Impedance spectroscopic studies of planetary ball-milled lithium titanium phosphate material

The ac electrical conductivity properties of LiTi₂(PO₄)₃ (LTP) polycrystalline material in two different crystallite sizes are compared. Micrometer sized LTP is prepared by conventional solid-state reaction. LTP crystallites of 71 nm size are prepared by solid-state reaction of 40 h planetary milled stoichiometric mixture. The XRD and SEM are used as characterization techniques. Electrical properties are studied using impedance spectroscopic technique. Ball-milled LTP shows one order increase in grain-interior conduction compared to microcrystalline LTP at 388 K. The increase in conduction results from decreased crystallite size.     

Numerical analysis of a moving boundary problem in coastal hydrodynamics

A finite element model to tackle the moving boundary problem of wave run-up on moderately steep slopes is developed. The special aspects considered in this study are (1) the modification of shallow water equations to accommodate the effect of vertical accelerations and (2) the use of Lagrangian acceleration coupled with an element that adapts itself to the moving boundary closely. The pressure term in the one-dimensional momentum equation is derived using the Eulerian equation in the vertical direction. This takes care of the vertical accelerations which are significant during the motion of a wave on moderately steep slopes. The element near the boundary is allowed to change its dimension so that the fluid boundary is closely followed. Such a flexible element precludes the need for approximation of the variables with regard to the indefinite position of the boundary. This element is split into two when its dimension becomes unduly large compared to the unchanging elements. The need for such a splitting is shown by an examination of the entries in the global matrix. Results of water profile as a wave runs up a structure are given. A brief history of the work on similar problems is outlined.     

Ruthenium(IV) pyrochlore oxides: Realization of novel electronic properties through substitution at A- and B-sites

We describe an exploratory investigation of the structure and electronic properties of new ruthenium(IV) pyrochlore oxides and their manganese-substituted derivatives. Our investigations have revealed several, hitherto unreported, electronic ground states for these materials: a metallic and Pauli paramagnetic state for BiPbRu₂O_6.5 that turns into a semiconducting ferromagnetic spin-glass state at 50 K for BiPbRuMnO_6.5; a metallic state that likely shows a charge density wave (CDW) instability at 50–225 K for Bi_1.50Zn_0.50Ru₂O_6.75 that is suppressed by manganese substitution in Bi_1.50Zn_0.50Ru_1.75Mn_0.25O_6.50; and a metallic ferromagnetic spin-glass like state for Pb₂Ru_1.75Mn_0.25O_6.15. The results indeed affirm the richness of the electronic properties of ruthenium-based metal oxides.     

A rapid, acetonitrile-free, HPLC method for determination of melamine in infant formula

A simple, precise, accurate and validated, acetonitrile-free, reverse phase high performance liquid chromatography (HPLC) method is developed for the determination of melamine in dry and liquid infant formula. The separation is performed on a Kromasil C18 column (150 mm × 3.2 mm I.D., 5 μm particle size) at room temperature. The mobile phase (0.1% TFA/methanol 90:10) is pumped at a flow rate of 0.3 mL min⁻¹ with detection at 240 nm. Melamine elutes at 3.7 min. A linear response (r > 0.999) is observed for samples ranging from 1.0 to 80 μg mL⁻¹. The method provides recoveries of 97.2-101.2% in the concentration range of 5-40 μg mL⁻¹, intra- and inter-day variation in <1.0% R.S.D. The limit of detection (LOD) and limit of quantification (LOQ) values are 0.1 μg mL⁻¹ and 0.2 μg mL⁻¹, respectively.     

Magnetization and EPR of a series of Cr squarate dimers

A series of Cr(III) dimers were synthesized from a parent compound [Cr₂(μ-oxo)₂(μ_1,2-C₄O₄)₂(H₂O)₄]·2H₂O (I) by ligand substitution. The compounds have been analyzed using variable frequency EPR (9–110 GHz) and magnetic susceptibility as a function of field (0–9 T) and temperature (1.9–300 K) to obtain their electronic g-values, exchange energies, and zero-field parameters. The parent compound exhibits a broad maximum around 34 K characteristic of a dimer with antiferromagnetic coupling that fit the Van Vleck susceptibility model well. It was found that the maxima could be tuned from 34 to 80 K by ligand substitution of the waters. Each compound possesses a characteristic color spanning the range of teal to pink. The g-value of each compound was found to be ∼1.98 using spectral simulation. The DMSO derivative is water soluble and has a high LC₅₀ for PC3 cancer cells, suggesting its use as a magnetic resonance imaging agent. X-ray crystal structure of the DMSO derivative [Cr₂(μ-oxo)₂(μ_1,2-C₄O₄)₂(C₂H₆SO)₄]·2H₂O (II) revealed that the DMSO ligands are equatorial, and the squarate groups bridge the two chromiums. This is in contrast to the previously proposed structure of the parent compound where the water ligands were axial and the equatorial squarate groups did not bridge the chromiums. These compounds are interesting because of their ease of synthesis, and their wide range of magnetic behavior. The compounds are good probes into antiferromagnetic dimer exchange by controlling the ligand field surrounding the superexchange pathway present in the molecule.     

Photophysical investigation of 3-substituted 4-alkyl and/or 7-acetoxy coumarin derivatives—A study of the effect of substituents on fluorescence

In the present work an array of novel substituted 2H-chromen-2-one (coumarin) derivatives has been subjected to photophysical analysis. Though the influence of the electron-donating groups such as amino, substituted amino, hydroxyl, alkoxy groups, etc. at position 7 of the coumarin ring system has been extensively studied, the luminescent properties of the coumarin moieties with an acetoxy substituent have not been explored. Herein it is attempted to study the variation of fluorescence behavior of substituted coumarin derivatives with change of nature and position of the substituents on the 2H-chromen-2-one skeleton. Effect of a methyl substituent at position 4 which imposes abnormal photophysical behavior to the chromenone unit has also been briefly described.     

Synthesis of poly(p‐phenylenediamine‐ co‐o‐aminophenol)/multi‐walled carbon nanotube composites by emulsion polymerization

Organic–inorganic composites composed of electrically conducting copolymer p‐phenylenediamine‐ co‐o‐aminophenol and carboxylic acid functionalized multi‐walled carbon nanotubes [poly(pPD‐co‐oAP)/c‐MWNTs] were prepared via in situ emulsion pathway using sodium dodecyl sulphate (SDS) as an emulsifier and potassium persulphate as an oxidant. Acid functionalized MWNTs were used as cores in the formation of tubular shells of the composites. TEM and FESEM analysis showed that a tubular layer of coated copolymer film of several nanometer thicknesses is present on the c‐MWNTs surfaces. FT‐IR spectra endorsed the formation of composites. TGA results indicated that the decomposition temperatures of composites were higher than the bare copolymer. UV‐visible absorption spectra of diluted colloidal dispersion of composites were similar to those of the bare copolymer. The composites were also confirmed by XRD and XPS. Room‐temperature conductivity increases with an increasing fraction of c‐MWNTs. Copyright © 2009 John Wiley & Sons, Ltd.     

Growth and characterization of 2-amino-4-picolinium 4-aminobenzoate single crystals

The organic material of 2-amino-4-picolinium 4-aminobenzoate (C₆H₉N₂⁺·C₇H₆NO₂^?) was synthesized and grown as single crystals at room temperature by slow evaporation solution growth technique in the constant temperature bath (±0.01 °C) using ethanol as solvent. The grown crystals were characterized by XRD and FT-IR spectral analyses. The melting point, density, UV–visible spectral studies were carried out for the grown crystals. The theoretical factor group analysis predicts 372 internal modes of vibration and optical modes in the grown title compound. The second harmonic generation (SHG) output of 2-amino-4-picolinium 4-aminobenzoate was recorded by Kurtz–Perry powder technique and it is found to be 355 mV at a given pulse energy of 1.45 mJ/s and for urea the SHG output was 525 mV. The dielectric behaviour of 2-amino-4-picolinium 4-aminobenzoate was investigated with different frequencies and temperatures.     

A class of discontinuous Petrov–Galerkin methods. II. Optimal test functions

We lay out a program for constructing discontinuous Petrov–Galerkin (DPG) schemes having test function spaces that are automatically computable to guarantee stability. Given a trial space, a DPG discretization using its optimal test space counterpart inherits stability from the well posedness of the undiscretized problem. Although the question of stable test space choice had attracted the attention of many previous authors, the novelty in our approach lies in the fact we identify a discontinuous Galerkin (DG) framework wherein test functions, arbitrarily close to the optimal ones, can be locally computed. The idea is presented abstractly and its feasibility illustrated through several theoretical and numerical examples. © 2010 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq 2010     

Experimental investigation on the flow instability behavior of a multi-channel boiling natural circulation loop at low-pressures

Natural circulation as a mode of heat removal is being considered as a prominent passive feature in the innovative nuclear reactor designs, particularly in boiling-water-reactors, due to its simplicity and economy. However, boiling natural circulation system poses many challenges to designer due to occurrence of various kinds of instabilities such as excursive instability, density wave oscillations, flow pattern transition instability, geysering and metastable states in parallel channels. This problem assumes greater significance particularly at low-pressures i.e. during startup, where there is great difference in the properties of two phases. In light of this, a parallel channel loop has been designed and installed that has a geometrical resemblance to the pressure-tube-type boiling-water-reactor, to investigate into the behavior of boiling natural circulation. The loop comprises of four identical parallel channels connected between two common plenums i.e. steam drum and header. The recirculation path is provided by a single downcomer connected between steam drum and header. Experiments have been conducted over a wide range of power and pressures (1–10 bar). Two distinct unstable zones are observed with respect to power i.e. corresponding to low power (Type-I) and high power (Type-II) with a stable zone at intermediate powers. The nature of oscillations in terms of their amplitude and frequency and their evolution for Type-I and Type-II instabilities are studied with respect to the effect of heater power and pressure. This paper discusses the evolution of unstable and stable behavior along with the nature of flow oscillation in the channels and the effect of pressure on it.