Evolution of Jahn-Teller distortion, transport and dielectric properties with doping in perovskite NdFe1-xMnxO3 (0 <= x <= 1) compounds

We have carried out dielectric and transport measurements in NdFe1-xMnxO3 (0 <= x <= 1) series of compounds and studied the variation of activation energy due to a change in Mn concentration. Despite similar ionic radii in Mn3+ and Fe3+, large variation is observed in the lattice parameters and a crossover from dynamic to static Jahn-Teller distortion is discernible. The Fe/Mn-O-Fe/Mn bond angle on the ab plane shows an anomalous change with doping. With an increase in the Mn content, the bond angle decreases until x = 0.6; beyond this, it starts rising until x = 0.8 and again falls after that. A similar trend is observed in activation energies estimated from both transport and dielectric relaxation by assuming a small polaron hopping (SPH) model. Impedance spectroscopy measurements delineate grain and grain boundary contributions separately both of which follow the SPH model. Frequency variation of the dielectric constant is in agreement with the modified Debye law from which relaxation dispersion is estimated.

How to be a dioecious fig: Chemical mimicry between sexes matters only when both sexes flower synchronously

In nursery pollination mutualisms, which are usually obligate interactions, olfactory attraction of pollinators by floral volatile organic compounds (VOCs) is the main step in guaranteeing partner encounter. However, mechanisms ensuring the evolutionary stability of dioecious fig-pollinator mutualisms, in which female fig trees engage in pollination by deceit resulting in zero reproductive success of pollinators that visit them, are poorly understood. In dioecious figs, individuals of each sex should be selected to produce odours that their pollinating wasps cannot distinguish, especially since pollinators have usually only one choice of a nursery during their lifetime. To test the hypothesis of intersexual chemical mimicry, VOCs emitted by pollen-receptive figs of seven dioecious species were compared using headspace collection and gas chromatography-mass spectrometry analysis. First, fig-flower scents varied significantly among species, allowing host-species recognition. Second, in species in which male and female figs are synchronous, intersexual VOC variation was not significant. However, in species where figs of both sexes flower asynchronously, intersexual variation of VOCs was detectable. Finally, with one exception, there was no sexual dimorphism in scent quantity. We show that there are two ways to use scent to be a dioecious fig based on differences in flowering synchrony between the sexes.

Nanomechanical Mapping, Hierarchical Polymer Dynamics, and Miscibility in the Presence of Chain-End Grafted Nanoparticles

To improve the spatial distribution of nano particles in a polymeric host and to enhance the interfacial interaction with the host, the use of chain-end grafted nanoparticle has gained popularity in the field of polymeric nanocomposites. Besides changing the material properties of the host, these grafted nanoparticles strongly alter the dynamics of the polymer chain at both local and cooperative length scales (relaxations) by manipulating the enthalpic and entropic interactions. It is difficult to map the distribution of these chain-end grafted nanoparticles in the blend by conventional techniques, and herein, we attempted to characterize it by unique technique(s) like peak force quantitative nanomechanical mapping (PFQNM) through AFM (atomic force microscopy) imaging and dielectric relaxation spectroscopy (DRS). Such techniques, besides shedding light on the spatial distribution of the nanoparticles, also give critical information on the changing elasticity at smaller length scales and hierarchical polymer chain dynamics in the vicinity of the nanoparticles. The effect of one-dimensional rodlike multiwall carbon nanotubes (MWNTs), with the characteristic dimension of the order of the radius of gyration of the polymeric chain, on the phase miscibility and chain dynamics in a classical LCST mixture of polystyrene/ poly(vinyl methyl ether) (PS/PVME) was examined in detail using the above techniques. In order to tune the localization of the nanotubes, different molecular weights of PS (13, 31, and 46 kDa), synthesized using RAFT (reversible addition fragmentation chain transfer) polymerization, was grafted onto MWNTs in situ. The thermodynamic miscibility in the blends was assessed by low-amplitude isochronal temperature sweeps, the spatial distribution of MWNTs in the blends was evaluated by PFQNM, and the hierarchical polymer chain dynamics was studied by DRS. It was observed that the miscibility, concentration fluctuation, and cooperative relaxations of the PS/PVME blends are strongly governed by the spatial distribution of MWNTs in the blends. These findings should help guide theories and simulations of hierarchical chain dynamics in LCST mixtures containing rodlike nanoparticles.

Gradient echo single scan inversion recovery: application to proton and fluorine relaxation studies

Single scan longitudinal relaxation measurement experiments enable rapid estimation of the spin-lattice relaxation time (T-1) as the time series of spin relaxation is encoded spatially in the sample at different slices resulting in an order of magnitude saving in time. We consider here a single scan inversion recovery pulse sequence that incorporates a gradient echo sequence. The proposed pulse sequence provides spectra with significantly enhanced signal to noise ratio leading to an accurate estimation of T-1 values. The method is applicable for measuring a range of T-1 values, thus indicating the possibility of routine use of the method for several systems. A comparative study of different single scan methods currently available is presented, and the advantage of the proposed sequence is highlighted. The possibility of the use of the method for the study of cross-correlation effects for the case of fluorine in a single shot is also demonstrated. Copyright (C) 2015 John Wiley & Sons, Ltd.

Short-Time Beta Relaxation in Glass-Forming Liquids Is Cooperative in Nature

Temporal relaxation of density fluctuations in supercooled liquids near the glass transition occurs in multiple steps. Using molecular dynamics simulations for three model glass-forming liquids, we show that the short-time beta relaxation is cooperative in nature. Using finite-size scaling analysis, we extract a growing length scale associated with beta relaxation from the observed dependence of the beta relaxation time on the system size. We find, in qualitative agreement with the prediction of the inhomogeneous mode coupling theory, that the temperature dependence of this length scale is the same as that of the length scale that describes the spatial heterogeneity of local dynamics in the long-time alpha-relaxation regime.

Electrochemical, gravimetric and quantum chemical analysis of mild steel corrosion inhibition by colchicine in 1 M HCl medium

The inhibition effect of colchicine (CC) on mild steel (MS) corrosion in 1 M HCl solution has been investigated by electrochemical techniques such as electrochemical impedance spectroscopy, potentiodynamic polarization, chronoamperometry and also by the gravimetric method. Polarization studies showed that CC acts as mixed type corrosion inhibitor. The inhibitor adsorption process in the MS/CC/HCl system was studied at different temperatures (303-333 K). The adsorption of CC on MS surface is an exothermic process and obeys the Langmuir adsorption isotherm. Based on potential of zero charge values and quantum chemical parameters, the mechanism of adsorption has been proposed.

Comments on ``Influence of chemical reaction and viscous dissipation on MHD mixed convection flow'' by K. Das JMST 28 (5) (2014) 1881 similar to 1885] and ``Cu-water nanofluid flow and heat transfer over a shrinking sheet'' by K. Das JMST 28 (12) 5089 similar to 5094]

In this letter, we submit our comment on the following recently published papers by Kalidas Das: (1) ``Influence of chemical reaction and viscous dissipation on MHD mixed convection flow,'' Journal of Mechanical Science and Technology 28 (5) (2014) 1881-1885; and (2) ``Cu-water nanofluid flow and heat transfer over a shrinking sheet,'' Journal of Mechanical Science and Technology 28 (12) (2014) 5089-5094. The authors attempt to present the similarity solutions in both papers. We comment that the similarity transformations considered in Refs. 1, 2] are incorrect. Thus, the results presented by Kalidas Das lead to invalid conclusions.

Electrical conductivity and dielectric relaxation studies on microwave synthesized Na2SO4 center dot NaPO3 center dot MoO3 glasses

Electrical conductivity and dielectric relaxation studies on SO4 (2-) doped modified molybdo-phosphate glasses have been carried out over a wide range of composition, temperature and frequency. The d.c. conductivities which have been measured by both digital electrometer (four-probe method) and impedance analyser are comparable. The relaxation phenomenon has been rationalized using electrical modulus formalism. The use of modulus representation in dielectric relaxation studies has inherent advantages viz., experimental errors arising from the contributions of electrode-electrolyte interface capacitances are minimized. The relaxation observed in the present study is non-Debye type. The activation energies for relaxation were determined using imaginary parts of electrical modulus peaks which were close to those of the d.c. conductivity implying the involvement of similar energy barriers in both the processes. The enhanced conductivity in these glasses can be attributed to the migration of Na+, in expanded structures due to the introduction of SO4 (2-) ions.

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.