Synthesis and characterization of nano-MnO2 for electrochemical supercapacitor studies

Nanostructured MnO2 was synthesized at ambient condition by reduction of potassium permanganate with aniline. Powder X-ray diffraction, thermal analysis (thermogravimetric and differential thermal analysis), Brunauer-Emmett-Teller surface area, and infrared spectroscopy studies were carried out for physical and chemical characterization. The as-prepared MnO2 was amorphous and contained particles of 5-10 nm diameter. Upon annealing at temperatures >400°C, the amorphous MnO2 attained crystalline α-phase with a concomitant change in morphology. A gradual conversion of nanoparticles to nanorods is evident from scanning electron microscopy and transmission electron microscopy (TEM) studies. High-resolution TEM images suggested that nanoparticles and nanorods grow in different crystallographic planes. Capacitance behavior was studied by cyclic voltammetry and galvanostatic charge-discharge cycling in a potential range from -0.2 to 1.0 V vs SCE in 0.1 M sodium sulfate solution. Specific capacitance of about 250 F g-1 was obtained at a current density of 0.5 mA cm-2(0.8 A g-1).

Investigation of true remnant polarization response in heterostructured artificial biferroics

Epitaxial bilayered thin films composed of ferromagnetic La0.6Sr0.4MnO3 and ferroelectric 0.7Pb (Mg1/3Nb2/3)O3-0.3(PbTiO3) were fabricated on LaAlO3 (100) substrates by pulsed laser ablation. Ferroelectric, ferromagnetic and magneto-dielectric characterizations performed earlier indicated the possible existence of strain-mediated magneto-electric coupling in these biferroic heterostructures. In order to investigate their true remnant polarization characteristics, usable in devices, room-temperature polarization versus electric field, positive-up negative-down (PUND) pulse polarization studies and remnant hysteresis measurements were carried out. The PUND and remnant hysteresis measurements revealed the significant contribution of the non-remnant component in the observed polarization hysteresis response of these heterostructures. (C) 2010 Published by Elsevier Ltd

Scattering polarization in the presence of magnetic and electric fields

The polarization of radiation by scattering on an atom embedded in combined external quadrupole electric and uniform magnetic fields is studied theoretically. Limiting cases of scattering under Zeeman effect, and Hanle effect in weak magnetic fields are discussed. The theory is general enough to handle scattering in intermediate magnetic fields (Hanle-Zeeman effect) and for arbitrary orientation of magnetic field. The quadrupolar electric field produces asymmetric line shifts, and causes interesting level-crossing phenomena either in the absence of an ambient magnetic field, or in its presence. It is shown that the quadrupolar electric field produces an additional depolarization in the Q/I profiles and rotation of the plane of polarization in the U/I profile over and above that arising from magnetic field itself. This characteristic may have a diagnostic potential to detect steady-state and time-varying electric fields that surround radiating atoms in solar atmospheric layers. (c) 2007 Elsevier Ltd. All rights reserved.

Physicochemical, spectroscopic and electrochemical characterization of magnesium ion-conducting, room temperature, ternary molten electrolytes

Room temperature, magnesium ion-conducting molten electrolytes are prepared using a combination of acetamide, urea and magnesium triflate or magnesium perchlorate. The molten liquids show high ionic conductivity, of the order of mS cm(-1) at 298 K. Vibrational spectroscopic studies based on triflate/perchlorate bands reveal that the free ion concentration is higher than that of ion-pairs and aggregates in the melt. Electrochemical reversibility of magnesium deposition and dissolution is demonstrated using cyclic voltammetry and impedance studies. The transport number of Mg2+ ion determined by means of a combination of d.c. and ac. techniques is similar to 0.40. Preliminary studies on the battery characteristics reveal good capacity for the magnesium rechargeable cell and open up the possibility of using this unique class of acetamide-based room temperature molten electrolytes in secondary magnesium batteries. (C) 2010 Elsevier B.V. All rights reserved.

Measurement of W-Boson Polarization in Top-Quark Decay in pp̅ Collisions at √s=1.96 TeV

We report measurements of the polarization of W bosons from top-quark decays using 2.7 fb^-1 of ppbar collisions collected by the CDF II detector. Assuming a top-quark mass of 175 GeV/c^2, three measurements are performed. A simultaneous measurement of the fraction of longitudinal (f_0) and right-handed (f_+) W bosons yields the model-independent results f_0 = 0.88 \pm 0.11 (stat) \pm 0.06 (syst) and f_+ = -0.15 \pm 0.07 (stat) \pm 0.06 (syst) with a correlation coefficient of -0.59. A measurement of f_0 (f_+) constraining f_+ (f_0) to its standard model value of 0.0 (0.7) yields f_0 = 0.70 \pm 0.07 (stat) \pm 0.04 (syst) (f_+ = -0.01 \pm 0.02 (stat) \pm 0.05 (syst)). All these results are consistent with standard model expectations.

Top polarization as a probe of new physics

We investigate the effects of new physics scenarios containing a high mass vector resonance on top pair production at the LHC, using the polarization of the produced top. In particular we use kinematic distributions of the secondary lepton coming from top decay, which depends on top polarization, as it has been shown that the angular distribution of the decay lepton is insensitive to the anomalous tbW vertex and hence is a pure probe of new physics in top quark production. Spin sensitive variables involving the decay lepton are used to probe top polarization. Some sensitivity is found for the new couplings of the top.

Electric-polarization and structure of molecular complexes of the metallic halides of group II of the periodic table

Dielectric measurements have been made on a number of molecular complexes of beryllium, zinc, cadmium and mercuric halides. The polarizations observed have been interpreted in terms of a tetrahedral configuration for the undissociated beryllium, zinc and cadmium halide complexes. In other cases the observed polarization has been shown to be due to the dissociation of the complex in solution.

Electrochemical insertion of Sr2+ ions onto nano delta-MnO2 particles

Manganese dioxide is known to be an important electroactive material for supercapacitors. Generally, delta-MnO2 is subjected to electrochemical characterization studies in aqueous electrolytes of Na2SO4. It exhibits capacitance behaviour in the potential range between 0 and 1.0 V vs. SCE (saturated calomel electrode). In the present study, it is shown that delta-MnO2 exhibits capacitance behaviour in Sr(NO3)(2) electrolytes also. The suitable potential range in this electrolyte is also found to be 0-1.0 V. Specific capacitancemeasured in Sr(NO3)(2) electrolyte is 192 F g(-1). X-ray photoelectron spectroscopy data confirm that Sr2+ ions get inserted onto delta-MnO2 anoparticles. (C) 2010 Elsevier B.V. All rights reserved.

A Durable PEFC with Carbon-Supported Pt-TiO2 Cathode: A Cause and Effect Study

Durability is central to the commercialization of polymer electrolyte fuel cells (PEFCs). The incorporation of TiO2 with platinum (Pt) ameliorates both the stability and catalytic activity of cathodes in relation to pristine Pt cathodes currently being used in PEFCs. PEFC cathodes comprising carbon-supported Pt-TiO2 (Pt-TiO2/C) exhibit higher durability in relation to Pt/C cathodes as evidenced by cell polarization, impedance, and cyclic voltammetry data. The degradation in performance of the Pt-TiO2/C cathodes is 10% after 5000 test cycles as against 28% for Pt/C cathodes. These data are in conformity with the electrochemical surface area and impedance values. Pt-TiO2/C cathodes can withstand even 10,000 test cycles with nominal effect on their performance. X-ray diffraction, transmission electron microscope, and cross-sectional field-emission-scanning electron microscope studies on the catalytic electrodes reflect that incorporating TiO2 with Pt helps in mitigating the aggregation of Pt particles and protects the Nafion membrane against peroxide radicals formed during the cathodic reduction of oxygen. (C) 2010 The Electrochemical Society. [DOI: 10.1149/1.3421970] All rights reserved.

Polarization switching in near-stoichiometric Zn:LiNbO3 at high temperatures

The effect of temperature and stoichiometry on the polarization switching rate in lithium niobate is presented. An increased polarization switching rate in congruent and near-stoichiometric lithium niobate (CLN and SLN) and SLN doped with 1.6 mol% Zn (SLN:Zn(1.6)) is observed using a pulsed field switching technique near the transition temperature (TO. Compared to CLN, the observed switching rate and domain wall mobility for SLN and SLN:Zn(1.6) are higher. The extra charge flow was observed during switching at high temperatures,and is attributed to the creation of defect dipoles and increase in ionic conductivity. Forward domain motion is expected to be the mechanism involved in switching. (C) 2010 Elsevier Ltd. All rights reserved.

Electro-Oxidation of Borohydride on Rhodium, Iridium, and Rhodium-Iridium Bimetallic Nanoparticles with Implications to Direct Borohydride Fuel Cells

Electrochemical oxidation of borohydride is studied on nanosized rhodium, iridium, and bimetallic rhodium-iridium catalysts supported onto Vulcan XC72R carbon. The catalysts are characterized by X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy in conjunction with cyclic voltammetry and polarization studies. The studies reveal that a 20 wt % bimetallic Rh-Ir catalyst supported onto carbon (Rh-Ir/C) is quite effective for the oxidation of borohydride. Direct borohydride fuel cell with Rh-Ir/C as the anode catalyst and Pt/C as the cathode catalyst exhibits a peak power density of 270 mW/cm(2) at a load current density of 290 mA/cm(2) as against 200 mW/cm(2) at 225 mA/cm(2) for Rh/C and 140 mW/cm(2) at 165 mA/cm(2) for Ir/C while operating at 80 degrees C. The synergistic catalytic activity for the bimetallic Rh-Ir nanoparticles toward borohydride oxidation is corroborated by density-functional theory calculations using electron-localization function. (C) 2010 The Electrochemical Society. [DOI:10.1149/1.3442372] All rights reserved.

Refinement of the thermodynamic properties of ruthenium dioxide and osmium dioxide

The standard Gibbs energies of formation of RuO2 and OsO2 at high temperature have been determined with high precision, using a novel apparatus that incorporates a buffer electrode between the reference and working electrodes, The buffer electrode absorbs the electrochemical flux of oxygen through the solid electrolyte from the electrode with higher oxygen chemical potential to the electrode with lower oxygen potential, The buffer electrode prevents polarization of the measuring electrode and ensures accurate data, The standard Gibbs energies of formation (Delta(f)G degrees) of RuO2, in the temperature range of 900-1500 K, and OsO2, in the range of 900-1200 K, can be represented by the equations Delta(f)G degrees(RuO2)(J/mol) = -324 720 + 354.21T - 23.490T In T Delta(f)G degrees(OsO2)(J/mol) = -304 740 + 318.80T - 18.444T In T where the temperature T is given in Kelvin and the deviation of the measurement is +/- 80 J/mol, The high-temperature heat ;capacities of RuO2 and OsO2 are measured using differential scanning calorimetry. The information for both the low- and high-temperature heat rapacity of RuO2 is coupled with the Delta(f)G degrees data obtained in this study to evaluate the standard enthalpy of formation of RuO2 at 298.15 K (Delta(f)H degrees(298.15K)). The low-temperature heat capacity of OsO2 has not been measured: therefore, the standard enthalpy and entropy of formation of OsO2 at 298.15 K (Delta(f)H degrees(298.15K) and S degrees(298.15K), respectively) are derived simultaneously through an optimization procedure from the high-temperature heat capacity and the Gibbs energy of formation. Both Delta fH degrees(298.15K) and S degrees(298.15K) are treated as variables in the optimization routine, For RuO2, the standard enthalpy of formation at 298.15 K is Delta fH degrees(298.15K) (RuO2) -313.52 +/- 0.08 kJ/mol, and that for OsO2 is Delta(f)H degrees(298.15K) (OSO2) = -295.96 +/- 0.08 kJ/mol. The standard entropy of OsO2 at 298.15 K that has been obtained from the optimization is given as S degrees(298.15K) (OsO2) = 49.8 +/- 0.2 J (mol K)(-1).

Polarization reversal studies in ferroelectric taap

Telluric Acid Ammonium Phosphate (Te(OH)62(NH4)H2PO4(NH4)2HPO4) reffered to as TAAP is a recently discovered class m ferroelectric.1 It undergoes FE-PE transition at 48°C. Switching studies in this crystal has been carried out in the temperature range -14°C to 39°C by applying fields up to 4 kV/cm. Measurements were carried out on (101) plates cut from the crystals grown from solution. X-ray irradiation was carried out at room temperature by means of an x-ray tube operating at 25 kV and 15 mA with copper target. Air drying silver paste was used as electrodes. Samples were checked for hysteresis loop using a modified Sawyer-Tower circuit. The Ps value obtained from the loop is 2.1 μC/cm2 which is comparable to the earlier reported value. It was however noticed that the loop was slightly shifted to right with respect to the origin indicating the presence of a small internal bias which was 100 V/cm in the virgin crystal. This bias could not be removed even after repeated crystallization. On irradiation the internal biasing field increased which was indicated by a further shift of the hysteresis loop. The bias seems to saturate at about 750 V/cm for which the crystal had to be irradiated for about 3 hours.

Polarization enhancement in compositionally graded vanadium doped bismuth titanate thin films

Compositionally up and downgraded Bi4-x/3Ti3-xVxO12 (x=0.0, 0.012,0.03, 0.06) thin films were grown on Pt coated silicon substrates by pulsed laser deposition technique. Downgraded fabrication showed improved ferroelectric polarization in comparison to upgraded fabrication. Films deposited at 650 and 700 degrees C showed very large remnant polarization (2P(r)) value of 82 mu C cm(-2), which is comparatively large among all bismuth based thin films reported so far. A mechanism based on vanadium enrich seeded layer formation in the downgraded structure is proposed for the improvement. Moreover, frequency independent behavior (100Hz-5kHz) of the graded films ensures its potential application for various microelectronic devices. (c) 2010 American Institute of Physics. [doi :10.1063/1.3431543].