Oxygen-participated electrochemistry of new lithium-rich layered oxides Li3MRuO5 M = Mn, Fe)

We describe the synthesis, crystal structure and lithium deinsertion-insertion electrochemistry of two new lithium-rich layered oxides, Li3MRuO5 (M = Mn, Fe), related to rock salt based Li2MnO3 and LiCoO2. The Li3MnRuO5 oxide adopts a structure related to Li2MnO3 (C2/m) where Li and (Li0.2Mn0.4Ru0.4) layers alternate along the c-axis, while the Li3FeRuO5 oxide adopts a near-perfect LiCoO2 (R (3) over barm) structure where Li and (Li0.2Fe0.4Ru0.4) layers are stacked alternately. Magnetic measurements indicate for Li3MnRuO5 the presence of Mn3+ and low spin configuration for Ru4+ where the itinerant electrons occupy a pi*-band. The onset of a net maximum in the chi vs. T plot at 9.5 K and the negative value of the Weiss constant (theta) of -31.4 K indicate the presence of antiferromagnetic superexchange interactions according to different pathways. Lithium electrochemistry shows a similar behaviour for both oxides and related to the typical behaviour of Li-rich layered oxides where participation of oxide ions in the electrochemical processes is usually found. A long first charge process with capacities of 240 mA h g(-1) (2.3 Li per f.u.) and 144 mA h g(-1) (1.38 Li per f.u.) is observed for Li3MnRuO5 and Li3FeRuO5, respectively. An initial sloping region (OCV to ca. 4.1 V) is followed by a long plateau (ca. 4.3 V). Further discharge-charge cycling points to partial reversibility (ca. 160 mA h g(-1) and 45 mA h g(-1) for Mn and Fe, respectively). Nevertheless, just after a few cycles, cell failure is observed. X-ray photoelectron spectroscopy (XPS) characterisation of both pristine and electrochemically oxidized Li3MRuO5 reveals that in the Li3MnRuO5 oxide, Mn3+ and Ru4+ are partially oxidized to Mn4+ and Ru5+ in the sloping region at low voltage, while in the long plateau, O2- is also oxidized. Oxygen release likely occurs which may be the cause for failure of cells upon cycling. Interestingly, some other Li-rich layered oxides have been reported to cycle acceptably even with the participation of the O2- ligand in the reversible redox processes. In the Li3FeRuO5 oxide, the oxidation process appears to affect only Ru (4+ to 5+ in the sloping region) and O2- (plateau) while Fe seems to retain its 3+ state.

Estimates of site response based on spectral ratio between horizontal and vertical components of ambient vibrations in the source zone of 2001 Bhuj earthquake

We investigated the site response characteristics of Kachchh rift basin over the meizoseismal area of the 2001, Mw 7.6, Bhuj (NW India) earthquake using the spectral ratio of the horizontal and vertical components of ambient vibrations. Using the available knowledge on the regional geology of Kachchh and well documented ground responses from the earthquake, we evaluated the H/V curves pattern across sediment filled valleys and uplifted areas generally characterized by weathered sandstones. Although our HIV curves showed a largely fuzzy nature, we found that the hierarchical clustering method was useful for comparing large numbers of response curves and identifying the areas with similar responses. Broad and plateau shaped peaks of a cluster of curves within the valley region suggests the possibility of basin effects within valley. Fundamental resonance frequencies (f(0)) are found in the narrow range of 0.1-2.3 Hz and their spatial distribution demarcated the uplifted regions from the valleys. In contrary, low HIV peak amplitudes (A(0) = 2-4) were observed on the uplifted areas and varying values (2-9) were found within valleys. Compared to the amplification factors, the liquefaction indices (kg) were able to effectively indicate the areas which experienced severe liquefaction. The amplification ranges obtained in the current study were found to be comparable to those obtained from earthquake data for a limited number of seismic stations located on uplifted areas; however the values on the valley region may not reflect their true amplification potential due to basin effects. Our study highlights the practical usefulness as well as limitations of the HIV method to study complex geological settings as Kachchh. (C) 2014 Elsevier Ltd. All rights reserved.

Influence of dynamic operating conditions on the performance of metal hydride based solid sorption cooling systems

The performance of metal hydride based solid sorption cooling systems depends on the driving pressure differential, and the rate of hydrogen transfer between coupled metal hydride beds during cooling and regeneration processes. Conventionally, the mid-plateau pressure difference obtained from `static' equilibrium PCT data are used for the thermodynamic analysis. It is well known that the processes are `dynamic' because the pressure and temperature, and hence the concentration of the hydride beds, are continuously changing. Keeping this in mind, the pair of La0.9Ce0.1Ni5 - LaNi4.7Al0.3 metal hydrides suitable for solid sorption cooling systems were characterised using both static and dynamic methods. It was found that the PCT characteristics, and the resulting enthalpy (Delta H) and entropy (Delta S) values, were significantly different for static and dynamic modes of measurements. In the present study, the solid sorption metal hydride cooling system is analysed taking in to account the actual variation in the pressure difference (Delta P) and the dynamic enthalpy values. Compared to `static' property based analysis, significant decrease in the driving potentials and transferrable amounts of hydrogen, leading to decrease in cooling capacity by 57.8% and coefficient of performance by 31.9% are observed when dynamic PCT data at the flow rate of 80 ml/min are considered. Copyright 2014 (C) Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

Tectono-geomorphic and environmental set-up deduced during deposition of Mio-Pleistocene sediments in NW Himalaya, India

Detailed pedofacies characterization along-with lithofacies investigations of the Mio-Pleistocene Siwalik sediments exposed in the Ramnagar sub-basin have been studied so as to elucidate variability in time and space of fluvial processes and the role of intra- and extra-basinal controls on fluvial sedimentation during the evolution of the Himalayan foreland basin (HFB). Dominance of multiple, moderately to strongly developed palaeosol assemblages during deposition of Lower Siwalik (similar to 12-10.8 Ma) sediments suggest that the HFB was marked by Upland set-up of Thomas et al. (2002). Activity of intra-basinal faults on the uplands and deposition of terminal fans at different times caused the development of multiple soils. Further, detailed pedofacies along-with lithofacies studies indicate prevalence of stable tectonic conditions and development of meandering streams with broad floodplains. However, the Middle Siwalik (similar to 10.8-4.92 Ma) sub-group is marked by multistoried sandstones and minor mudstone and mainly weakly developed palaeosols, indicating deposition by large braided rivers in the form of megafans in a Lowland set-up of Thomas et al. (2002). Significant change in nature and size of rivers from the Lower to Middle Siwalik at similar to 10 Ma is found almost throughout of the basin from Kohat Plateau (Pakistan) to Nepal because the Himalayan orogeny witnessed its greatest tectonic upheaval at this time leading to attainment of great heights by the Himalaya, intensification of the monsoon, development of large rivers systems and a high rate of sedimentation, hereby a major change from the Upland set-up to the Lowland set-up over major parts of the HFB. An interesting geomorphic environmental set-up prevailed in the Ramnagar sub-basin during deposition of the studied Upper Siwalik (similar to 4.92 to <1.68 Ma) sediments as observed from the degree of pedogenesis and the type of palaeosols. In general, the Upper Siwalik sub-group in the Ramnagar sub-basin is subdivided from bottom to top into the Purmandal sandstone (4.92-4.49 Ma), Nagrota (4.49-1.68 Ma) and Boulder Conglomerate (<1.68 Ma) formations on the basis of sedimentological characters and change in dominant lithology. Presence of mudstone, a few thin gravel beds and dominant sandstone lithology with weakly to moderately developed palaeosols in the Purmandal sandstone Fm. indicates deposition by shallow braided fluvial streams. The deposition of mudstone dominant Nagrota Fm. with moderately to some well developed palaeosols and a zone of gleyed palaeosols with laminated mudstones and thin sandstones took place in an environment marked by numerous small lakes, water-logged regions and small streams in an environment just south of the Piedmont zone, perhaps similar to what is happening presently in the Upland region/the Upper Gangetic plain. This area is locally called the `Trai region' (Pascoe, 1964). Deposition of Boulder Conglomerate Fm. took place by gravelly braided river system close to the Himalayan Ranges. Activity along the Main Boundary Fault led to progradation of these environments distal-ward and led to development of on the whole a coarsening upward sequence. (C) 2014 Elsevier B.V. All rights reserved.

A Comparative Study of Early Afterdepolarization-Mediated Fibrillation in Two Mathematical Models for Human Ventricular Cells

Early afterdepolarizations (EADs), which are abnormal oscillations of the membrane potential at the plateau phase of an action potential, are implicated in the development of cardiac arrhythmias like Torsade de Pointes. We carry out extensive numerical simulations of the TP06 and ORd mathematical models for human ventricular cells with EADs. We investigate the different regimes in both these models, namely, the parameter regimes where they exhibit (1) a normal action potential (AP) with no EADs, (2) an AP with EADs, and (3) an AP with EADs that does not go back to the resting potential. We also study the dependence of EADs on the rate of at which we pace a cell, with the specific goal of elucidating EADs that are induced by slow or fast rate pacing. In our simulations in two-and three-dimensional domains, in the presence of EADs, we find the following wave types: (A) waves driven by the fast sodium current and the L-type calcium current (Na-Ca-mediated waves); (B) waves driven only by the L-type calcium current (Ca-mediated waves); (C) phase waves, which are pseudo-travelling waves. Furthermore, we compare the wave patterns of the various wave-types (Na-Ca-mediated, Ca-mediated, and phase waves) in both these models. We find that the two models produce qualitatively similar results in terms of exhibiting Na-Ca-mediated wave patterns that are more chaotic than those for the Ca-mediated and phase waves. However, there are quantitative differences in the wave patterns of each wave type. The Na-Ca-mediated waves in the ORd model show short-lived spirals but the TP06 model does not. The TP06 model supports more Ca-mediated spirals than those in the ORd model, and the TP06 model exhibits more phase-wave patterns than does the ORd model.

Deformation pathways and breakup modes in acoustically levitated bicomponent droplets under external heating

Controlled breakup of droplets using heat or acoustics is pivotal in applications such as pharmaceutics, nanoparticle production, and combustion. In the current work we have identified distinct thermal acoustics-induced deformation regimes (ligaments and bubbles) and breakup dynamics in externally heated acoustically levitated bicomponent (benzene-dodecane) droplets with a wide variation in volatility of the two components (benzene is significantly more volatile than dodecane). We showcase the physical mechanism and universal behavior of droplet surface caving in leading to the inception and growth of ligaments. The caving of the top surface is governed by a balance between the acoustic pressure field and the restrictive surface tension of the droplet. The universal collapse of caving profiles for different benzene concentration (<70% by volume) is shown by using an appropriate time scale obtained from force balance. Continuous caving leads to the formation of a liquid membrane-type structure which undergoes radial extension due to inertia gained during the precursor phase. The membrane subsequently closes at the rim and the kinetic energy leads to ligament formation and growth. Subsequent ligament breakup is primarily Rayleigh-Plateau type. The breakup mode shifts to diffusional entrapment-induced boiling with an increase in concentration of the volatile component (benzene >70% by volume). The findings are portable to any similar bicomponent systems with differential volatility.

The impact of latent heating on the location and strength of the tropical easterly jet

The tropical easterly jet (TEJ) is a prominent atmospheric circulation feature observed during the Asian summer monsoon. It is generally assumed that sensible heating over the Tibetan Plateau directly influences the location of the TEJ. However, other studies have suggested the importance of latent heating in determining the jet location. In this paper, the relative importance of latent heating on the maintenance of the TEJ is explored through simulations with a general circulation model. The simulation of the TEJ by the Community Atmosphere Model, version 3.1 is discussed in detail. These simulations showed that the location of the TEJ is well correlated with the location of the precipitation. Significant zonal shifts in the location of the precipitation resulted in similar shifts in the zonal location of the TEJ. These zonal shifts had minimal effect on the large-scale structure of the jet. Further, provided that precipitation patterns were relatively unchanged, orography did not directly impact the location of the TEJ. These changes were robust even with changes in the cumulus parameterization. This suggests the potential important role of latent heating in determining the location and structure of the TEJ. These results were used to explain the significant differences in the zonal location of the TEJ in the years 1988 and 2002. To understand the contribution of the latitudinal location of latent heating on the strength of the TEJ, aqua-planet simulations were carried out. It has been shown that for similar amounts of net latent heating, the jet is stronger when heating is in the higher tropical latitudes. This may partly explain the reason for the jet to be very strong during the JJA monsoon season.

Advancing Edge Speeds of Epithelial Monolayers Depend on Their Initial Confining Geometry

Collective cell migrations are essential in several physiological processes and are driven by both chemical and mechanical cues. The roles of substrate stiffness and confinement on collective migrations have been investigated in recent years, however few studies have addressed how geometric shapes influence collective cell migrations. Here, we address the hypothesis that the relative position of a cell within the confinement influences its motility. Monolayers of two types of epithelial cells-MCF7, a breast epithelial cancer cell line, and MDCK, a control epithelial cell line-were confined within circular, square, and cross-shaped stencils and their migration velocities were quantified upon release of the constraint using particle image velocimetry. The choice of stencil geometry allowed us to investigate individual cell motility within convex, straight and concave boundaries. Cells located in sharp, convex boundaries migrated at slower rates than those in concave or straight edges in both cell types. The overall cluster migration occurred in three phases: an initial linear increase with time, followed by a plateau region and a subsequent decrease in cluster speeds. An acto-myosin contractile ring, present in the MDCK but absent in MCF7 monolayer, was a prominent feature in the emergence of leader cells from the MDCK clusters which occurred every similar to 125 mu m from the vertex of the cross. Further, coordinated cell movements displayed vorticity patterns in MDCK which were absent in MCF7 clusters. We also used cytoskeletal inhibitors to show the importance of acto-myosin bounding cables in collective migrations through translation of local movements to create long range coordinated movements and the creation of leader cells within ensembles. To our knowledge, this is the first demonstration of how bounding shapes influence long-term migratory behaviours of epithelial cell monolayers. These results are important for tissue engineering and may also enhance our understanding of cell movements during developmental patterning and cancer metastasis.