electrical resistivity, and magnetization are reported across the Jahn-Teller phase transition in LaMnO(3). Using a thermodynamic equation, we obtained the pressure derivative of the critical temperature (T(JT)), dT(JT)/dP = -28.3 K GPa(-1). This approach also reveals that 5.7(3)J(mol K)(-1) comes from the volume change and 0.8(2)J(mol K)(-1) from the magnetic exchange interaction change across the phase transition. Around T(JT), a robust increase in the electrical conductivity takes place and the electronic entropy change, which is assumed to be negligible for the majority of electronic systems, was found to be 1.8(3)J(mol K)(-1).

Temperature Dependence of the Intergranular Critical Current Density in Uniaxially Pressed Bi(1.65)Pb(0.35)Sr(2)Ca(2)Cu(3)O(10+delta) Samples

We have studied the normal and superconducting transport properties of Bi(1.65)Pb(0.35)Sr(2)Ca(2)Cu(3)O(10+delta) (Bi-2223) ceramic samples. Four samples, from the same batch, were prepared by the solid-state reaction method and pressed uniaxially at different compacting pressures, ranging from 90 to 250 MPa before the last heat treatment. From the temperature dependence of the electrical resistivity, combined with current conduction models for cuprates, we were able to separate contributions arising from both the grain misalignment and microstructural defects. The behavior of the critical current density as a function of temperature at zero applied magnetic field, J (c) (T), was fitted to the relationship J (c) (T)ae(1-T/T (c) ) (n) , with na parts per thousand 2 in all samples. We have also investigated the behavior of the product J (c) rho (sr) , where rho (sr) is the specific resistance of the grain-boundary. The results were interpreted by considering the relation between these parameters and the grain-boundary angle, theta, with increasing the uniaxial compacting pressure. We have found that the above type of mechanical deformation improves the alignment of the grains. Consequently the samples exhibit an enhance in the intergranular properties, resulting in a decrease of the specific resistance of the grain-boundary and an increase in the critical current density.

Electrical transport in disordered and ordered magnetic domains under pressures and magnetic fields

Magnetic M( T, H, P) and electrical transport.( T, H, P) measurements in a strong spin-lattice-charge coupled La(0.7)Ca(0.3)MnO(3) system have been conducted. The application of H and P leads to the formation of different magnetic domain structures in the vicinity and below the polaronic-to-ferromagnetic transition temperature. The charge mobility is more sensitive to the variation of the spatial wave function overlap between Mn(3+) eg and O(2-) 2p orbitals due to the applied compacting pressure rather than the relative spin orientation between neighbouring Mn ions when the magnetic field is applied. In spite of the presence of different magnetic domain structures due to the sample history, the effect of magnetic field and pressure is less pronounced at lower temperatures on electrical transport properties.

Microstructural, structural and electrical properties of La(3+)-modified Bi(4)Ti(3)O(12) ferroelectric ceramics

Bi(4-x)La(x)Ti(3)O(12) (BLT) ceramics were prepared and studied in this work in terms of La(3+)-modified microstructure and phase development as well as electrical response. According to the results processed from X-ray diffraction and electrical measurements, the solubility limit (XL) of La(3+) into the Bi(4)Ti(3)O(12) (BIT) matrix was here found to locate slightly above x = 1.5. Further, La(3+) had the effect of reducing the material grain size, while changing its morphology from the plate-like form, typical of BIT ceramics, to a spherical-like one. The electrical results presented and discussed here also include the behavior of the temperature of the ferroelectric-paraelectric phase transition as well as the normal or diffuse and/or relaxor nature of this transition depending on the La(3+) content. (c) 2008 Elsevier Ltd. All fights reserved.

Dendrimer-assisted immobilization of alcohol dehydrogenase in nanostructured films for biosensing: Ethanol detection using electrical capacitance measurements

The selective determination of alcohol molecules either in aqueous solutions or in vapor phase is of great importance for several technological areas. In the last years, a number of researchers have reported the fabrication of highly sensitive sensors for ethanol detection, based upon specific enzymatic reactions occurring at the surface of enzyme-containing electrodes. In this study, the enzyme alcohol dehydrogenase (ADH) was immobilized in a layer-by-layer fashion onto Au-interdigitated electrodes (IDEs), in conjunction with layers of PAMAM dendrimers. The immobilization process was followed in Teal time using quartz crystal microbalance (QCM), indicating that an average mass of 52.1 ng of ADH was adsorbed at each deposition step. Detection was carried out using a novel strategy entirely based upon electrical capacitance measurements, through which ethanol could be detected at concentrations of 1 part per million by volume (ppmv). (C) 2007 Elsevier B.V. All rights reserved.

Magnetic resonance and conductivity study of gelatin-based proton conductor polymer electrolytes

This work report results from proton nuclear magnetic resonance (NMR), continuous-wave (CW-EPR) and pulsed electron paramagnetic resonance (P-EPR) and complex impedance spectroscopy of gelatin-based polymer gel electrolytes containing acetic acid. cross-linked with formaldehyde and plasticized with glycerol. Ionic conductivity of 2 x 10(-5) S/cm was obtained at room temperature for samples prepared with 33 wt% of acetic acid. Proton ((1)H) line shapes and spin-lattice relaxation times were measured as a function of temperature. The NMR results show that the proton mobility is dependent on acetic acid content in the plasticized polymer gel electrolytes. The CW-EPR spectra, which were carried out in samples doped with copper perchlorate, indicate the presence of the paramagnetic Cu(2+) ions in axially distorted sites. The P-EPR technique, known as electron spin echo envelope modulation (ESEEM), was employed to show the involvement of both, hydrogen and nitrogen atoms, in the copper complexation of the gel electrolyte. (C) 2009 Elsevier Ltd. All rights reserved.

Elastomeric Composites Based on Ethylene-Propylene-Diene Monomer Rubber and Conducting Polymer-Modified Carbon Black

Thermally stable elastomeric composites based on ethylene-propylene-diene monomer (EPDM) and conducting polymer-modified carbon black (CPMCB) additives were produced by casting and crosslinked by compression molding. CPMCB represent a novel thermally stable conductive compound made via ""in situ"" deposition of intrinsically conducting polymers (ICP) such as polyaniline or polypyrrole on carbon black particles. Thermogravimetric analysis showed that the composites are thermally stable with no appreciable degradation at ca. 300 degrees C. Incorporating CPMCB has been found to be advantageous to the processing of composites, as the presence of ICP lead to a better distribution of the filler within the rubber matrix, as confirmed by morphological analysis. These materials have a percolation threshold range of 5-10 phr depending on the formulation and electrical dc conductivity values in the range of 1 x 10(-3) to 1 x 10(-2) S cm(-1) above the percolation threshold. A less pronounced reinforcing effect was observed in composites produced with ICP-modified additives in relation to those produced only with carbon black. The results obtained in this study show the feasibility of this method for producing stable, electrically conducting composites with elastomeric characteristics. POLYM. COMPOS., 30:897-906, 2009. (C) 2008 Society of Plastics Engineers

NMR and conductivity study of gelatin-based polymer electrolytes

Nuclear Magnetic Resonance spectroscopy (NMR) and complex impedance spectroscopy have been used to study gelatin-based polymer electrolytes plasticized with glycerol and containing lithium perchlorate. The studied samples were prepared with salt concentration of 7.9 wt% and 10.3 wt%. Ionic conductivity of about 10(-5) S/cm was obtained at room temperature for both samples. Lithium (Li-7) and proton (H-1) lineshapes and spin-lattice relaxation times were measured as a function of temperature. The Li-7 NMR relaxation results indicate that the ionic mobility in this system is comparable to those found in other plasticized polymer electrolytes.

Development of zirconia-magnesia/zirconia-yttria composite solid electrolytes

Composite solid electrolytes were prepared by thoroughly mixing ZrO2:8 mol% MgO (Z8Mg) and ZrO(2):3 mol% Y(2)O(3) (Z3Y) ceramic powders followed by pressing and sintering at 1500 degrees C/1 h. The properties of the sintered pellets were studied by X-ray diffraction for evaluation of the structural phases by the Rietveld method, by high-temperature dilatometry for analysis of the thermal shrinkage/expansion behavior, and by impedance spectroscopy for determination of the oxide ion conductivity. The x(Z8Mg)+(1-x)(Z3Y) specimens, x= 0.2, 0.4, 0.5, 0.6, 0.8 and 1.0, are partially stabilized (monoclinic, cubic and tetragonal phases) with density >94% of the theoretical density and show thermal shock resistance and electrical conductivity values suitable for high-temperature oxygen gas detection. One-end closed tube samples of the composite solid electrolytes were assembled in Pt/Z8Mg+Z3Y/Cr+Cr(2)O(3)/Pt electrochemical cells for exposure to different levels of oxygen in the 1-850 ppm range. The total electrical conductivity increases for increasing the relative Z3Y content. Addition of Z3Y to Z8Mg (80 wt.%-20 wt.%) suppresses the electronic contribution to the electrical conductivity at 620 degrees C. (c) 2008 Elsevier B.V. All rights reserved.

Covalent attachment of 3,4,9,10-perylenediimides onto the walls of mesoporous molecular sieves MCM-41 and SBA-15

This work describes the covalent grafting of 3,4,9,10-perylenediimides (PDI), which are fluorescent dyes with very interesting optical properties, onto the walls of mesoporous molecular sieves MCM-41 and SBA-15. The mesoporous materials were first treated with 3-aminopropyltriethoxysilane (APTES) in anhydrous toluene, generating amine-containing surfaces. The amine-containing materials were then reacted with 3,4,9,10-perylenetetracarboxylic dianhydride (PTCA), generating surface-grafted PDI. Infrared spectra of the materials showed that the reaction with amino groups took place at both anhydride ends of the PTCA molecule, resulting in surface attached diimides. No sign of unreacted anhydride groups were found. The new materials, designated as MCMN2PDI and SBAN(2)PDI, presented absorption and emission spectra corresponding to weakly coupled PDI chromophores, in contrast to the strongly coupled rings usually found in solid PDI samples. The materials showed a red fluorescence, which could be observed by the naked eye under UV irradiation or with a fluorescence microscope. The PDI-modified mesoporous materials showed electrical conductivity when pressed into a pellet. The results presented here show that the new materials are potentially useful in the design of nanowires. (C) 2007 Elsevier Inc. All rights reserved.

Fully electrochemical hyphenated flow system for preconcentration, cleanup, stripping, capillary electrophoresis with stacking and contactless conductivity detection of trace heavy metals

Successful coupling of electrochemical preconcentration (EPC) to capillary electrophoresis (CE) with contactless conductivity detection (C(4)D) is reported for the first time. The EPC-CE interface comprises a dual glassy carbon electrode (GCE) block, a spacer and an upper block with flow inlet and outlet, pseudo-reference electrode and a fitting for the CE silica column, consisting of an orifice perpendicular to the surface of a glassy carbon electrode with a bushing inside to ensure a tight press fit. The end of the capillary in contact with the GCE is slant polished, thus defining a reproducible distance from the electrode surface to the column bore. First results with EPC-CE-C(4)D are very promising, as revealed by enrichment factors of two orders of magnitude for Tl, Cu, Pb and Cd ion peak area signals. Detection limits for 10 min deposition time fall around 20 nmol L(-1) with linear calibration curves over a wide range. Besides preconcentration, easy matrix exchange between accumulation and stripping/injection favors procedures like sample cleanup and optimization of pH, ionic strength and complexing power. This was demonstrated for highly saline samples by using a low conductivity buffer for stripping/injection to improve separation and promote field-enhanced sample stacking during electromigration along the capillary. (C) 2010 Elsevier B.V. All rights reserved.

Evidence of redox interactions between polypyrrole and Fe(3)O(4) in polypyrrole-Fe(3)O(4) composite films

The electrical properties of conducting polymers make them useful materials in a wide number of technological applications. In the last decade, an important effect on the properties of the conducting polymer when iron oxides particles are incorporated into the conductive matrix was shown. In the present study, films of polypyrrole were synthesized in the presence of magnetite particles. The effect of the magnetite particles on the structure of the polymer matrix was determined using Raman spectroscopy. Mass variations at different concentrations of Fe(3)O(4) incorporated into the conducting matrix were also measured by means of quartz crystal microbalance. Additionally, the changes in the resistance of the films were evaluated over time by electrochemical impedance spectroscopy in solid state. These results show that the magnetite incorporation decreases polymeric film resistance and Raman experiments have evidenced that the incorporation of magnetite into polymeric matrix not only stabilizes the polaronic form of the polypyrrole, but also preserves the polymer from further oxidation. (C) 2009 Elsevier Ltd. All rights reserved.

A compact and high-resolution version of a capacitively coupled contactless conductivity detector

An all-in-one version of a capacitively coupled contactless conductivity detector is introduced. The absence of moving parts (potentiometers and connectors) makes it compact (6.5 cm(3)) and robust. A local oscillator, working at 1.1 MHz, was optimized to use capillaries of id from 20 to 100 lam. Low noise circuitry and a high-resolution analog-to-digital converter (ADC) (21 bits effective) grant good sensitivities for capillaries and background electrolytes currently used in capillary electrophoresis. The fixed frequency and amplitude of the signal generator is a drawback that is compensated by the steady calibration curves for conductivity. Another advantage is the possibility of determining the inner diameter of a capillary by reading the ADC when air and subsequently water flow through the capillary. The difference of ADC reading may be converted into the inner diameter by a calibration curve. This feature is granted by the 21-bit ADC, which eliminates the necessity of baseline compensation by hardware. In a typical application, the limits of detection based on the 3 sigma criterion (without baseline filtering) were 0.6, 0.4, 0.3, 0.5, 0.6, and 0.8 mu mol/L for K(+), Ba(2+), Ca(2+), Na(+), Mg(2+), and Li(+), respectively, which is comparable to other high-quality implementations of a capacitively coupled contactless conductivity detector.

Environmental formaldehyde analysis by active diffusive sampling with a bundle of polypropylene porous capillaries followed by capillary zone electrophoretic separation and contactless conductivity detection

Compared to other volatile carbonylic compounds present in outdoor air, formaldehyde (CH2O) is the most toxic, deserving more attention in terms of indoor and outdoor air quality legislation and control. The analytical determination of CH2O in air still presents challenges due to the low-level concentration (in the sub-ppb range) and its variation with sampling site and time. Of the many available analytical methods for carbonylic compounds, the most widespread one is the time consuming collection in cartridges impregnated with 2,4-dinitrophenylhydrazine followed by the analysis of the formed hydrazones by HPLC. The present work proposes the use of polypropylene hollow porous capillary fibers to achieve efficient CH2O collection. The Oxyphan (R) fiber (designed for blood oxygenation) was chosen for this purpose because it presents good mechanical resistance, high density of very fine pores and high ratio of collection area to volume of the acceptor fluid in the tube, all favorable for the development of air sampling apparatus. The collector device consists of a Teflon pipe inside of which a bundle of polypropylene microporous capillary membranes was introduced. While the acceptor passes at a low flow rate through the capillaries, the sampled air circulates around the fibers, impelled by a low flow membrane pump (of the type used for aquariums ventilation). The coupling of this sampling technique with the selective and quantitative determination of CH2O, in the form of hydroxymethanesulfonate (HMS) after derivatization with HSO3-, by capillary electrophoresis with capacitively coupled contactless conductivity detection (CE-(CD)-D-4) enabled the development of a complete analytical protocol for the CH2O evaluation in air. (C) 2008 Published by Elsevier B.V.

Investigating the formation and the properties of monoalkyl carbonates in aqueous medium using capillary electrophoresis with capacitively coupled contactless conductivity detection

Although alkyl carbonic acids (ACAs) and their salts are referred to as instable species in aqueous medium, we demonstrate that a monoalkyl carbonate (MAC) can in fact be easily formed from bicarbonate and an alcohol even in the presence of a high amount of water. A CE system with two capacitively coupled contactless conductivity detectors (C(4)Ds) was used to obtain different parameters about these species and their reactions. Based on the mobilities obtained for a series of alcohols ranging from 1 to 5 carbons, the coefficients of diffusion and the hydrodynamic radii were calculated. When compared with the equivalent carboxylates, MACs have radii systematically smaller. Although the precise pK(a) values of the ACAs could not be obtained, because of the fast decomposition in acid medium, it was possible, for the first time, to show that they are below 4.0. This result suggests that the acidity of an ACA is quite similar to the first hydrogen of H(2)CO(3). Using a new approach to indirectly calibrate the C(4)D, the kinetic constants and the equilibrium constants of formation were also obtained. The results suggest that the increase in the chain length makes the MACs less stable and more inert.