Substrate integrated Lead-Carbon hybrid ultracapacitor with flooded, absorbent glass mat and silica-gel electrolyte configurations

Lead-Carbon hybrid ultracapacitors (Pb-C HUCs) with flooded, absorbent-glass-mat (AGM) and silica-gel sulphuric acid electrolyte configurations are developed and performance tested. Pb-C HUCs comprise substrate-integrated PbO2 (SI-PbO2) as positive electrodes and high surface-area carbon with graphite-sheet substrate as negative electrodes. The electrode and silica-gel electrolyte materials are characterized by XRD, XPS, SEM, TEM, Rheometry, BET surface area, and FTIR spectroscopy in conjunction with electrochemistry. Electrochemical performance of SI-PbO2 and carbon electrodes is studied using cyclic voltammetry with constant-current charge and discharge techniques by assembling symmetric electrical-double-layer capacitors and hybrid Pb-C HUCs with a dynamic Pb(porous)/PbSO4 reference electrode. The specific capacitance values for 2 V Pb-C HUCs are found to be 166 F/g, 102 F/g and 152 F/g with a faradaic efficiency of 98%, 92% and 88% for flooded, AGM and gel configurations, respectively.

Anomalous structural and dynamical phase transitions of soft colloidal binary mixtures

We report microscopic structural and dynamical measurements on binary mixtures of homopolymers and polymer grafted nanoparticles at high densities in good solvent. We find strong and unexpected anomalies in the structure and dynamics of these binary mixtures, including appearance of spontaneous orientational alignment, as a function of added homopolymers of different molecular weights. Our experiments point to the possibility of exploiting the phase space in density and homopolymer size, of such hybrid systems, to create new materials with novel structural and physical properties.

Electrical properties of buckled multiwalled carbon nanotube arrays in the diffusive regime

We report the geometrical effect of graded buckled multiwalled carbon nanotube arrays on the electrical transport properties in the diffusive regime, via successive breakdown caused by the Joule heating. This breakdown occurs in the straighter region. Empirical relations involving the current-carrying ability, resistance, breakdown power, threshold voltage, diameter and length of carbon nanotube arrays are discussed on the basis of an extensive set of experimental data along with justification. The experimental results are corroborated by the density functional tight-binding calculations of electronic band structure. The band gap decreases as buckleness increases leading to the enhancement in the current-carrying ability and elucidating the role of buckleness in carbon nanotubes. Copyright (c) EPLA, 2012

Meso-Structured Silica-Nafion Hybrid Membranes for Direct Methanol Fuel Cells

A series of novel organic-inorganic hybrid membranes have been prepared employing Nafion and acid-functionalized meso-structured molecular sieves (MMS) with varying structures and surface area. Acid-functionalized silica nanopowder of surface area 60 m(2)/g, silica meso-structured cellular foam (MSU-F) of surface area 470 m(2)/g and silica meso-structured hexagonal frame network (MCM-41) of surface area 900 m(2)/g have been employed as potential filler materials to form hybrid membranes with Nafion framework. The structural behavior, water uptake, proton conductivity and methanol permeability of these hybrid membranes have been investigated. DMFCs employing Nafion-silica MSU-F and Nafion-silica MCM-41 hybrid membranes deliver peak-power densities of 127 mW/cm(2) and 100 mW/cm(2), respectively; while a peak-power density of only 48 mW/cm(2) is obtained with the DMFC employing pristine recast Nafion membrane under identical operating conditions. The aforesaid characteristics of the hybrid membranes could be exclusively attributed to the presence of pendant sulfonic acid groups in the filler, which provide fairly continuous proton-conducting pathways between filler and matrix in the hybrid membranes facilitating proton transport without any trade-off between its proton conductivity and methanol crossover. (C) 2012 The Electrochemical Society. DOI: 10.1149/2.036211jes] All rights reserved.

Probing ultrafast carrier dynamics, nonlinear absorption and refraction in core-shell silicon nanowires

We investigate the relaxation dynamics of photogenerated carriers in silicon nanowires consisting of a crystalline core and a surrounding amorphous shell, using femtosecond time-resolved differential reflectivity and transmission spectroscopy at 3.15 eV and 1.57 eV photon energies. The complex behaviour of the differential transmission and reflectivity transients is the mixed contributions from the crystalline core and the amorphous silicon on the nanowire surface and the substrate where competing effects of state-filling and photoinduced absorption govern the carrier dynamics. Faster relaxation rates are observed on increasing the photogenerated carrier density. Independent experimental results on crystalline silicon-on-sapphire (SOS) help us in separating the contributions from the carrier dynamics in crystalline core and the amorphous regions in the nanowire samples. Further, single-beam z-scan nonlinear transmission experiments at 1.57 eV in both open- and close-aperture configurations yield two-photon absorption coefficient beta (similar to 3 cm/GW) and nonlinear refraction coefficient gamma (-2.5 x 10 (-aEuro parts per thousand 4) cm(2)/GW).

Unraveling siRNA unzipping kinetics with graphene

Using all atom molecular dynamics simulations, we report spontaneous unzipping and strong binding of small interfering RNA (siRNA) on graphene. Our dispersion corrected density functional theory based calculations suggest that nucleosides of RNA have stronger attractive interactions with graphene as compared to DNA residues. These stronger interactions force the double stranded siRNA to spontaneously unzip and bind to the graphene surface. Unzipping always nucleates at one end of the siRNA and propagates to the other end after few base-pairs get unzipped. While both the ends get unzipped, the middle part remains in double stranded form because of torsional constraint. Unzipping probability distributions fitted to single exponential function give unzipping time (tau) of the order of few nanoseconds which decrease exponentially with temperature. From the temperature variation of unzipping time we estimate the energy barrier to unzipping. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4742189]

Evolution of structural phase coexistence in a half doped manganite Pr0.5Sr0.5MnO3: An evidence for magneto-structural coupling

Temperature dependent x-ray diffraction measurements have been performed to understand the implications of magnetic phase coexistence on crystallographic structure in a half-doped manganite Pr0.5Sr0.5MnO3. The compound shows a structural phase transition from high-temperature tetragonal-I4/mcm to low-temperature orthorhombic-Fmmm symmetry around the ferromagnetic to antiferro-magnetic transition. Rietveld analysis shows the coexistence of these two structures emerges at high temperature within the ferromagnetic state, and persists down to lowest temperature. Below around 40 K, however, this structural evolution stops, and a significant fraction (similar to 22%) of untransformed high-temperature phase remains. This agrees with earlier magnetization study, thus establishing its magneto-structural coupling. (C) 2012 Elsevier B.V. All rights reserved.

On the linkage of mesospheric planetary waves with those of the lower atmosphere and ionosphere: A case study from Indian low latitudes

In this paper we study the planetary-scale wave features using concurrent observations of mesospheric wind and temperature, ionospheric h'F, and tropospheric wind from Tirunelveli, Gadanki, and Kolhapur, all located in the Indian low latitudes, made during February 2009. Our investigations reveal that 3 to 5 day periodicity, characterized as ultrafast Kelvin (UFK) waves, was persistent throughout the atmosphere during this period. These waves show clear signatures of upward wave propagation from troposphere to the upper mesosphere, linking the ionosphere through a clear correlation between mesospheric winds and h'F variations. We also note that the amplitude of this wave decreased as we moved away from the equator. These results are the first of their kind from Indian sector, portraying the vertical as well as latitudinal characteristics of the 3 to 5 day UFK waves simultaneously from the troposphere to the ionosphere.

Structure of a carbon nanotube-dendrimer composite

Using all atomistic molecular dynamics (MD) simulations we report a microscopic picture of the carbon nanotube (6,5)-dendrimer complex for PAMAM dendrimers of generations 2 to 4. We study the compact wrapping conformations of the dendrimer onto the nanotube surface for all the three generations of PAMAM dendrimer. A high degree of wrapping for the non-protonated dendrimer is observed as compared to the protonated dendrimer. For comparison, we also study the interaction of another dendrimer, poly(propyl ether imine) (PETIM), with the nanotube. The results of the distance of closest approach as well as the number of close contacts between the nanotube and the dendrimer reveal that the PAMAM dendrimer interacts strongly as compared to the PETIM dendrimer. We also calculate the binding energy between the nanotube and the dendrimer using MM/PBSA methods and attribute the strong binding to the charge transfer between them. Dendrimer wrapping on the CNT will make it soluble and the dendrimer can act as an efficient dispersing agent for the nanotubes.

Directional grain growth from anisotropic kinetic roughening of grain boundaries in sheared colloidal crystals

The fabrication of functional materials via grain growth engineering implicitly relies on altering the mobilities of grain boundaries (GBs) by applying external fields. Although computer simulations have alluded to kinetic roughening as a potential mechanism for modifying GB mobilities, its implications for grain growth have remained largely unexplored owing to difficulties in bridging the widely separated length and time scales. Here, by imaging GB particle dynamics as well as grain network evolution under shear, we present direct evidence for kinetic roughening of GBs and unravel its connection to grain growth in driven colloidal polycrystals. The capillary fluctuation method allows us to quantitatively extract shear-dependent effective mobilities. Remarkably, our experiments reveal that for sufficiently large strains, GBs with normals parallel to shear undergo preferential kinetic roughening, resulting in anisotropic enhancement of effective mobilities and hence directional grain growth. Single-particle level analysis shows that the mobility anisotropy emerges from strain-induced directional enhancement of activated particle hops normal to the GB plane. We expect our results to influence materials fabrication strategies for atomic and block copolymeric polycrystals as well.

Electrochemical capacitors: Technical challenges and prognosis for future markets

Electrochemical capacitors are potential devices that could help bringing about major advances in future energy storage. They are lightweight and their manufacture and disposal has no detrimental effects on the environment. A comprehensive description of fundamental science of electrochemical capacitors is presented. Similarities and differences between electrochemical capacitors and secondary batteries for electrical energy storage are highlighted and various types of electrochemical capacitors are discussed with special reference to lead-carbon hybrid ultracapacitors. Some envisaged applications of electrochemical capacitors are described along with the technical challenges and prognosis for future markets. (C) 2012 Published by Elsevier Ltd.

Acoustic and optical phonon dynamics from femtosecond time-resolved optical spectroscopy of the superconducting iron pnictide Ca(Fe0.944Co0.056)(2)As-2

We report the temperature evolution of coherently excited acoustic and optical phonon dynamics in the superconducting iron pnictide single crystal Ca(Fe0.944Co0.056)(2)As-2 across the spin density wave transition at T-SDW similar to 85 K and the superconducting transition at T-SC similar to 20 K. The strain pulse propagation model applied to the generation of the acoustic phonons yields the temperature dependence of the optical constants, and longitudinal and transverse sound velocities in the temperature range from 3.1 K to 300 K. The frequency and dephasing times of the phonons show anomalous temperature dependence below T-SC indicating a coupling of these low-energy excitations with the Cooper-pair quasiparticles. A maximum in the amplitude of the acoustic modes at T similar to 170 is seen, attributed to spin fluctuations and strong spin-lattice coupling before T-SDW. Copyright (c) EPLA, 2012

Nanomechanical and optical properties of highly a-axis oriented AlN films

This paper reports optical and nanomechanical properties of predominantly a-axis oriented AlN thin films. These films were deposited by reactive DC magnetron sputtering technique at an optimal target to substrate distance of 180 mm. X-ray rocking curve (FWHM = 52 arcsec) studies confirmed the preferred orientation. Spectroscopic ellipsometry revealed a refractive index of 1.93 at a wavelength of 546 nm. The hardness and elastic modulus of these films were 17 and 190 GPa, respectively, which are much higher than those reported earlier can be useful for piezoelectric films in bulk acoustic wave resonators. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4772204]

Thermally reversing window in Ge15Te85-xInx glasses: Nanoindentation and micro-Raman studies

Nanoindentation studies on Ge15Te85-xInx glasses indicate that the hardness and elastic modulus of these glasses increase with indium concentration. While a pronounced plateau is seen in the elastic modulus in the composition range 3 <= x <= 7, the hardness exhibits a change in slope at compositions x = 3 and x = 7. Also, the density exhibits a broad maximum in this composition range. The observed changes in the mechanical properties and density are clearly associated with the thermally reversing window in Ge15Te85-xInx glasses in the composition range 3 <= x <= 7. In addition, a local minimum is seen in density and hardness around x = 9, the chemical threshold of the system. Further, micro-Raman studies reveal that as-quenched Ge15Te85-xInx samples exhibit two prominent peaks, at 123 cm(-1) and 155 cm(-1). In thermally annealed samples, the peaks at 120 cm(-1) and 140 cm(-1), which are due to crystalline Te, emerge as the strongest peaks. The Raman spectra of polished samples are similar to those of annealed samples, with strong peaks at 123 cm(-1) and 141 cm(-1). The spectra of lightly polished samples outside the thermally reversing window resemble those of thermally annealed samples; however, the spectra of glasses with compositions in the thermally reversing window resemble those of as-quenched samples. This observation confirms the earlier idea that compositions in the thermally reversing window are non-aging and are more stable. (C) 2012 Elsevier B.V. All rights reserved.

A Durable Graphitic-Carbon Support for Pt and Pt3Co Cathode Catalysts in Polymer Electrolyte Fuel Cells

The high efficiency of fuel-cell-powered electric vehicles makes them a potentially viable option for future transportation. Polymer Electrolyte Fuel Cells (PEFCs) are most promising among various fuel cells for electric traction due to their quick start-up and low-temperature operation. In recent years, the performance of PEFCs has reached the acceptable level both for automotive and stationary applications and efforts are now being expended in increasing their durability, which remains a major concern in their commercialization. To make PEFCs meet automotive targets an understanding of the factors affecting the stability of carbon support and platinum catalyst is critical. Alloying platinum (Pt) with first-row transition metals such as cobalt (Co) is reported to facilitate both higher degree of crystallinity and enhanced activity in relation to pristine Pt. But a major challenge for the application of Pt-transition metal alloys in PEFCs is to improve the stability of these binary catalysts. Dissolution of the non-precious metal in the acidic environment could alleviate the activity of the catalysts and hence cell performance. The use of graphitic carbon as cathode-catalyst support enhances the long-term stability of Pt and its alloys in relation to non-graphitic carbon as the former exhibits higher resistance to carbon corrosion in relation to the latter in PEFC cathodes during accelerated-stress test (AST). Changes in electrochemical surface area (ESA), cell performance and charge-transfer resistance are monitored during AST through cyclic voltammetry, cell polarization and impedance measurements, respectively. Studies on catalytic electrodes with X-ray diffraction, Raman spectroscopy and transmission electron microscopy reflect that graphitic carbon-support resists carbon corrosion and helps mitigating aggregation of Pt and Pt3Co catalyst particles. (C) 2012 The Electrochemical Society. DOI: 10.1149/2.051301jes] All rights reserved.