Synthesis and Microstructure of Laser Surface Alloyed Al–Sn–Si Layer on Commercial Aluminum Substrate

A new type of bearing alloy containing ultrafine sized tin and silicon dispersions in aluminum was designed using laser surface alloying and laser remelting techniques. The microstructures of these non-equilibrium processed alloys were studied in detail using scanning and transmission electron microscopy. The microstructures revealed three distinct morphologies of tin particles namely elongated particles co-existing with silicon, globular particles, and very fine particles. Our detailed analyses using cellular growth theories showed that the formation of these globular tin particles was due to the pinching off of the tin rich liquid in the inter-cellular space by the growth of aluminum secondary dendrite arms. Evidence of fine recrystallized aluminum grains at the top layer due to constrained solidification was shown. Thermal analyses suggested that melting of the spherical shaped tin particles was controlled by the binary aluminum-tin eutectic reaction, whereas non-spherical tin particles melted via the tin-silicon eutectic reaction.

Microscopic modelling of adsorption and the generalised surface layer hypothesis

Two- and three-state models for the adsorption of organic compounds at the electrode/electrolyte interface are proposed. Different size requirements, if any, for the neutral molecule and the adsorbing solvent are also considered. It is shown how the empirical, generalised surface layer (GSL) relationship (between the potential difference and the electrode charge) formulated by Damaskin et al. can be understood at the molecular level.

A Multi-layer Perceptron based Non-linear Mixture Model to estimate class abundance from mixed pixels

Sub-pixel classification is essential for the successful description of many land cover (LC) features with spatial resolution less than the size of the image pixels. A commonly used approach for sub-pixel classification is linear mixture models (LMM). Even though, LMM have shown acceptable results, pragmatically, linear mixtures do not exist. A non-linear mixture model, therefore, may better describe the resultant mixture spectra for endmember (pure pixel) distribution. In this paper, we propose a new methodology for inferring LC fractions by a process called automatic linear-nonlinear mixture model (AL-NLMM). AL-NLMM is a three step process where the endmembers are first derived from an automated algorithm. These endmembers are used by the LMM in the second step that provides abundance estimation in a linear fashion. Finally, the abundance values along with the training samples representing the actual proportions are fed to multi-layer perceptron (MLP) architecture as input to train the neurons which further refines the abundance estimates to account for the non-linear nature of the mixing classes of interest. AL-NLMM is validated on computer simulated hyperspectral data of 200 bands. Validation of the output showed overall RMSE of 0.0089±0.0022 with LMM and 0.0030±0.0001 with the MLP based AL-NLMM, when compared to actual class proportions indicating that individual class abundances obtained from AL-NLMM are very close to the real observations.

Enhanced Survival of Probiotic Lactobacillus acidophilus by Encapsulation with Nanostructured Polyelectrolyte Layers through Layer-by-Layer Approach

The encapsulation of probiotic Lactobacillus acidophilus through layer-by-layer self-assembly of polyelectrolytes (PE) chitosan (CHI) and carboxymethyl cellulose (CMC) has been investigated,to enhance its survival m adverse conditions encountered in the GI tract The survival of encapsulated cells in simulated gastric (SGF) and intestinal fluids (SIF) is significant when compared to nonencapsulated cells On sequential exposure to SGF and SIF fox 120 nun, almost complete death of free cells is observed However, for cells coated with three nanolayers of PEs (CHI/CMC/CHI) about 33 log % of the cells (6 log cfu/500 mg) survived under the same conditions The enhanced survival rate of encapsulated L acidophilus can be attributed to the impermeability of polyelectrolyte nanolayers to large enzyme molecules like pepsin, and pancreatin that cause proteolysis and to the stability of the polyelectrolyte nanolayers in gastric and intestinal pH The PE coating also serves to reduce viability losses during freezing and freeze- drying About 73 and 92 log % of uncoated and coated cells survived after freeze:drying, and the losses occurring between freezing and freeze-drying were found to be lower for coated cells

Nonlinear dielectric behavior in three-component ferroelectric superlattices

Three-component ferroelectric superlattices consisting of alternating layers of SrTiO3, BaTiO3, and CaTiO3 (SBC) with variable interlayer thickness were fabricated on Pt(111)/TiO2/SiO2/Si (100) substrates by pulsed laser deposition. The presence of satellite reflections in x-ray-diffraction analysis and a periodic concentration of Sr, Ba, and Ca throughout the film in depth profile of secondary ion mass spectrometry analysis confirm the fabrication of superlattice structures. The Pr (remnant polarization) and Ps (saturation polarization) of SBC superlattice with 16.4-nm individual layer thickness (SBC16.4) were found to be around 4.96 and 34 μC/cm2, respectively. The dependence of polarization on individual layer thickness and lattice strain were studied in order to investigate the size dependence of the dielectric properties. The dielectric constant of these superlattices was found to be much higher than the individual component layers present in the superlattice configuration. The relatively higher tunability ( ∼ 55%) obtained around 300 K indicates that the superlattice is a potential electrically tunable material for microwave applications at room temperature. The enhanced dielectric properties were thus discussed in terms of the interfacial strain driven polar region due to high lattice mismatch and electrostatic coupling due to polarization mismatch between individual layers.

Free Energy Barriers for Escape of Water Molecules from Protein Hydration Layer

Free energy barriers separating interfacial water molecules from the hydration layer at the surface of a protein to the bulk are obtained by using the umbrella sampling method of free energy calculation. We consider hydration layer of chicken villin head piece (HP-36) which has been studied extensively by molecular dynamics simulations. The free energy calculations reveal a strong sensitivity to the secondary structure. In particular, we find a region near the junction of first and second helix that contains a cluster of water molecules which are slow in motion, characterized by long residence times (of the order of 100 ps or more) and separated by a large free energy barrier from the bulk water. However, these ``slow'' water molecules constitute only about 5-10% of the total number of hydration layer water molecules. Nevertheless, they play an important role in stabilizing the protein conformation. Water molecules near the third helix (which is the important helix for biological function) are enthalpically least stable and exhibit the fastest dynamics. Interestingly, barrier height distributions of interfacial water are quite broad for water surrounding all the three helices (and the three coils), with the smallest barriers found for those near the helix-3. For the quasi-bound water molecules near the first and second helices, we use well-known Kramers' theory to estimate the residence time from the free energy surface, by estimating the friction along the reaction coordinate from the diffusion coefficient by using Einstein relation. The agreement found is satisfactory. We discuss the possible biological function of these slow, quasi-bound (but transient) water molecules on the surface.

Simultaneous refolding and purification of recombinant proteins by macro-(affinity ligand) facilitated three-phase partitioning

A strategy called macro-(affinity ligand) facilitated three-phase partitioning (MLFTPP) is described for refolding of a diverse set of recombinant proteins starting from the solubilized inclusion bodies. It essentially consists of: (i) binding of the protein with a suitable smart polymer and (ii) precipitating the polymer-protein complex as an interfacial layer by mixing in a suitable amount of ammonium sulfate and t-butanol. Smart polymers are stimuli-responsive polymers that become insoluble on the application of a suitable stimulus (e.g., a change in the temperature, pH, or concentration of a chemical species such as Ca 2+ or K +). The MLFTPP process required approximately 10min, and the refolded proteins were found to be homogeneous on sodium dodecyl sulfate-polyacrylamide gel electrophoresis. The folded proteins were characterized by fluorescence emission spectroscopy, circular dichroism spectroscopy, biological activity, melting temperature, and surface hydrophobicity measurements by 8-anilino-1-naphthalenesulfonate fluorescence. Two refolded antibody fragments were also characterized by measuring K D by Biacore by using immobilized HIV-1 gp120. The data demonstrate that MLFTPP is a rapid and convenient procedure for refolding a variety of proteins from inclusion bodies at high concentration. Although establishing the generic nature of the approach would require wider trials by different groups, its success with the diverse kinds of proteins tried so far appears to be promising.

A physics-based flexural phonon-dependent thermal conductivity model for single layer graphene

In this paper, we address a physics-based closed-form analytical model of flexural phonon-dependent diffusive thermal conductivity (kappa) of suspended rectangular single layer graphene sheet. A quadratic dependence of the out-of-plane phonon frequency, generally called flexural phonons, on the phonon wave vector has been taken into account to analyze the behavior of kappa at lower temperatures. Such a dependence has further been used for the determination of second-order three-phonon Umklapp and isotopic scatterings. We find that these behaviors in our model are best explained through the upper limit of Debye cut-off frequency in the second-order three-phonon Umklapp scattering of the long phonon waves that actually remove the thermal conductivity singularity by contributing a constant scattering rate at low frequencies and note that the out-of-plane Gruneisen parameter for these modes need not be too high. Using this, we clearly demonstrate that. follows a T-1.5 and T-2 law at lower and higher temperatures in the absence of isotopes, respectively. However in their presence, the behavior of kappa sharply deviates from the T-2 law at higher temperatures. The present geometry-dependent model of kappa is found to possess an excellent match with various experimental data over a wide range of temperatures which can be put forward for efficient electro-thermal analyses of encased/supported graphene.

Model-free simulations for compressible mixing layer

Confined supersonic mixing layer is explored through model-free simulations. Both two- and three-dimensional spatio-temporal simulations were carried out employing higher order finite difference scheme as well as finite volume scheme based on open source software (OpenFOAM) to understand the effect of three-dimensionality on the development of mixing layer. It is observed that although the instantaneous structures exhibit three-dimensional features, the average pressure and velocities are predominantly two-dimensional. The computed wall pressures match well with experimental results fairly well, although three-dimensional simulation underpredicts the wall pressure in the downstream direction. The self-similarity of the velocity profiles is obtained within the duct length for all the simulations. Although the mixing layer thicknesses differ among different simulations, their growth rate is nearly the same. Significant differences are observed for species and temperature distribution between two- and three-dimensional calculations, and two-dimensional calculations do not match the experimental observation of smooth variations in species mass fraction profiles as reported in literature. Reynolds stress distribution for three-dimensional calculations show profiles with less peak values compared to two-dimensional calculations; while normal stress anisotropy is higher for three-dimensional case.

Structural characterization and molecular order of rodlike mesogens with three- and four-ring core by XRD and C-13 NMR spectroscopy

Structural characterizations using XRD and C-13 NMR spectroscopy of two rodlike mesogens consisting of (i) three phenyl ring core with a polar cyano terminal and (ii) four phenyl ring core with flexible dodecyl terminal chain are presented. The three-ring-core mesogen with cyano terminal exhibits enantiotropic smectic A phase while the four-ring mesogen reveals polymesomorphism and shows enantiotropic nematic, smectic C, and tilted hexatic phases. The molecular organization in the three-ring mesogen is found to be partial bilayer smectic Ad type, and the interdigitation of the molecules in the neighboring layers is attributed to the presence of the polar terminal group. For the four-ring mesogen, the XRD results confirm the existence of the smectic C and the tilted hexatic mesophases. A thermal variation of the layer spacing across the smectic C phase followed by a discrete jump at the transition to the tilted hexatic phase is also observed. The tilt angles have been estimated to be about 45 degrees in the smectic C phase and about 40 degrees in tilted hexatic phase. C-13 NMR results indicate that in the mesophase the molecules are aligned parallel to the magnetic field. From the C-13-H-1 dipolar couplings determined from the 2D experiments, the overall order parameter for the three-ring mesogen in its smectic A phase has been estimated to be 0.72 while values ranging from 0.88 to 0.44 have been obtained for the four-ring mesogen as it passes from the tilted hexatic to the nematic phase. The orientations of the different rings of the core unit with respect to each other and also with respect to the long axis of the molecule have also been obtained.

Wireless network-coded three-way relaying using Latin Cubes

The design of modulation schemes for the physical layer network-coded three-way wireless relaying scenario is considered. The protocol employs two phases: Multiple Access (MA) phase and Broadcast (BC) phase with each phase utilizing one channel use. For the two-way relaying scenario, it was observed by Koike-Akino et al. [4], that adaptively changing the network coding map used at the relay according to the channel conditions greatly reduces the impact of multiple access interference which occurs at the relay during the MA phase and all these network coding maps should satisfy a requirement called exclusive law. This paper does the equivalent for the three-way relaying scenario. We show that when the three users transmit points from the same 4-PSK constellation, every such network coding map that satisfies the exclusive law can be represented by a Latin Cube of Second Order. The network code map used by the relay for the BC phase is explicitly obtained and is aimed at reducing the effect of interference at the MA stage.

Excellent Performance of Few-Layer Borocarbonitrides as Anode Materials in Lithium-Ion Batteries

Borocarbonitrides (BxCyNz) with a graphene-like structure exhibit a remarkable high lithium cyclability and current rate capability. The electrochemical performance of the BxCyNz materials, synthesized by using a simple solid-state synthesis route based on urea, was strongly dependent on the composition and surface area. Among the three compositions studied, the carbon-rich compound B0.15C0.73N0.12 with the highest surface area showed an exceptional stability (over 100cycles) and rate capability over widely varying current density values (0.05-1Ag(-1)). B0.15C0.73N0.12 has a very high specific capacity of 710mAhg(-1) at 0.05Ag(-1). With the inclusion of a suitable additive in the electrolyte, the specific capacity improved drastically, recording an impressive value of nearly 900mAhg(-1) at 0.05Ag(-1). It is believed that the solid-electrolyte interphase (SEI) layer at the interface of BxCyNz and electrolyte also plays a crucial role in the performance of the BxCyNz .

Free turbulent shear layer in a point vortex gas as a problem in nonequilibrium statistical mechanics

This paper attempts to unravel any relations that may exist between turbulent shear flows and statistical mechanics through a detailed numerical investigation in the simplest case where both can be well defined. The flow considered for the purpose is the two-dimensional (2D) temporal free shear layer with a velocity difference Delta U across it, statistically homogeneous in the streamwise direction (x) and evolving from a plane vortex sheet in the direction normal to it (y) in a periodic-in-x domain L x +/-infinity. Extensive computer simulations of the flow are carried out through appropriate initial-value problems for a ``vortex gas'' comprising N point vortices of the same strength (gamma = L Delta U/N) and sign. Such a vortex gas is known to provide weak solutions of the Euler equation. More than ten different initial-condition classes are investigated using simulations involving up to 32 000 vortices, with ensemble averages evaluated over up to 10(3) realizations and integration over 10(4)L/Delta U. The temporal evolution of such a system is found to exhibit three distinct regimes. In Regime I the evolution is strongly influenced by the initial condition, sometimes lasting a significant fraction of L/Delta U. Regime III is a long-time domain-dependent evolution towards a statistically stationary state, via ``violent'' and ``slow'' relaxations P.-H. Chavanis, Physica A 391, 3657 (2012)], over flow time scales of order 10(2) and 10(4)L/Delta U, respectively (for N = 400). The final state involves a single structure that stochastically samples the domain, possibly constituting a ``relative equilibrium.'' The vortex distribution within the structure follows a nonisotropic truncated form of the Lundgren-Pointin (L-P) equilibrium distribution (with negatively high temperatures; L-P parameter lambda close to -1). The central finding is that, in the intermediate Regime II, the spreading rate of the layer is universal over the wide range of cases considered here. The value (in terms of momentum thickness) is 0.0166 +/- 0.0002 times Delta U. Regime II, extensively studied in the turbulent shear flow literature as a self-similar ``equilibrium'' state, is, however, a part of the rapid nonequilibrium evolution of the vortex-gas system, which we term ``explosive'' as it lasts less than one L/Delta U. Regime II also exhibits significant values of N-independent two-vortex correlations, indicating that current kinetic theories that neglect correlations or consider them as O(1/N) cannot describe this regime. The evolution of the layer thickness in present simulations in Regimes I and II agree with the experimental observations of spatially evolving (3D Navier-Stokes) shear layers. Further, the vorticity-stream-function relations in Regime III are close to those computed in 2D Navier-Stokes temporal shear layers J. Sommeria, C. Staquet, and R. Robert, J. Fluid Mech. 233, 661 (1991)]. These findings suggest the dominance of what may be called the Kelvin-Biot-Savart mechanism in determining the growth of the free shear layer through large-scale momentum and vorticity dispersal.

Stepwise Crystallization: Illustrative Examples of the Use of Metalloligands Cu-6(mna)(6)](6-) and (Ag-6(Hmna)(2)(mna)(4)](4-) (H(2)mna=2-Mercapto Nicotinic Acid) in the Formation of Heterometallic Two- and Three-Dimensional Assemblies with brucite, pcu, and sql Topologies

Three new inorganic coordination polymers, {Mn(H2O)(6)]-Mn-2(H2O)(6)](Cu-6(mna)(6)]center dot 6H(2)O}, 1, {Mn-4(OH)(2)(H2O)(10)] (Cu-6(mna)6]center dot 8H(2)O}, 2, and {Mn-2(H2O)(5)]Ag-6(Hmna)(2)(mna)(4)]center dot 20H(2)O}, 3, have been synthesized at room temperature through a sequential crystallization route. In addition, we have also prepared and characterized the molecular precursor Cu-6(Hmna)(6)]. Compounds 1 and 3 have a two-dimensional structure, whereas 2 has a three-dimensional structure. The formation of 2 has been achieved by minor modification in the synthetic composition, suggesting the subtle relationship between the reactant composition and the structure. The hexanudear copper and silver duster cores have Cu center dot center dot center dot Cu and Ag center dot center dot center dot Ag distances close to the sum of the van der Waals radii of Cu1+ and Ag1+, respectively. The connectivity between Cu-6(mna)(6)](6-) cluster units and Mn2+ ions gives rise to a brucite related layer in 1 and a pcu-net in 2. The Ag-6(Hmna)(2)(mna)(4)](4-) cluster in 3, on the other hand, forms a sql-net with Mn2+. Compound 1 exhibits an interesting and reversible hydrochromic behavior, changing from pale yellow to red, on heating at 70 degrees C or treatment under a vacuum. Electron paramagnetic resonance studies indicate no change in the valence states, suggesting the color change could be due to changes in the coordination environment only. The magnetic studies indicate weak antiferromagnetic behavior. Proton conductivity studies indicate moderate proton migrations in 1 and 3. The present study dearly establishes sequential crystallization as an important pathway for the synthesis of heterometallic coordination polymers.

Investigation of the separated region ahead of three-dimensional protuberances on plates and cones in hypersonic flows with laminar boundary layers

Heat transfer rate and pressure measurements were made upstream of surface pro-tuberances on a flat plate and a sharp cone subjected to hypersonic flow in a conventional shock tunnel. Heat flux was measured using platinum thin-film sensors deposited on macor substrate and the pressure measurements were made using fast acting piezoelectric sensors. A distinctive hot spot with highest heat flux was obtained near the foot of the protuberance due to heavy vortex activity in the recirculating region. Schlieren flow visualization was used to capture the shock structures and the separation distance ahead of the protrusions was quantitatively measured for varying protuberance heights. A computational analysis was conducted on the flat plate model using commercial computational fluid dynamics software and the obtained trends of heat flux and pressure were compared with the experimental observation. Experiments were also conducted by physically disturbing the laminar boundary layer to check its effect on the magnitude of the hot spot heat flux. In addition to air, argon was also used as test gas so that the Reynolds number can be varied. (C) 2014 AIP Publishing LLC.