Relation Between the Diffusivity, Viscosity, and Ionic Radius of LiCl in Water, Methanol, and Ethylene Glycol: A Molecular Dynamics Simulation

A molecular dynamics (MD) investigation of LiCl in water, methanol, and ethylene glycol (EG) at 298 K is reported. Several; structural and dynamical properties of the ions as well as the solvent such as self-diffusivity, radial distribution functions, void and neck distributions, velocity autocorrelation functions, and mean residence times of solvent in the first solvation shell have been computed. The results show that the reciprocal relationship between the self-diffusivity of the ions and the viscosity is valid in almost all solvents with the exception of water. From an analysis of radial distribution functions and coordination numbers the nature of hydrogen bonding within the solvent and its influence on the void and neck distribution becomes evident. It is seen that the solvent solvent interaction is important in EG while solute solvent interactions dominate in water and methanol. From Voronoi tessellation, it is seen that the voids and necks within methanol are larger as compared to those within water or EG. On the basis of the void and neck distributions obtained from MD simulations and literature experimental data of limiting ion conductivity for various ions of different sizes we show that there is a relation between the void and neck radius on e one hand and dependence of conductivity on the ionic radius on the other. It is shown that the presence of large diameter voids and necks in methanol is responsible for maximum in limiting ion conductivity (lambda(0)) of TMA(+), while in water in EG, the maximum is seen for Rb+. In the case of monovalent anions, maximum in lambda(0) as a function ionic radius is seen for Br- in water EG but for the larger ClO4- ion in methanol. The relation between the void and neck distribution and the variation in lambda(0) with ionic radius arises via the Levitation effect which is discussed. These studies show the importance of the solvent structure and the associated void structure.

Scale-dependent relationships between tree species richness and ecosystem function in forests

1. The relationship between species richness and ecosystem function, as measured by productivity or biomass, is of long-standing theoretical and practical interest in ecology. This is especially true for forests, which represent a majority of global biomass, productivity and biodiversity. 2. Here, we conduct an analysis of relationships between tree species richness, biomass and productivity in 25 forest plots of area 8-50ha from across the world. The data were collected using standardized protocols, obviating the need to correct for methodological differences that plague many studies on this topic. 3. We found that at very small spatial grains (0.04ha) species richness was generally positively related to productivity and biomass within plots, with a doubling of species richness corresponding to an average 48% increase in productivity and 53% increase in biomass. At larger spatial grains (0.25ha, 1ha), results were mixed, with negative relationships becoming more common. The results were qualitatively similar but much weaker when we controlled for stem density: at the 0.04ha spatial grain, a doubling of species richness corresponded to a 5% increase in productivity and 7% increase in biomass. Productivity and biomass were themselves almost always positively related at all spatial grains. 4. Synthesis. This is the first cross-site study of the effect of tree species richness on forest biomass and productivity that systematically varies spatial grain within a controlled methodology. The scale-dependent results are consistent with theoretical models in which sampling effects and niche complementarity dominate at small scales, while environmental gradients drive patterns at large scales. Our study shows that the relationship of tree species richness with biomass and productivity changes qualitatively when moving from scales typical of forest surveys (0.04ha) to slightly larger scales (0.25 and 1ha). This needs to be recognized in forest conservation policy and management.

Employing synergistic interactions between few-layer WS2 and reduced graphene oxide to improve lithium storage, cyclability and rate capability of Li-ion batteries

The aim of the contribution is to introduce a high performance anode alternative to graphite for lithium-ion batteries (LiBs). A simple process was employed to synthesize uniform graphene-like few-layer tungsten sulfide (WS2) supported on reduced graphene oxide (RGO) through a hydrothermal synthesis route. The WS2-RGO (80:20 and 70:30) composites exhibited good enhanced electrochemical performance and excellent rate capability performance when used as anode materials for lithium-ion batteries. The specific capacity of the WS2-RGO composite delivered a capacity of 400-450 mAh g(-1) after 50 cycles when cycled at a current density of 100 mA g(-1). At 4000 mA g(-1), the composites showed a stable capacity of approximately 180-240 mAh g(-1), respectively. The noteworthy electrochemical performance of the composite is not additive, rather it is synergistic in the sense that the electrochemical performance is much superior compared to both WS2 and RGO. As the observed lithiation/delithiation for WS2-RGO is at a voltage 1.0 V (approximate to 0.1 V for graphite, Li* /Li), the lithium-ion battery with WS2-RGO is expected to possess high interface stability, safety and management of electrical energy is expected to be more efficient and economic. (C) 2013 Elsevier Ltd. All rights reserved.

Correlation between thermodynamic anomalies and pathways of ice nucleation in supercooled water

The well-known classical nucleation theory (CNT) for the free energy barrier towards formation of a nucleus of critical size of the new stable phase within the parent metastable phase fails to take into account the influence of other metastable phases having density/order intermediate between the parent metastable phase and the final stable phase. This lacuna can be more serious than capillary approximation or spherical shape assumption made in CNT. This issue is particularly significant in ice nucleation because liquid water shows rich phase diagram consisting of two (high and low density) liquid phases in supercooled state. The explanations of thermodynamic and dynamic anomalies of supercooled water often invoke the possible influence of a liquid-liquid transition between two metastable liquid phases. To investigate both the role of thermodynamic anomalies and presence of distinct metastable liquid phases in supercooled water on ice nucleation, we employ density functional theoretical approach to find nucleation free energy barrier in different regions of phase diagram. The theory makes a number of striking predictions, such as a dramatic lowering of nucleation barrier due to presence of a metastable intermediate phase and crossover in the dependence of free energy barrier on temperature near liquid-liquid critical point. These predictions can be tested by computer simulations as well as by controlled experiments. (C) 2014 AIP Publishing LLC.

Correlation between Optical Properties and Nanomorphology of Fluoranthene-Based Conjugated Copolymer

Nanoparticles of conjugated polymers are receiving attention due to their interesting optical properties. Here we report nanoparticles of fluoranthene-based conjugated copolymer prepared by the Suzuki coupling reaction. The copolymer forms nanoparticles by the spontaneous self-assembly after evaporation of organic solvent. The mean diameter of the nanoparticles can be manipulated by varying solvent composition. We investigated the parameters that govern the nanostructured morphology of polymer by systematic variation of good and poor solvent. The UV vis and time-resolved fluorescence spectroscopy measurement reveal the use of poor solvent in the organization of nanostructures. Furthermore, transmission electron microscopy highlights the importance of rigidity of the polymer backbone in morphological development.

Formation of annular austenitic ring between outer ferrite layer and solid globule in a semi-solid processed SS 304L

The microstructure of an austenitic SS 304L rapidly quenched from its semi-solid state shows a unique annular austenitic ring in between the core of each globule and its ferritic outer layer. On the basis of experimental results and microstructural analysis, it is proposed that the ring is formed as a result of preferential austenitic phase nucleation in a small quantity of liquid entrapped between adjacent solid globules during rapid quenching, in spite of the fact that ferrite is the thermodynamically stable phase for the alloy. (C) 2014 Elsevier B.V. All rights reserved.

Structure, dynamics and thermodynamics of single-file water under confinement: effects of polarizability of water molecules

Various structural, dynamic and thermodynamic properties of water molecules confined in single-wall carbon nanotubes (CNTs) are investigated using both polarizable and non-polarizable water models. The inclusion of polarizability quantitatively affects the nature of hydrogen bonding, which governs many properties of confined water molecules. Polarizable water leads to tighter hydrogen bonding and makes the distance between neighboring water molecules shorter than that for non-polarizable water. Stronger hydrogen bonding also decreases the rotational entropy and makes the diffusion constant smaller than in TIP3P and TIP3PM water models. The reorientational dynamics of the water molecules is governed by a jump mechanism, the barrier for the jump being highest for the polarizable water model. Our results highlight the role of polarizability in governing the dynamics of confined water and demonstrate that the inclusion of polarizability is necessary to obtain agreement with the results of ab initio simulations for the distributions of waiting and jump times. The SPC/E water model is found to predict various water properties in close agreement with the results of polarizable water models with much lower computational costs.

A trade-off between maxima in efficiency and specific work output of super- and trans-critical CO2 Brayton cycles

Several operational aspects for thermal power plants in general are non-intuitive and involve simultaneous optimization of a number of operational parameters. In the case of solar operated power plants, it is even more difficult due to varying heat source temperatures induced by variability in insolation levels. This paper introduces a quantitative methodology for load regulation of a CO2 based Brayton cycle power plant using the `thermal efficiency and specific work output' coordinate system. The analysis shows that a transcritical CO2 cycle offers more flexibility under part load performance than the supercritical cycle in case of non-solar power plants. However, for concentrated solar power, where efficiency is important, supercritical CO2 cycle fares better than transcritical CO2 cycle. A number of empirical equations relating heat source temperature, high side pressure with efficiency and specific work output are proposed which could assist in generating control algorithms. (C) 2015 Elsevier B.V. All rights reserved.

Correlation between band propagation property and the nature of serrations in the Portevin-Le Chatelier effect

We investigate the correlation between the band propagation property and the nature and amplitude of serrations in the Portevin-Le Chatelier effect within the framework of the Ananthakrishna model. Several significant results emerge. First, we find that spatial and temporal correlations continuously increase with strain rate from type C to type A bands. Consequently, the nature of the bands also changes continuously from type C to A bands, and so do the changes in the associated serrations. Second, even the smallest extent of propagation induces small amplitude serrations. The spatial extent of band propagation is directly correlated with the duration of small amplitude serrations, a result that is consistent with recent experiments. This correspondence allows one to estimate the spatial extent of band propagation by just measuring the temporal stretch of small amplitude serrations. Therefore, this should be of practical value when only stress versus strain is recorded. Third, the average stress drop magnitude of the small amplitude serrations induced by the propagating bands remains small and nearly constant with strain rate. As a consequence, the fully propagating type A bands are in a state of criticality. We rationalize the increasing levels of spatial and temporal correlations found with increasing strain rates. Lastly, the model also predicts several band morphologies seen in experiments including the Luders-like propagating band. (C) 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Correlation Between Decay Rate and Amplitude of Solar Cycles as Revealed from Observations and Dynamo Theory

Using different proxies of solar activity, we have studied the following features of the solar cycle: i) The linear correlation between the amplitude of cycle and its decay rate, ii) the linear correlation between the amplitude of cycle and the decay rate of cycle , and iii) the anti-correlation between the amplitude of cycle and the period of cycle . Features ii) and iii) are very useful because they provide precursors for future cycles. We have reproduced these features using a flux-transport dynamo model with stochastic fluctuations in the Babcock-Leighton effect and in the meridional circulation. Only when we introduce fluctuations in meridional circulation, are we able to reproduce different observed features of the solar cycle. We discuss the possible reasons for these correlations.

Structure and Dynamics of Octamethylcyclotetrasiloxane Confined between Mica Surfaces

Using a molecular model for octamethylcydotetrasiloxane (OMCTS), molecular dynamics simulations are carried out to probe the phase state of OMCTS confined between two mica surfaces in equilibrium With a reservoir. Molecular dynamics simulations are carried out for elevations ranging from 5 to 35 K above the melting point for the OMCTS model used in this study. The Helmholtz free energy is, computed for a specific confinement using the :two-phase thermodynamic (2PT) method. Analysis of the in-plane pair correlation functions did not reveal signatures of freezing even under an extreme confinement of two layers. OMCTS is found to orient with a wide distribution of orientations with respect to the mica surface, with a distinct preference for the surface parallel configuration in the contact layers. The self-intermediate scattering function is found to decay with increasing relaxation times as the surface separation is decreased, and the two-step relaxation in the scattering function, a signature of glassy dynamics, distinctly evolves as the temperature is lowered. However, even at 5 K above the melting point, we did not observe a freezing transition and the self-intermediate scattering functions relax within 200 ps for the seven-layered confined system. The self diffusivity and relaxation times obtained from the Kohlrausch-Williams-Watts stretched exponential fits to the late alpha-relaxation exhibit power law scalings with the packing fraction as predicted by mode coupling theory. A distinct discontinuity in the Helmholtz free energy, potential energy, and a sharp change in the local bond order parameter, Q(4), was observed at 230 K for a five-layered system upon cooling, indicative of a first-order transition. A freezing point depression of about 30 K was observed for this five-layered confined system, and at the lower temperatures, contact layers were found to be disordered with long-range order present only in the inner layers. These dynamical signatures indicate that confined OMCTS undergoes a slowdown akin to a fluid approaching a glass transition upon increasing confinement, and freezing under confinement would require substantial subcooling below the bulk melting point of OMCTS.