Role of silica nanoparticles in conductivity enhancement of nanocomposite solid polymer electrolytes: (PEG(x) NaBr): ySiO(2)

Nanocomposite solid polymer electrolytes (NCSPEs) with conducting species other than Li ions are being investigated for solid-state battery applications. Pristine solid polymer electrolytes (SPEs) do not show ionic conductivity suitable for batteries. Addition of inert fillers to SPEs is known to enhance the ionic conductivity. In this paper, we present the role of silica nanoparticles in enhancing the ionic conductivity in NCSPEs with sodium as conducting species. Sodium bromide is complexed with the host polyethylene glycol polymer by solution cast method and silica nanoparticles (SiO2, average particle size 7 nm) are incorporated into the complex in small amounts. The composites are characterized by powder XRD and IR spectroscopy. Conductivity measurements are undertaken as a function of concentration of salt and also as a function of temperature using impedance spectroscopy. Addition of silica nanoparticles shows an enhancement in conductivity by 1-2 orders of magnitude. The results are discussed in terms of interaction of nanoparticles with the nonconducting anions.

Platinum Ion-Doped TiO2: High Catalytic Activity of Pt2+ with Oxide Ion Vacancy in Ti1-x4+Ptx2+O2-x Compared to Pt4+ without Oxide Ion Vacancy in Ti1-x4+Ptx4+O2

Ti0.97Pt0.032+O1.97 and Ti0.97Pt0.034+O2 have been synthesized by a solution combustion method using alanine and glycine as the fuels, respectively. Both crystallize in anatase TiO2 structure with 15 nm average crystallite size. X-ray photoelectron spectroscopy (XPS) confirmed Pt ions are in the 2+ state in Ti0.97Pt0.03O1.97 (alanine) and 4+ state in Ti0.97Pt0.03O2 (glycine). The rate of CO oxidation occurring over Ti0.97Pt0.032+O1.97 (0.76 mu mol.g(-1).s(-1)) is similar to 10, times more than that over Ti0.97Pt0.034+O2 at 60 degrees C (0.08 mu mol.g(-1).s(-1)). A large shift in 100% hydrocarbons conversion to lower temperature was observed for Pt2+ ion-substituted TiO2 relative 10 that for Pt4+ ion-substituted TiO2. After reoxidation of the reduced compound by H-2 as well as CO, Pt ions are stabilized in mixed valences, 2+ and 4+ states. The role of oxide ion vacancy has been demonstrated by CO oxidation and H-2 + O-2 recombination reactions in the presence and absence of O-2. We analyze the activated lattice oxygens upon substitution of Pt2+ and Pt4+ ions in TiO2, using first-principles density functional theory (DFT) calculations with supercells of Ti31Pt1O63, Ti30Pt2O62, and Ti29Pt3O61 for Pt2+ ion substitution and Ti31Pt1O64, Ti30Pt2O62, and Ti29Pt3O61 for Pt4+ ion substitution in TiO2. We find that the local structure of Pt2+ ion has a distorted square planar geometry and that of Pt4+ ion has an octahedral geometry similar to that of Ti4+ ion in pure TiO2. The change in coordination of Pt2+ ion gives rise to weakly bonded oxygens, and these oxygens are involved in high rates of catalytic reaction. Thus, the high catalytic activity results from synergistic roles of Pt2+ ion and oxide ion vacancy and weakly bonded lattice oxygen.

A fast NMR method for resonance assignments: application to metabolomics

We present a new method for rapid NMR data acquisition and assignments applicable to unlabeled (C-12) or C-13-labeled biomolecules/organic molecules in general and metabolomics in particular. The method involves the acquisition of three two dimensional (2D) NMR spectra simultaneously using a dual receiver system. The three spectra, namely: (1) G-matrix Fourier transform (GFT) (3,2)D C-13, H-1] HSQC-TOCSY, (2) 2D H-1-H-1 TOCSY and (3) 2D C-13-H-1 HETCOR are acquired in a single experiment and provide mutually complementary information to completely assign individual metabolites in a mixture. The GFT (3,2)D C-13, H-1] HSQC-TOCSY provides 3D correlations in a reduced dimensionality manner facilitating high resolution and unambiguous assignments. The experiments were applied for complete H-1 and C-13 assignments of a mixture of 21 unlabeled metabolites corresponding to a medium used in assisted reproductive technology. Taken together, the experiments provide time gain of order of magnitudes compared to the conventional data acquisition methods and can be combined with other fast NMR techniques such as non-uniform sampling and covariance spectroscopy. This provides new avenues for using multiple receivers and projection NMR techniques for high-throughput approaches in metabolomics.

Two-step Synthesis of MoS2 Nanotubes using Shock Waves with Lead as Growth Promoter

A new two-step procedure for the synthesis of MoS2 nanotubes using lead as a growth promoter is reported. In the first step, molybdenum suboxide nanowhiskers containing a small amount of lead atoms were created by exposing a pressed MoS2+Pb mixture to highly compressed shock-heated argon gas, with estimated temperatures exceeding 9900 K. In the second step, these molybdenum suboxide nanowhiskers served as templates for the sulfidization of the oxide into MoS2 nanotubes (by using H2S gas in a reducing atmosphere at 820 degrees C). Unlike the case of WS2 nanotubes, the synthesis of a pure phase of MoS2 nanotubes from molybdenum oxide has proven challenging, due mostly to the volatile nature of the latter at the high requisite reaction temperatures (>800 degrees C). In contrast, the nature and apparent reaction mechanism of the method reported herein are amenable to future scale-up. The high-temperature shockwave system should also facilitate the synthesis of new nanostructures from other layered materials.

Numerical modeling of the non-isothermal liquid droplet impact on a hot solid substrate

The heat transfer from a solid phase to an impinging non-isothermal liquid droplet is studied numerically. A new approach based on an arbitrary Lagrangian-Eulerian (ALE) finite element method for solving the incompressible Navier Stokes equations in the liquid and the energy equation within the solid and the liquid is presented. The novelty of the method consists in using the ALE-formulation also in the solid phase to guarantee matching grids along the liquid solid interface. Moreover, a new technique is developed to compute the heat flux without differentiating the numerical solution. The free surface and the liquid solid interface of the droplet are represented by a moving mesh which can handle jumps in the material parameter and a temperature dependent surface tension. Further, the application of the Laplace-Beltrami operator technique for the curvature approximation allows a natural inclusion of the contact angle. Numerical simulation for varying Reynold, Weber, Peclet and Biot numbers are performed to demonstrate the capabilities of the new approach. (C) 2014 Elsevier Ltd. All rights reserved.

Luminescence enhancement in monoclinic CaAl2O4:Eu2+, Cr3+ nanophosphor by fuel-blend combustion synthesis

Eu2+ ion doped into a suitable host results in an efficient luminophore with engineering relevance; however stabilizing this ion in a host is known to be a challenge. Here we report a novel approach for the synthesis of efficient CaAl2O4 phosphor containing Eu2+ luminophore and Cr3+ activator. CaAl2O4:Eu2+, Cr3+ is prepared by a solution combustion (SCS) method using (i) urea, (ii) oxalyl dihydrazide (ODH) and (iii) fuel-blend (in which overall fuel to oxidizer ratio (F/O) = 1). A Multi-channel thermocouple setup is used to measure the flame temperatures to study the nature of combustion of various fuel mixtures. The variation of adiabatic flame temperature is calculated theoretically for different urea/ODH mixture ratios according to thermodynamic concept and correlated with the observed flame temperatures. Blue emission of the CaAl2O4:Eu2+ phosphor is enhanced similar to 20 times using the fuel-blend approach. Using the observed reaction kinetics, and the known chemistry of smoldering type combustion, a mechanism is proposed for the observed stabilization of Eu2+ ion in the fuel-blend case. This also explains the observed improvement in blue light emission. We show that the right choice of the fuel ratio is essential for enhancing photoluminescence (PL) emission. The PL intensity is highest for ODH lean and urea rich combination (i.e. when the ratio of ODH:urea is 1:5); measured color purity is comparable to commercial blue phosphor, BAM:Eu2+. (C) 2015 Elsevier B.V. All rights reserved.

Inter molecular azide-diisocyanate coupling: new insights for energetic solid propellants

Hydroxyl terminated azide binders can undergo a spurious reaction with diisocyanates to form tetrazoline-5-one via an inter molecular 1,3-dipolar cycloaddition reaction apart from urethane/allophanate groups which has been overlooked. This has serious implications on solid propellants. The computed activation barrier using density functional theory (DFT) for urethane formation reaction is 28.4 kJ mol(-1) and that for tetrazoline-5-one formation reaction is 108.0 kJ mol(-1). DFT studies reveal that the rate limiting step of the reaction is 1,3-dipolar cycloaddition between azide and isocyanate. A dual cure was observed in the temperature ranges 42-77 degrees C and 78-146 degrees C by differential scanning calorimetry (DSC) and rheological studies, confirming multiple reactions. Tetrazoline-5-one formation was confirmed by Fourier transform infrared spectroscopy (FTIR) and solid state nuclear magnetic resonance spectroscopy (NMR).

Efficient visible light photocatalytic activity and enhanced stability of BiOBr/Cd(OH)(2) heterostructures

Novel BioBr/Cd(OH)(2) heterostructures were synthesized by a facile chemical bath method under ambient conditions. A series of BiOBr/Cd(OH)(2) heterostructures were obtained by tuning the Bi/Cd molar ratios. The obtained heterostructures were characterized by powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and energy dispersive spectroscopy (EDS). Optical properties were studied by UV-visible spectroscopy, diffuse reflectance spectroscopy and photoluminescence (PL). Photocatalytic studies on rhodamine B (RhB) under visible light irradiation showed that the heterostructures are very efficient photocatalysts in mild basic medium. Scavenger test studies confirmed that the photogenerated holes and superoxide radicals (O-2(center dot-)) are the main active species responsible for RhB degradation. Comparison of photoluminescence (PL) intensity suggested that an inhibited charge recombination is crucial for the degradation process over these photocatalysts. Moreover, relative positioning of the valence and conduction band edges of the semiconductors, O-2/O-2(center dot-) and (OH)-O-center dot/H2O redox potentials and HOMO-LUMO levels of RhB appear to be responsible for the hole-specificity of degradation. Photocatalytic recycling experiments indicated the high stability of the catalysts in the reaction medium without any significant loss of activity. This study hence concludes that the heterojunction constructed between Cd(OH)(2) and BiOBr interfaces play a crucial role in influencing the charge carrier dynamics and subsequent photocatalytic activity.

A method for coupling the phase-field model based on a grand-potential formalism to thermodynamic databases

In this paper we derive an approach for the effective utilization of thermodynamic data in phase-field simulations. While the most widely used methodology for multi-component alloys is following the work by Eiken et al. (2006), wherein, an extrapolative scheme is utilized in conjunction with the TQ interface for deriving the driving force for phase transformation, a corresponding simplistic method based on the formulation of a parabolic free-energy model incorporating all the thermodynamics has been laid out for binary alloys in the work by Folch and Plapp (2005). In the following, we extend this latter approach for multi-component alloys in the framework of the grand-potential formalism. The coupling is applied for the case of the binary eutectic solidification in the Cr-Ni alloy and two-phase solidification in the ternary eutectic alloy (Al-Cr-Ni). A thermodynamic justification entails the basis of the formulation and places it in context of the bigger picture of Integrated Computational Materials Engineering. (C) 2015 Elsevier Ltd. All rights reserved.

High-kappa TiO2 Thin Film Prepared by Sol-Gel Spin-Coating Method

High-k TiO2 thin film on p-type silicon substrate was fabricated by a combined sol-gel and spin coating method. Thus deposited titania film had anatase phase with a small grain size of 16 nm and surface roughness of congruent to 0.6 nm. The oxide capacitance (C-ox), flat band capacitance (C-FB), flat band voltage (V-FB), oxide trapped charge (Q(ot)), calculated from the high frequency (1 MHz) C-V curve were 0.47 nF, 0.16 nF, -0.91 V, 4.7x10(-12) C, respectively. As compared to the previous reports, a high dielectric constant of 94 at 1 MHz frequency was observed in the devices investigated here and an equivalent oxide thickness (EOT) was 4.1 nm. Dispersion in accumulation capacitance shows a linear relationship with AC frequencies. Leakage current density was found in acceptable limits (2.1e-5 A/cm(2) for -1 V and 5.7e-7 A/cm(2) for +1 V) for CMOS applications.

Hetero-atom Doped Carbon Nanotubes for Dye Degradation and Oxygen Reduction Reaction

We report the synthesis of nitrogen doped vertically aligned multi-walled (MWNCNTs) carbon nanotubes by pyrolysis and its catalytic performance for degradation of methylene blue (MB) dye & oxygen reduction reaction (ORR). The degradation of MB was monitored spectrophotometrically with time. Kinetic studies show the degradation of MB follows a first order kinetic with rate constant k=0.0178 min(-1). The present rate constant is better than that reported for various supported/non-supported semiconducting nanomaterials. Further ORR performance in alkaline media makes MWNCNTs a promising cost-effective, fuel crossover tolerance, metal-free, eco-friendly cathode catalyst for direct alcohol fuel cell.

Study on Low Temperature DC Electrical Conductivity of SnO2 Nanomaterial Synthesized by Simple Gel Combustion Method

Nanocrystalline tin oxide (SnO2) material of different particle size was synthesized using gel combustion method by varying oxidizer (HNO3) and keeping fuel as a constant. The prepared samples were characterized by X-Ray Diffraction (XRD), Scanning Electron Microscope (SEM) and Energy Dispersive Analysis X-ray Spectroscope (EDAX). The effect of oxidizer in the gel combustion method was investigated by inspecting the particle size of nano SnO2 powder. The particle size was found to be increases with the increase of oxidizer from 8 to 12 moles. The X-ray diffraction patterns of the calcined product showed the formation of high purity tetragonal tin (IV) oxide with the particle size in the range of 17 to 31 nm which was calculated by Scherer's formula. The particles and temperature dependence of direct (DC) electrical conductivity of SnO2 nanomaterial was studied using Keithley source meter. The DC electrical conductivity of SnO2 nanomaterial increases with the temperature from 80 to 300K and decrease with the particle size at constant temperature.

High-kappa TiO2 Thin Film Prepared by Sol-Gel Spin-Coating Method

High-k TiO2 thin film on p-type silicon substrate was fabricated by a combined sol-gel and spin coating method. Thus deposited titania film had anatase phase with a small grain size of 16 nm and surface roughness of congruent to 0.6 nm. The oxide capacitance (C-ox), flat band capacitance (C-FB), flat band voltage (V-FB), oxide trapped charge (Q(ot)), calculated from the high frequency (1 MHz) C-V curve were 0.47 nF, 0.16 nF, -0.91 V, 4.7x10(-12) C, respectively. As compared to the previous reports, a high dielectric constant of 94 at 1 MHz frequency was observed in the devices investigated here and an equivalent oxide thickness (EOT) was 4.1 nm. Dispersion in accumulation capacitance shows a linear relationship with AC frequencies. Leakage current density was found in acceptable limits (2.1e-5 A/cm(2) for -1 V and 5.7e-7 A/cm(2) for +1 V) for CMOS applications.

An auto-focusing method for imaging ellipsometry system

An auto-focusing method based on the image brightness gradient sharpness function is presented for imaging ellipsometry system, in which the image plane of the thin-film specimen is not perpendicular to the optical axis. The clear image of a specimen with large area is obtained by moving the imaging sensor in optical axis direction and around its sensitive surface centre successively. The experimental results demonstrate its feasibility.

Phase behavior of complex superprotonic solid acids

Superprotonic phase transitions and thermal behaviors of three complex solid acid systems are presented, namely Rb3H(SO4)2-RbHSO4 system, Rb3H(SeO4)2-Cs3H(SeO4)2 solid solution system, and Cs6(H2SO4)3(H1.5PO4)4. These material systems present a rich set of phase transition characteristics that set them apart from other, simpler solid acids. A.C. impedance spectroscopy, high-temperature X-ray powder diffraction, and thermal analysis, as well as other characterization techniques, were employed to investigate the phase behavior of these systems.

Rb3H(SO4)2 is an atypical member of the M3H(XO4)2 class of compounds (M = alkali metal or NH4+ and X = S or Se) in that a transition to a high-conductivity state involves disproportionation into two phases rather than a simple polymorphic transition [1]. In the present work, investigations of the Rb3H(SO4)2-RbHSO4 system have revealed the disproportionation products to be Rb2SO4 and the previously unknown compound Rb5H3(SO4)4. The new compound becomes stable at a temperature between 25 and 140 °C and is isostructural to a recently reported trigonal phase with space group P3̅m of Cs5H3(SO4)4 [2]. At 185 °C the compound undergoes an apparently polymorphic transformation with a heat of transition of 23.8 kJ/mol and a slight additional increase in conductivity.

The compounds Rb3H(SeO4)2 and Cs3H(SeO4)2, though not isomorphous at ambient temperatures, are quintessential examples of superprotonic materials. Both adopt monoclinic structures at ambient temperatures and ultimately transform to a trigonal (R3̅m) superprotonic structure at slightly elevated temperatures, 178 and 183 °C, respectively. The compounds are completely miscible above the superprotonic transition and show extensive solubility below it. Beyond a careful determination of the phase boundaries, we find a remarkable 40-fold increase in the superprotonic conductivity in intermediate compositions rich in Rb as compared to either end-member.

The compound Cs6(H2SO4)3(H1.5PO4)4 is unusual amongst solid acid compounds in that it has a complex cubic structure at ambient temperature and apparently transforms to a simpler cubic structure of the CsCl-type (isostructural with CsH2PO4) at its transition temperature of 100-120 °C [3]. Here it is found that, depending on the level of humidification, the superprotonic transition of this material is superimposed with a decomposition reaction, which involves both exsolution of (liquid) acid and loss of H2O. This reaction can be suppressed by application of sufficiently high humidity, in which case Cs6(H2SO4)3(H1.5PO4)4 undergoes a true superprotonic transition. It is proposed that, under conditions of low humidity, the decomposition/dehydration reaction transforms the compound to Cs6(H2-0.5xSO4)3(H1.5PO4)4-x, also of the CsCl structure type at the temperatures of interest, but with a smaller unit cell. With increasing temperature, the decomposition/dehydration proceeds to greater and greater extent and unit cell of the solid phase decreases. This is identified to be the source of the apparent negative thermal expansion behavior.

References

[1] L.A. Cowan, R.M. Morcos, N. Hatada, A. Navrotsky, S.M. Haile, Solid State Ionics 179 (2008) (9-10) 305.

[2] M. Sakashita, H. Fujihisa, K.I. Suzuki, S. Hayashi, K. Honda, Solid State Ionics 178 (2007) (21-22) 1262.

[3] C.R.I. Chisholm, Superprotonic Phase Transitions in Solid Acids: Parameters affecting the presence and stability of superprotonic transitions in the MHnXO4 family of compounds (X=S, Se, P, As; M=Li, Na, K, NH4, Rb, Cs), Materials Science, California Institute of Technology, Pasadena, California (2003).