Influence of water and thermal history on ion transport in lithium salt-succinonitrile plastic crystalline electrolytes

Important issues of water and thermal history affecting ion transport in a representative plastic crystalline lithium salt electrolyte: succinonitrile (SN)-lithium perchlorate (LiClO4) are discussed here. Ionic conductivity of electrolytes with high lithium salt amounts (similar to 1 M) in SN at a particular temperature is known to be influenced both by the trans-gauche isomerism and ion association (solvation), the two most important intrinsic parameters of the plastic solvent. In the present study both water and thermal history influence SN and result in enhancement of ionic conductivity of 1 M LiClO4-SN electrolyte. Systematic observations reveal that the presence of water in varying amounts promote ion-pair dissociation in the electrolyte. While trace amounts (approximate to 1-15 ppm) do not affect the trans-gauche isomerism of SN, the presence of water in large amounts (approximate to 5500 ppm) submerges the plasticity of SN. Subjugating the electrolyte to different thermal protocol resulted in enhancement of trans concentration only. This is an interesting observation as it demonstrates a simple and effective procedure involving utilization of an optimized set of external parameters to decouple solvation from trans-gauche isomerism. Observations from the ionic conductivity of various samples were accounted by changes in signature isomer and ion-association bands in the mid-IR regime and also from plastic to normal crystal transition temperature peak obtained from thermal studies. (C) 2010 Elsevier B.V. All rights reserved.

A possible origin of viscosity in Keplerian accretion disks due to secondary perturbation: Turbulent transport without magnetic fields

The origin of hydrodynamic turbulence in rotating shear flow is a long standing puzzle. Resolving it is especially important in astrophysics when the flow's angular momentum profile is Keplerian which forms an accretion disk having negligible molecular viscosity. Hence, any viscosity in such systems must be due to turbulence, arguably governed by magnetorotational instability, especially when temperature T greater than or similar to 10(5). However, such disks around quiescent cataclysmic variables, protoplanetary and star-forming disks, and the outer regions of disks in active galactic nuclei are practically neutral in charge because of their low temperature, and thus are not expected to be coupled with magnetic fields enough to generate any transport due to the magnetorotational instability. This flow is similar to plane Couette flow including the Coriolis force, at least locally. What drives their turbulence and then transport, when such flows do not exhibit any unstable mode under linear hydrodynamic perturbation? We demonstrate that the three-dimensional secondary disturbance to the primarily perturbed flow that triggers elliptical instability may generate significant turbulent viscosity in the range 0.0001 less than or similar to nu(t) less than or similar to 0.1, which can explain transport in accretion flows.

Temperature dependent electrical transport behavior of InN/GaN heterostructure based Schottky diodes

InN/GaN heterostructure based Schottky diodes were fabricated by plasma-assisted molecular beam epitaxy. The temperature dependent electrical transport properties were carried out for InN/GaN heterostructure. The barrier height and the ideality factor of the Schottky diodes were found to be temperature dependent. The temperature dependence of the barrier height indicates that the Schottky barrier height is inhomogeneous in nature at the heterostructure interface. The higher value of the ideality factor and its temperature dependence suggest that the current transport is primarily dominated by thermionic field emission (TFE) other than thermionic emission (TE). The room temperature barrier height obtained by using TE and TFE models were 1.08 and 1.43 eV, respectively. (C) 2011 American Institute of Physics. doi: 10.1063/1.3549685]

Electrical Relaxation and Transport in 0.5Cs(2)O-0.5Li(2)O-3B(2)O(3) Glasses

The frequency and temperature dependence of the dielectric constant and the electrical conductivity of the transparent glasses in the composition 0.5Cs(2)O-0.5Li(2)O-3B(2)O(3) (CLBO) were investigated in the 100 Hz - 10 MHz frequency range. The dielectric constant for the as-quenched glass increased with increasing temperature, exhibiting anomalies in the vicinity of the glass transition and crystallization temperatures. The temperature coefficient of dielectric constant was estimated (35 +/- 2 ppm. K-1) using Havinga's formula. The dielectric loss at 313 K is 0.005 +/- 0.0005 at all the frequencies understudy. The activation energy associated with the electrical relaxation determined from the electric modulus spectra was found to be 1.73 +/- 0.05 eV, close to that of the activation energy obtained for DC conductivity (1.6 +/- 0.06 eV). The frequency dependent electrical conductivity was analyzed using Jonscher's power law. The combination of these dielectric characteristics suggests that these are good candidates for electrical energy storage device applications.

Dielectric Relaxation Spectroscopy for Evaluation of the Influence of Solvent Dynamics on Ion Transport in Succinonitrile-Salt Plastic Crystalline Electrolytes

Influence of succinonitrile (SN) dynamics on ion transport in SN-lithium perchlorate (LiClO4) electrolytes is discussed here via dielectric relaxation spectroscopy. Dielectric relaxation spectroscopy (similar to 2 x 10(-3) Hz to 3 MHz) of SN and SN-LiClO4 was studied as a function of salt content (up to 7 mol % or 1 M) and temperature (-20 to +60 degrees C). Analyses of real and imaginary parts of permittivity convincingly reveal the influence Of trans gauche isomerism and solvent-salt association (solvation) effects on ion transport. The relaxation processes are highly dependent on the salt concentration and temperature. While pristine SN display only intrinsic dynamics (i.e., trans-gauche isomerism) which enhances with an increase in temperature, SN-LiClO4 electrolytes especially at high salt concentrations (similar to 0.04-1 M) show salt-induced relaxation processes. In the concentrated electrolytes, the intrinsic dynamics was observed to be a function of salt content, becoming faster with an increase in salt concentration. Deconvolution of the imaginary part of the permittivity spectra using Havriliak-Negami (HN) function show a relaxation process corresponding to the above phenomena. The permittivity data analyzed using HN and Kohlrausch-Williams-Watta (KWW) functions show non-Debye relaxation processes and enhancement in the trans phase (enhanced solvent dynamics) as a function of salt concentration and temperature.

Molecular Dynamics Investigation of Structure and Transport in the K2O-2SiO2 System Using a Partial Charge Based Model Potential

Potassium disilicate glass and melt have been investigated by using a new partial charge based potential model in which nonbridging oxygens are differentiated from bridging oxygens by their charges. The model reproduces the structural data pertaining to the coordination polyhedra around potassium and the various bond angle distributions excellently. The dynamics of the glass has been studied by using space and time correlation functions. It is found that K ions migrate by a diffusive mechanism in the melt and by hops below the glass transition temperature. They are also found to migrate largely through nonbridging oxygenrich sites in the silicate matrix, thus providing support to the predictions of the modified random network model.

Probing the inter-tube transport in aligned and random multiwall carbon nanotubes

The temperature and magnetic field dependence of conductivity has been used to probe the inter-tube transport in multiwall carbon nanotubes (MWNTs). The scanning electron microscopy images show highly aligned and random distribution of MWNTs. The conductivity in aligned carbon nanotube (ACNT) and random carbon nanotube (RCNT) samples at low temperature follows T-1/2 (at T < 8 K) and T-3/4 (at T > 8 K) dependence in accordance with the weak localization and electron-electron (e-e) interaction model. The values of diffusion coefficient in ACNT and RCNT are 0.25 x 10(-2) and 0.71 x 10(-2) cm(2) s(-1), respectively, indicating that larger number of inter-tube junctions in later enhances the bulk transport. The positive magnetoconductance (MC) data in both samples show that the weak localization contribution is dominant. However, the saturation of MC at higher fields and lower temperatures indicate that e-e interaction is quite significant in RCNT. The T-3/4 and T-1/2 dependence of inelastic scattering length (l(in)) in ACNT and RCNT samples show that the inelastic e-e scattering is more important in aligned tubes. (C) 2011 American Institute of Physics. doi:10.1063/1.3552911]

Molecular dynamics Investigation of structure and transport in the K2O-2SiO2 system using a partial charge based model potential

Potassium disilicate glass and melt have been investigated by using anew partial charge based potential model in which nonbridging oxygens are differentiated from bridging oxygens by their charges. The model reproduces the structural data pertaining to the coordination polyhedra around potassium and the various bond angle distributions excellently. The dynamics of the glass has been studied by using space and time correlation functions. It is found that K ions migrate by a diffusive mechanism in the melt and by hops below the glass transition temperature. They are also found to migrate largely through nonbridging oxygen-rich sites in the silicate matrix, thus providing support to the predictions of the modified random network model.

Imaging in vivo Neuronal Transport in Genetic Model Organisms Using Microfluidic Devices

Microfluidic devices have been developed for imaging behavior and various cellular processes in Caenorhabditis elegans, but not subcellular processes requiring high spatial resolution. In neurons, essential processes such as axonal, dendritic, intraflagellar and other long-distance transport can be studied by acquiring fast time-lapse images of green fluorescent protein (GFP)-tagged moving cargo. We have achieved two important goals in such in vivo studies namely, imaging several transport processes in unanesthetized intact animals and imaging very early developmental stages. We describe a microfluidic device for immobilizing C. elegans and Drosophila larvae that allows imaging without anesthetics or dissection. We observed that for certain neuronal cargoes in C. elegans, anesthetics have significant and sometimes unexpected effects on the flux. Further, imaging the transport of certain cargo in early developmental stages was possible only in the microfluidic device. Using our device we observed an increase in anterograde synaptic vesicle transport during development corresponding with synaptic growth. We also imaged Q neuroblast divisions and mitochondrial transport during early developmental stages of C. elegans and Drosophila, respectively. Our simple microfluidic device offers a useful means to image high-resolution subcellular processes in C. elegans and Drosophila and can be readily adapted to other transparent or translucent organisms.

Electrical transport properties of 0.5Li(2)O-0.5M(2)O-2B(2)O(3) (M = Li, Na and K) glasses

Transparent glasses in the system 0.5Li(2)O-0.5M(2)O-2B(2)O(3) (M = Li, Na and K) were fabricated via the conventional melt quenching technique. The amorphous and glassy nature of the samples was confirmed via the X-ray powder diffraction and the differential scanning calorimetry, respectively. The frequency and temperature dependent characteristics of the dielectric relaxation and the electrical conductivity were investigated in the 100 Hz-10 MHz frequency range. The imaginary part of the electric modulus spectra was modeled using an approximate solution of Kohrausch-Williams-Watts relation. The stretching exponent, (3, was found to be temperature independent for 0.5Li(2)O-0.5Na(2)O-2B(2)O(3) (LNBO) glasses. The activation energy associated with DC conduction was found to be higher (1.25 eV) for 0.5Li(2)O-0.5K(2)O-2B(2)O(3) (LKBO) glasses than that of the other glass systems under study. This is attributed to the mixed cation effect. (C) 2011 Elsevier By. All rights reserved.

Chemical and microstructural modifications in LiPON thin films exposed to atmospheric humidity

Lithium phosphorus oxynitride (LiPON), the widely used solid electrolyte for thin film microbatteries, is not compatible with the ambient humid temperatures. The reasons for reduction in ionic conductivity of LiPON thin films from 2.8 x 10(-6) Scm(-1) to 9.9 x 10(-10) Scm(-1) when exposed to air are analyzed with the aid of AC impedance measurements, SEM, XPS and stylus profilometry. Initially, particulate-free film surfaces obtained soon after rf sputter deposition in N-2 ambient conditions becomes covered with microstructures, forming pores in the film when exposed to air. LiPON films are deposited on Ti coated silicon in addition to bare silicon, ruling out the possibility of stress-related rupturing from the LiPON/Si interface. The reduction of nitrogen, phosphorus, and increased presence of lithium, oxygen and carbon over the film surface lowers the ionic conductivity of LiPON films when exposed to air. (c) 2011 Elsevier B.V. All rights reserved.

Diurnal variation of atmospheric CO2 concentration and delta C-13 in an urban atmosphere during winter-role of the Nocturnal Boundary Layer

The paper presents the importance of the Nocturnal Boundary Layer in driving the diurnal variability of the atmospheric CO2 mixing ratio and the carbon isotope ratio at ground level from an urban station in India. Our observations are the first of their kind from this region. The atmospheric CO2 mixing ratio and the carbon isotopic ratio were measured for both the morning (05:30-07:30 IST) and afternoon time (16:00-18:00 IST) air samples at 5 m above ground level in Bangalore city, Karnataka State (12 degrees 58' N, 77 degrees 38' E, masl = 920 m) for a 10 day period during the winter of 2008. We observed a change of similar to 7% the in CO2 mixing ratio between the morning and afternoon time air samples. A stable isotope analysis of CO2 from morning samples showed a depletion in the carbon isotope ratio by similar to 2 parts per thousand compared to the afternoon samples. Along with the ground-based measurement of air samples, data of radiosonde measurements were also obtained from the Indian Meteorological Department to identify the vertical atmospheric structure at different time in a day. We proposed the presence or absence of the NBL as a controlling factor for the observed variability in the mixing ratio as well as its isotopic composition. Here we used the Keeling model approach to find out the carbon isotope ratio for the local sources. The local sources have further been characterized as anthropogenic and biological respiration (in %) using a two-component mixing model. We also used a vertical mixing model based on the concept of the mixing of isotopically depleted (carbon isotope) ``polluted air'' (PA) with isotopically enriched ``free atmospheric air'' (FA) above. Using this modeling approach, the contribution of FA at ground level is being estimated for both the morning and afternoon time air samples.

Electrical transport studies in alkali borovanadate glasses

The ac conductivity and dielectric behaviors of sodium borovanadate glasses have been studied over wide ranges of composition and frequency. The de activation energies calculated from the complex impedance plots decrease linearly with the Na2O concentration, indicating that ionic conductivity dominates in these glasses. The possible origin of low-temperature departures of conductivity curves (from linearity) of vanadium-rich glasses in log sigma versus 1/T plots is discussed. The ac conductivities have been fitted to the Almond-West type power law expression with use of a single value of s. It is found that in most of the glasses s exhibits a temperature-dependent minimum. The dielectric data are converted into moduli (M*) and are analyzed using the Kohlrausch-William-Watts stretched exponential function, The activation barriers, W, calculated from the temperature-dependent dielectric loss peaks compare well with the activation barriers calculated from the de conductivity plots. The stretching exponent beta is found to be temperature independent and is not likely to be related as in the equation beta = 1 - s, An attempt is made to elucidate the origin of the stretching phenomena. It appears that either a model of the increased contribution of polarization energy (caused by the increased modifier concentration) and hence the increased monopole-induced dipole interactions or a model based on increased intercationic interactions can explain the slowing down of the primitive relaxation in ionically conducting glasses.

Hydrography and circulation in the western Bay of Bengal during the northeast monsoon

The Bay of Bengal, a semienclosed tropical basin that comes under the influence of monsoonal wind and freshwater influx, is distinguished by a strongly stratified surface layer and a seasonally reversing circulation. We discuss characteristics of these features in the western Bay during the northeast monsoon, when the East India Coastal Current (EICC) flows southward, using hydrographic data collected during December 1991. Vertical profiles show uniform temperature and salinity in a homogeneous surface layer, on average, 25 m deep but shallower northward and coastward. The halocline, immediately below, is approximately 50 m thick; salinity changes by approximately 3 parts per thousand. About two thirds of the profiles show temperature inversions in this layer. Salinity below the halocline hardly changes, and stratification is predominantly due to temperature variation, The halocline is noticeably better developed and the surface homogeneous layer is thinner in a low-salinity plume that hugs the coastline along the entire east coast of India, The plume is, on average, 50 km wide, with isohalines sloping down toward the coast. Most prominent in the geostrophic velocity field is the equatorward EICC. Its transport north of about 13 degrees N, computed with 1000 dbar as the level of reference, varies between 2.6 and 7.1 x 10(6) m(3) s(-1); just south of this latitude, a northwestward flow from offshore recurves and merges with the coastal current. At the southern end of the region surveyed, the transport is 7.7 x 10(6) m(3) s(-1). Recent model studies lead us to conclude that the EICC during the northeast monsoon is driven by winds along the east coast of India and Ekman pumping in the interior bay. In the south, Ekman pumping over the southwestern bay is responsible for the northwestward flow that merges with the EICC.

Transport properties, structure, and radiation induced defect studies in amorphous carbon films

Amorphous conducting carbon films are prepared by plasma assisted chemical vapour deposition and their d.c. conductivity (similar to 100 Scm(-1)) is studied from 300K down to 4.2K. The films were irradiated by high energy ion beam(I+13, 170 MeV) with a dose of 10(13) ions/cm(2). As a result a marked decrease in conductivity by two to three orders in magnitude was observed. The structural changes and the defects in the films caused by ion irradiation are studied using photoluminescence, persistent photoconductivity, and ESR spectroscopy.