Thermally induced phase separation in P alpha MSAN/PMMA blends in presence of functionalized multiwall carbon nanotubes: Rheology, morphology and electrical conductivity

The focus of this work is the evaluation and analysis of the state of dispersion of functionalized multiwall carbon nanotubes (CNTs), within different morphologies formed, in a model LCST blend (poly[(alpha-methylstyrene)-co-(acrylonitrile)]/poly(methyl-methacryla te), P alpha MSAN/PMMA). Blend compositions that are expected to yield droplet-matrix (85/15 P alpha MSAN/PMMA and 15/85 P alpha MSAN/PMMA, wt/wt) and co-continuous morphologies (60/40 P alpha MSAN/PMMA, wt/wt) upon phase separation have been combined with two types of CNTs; carboxylic acid functionalized (CNTCOOH) and polyethylene modified (CNTPE) up to 2 wt%. Thermally induced phase separation in the blends has been studied in-situ by rheology and dielectric (conductivity) spectroscopy in terms of morphological evolution and CNT percolation. The state of dispersion of CNTs has been evaluated by transmission electron microscopy. The experimental results indicate that the final blend morphology and the surface functionalization of CNT are the main factors that govern percolation. In presence of either of the CNTs, 60/40 P alpha MSAN/PMMA blends yield a droplet-matrix morphology rather than co-continuous and do not show any percolation. On the other hand, both 85/15 P alpha MSAN/PMMA and 15/85 P alpha MSAN/PMMA blends containing CNTPEs show percolation in the rheological and electrical properties. Interestingly, the conductivity spectroscopy measurements demonstrate that the 15/85 P alpha MSAN/PMMA blends with CNTPEs that show insulating properties at room temperature for the miscible blends reveal highly conducting properties in the phase separated blends (melt state) as a result of phase separation. By quenching this morphology, the conductivity can be retained in the blends even in the solid state. (C) 2011 Elsevier Ltd. All rights reserved.

Hydrothermal synthesis of CdTe QDs: Their luminescence quenching in the presence of bio-molecules and observation of bistable memory effect in CdTe QD/PEDOT:PSS heterostructure

We report one-pot hydrothermal synthesis of nearly mono-disperse 3-mercaptopropionic acid capped water-soluble cadmium telluride (CdTe) quantum dots (QDs) using an air stable Te source. The optical and electrical characteristics were also studied here. It was shown that the hydrothermal synthesis could be tuned to synthesize nano structures of uniform size close to nanometers. The emissions of the CdTe QDs thus synthesized were in the range of 500-700 nm by varying the duration of synthesis. The full width at half maximum (FWHM) of the emission peaks is relatively narrow (40-90 nm), which indicates a nearly uniform distribution of QD size. The structural and optical properties of the QDs were characterized by transmission electron microscopy (TEM), photoluminescence (PL) and Ultraviolet-visible (UV-Vis) spectroscopy. The photoluminescence quenching of CdTe QDs in the presence of L-cysteine and DNA confirms its biocompatibility and its utility for biosensing applications. The room temperature current-voltage characteristics of QD film on ITO coated glass substrate show an electrically induced switching between states with high and low conductivities. The phenomenon is explained on the basis of charge confinement in quantum dots. (C) 2011 Elsevier B.V. All rights reserved.

Real source-sink pair

This work is concerned with the interaction of a source-sink pair. The main parameters of the problem are source and sink flow rates, the axial and lateral separations of the source and sink, and the angle between the axes of source and sink. Of concern is the percentage of source fluid that enters the sink as a function of these parameters. The experiments have been carried using the source nozzle diameter of 6 mm and the sink pipe diameter of two sizes: 10 mm and 20 mm. The Reynolds numbers of the source jet is about 3200. The main diagnostics are flow visualization using dye, laser induced fluorescence (LIF), particle streak photographs and particle image velocimetry (Ply). To obtain the removal effectiveness (that is percentage of source fluid that is going through the sink pipe), titration method is used. The sink diameter and the angle between source and the sink axes do not influence efficiencies as do the sink flow rate and the lateral separation. Data from experiments have been consolidated so that these results can be used for designing sinks for removal of heat and pollutants. (C) 2011 Elsevier Ltd. All rights reserved.

Electrophile-Induced C-C Bond Activation of Vinylcyclopropanes for the Synthesis of Z-Alkylidenetetrahydrofurans

We present a detailed study on the behavior of vinylcyclopropanes as masked donor acceptor system toward the stereoselective synthesis of Z-alkylidenetetrahydrofurans. Results of bromenium catalyzed indirect activation of C-C bond of vinylcyclopropanes and concomitant cyclization to alkylidenetetrahydrofuran and other heterocycles have been discussed. The stereoselective formation of the Z-isomer is strongly controlled by the extent of destabilization of one of the gauche conformers of the vinylcyclopropane. The ring-opening/cyclization step was found to be stereospecific as in the case of DA cyclopropanes. The activation of the C-C bond leads to a tight-carbocation intermediate, which is evident from the complete retention of the stereochemistry. The retention of configuration has been established by a necessary control experiment that rules out the possibility of a double inversion pathway. The present results serve as direct stereochemical evidence in support of a tight ion-pair intermediate versus the controversial S(N)2 pathway. A 2D potential energy scan has been carried out at B3LYP/6-31G(d) level theory to obtain the relative energies of the conformers. The Z-selectivity observed has been explained on the basis of the relative population of the conformers and modeling the intermediate and transition state involved in the reaction at M06-2x/6-31+G(d) level. Energy profile for the cyclization step was modeled considering various possible pathways through which cyclization can happen. The methodology has been successfully demonstrated on vinylcyclobutanes as well.

High power microwave coupling with a buried twisted pair cable

This paper deals with the coupling of High Power Microwaves with a buried twisted pair cable. The electric field at a distance of 1km from the HPM antenna has been computed and is used for further computation of induced voltage and current. It is found that the peak of the induced current and voltage in a buried unshielded twisted pair cable at a distance of 1km from an HPM antenna of power level 10GW is 20A and 2kV respectively.

Sunlight-Induced Covalent Marriage of Two Triply Interlocked Pd-6 Cages and Their Facile Thermal Separation

A template-free triply interlocked Pd-6 cage (2) was synthesized by two-component self-assembly of cis-blocked 90 degrees acceptor cis-(tmen)Pd(NO3)(2) (M) and 1,3,5-tris((E)-2-(pyridin-3-yl)vinyl)benzene (L). Assembly 2 was characterized by H-1 NMR and ESI-MS, and the structure was confirmed by X-ray crystallography, which revealed a parallel conformation of the olefin double bonds belonging to the adjacent cages in the solid state at a distance of 3.656 angstrom, thereby indicating the feasibility of 2+2] photochemical reaction. Two adjacent interlocked cages were covalently married together by intermolecular 2+2] cycloaddition in a single crystal-to-single crystal fashion upon exposure to sunlight/UV irradiation. Most surprisingly, the covalently married pair was easily separated thermally in aqueous medium under mild reaction conditions.

Efficient charge transfer and field-induced tunneling transport in hybrid composite device of organic semiconductor and cadmium telluride quantum dots

Temperature and photo-dependent current-voltage characteristics are investigated in thin film devices of a hybrid-composite comprising of organic semiconductor poly(3,4-ethylenedioxythiophene): polystyrenesulfonate (PEDOT: PSS) and cadmium telluride quantum dots (CdTe QDs). A detailed study of the charge injection mechanism in ITO/PEDOT: PSS-CdTe QDs/Al device exhibits a transition from direct tunneling to Fowler-Nordheim tunneling with increasing electric field due to formation of high barrier at the QD interface. In addition, the hybrid-composite exhibits a huge photoluminescence quenching compared to aboriginal CdTe QDs and high increment in photoconductivity (similar to 400%), which is attributed to the charge transfer phenomena. The effective barrier height (Phi(B) approximate to 0.68 eV) is estimated from the transition voltage and the possible origin of its variation with temperature and photo-illumination is discussed. (C) 2015 AIP Publishing LLC.

Nanoparticle induced miscibility in LCST polymer blends: critically assessing the enthalpic and entropic effects

The use of copolymer and polymer blends widened the possibility of creating materials with multilayered architectures. Hierarchical polymer systems with a wide array of micro and nanostructures are generated by thermally induced phase separation (TIPS) in partially miscible polymer blends. Various parameters like the interaction between the polymers, concentration, solvent/non-solvent ratio, and quenching temperature have to be optimized to obtain these micro/nanophase structures. Alternatively, the addition of nanoparticles is another strategy to design materials with desired hetero-phase structures. The dynamics of the polymer nanocomposite depends on the statistical ordering of polymers around the nanoparticle, which is dependent on the shape of the nanoparticle. The entropic loss due to deformation of polymer chains, like the repulsive interactions due to coiling and the attractive interactions in the case of swelling has been highlighted in this perspective article. The dissipative particle dynamics has been discussed and is correlated with the molecular dynamics simulation in the case of polymer blends. The Cahn Hillard Cook model on variedly shaped immobile fillers has shown difference in the propagation of the composition wave. The nanoparticle shape has a contributing effect on the polymer particle interaction, which can change the miscibility window in the case of these phase separating polymer blends. Quantitative information on the effect of spherical particles on the demixing temperature is well established and further modified to explain the percolation of rod shaped particles in the polymer blends. These models correlate well with the experimental observations in context to the dynamics induced by the nanoparticle in the demixing behavior of the polymer blend. The miscibility of the LCST polymer blend depends on the enthalpic factors like the specific interaction between the components, and the solubility product and the entropic losses occurring due to the formation of any favorable interactions. Hence, it is essential to assess the entropic and enthalpic interactions induced by the nanoparticles independently. The addition of nanoparticles creates heterogeneity in the polymer phase it is localized. This can be observed as an alteration in the relaxation behavior of the polymer. This changes the demixing behavior and the interaction parameter between the polymers. The compositional changes induced due to the incorporation of nanoparticles are also attributed as a reason for the altered demixing temperature. The particle shape anisotropy causes a direction dependent depletion, which changes the phase behavior of the blend. The polymer-grafted nanoparticles with varying grafting density show tremendous variation in the miscibility of the blend. The stretching of the polymer chains grafted on the nanoparticles causes an entropy penalty in the polymer blend. A comparative study on the different shaped particles is not available up to date for understanding these aspects. Hence, we have juxtaposed the various computational studies on nanoparticle dynamics, the shape effect of NPs on homopolymers and also the cases of various polymer blends without nanoparticles to sketch a complete picture on the effect of various particles on the miscibility of LCST blends.

Thermal fracture characteristics induced by laser beam

The damage mechanism of a cracked material due to laser beam thermal shock is an important problem when the interactions of high power laser beam with materials are studied. The transient thermal stress intensity factors (TSIFs) for a center crack in an infinite plate subjected to laser beam thermal shock are investigated. When the crack is in the heat affected zone, the compressive thermal stress causes the crack surface to come into contact with each other over a certain contact length, but the high tensile stresses around the crack tip tend to open the crack. In this case, the problem may be treated as a pair of embedded cracks problem with a smooth closure condition of the center crack. The TSIFs and the crack contact lengths are calculated with different laser beam spatial shapes. The TSIFs induced by thermal shock are in marked different from those induced by general mechanical loading.

Study Of The Damage-Induced Anisotropy Of Quasi-Brittle Materials Using The Component Assembling Model

Damage-induced anisotropy of quasi-brittle materials is investigated using component assembling model in this study. Damage-induced anisotropy is one significant character of quasi-brittle materials coupled with nonlinearity and strain softening. Formulation of such complicated phenomena is a difficult problem till now. The present model is based on the component assembling concept, where constitutive equations of materials are formed by means of assembling two kinds of components' response functions. These two kinds of components, orientational and volumetric ones, are abstracted based on pair-functional potentials and the Cauchy - Born rule. Moreover, macroscopic damage of quasi-brittle materials can be reflected by stiffness changing of orientational components, which represent grouped atomic bonds along discrete directions. Simultaneously, anisotropic characters are captured by the naturally directional property of the orientational component. Initial damage surface in the axial-shear stress space is calculated and analyzed. Furthermore, the anisotropic quasi-brittle damage behaviors of concrete under uniaxial, proportional, and nonproportional combined loading are analyzed to elucidate the utility and limitations of the present damage model. The numerical results show good agreement with the experimental data and predicted results of the classical anisotropic damage models.

Study of the damage-induced anisotropy of quasi-brittle materials using the component assembling model

Damage-induced anisotropy of quasi-brittle materials is investigated using component assembling model in this study. Damage-induced anisotropy is one significant character of quasi-brittle materials coupled with nonlinearity and strain softening. Formulation of such complicated phenomena is a difficult problem till now. The present model is based on the component assembling concept, where constitutive equations of materials are formed by means of assembling two kinds of components' response functions. These two kinds of components, orientational and volumetric ones, are abstracted based on pair-functional potentials and the Cauchy - Born rule. Moreover, macroscopic damage of quasi-brittle materials can be reflected by stiffness changing of orientational components, which represent grouped atomic bonds along discrete directions. Simultaneously, anisotropic characters are captured by the naturally directional property of the orientational component. Initial damage surface in the axial-shear stress space is calculated and analyzed. Furthermore, the anisotropic quasi-brittle damage behaviors of concrete under uniaxial, proportional, and nonproportional combined loading are analyzed to elucidate the utility and limitations of the present damage model. The numerical results show good agreement with the experimental data and predicted results of the classical anisotropic damage models.

Flow-induced vibrations of long circular cylinders modeled by coupled nonlinear oscillators

The dynamics of long slender cylinders undergoing vortex-induced vibrations (VIV) is studied in this work. Long slender cylinders such as risers or tension legs are widely used in the field of ocean engineering. When the sea current flows past a cylinder, it will be excited due to vortex shedding. A three-dimensional time domain model is formulated to describe the response of the cylinder, in which the in-line (IL) and cross-flow (CF) deflections are coupled. The wake dynamics, including in-line and cross-flow vibrations, is represented using a pair of non-linear oscillators distributed along the cylinder. The wake oscillators are coupled to the dynamics of the long cylinder with the acceleration coupling term. A non-linear fluid force model is accounted for to reflect the relative motion of cylinder to current. The model is validated against the published data from a tank experiment with the free span riser. The comparisons show that some aspects due to VIV of long flexible cylinders can be reproduced by the proposed model, such as vibrating frequency, dominant mode number, occurrence and transition of the standing or traveling waves. In the case study, the simulations show that the IL curvature is not smaller than CF curvature, which indicates that both IL and CF vibrations are important for the structural fatigue damage.

Octopamine neurons mediate flight-induced modulation of visual processing in Drosophila melanogaster

Activity-dependent modulation of sensory systems has been documented in many organisms, and is likely to be essential for appropriate processing of information during different behavioral states. However, the mechanisms underlying these phenomena, and often their functional consequences, remain poorly characterized. I investigated the role of octopamine neurons in the flight-dependent modulation observed in visual interneurons in the fruit fly Drosophila melanogaster. The vertical system (VS) cells exhibit a boost in their response to visual motion during flight compared to quiescence. Pharmacological application of octopamine evokes responses in quiescent flies that mimic those observed during flight, and octopamine neurons that project to the optic lobes increase in activity during flight. Using genetic tools to manipulate the activity of octopamine neurons, I find that they are both necessary and sufficient for the flight-induced visual boost. This work provides the first evidence that endogenous release of octopamine is involved in state-dependent modulation of visual interneurons in flies. Further, I investigated the role of a single pair of octopamine neurons that project to the optic lobes, and found no evidence that chemical synaptic transmission via these neurons is necessary for the flight boost. However, I found some evidence that activation of these neurons may contribute to the flight boost. Wind stimuli alone are sufficient to generate transient increases in the VS cell response to motion vision, but result in no increase in baseline membrane potential. These results suggest that the flight boost originates not from a central command signal during flight, but from mechanosensory stimuli relayed via the octopamine system. Lastly, in an attempt to understand the functional consequences of the flight boost observed in visual interneurons, we measured the effect of inactivating octopamine neurons in freely flying flies. We found that flies whose octopamine neurons we silenced accelerate less than wild-type flies, consistent with the hypothesis that the flight boost we observe in VS cells is indicative of a gain control mechanism mediated by octopamine neurons. Together, this work serves as the basis for a mechanistic and functional understanding of octopaminergic modulation of vision in flying flies.

Gamma-ray induced color centers in Yb : YAG crystals grown by Czochralski method

20 at.% Yb:YAG single crystals have been grown by the CZ method and gamma-ray irradiation induced color centers and valence change of Fe3+ and Yb3+ ions in Yb:YAG have been studied. One significant 255 nm absorption band was observed in as-grown crystals and was attributed to Fe3+ ions. Two additional absorption (AA) bands located at 255 nm and 345 nm, respectively, were produced after gamma irradiation. The changes in the AA spectra after gamma irradiation and air annealing are mainly related to the charge exchange of the Fe3+, Fe2+, oxygen vacancies and F-type color centers. Analysis shows that the broad AA band is associated with Fe2+ ions and F-type color centers. The transition Yb3+ Yb2+ takes place as an effect of recharging of one of the Yb3+ ions from a pair in the process of gamma irradiation. (C) 2006 Elsevier Ltd. All rights reserved.

Laser pulse induced bumps in chalcogenide phase change films

Formation of bumps in chalcogenide phase change thin films during the laser writing process is theoretically and experimentally investigated. The process involves basically fast heating and quenching stages. Circular bumps are formed after cooling, and the shape and size of the bumps depend on various parameters such as temperatures, laser power, beam size, laser pulse duration, etc. In extreme cases, holes are formed at the apex of the bumps. To understand the bumps and their formation is of great interest for data storage. In the present work, a theoretical model is established for the formation process, and the geometric characters of the formed bumps can be analytically and quantitatively evaluated from various parameters involved in the formation. Simulations based on the analytic solution are carried out taking Ag8In14Sb55Te23 as an example. The results are verified with experimental observations of the bumps. (C) 2008 American Institute of Physics.