Investigation of dye functional group on the photocatalytic degradation of dyes by nano-TiO2

The photocatalytic degradation of five anionic, eight cationic and three solvent dyes using combustion-synthesized nano-TiO2 (CSTiO2) and commercial Degussa P-25 TiO2 (DP-25) were evaluated to determine the effect of the functional group in the dye. The degradation of the dyes was quantified using the initial rate of decolorization and mineralization. The decolorization of the anionic dyes with CSTiO2 followed the order: indigo carmine > eosin Y > amido black 10B > alizarin cyanine green > orange G. The decolorization of the cationic dyes with DP-25 followed the order: malachite green > pyronin Y > rhodamine 6G > azure B > nile blue sulfate > auramine O approximate to acriflavine P approximate to safranin O. CSTiO2 showed higher rates of decolorization and mineralization for all the anionic dyes compared to DP-25, while DP-25 was better in terms of decolorization for most of the cationic dyes. The solvent dyes exhibited adsorption dependent decolorization. The order of decolorization and mineralization of the anionic and cationic dyes (a) with CS TiO2 and DP-25 was different and correlated with the surface properties of these catalysts (b) were rationalized with the molecular structure of the dye and the degradation pathway of the dye. (C) 2009 Elsevier B.V. All rights reserved.

Polymer melt dynamics: Microscopic roots of fractional viscoelasticity

The rheological properties of polymer melts and other complex macromolecular fluids are often successfully modeled by phenomenological constitutive equations containing fractional differential operators. We suggest a molecular basis for such fractional equations in terms of the generalized Langevin equation (GLE) that underlies the renormalized Rouse model developed by Schweizer [J. Chem. Phys. 91, 5802 (1989)]. The GLE describes the dynamics of the segments of a tagged chain under the action of random forces originating in the fast fluctuations of the surrounding polymer matrix. By representing these random forces as fractional Gaussian noise, and transforming the GLE into an equivalent diffusion equation for the density of the tagged chain segments, we obtain an analytical expression for the dynamic shear relaxation modulus G(t), which we then show decays as a power law in time. This power-law relaxation is the root of fractional viscoelastic behavior.

Possible high-temperature superconducting state with a d plus id pairing symmetry in doped graphene

Motivated by a suggestion in our earlier work [G. Baskaran, Phys. Rev. B 65, 212505 (2002)], we study electron correlation driven superconductivity in doped graphene where on-site correlations are believed to be of intermediate strength. Using an extensive variational Monte Carlo study of the repulsive Hubbard model and a correlated ground state wave function, we show that doped graphene supports a superconducting ground state with a d+id pairing symmetry. We estimate superconductivity reaching room temperatures at an optimal doping of about 15%-20%. Our work suggests that correlations can stabilize superconductivity even in systems with intermediate coupling.

Network topological thresholds in gallium doped As-Te glasses Electrical and thermal investigations

Electrical switching and differential scanning calorimetric studies are undertaken on bulk As20Te80-xGax glasses, to elucidate the network topological thresholds. It is found that these glasses exhibit a single glass transition (T-g) and two crystallization reactions (T-cl & T-c2) upon heating. It is also found that there is only a marginal change in T-g with the addition of up to about 10% of Ga; around this composition an increase is seen in 7, which culminates in a local maximum around x = 15. The decrease exhibited in T, beyond this composition, leads to a local minimum at x = 17.5. Further, the As20Te80-xGax glasses are found to exhibit memory type electrical switching. The switching voltages (VT) increase with the increase in gallium content and a local maximum is seen in V-tau around x = 15. VT is found to decrease with x thereafter, exhibiting a local minimum around x = 17.5. The composition dependence of T-cl is found to be very similar to that of V-T of As20Te80-xGax glasses. Based on the present results, it is proposed that the composition x = 15 and x = 17.5 correspond to the rigidity percolation and chemical thresholds, respectively, of As20Te80-xGax glasses. (c) 2007 Elsevier B.V. All rights reserved.

Polymer assisted hydroxyapatite microspheres suitable for biomedical application

Hollow Microspheres of hydroxyapatite-polymer composite can be used as carriers in drug delivery and fillers in tissue engineering. Based on the concept of soft chemistry, a battery of technique is available in the literature to synthesize hollow microspheres, however, an economically viable synthesis route, having good control over the microarchitect and easy to be scaled up, is yet to be developed. Polymer matrix mediated synthesis of inorganic nanoparticles is known to synthesize nanoparticles with controlled morphology and dimensions. It is termed as biomimetic synthesis. Integrating the biomimetic synthesis of nano-particles and spray drying techniques, a novel process of producing hydroxyapatite-polymer composite hollow microspheres is briefly discussed here.

Polymer drift in a solvent by force acting on one polymer end

We investigate the effect of hydrodynamic interactions on the non-equilibrium drift dynamics of an ideal flexible polymer pulled by a constant force applied at one polymer end using the perturbation theory and the renormalization group method. For moderate force, if the polymer elongation is small, the hydrodynamic interactions are not screened and the velocity and the longitudinal elongation of the polymer are computed using the renormalization group method. Both the velocity and elongation are nonlinear functions of the driving force in this regime. For large elongation we found two regimes. For large force but finite chain length L the hydrodynamic interactions are screened. For large chain lengths and a finite force the hydrodynamic interactions are only partially screened, which in three dimensions results in unusual logarithmic corrections to the velocity and the longitudinal elongation.

Process-dependent magnetic properties of Co-doped ZnO in bulk and thin film form

Structural, optical and magnetic studies of Co-doped ZnO have been carried out for bulk as well as thin films. The magnetic studies revealed the superparamagnetic nature for low-temperature synthesized samples, indicating the presence of cobalt metallic clusters, and this is supported by the optical studies. For the high-temperature sintered samples one obtains paramagnetism. The optical studies reveal the presence of Co2+ ions in the tetrahedral sites indicating proper doping. Interestingly, the films deposited by laser ablation from the paramagnetic target showed room temperature ferromagnetism. It appears that the magnetic nature of this system is process dependent.

Energy harvesting using ionic electro-active polymer thin films with Ag-based electrodes

In this paper we employ the phenomenon of bending deformation induced transport of cations via the polymer chains in the thickness direction of an electro-active polymer (EAP)-metal composite thin film for mechanical energy harvesting. While EAPs have been applied in the past in actuators and artificial muscles, promising applications of such materials in hydrodynamic and vibratory energy harvesting are reported in this paper. For this, functionalization of EAPs with metal electrodes is the key factor in improving the energy harvesting efficiency. Unlike Pt-based electrodes, Ag-based electrodes have been deposited on an EAP membrane made of Nafion. The developed ionic metal polymer composite (IPMC) membrane is subjected to a dynamic bending load, hydrodynamically, and evaluated for the voltage generated against an external electrical load. An increase of a few orders of magnitude has been observed in the harvested energy density and power density in air, deionized water and in electrolyte solutions with varying concentrations of sodium chloride (NaCl) as compared to Pt-based IPMC performances reported in the published literature. This will have potential applications in hydrodynamic and residual environmental energy harvesting to power sensors and actuators based on micro-andn nano-electro-mechanical systems (MEMS and NEMS) for biomedical,maerospace and oceanic applications.

Spectroscopic ellipsometry investigations of the optical properties of manganese doped bismuth vanadate thin films

The optical properties of Bi(2)V(1-x)MnxO(5.5-x) (x=0.05, 0.1, 0.15 and 0.2 at.%) thin films fabricated by pulsed laser deposition on platinized Silicon Substrates were Studied in UV-visible spectral region (1.51-4.17 CV) using spectroscopic ellipsometry. The optical constants and thicknesses of these films have been obtained by fitting the ellipsometric data (Psi and Delta) using a multilayer four-phase model system and a relaxed Lorentz oscillator dispersion relation. The surface roughness and film thickness obtained by spectroscopic ellipsometry were found to be consistent with the results obtained by atomic force and scanning electron microscopy. The refractive index measured at 650 nm does not show any marginal increase with Mn content. Further, the extinction coefficient does not show much decrease with increasing Mn content. An increase in optical band gap energy from 2.52 to 2.77 eV with increasing Mn Content from x = 0.05 to 0.15 was attributed to the increase in oxygen ion vacancy disorder. (C) 2009 Elsevier Ltd. All rights reserved.

Experimental and Theoretical Charge Density Analysis of Polymorphic Structures: The Case of Coumarin 314 Dye

Experimental charge density distributions in two known conformational polymorphs (orange and yellow) of coumarin 314 dye are analyzed based on multipole modeling of X-ray diffraction data collected at 100 K. The experimental results are compared with the charge densities derived from multipole modeling of theoretical structure factors obtained from periodic quantum calculation with density functional theory (DFT) method and B3LYP/6-31G(d,p) level of theory. The presence of disorder at the carbonyl oxygen atom of ethoxycarbonyl group in the yellow form, which was not identified earlier, is addressed here. The investigationof intermolecular interactions, based on Hirshfeld surface analysis and topological properties via quantum theory of atoms in molecule and total electrostatic interaction energies, revealed significant differences between the polymorphs. The differences of electrostatic nature in these two polymorphic forms were unveiled via construction of three-dimensional deformation electrostatic potential maps plotted over the molecular surfaces. The lattice energies evaluated from ab initio calculations on the two polymorphic forms indicate that the yellow form is likely to be the most favorable thermodynamically. The dipole moments derived from experimental and theoretical charge densities and also from Lorentz tensor approach are compared with the single-molecule dipole moments. In each case, the differences of dipole moments between the polymorphs are identified.

Prevention of photooxidation in blue-green emitting Cu doped ZnSe nanocrystals

This communication highlights unstable blue-green emitting Cu doped ZnSe nanocrystals stabilized by diluting the surface Se with a calculated amount of S.

Anomalous temperature dependence of Fermi-edge singularity in modulation-doped AlGaAs/InGaAs/GaAs hetero-structures

The temperature and power dependence of Fermi-edge singularity (FES) in high-density two-dimensional electron gas, specific to pseudomorphic AlxGa1-xAs/InGa1-yAs/GaAs heterostructures is studied by photoluminescence (PL). In all these structures, there are two prominent transitions E-11 and E-21 considered to be the result of electron-hole recombination from first and second electron sub-bands with that of first heavy-hole sub-band. FES is observed approximately 5-10 meV below the E-21 transition. At 4.2 K, FES appears as a lower energy shoulder to the E-21 transition. The PL intensity of all the three transitions E-11, FES and E-21 grows linearly with excitation power. However, we observe anomalous behavior of FES with temperature. While PL intensity of E-11 and E-21 decrease with increasing temperature, FES transition becomes stronger initially and then quenches-off slowly (till 40K). Though it appears as a distinct peak at about 20 K, its maximum is around 7 - 13 K.

Characteristics of field-effect transistors based on undoped and B-and N-doped few-layer graphenes

Field-effect transistor characteristics of few-layer graphenes prepared by several methods have been investigated in comparison with those of single-layer graphene prepared by the in situ reduction of single-layer graphene oxide. Ambipolar features have been observed with single-layer graphene and n-type behaviour with all the few-layer graphenes, the best characteristics being found with the graphene possessing 2-3 layers prepared by arc-discharge of graphite in hydrogen. FETs based on boron and nitrogen doped graphene show n-type and p-type behaviour respectively. (C) 2010 Elsevier Ltd. All rights reserved.

Ion Transport in a Polymer-Plastic Solid Soft Matter Electrolyte in the Light of Solvent Dynamics and Ion Association

Ion transport in a recently demonstrated promising soft matter solid plastic-polymer electrolyte is discussed here in the context of solvent dynamics and ion association. The plastic-polymer composite electrolytes display liquid-like ionic conductivity in the solid state,compliable mechanical strength (similar to 1 MPa), and wide electrochemical voltage stability (>= 5 V). Polyacrylonitrile (PAN) dispersed in lithium perchlorate (LiClO4)-succinonitrile (SN) was chosen as the model system for the study (abbreviated LiClO4-SN:PAN). Systematic observation of various mid-infrared isomer and ion association bands as a function of temperature and polyme concentration shows an effective increase in trans conformer concentration along with free Li+ ion concentration. This strongly supports the view that enhancement in LiClO4-SN:PAN ionic conductivity over the neat plastic electrolyte (LiClO4-SN) is due to both increase in charge mobility and concentration. The ionic conductivity and infrared spectroscopy studies are supported by Brillouin light scattering. For the LiClO4-SN:PAN composites, a peak at 17 GHz was observed in addition to the normal trans-gauche isomerism (as in neat SN) at 12 GHz. The fast process is attributed to increased dynamics of those SN molecules whose energy barrier of transition from gauche to trans has reduced under influences induced by the changes in temperature and polymer concentration. The observations from ionic conductivity, spectroscopy, and light scattering studies were further supplemented by temperature dependent nuclear magnetic resonance H-1 and Li-7 line width measurements.

Reverse bias capacitance measurements on copper-doped germanium p-n junctions in the breakdown region

Results of measurements at a high frequency on reverse bias capacitance of copper-doped germanium junctions are reported. Phenomenal increase in capacitance is found in the breakdown region, particularly at low temperatures.