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.

Seismic characterization and dynamic site response of a municipal solid waste landfill in Bangalore, India

Seismic design of landfills requires an understanding of the dynamic properties of municipal solid waste (MSW) and the dynamic site response of landfill waste during seismic events. The dynamic response of the Mavallipura landfill situated in Bangalore, India, is investigated using field measurements, laboratory studies and recorded ground motions from the intraplate region. The dynamic shear modulus values for the MSW were established on the basis of field measurements of shear wave velocities. Cyclic triaxial testing was performed on reconstituted MSW samples and the shear modulus reduction and damping characteristics of MSW were studied. Ten ground motions were selected based on regional seismicity and site response parameters have been obtained considering one-dimensional non-linear analysis in the DEEPSOIL program. The surface spectral response varied from 0.6 to 2g and persisted only for a period of 1s for most of the ground motions. The maximum peak ground acceleration (PGA) obtained was 0.5g and the minimum and maximum amplifications are 1.35 and 4.05. Amplification of the base acceleration was observed at the top surface of the landfill underlined by a composite soil layer and bedrock for all ground motions. Dynamic seismic properties with amplification and site response parameters for MSW landfill in Bangalore, India, are presented in this paper. This study shows that MSW has less shear stiffness and more amplification due to loose filling and damping, which need to be accounted for seismic design of MSW landfills in India.

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.

Laboratory determination of coefficient of consolidation from pore water pressure measurement

In the recent past, many studies have been carried out on the determination of coefficient of consolidation (c(v)) from the time (t)-deformation (d) data obtained from conventional consolidation tests. Several researchers have also proposed different curve fitting procedures for determining cv from the t-d data. It is anticipated that the cv values obtained from the t-d data may be influenced by initial and secondary compressions. Nevertheless, the pore water pressure data measured during the consolidation process will be independent of initial and secondary compressions. In this study, the conventional Asaoka (1978) method is extended to evaluate cv and end-of-primary (EOP) consolidation from the pore water pressure data measured from laboratory experiments. Laboratory experiments were carried out on the modified one-dimensional consolidation apparatus on different remoulded clay samples measuring pore water pressure during the consolidation process. The cv and EOP computed from the proposed approach have been compared with the results of the t-d data and found to be in good agreement.

Full current statistics for a disordered open exclusion process

We consider the nonabelian sandpile model defined on directed trees by Ayyer et al. (2015 Commun. Math. Phys. 335 1065). and restrict it to the special case of a one-dimensional lattice of n sites which has open boundaries and disordered hopping rates. We focus on the joint distribution of the integrated currents across each bond simultaneously, and calculate its cumulant generating function exactly. Surprisingly, the process conditioned on seeing specified currents across each bond turns out to be a renormalised version of the same process. We also remark on a duality property of the large deviation function. Lastly, all eigenvalues and both Perron eigenvectors of the tilted generator are determined.

Primary and rechargeable zinc-air batteries using ceramic and highly stable TiCN as an oxygen reduction reaction electrocatalyst

Primary and secondary zinc-air batteries based on ceramic, stable, one dimensional titanium carbonitride (TiCN) nanostructures are reported. The optimized titanium carbonitride composition by density functional theory reveals their good activity towards the oxygen reduction reaction (ORR). Electrochemical measurements show their superior performance for the ORR in alkaline media coupled with favourable kinetics. The nanostructured TiCN lends itself amenable to be used as an air cathode material in primary and rechargeable zinc-air batteries. The battery performance and cyclability are found to be good. Further, we have demonstrated a gel-based electrolyte for rechargeable zinc-air batteries based on a TiCN cathode under ambient, atmospheric conditions without any oxygen supply from a cylinder. The present cell can work at current densities of 10-20 mA cm(2) (app. 10 000 mA g(-1) of TiCN) for several hours (63 h in the case of 10 mA cm(-2)) with a charge retention of 98%. The low cost, noble metal-free, mechanically stable and corrosion resistant TiCN is a very good alternative to Pt for metal-air battery chemistry.

Interpenetrated and Catenated Zinc Thiosulfates Frameworks with dia and qtz Nets: Synthesis, Structure, and Properties

Reactions between Zn(NO3)(2)center dot 6H(2)O, Na2S2O3, 4,4'-bipyridine (bpy), 1,2-bis(4-pyridyl)ethene (bpe), 1,2-bis (4-pyridyl) ethane (bpa), and 1,3-bis(4-pyridyl)propane (bpp) under solvothermal conditions resulted in four new zinc thiosulfate hybrid compounds. Compound I has four-membered zinc thiosulfate rings connected by the ligand, 1,3-bis(4-pyridyl)propane (bpp) forming a two-dimensional structure. Compounds II-IV have one-dimensional zinc thiosulfate chains connected by the ligands, bpy (II), bpe (III), and bpa (IV) giving rise to three-dimensional structures. All the four-structures exhibit 3-fold interpenetration. Proton conductivity studies indicate reasonable proton mobility at 34 degrees C and at 98% relative humidity. The compounds also exhibit Lewis acid character and good photocatalytic activity for the decomposition of cationic dyes.

Traveling waves in trimer granular lattice I: Bifurcation structure of traveling waves in the unit-cell model

Present paper is the first one in the series devoted to the dynamics of traveling waves emerging in the uncompressed, tri-atomic granular crystals. This work is primarily concerned with the dynamics of one-dimensional periodic granular trimer (tri-atomic) chains in the state of acoustic vacuum. Each unit cell consists of three spherical particles of different masses subject to periodic boundary conditions. Hertzian interaction law governs the mutual interaction of these particles. Under the assumption of zero pre-compression, this interaction is modeled as purely nonlinear, which means the absence of linear force component. The dynamics of such chains is governed by the two system parameters that scale the mass ratios between the particles of the unit cell. Such a system supports two different classes of periodic solutions namely the traveling and standing waves. The primary objective of the present study is the numerical analysis of the bifurcation structure of these solutions with emphasis on the dynamics of traveling waves. In fact, understanding of the bifurcation structure of the traveling wave solutions emerging in the unit-cell granular trimer is rather important and can shed light on the more complex nonlinear wave phenomena emerging in semi-infinite trimer chains. (c) 2016 Elsevier B.V. All rights reserved.

The Liquefaction and Displacement of Highly Saturated Sand under Water Pressure Oscillation

In order to investigate the characteristics of water wave induced liquefaction in highly saturated sand in vertical direction, a one-dimensional model of highly saturated sand to water pressure oscillation is presented based oil the two-phase continuous media theory. The development of the effective stresses and the liquefaction thickness are analyzed. It is shown that water pressure oscillating loading affects liquefaction severely and the developing rate of liquefaction increases with the decreasing of the sand strength or the increasing of the loading strength. It is shown also that there is obvious phase lag in the sand Column. If the sand permeability is non-uniform, the pore pressure and the strain rise sharply at which the smallest permeability occurs. This solution may explain Why the fracture occurs in the sand column in some conditions.

Kramers Escape Rate in Nonlinear Diffusive Media

In this paper, we study nonlinear Kramers problem by investigating overdamped systems ruled by the one-dimensional nonlinear Fokker-Planck equation. We obtain an analytic expression for the Kramers escape rate under quasistationary conditions by employing