Effect of nanoscale CeO<Subscript>2</Subscript> on PVDF-HFP-based nanocomposite porous polymer electrolytes for Li-ion batteries

New poly (vinylidenefluoride-co-hexafluoro propylene) (PVDF-HFP)/CeO₂-based microcomposite porous polymer membranes (MCPPM) and nanocomposite porous polymer membranes (NCPPM) were prepared by phase inversion technique using N-methyl 2-pyrrolidone (NMP) as a solvent and deionized water as a nonsolvent. Phase inversion occurred on the MCPPM/NCPPM when it is treated by deionized water (nonsolvent). Microcomposite porous polymer electrolytes (MCPPE) and nanocomposite porous polymer electrolytes (NCPPE) were obtained from their composite porous polymer membranes when immersed in 1.0 M LiClO₄ in a mixture of ethylene carbonate/dimethyl carbonate (EC/DMC) (v/v = 1:1) electrolyte solution. The structure and porous morphology of both composite porous polymer membranes was examined by scanning electron microscope (SEM) analysis. Thermal behavior of both MCPPM/NCPPM was investigated from DSC analysis. Optimized filler (8 wt% CeO₂) added to the NCPPM increases the porosity (72%) than MCPPM (59%). The results showed that the NCPPE has high electrolyte solution uptake (150%) and maximum ionic conductivity value of 2.47 × 10⁻³ S cm⁻¹ at room temperature. The NCPPE (8 wt% CeO₂) between the lithium metal electrodes were found to have low interfacial resistance (760 Ω cm²) and wide electrochemical stability up to 4.7 V (vs Li/Li⁺) investigated by impedance spectra and linear sweep voltammetry (LSV), respectively. A prototype battery, which consists of NCPPE between the graphite anode and LiCoO₂ cathode, proves good cycling performance at a discharge rate of C/2 for Li-ion polymer batteries.     

Sol–gel synthesis and optical behavior of Mg–Ce–O nano-crystallites

The Mg–Ce–O powder are shown to contain periclase-type MgO and/or fluoride-type cerium oxide (CeO₂) depending upon the composition (x) defined by Ce/(Ce + Mg) atomic ratio. Lattice contraction of pariclase phase of MgO (average crystallite size ~8.8 nm) at Ce content of ‘x’ = 0.20 in comparison to pure MgO (crystallite size ~9.5 nm) has been realized due to oxygen vacancy formation. The optical band gap values of CeO₂ varies (3.0–3.2 eV) due to oxygen vacancy formation in CeO₂ phase, crystallite size and/or Ce³⁺/Ce⁴⁺ ratio. Further, the addition of Ce has shown to reduce the physisorption and chemisorption of water significantly as reflected by (1) suppression of related absorption peaks and (2) absence of magnesium hydroxide, Mg(OH)₂, bands in Fourier transform infrared spectra.     

Demonstration of high‐precision continuous measurements of water vapor isotopologues in laboratory and remote field deployments using wavelength‐scanned cavity ring‐down spectroscopy (WS‐CRDS) technology

This study demonstrates the application of Wavelength‐Scanned Cavity Ring‐Down Spectroscopy (WS‐CRDS) technology which is used to measure the stable isotopic composition of water. This isotopic water analyzer incorporates an evaporator system that allows liquid water as well as water vapor to be measured with high precision. The analyzer can measure HO, HO and HD¹⁶O content of the water sample simultaneously. The results of a laboratory test and two field trials with this analyzer are described. The results of these trials show that the isotopic water analyzer gives precise, accurate measurements with little or no instrument drift for the two most common isotopologues of water. In the laboratory the analyzer has a precision of 0.5 per mil for δD and 0.1 per mil for δ¹⁸O which is similar to the precision obtained by laboratory‐based isotope ratio mass spectrometers. In the field, when measuring vapor samples, the analyzer has a precision of 1.0 per mil for δD and 0.2 per mil for δ¹⁸O. These results demonstrate that the isotopic water analyzer is a powerful tool that is appropriate for use in a wide range of applications and environments. Copyright © 2009 John Wiley & Sons, Ltd.     

Synthesis, spectroscopic, redox, catalytic and antimicrobial properties of some ruthenium(II) Schiff base complexes

A new series of mixed ligand semicarbazone or thiosemicarbazone complexes of Ru(II) having the general formula [RuCO(EPh₃)(B)L] (where E = P or As; B = PPh₃, AsPh₃ or Pyridine; L = dibasic tridentate ligand derived by the condensation of ethylacetoacetate/methylacetoacetate and thiosemicarbazide/semicarbazide) have been synthesized and characterized by physico-chemical, spectroscopic and electrochemical studies. A comparative study on the catalysis of oxidation of benzyl alcohol, cyclohexanol, cinnamyl alcohol, n-butanol, n-propanol and iso-butyl alcohol has been done with N-methylmorpholine-N-oxide and molecular oxygen as co-oxidants. Catalytic activity studies of the complexes in coupling reactions have been carried out. The antibacterial properties of the complexes have also been examined.     

Infrared matrix isolation study of the thermal and photochemical reactions of ozone with dimethylzinc

The matrix isolation technique has been combined with infrared spectroscopy and theoretical calculations to explore the reaction of (CH3)2Zn with O3 over a range of time scales. Upon twin jet deposition, an initial cage pair complex was observed, along with formation of the novel H3COZnCH3 species. Subsequent UV irradiation destroyed the complex and greatly increased the yield of H3COZnCH3. An extensive set of bands were seen for this molecule, and (18)O spectroscopic data were obtained as well. The identification of this species was supported by theoretical calculations at the B3LYP/6-311++g(d,2p) level. Merged jet deposition led to a very different set of products, including H2CO, CH3OH and C2H6, identifications that were confirmed by (18)O substitution. In addition, a new variable length concentric deposition technique was developed to permit study of the time scales between twin (relatively short) and merged (relatively longer) reaction times. Mechanistic inferences for this reaction are discussed.     

Preparation and dielectric properties of oxide added NaCl-KCl polycrystals

Pure and ZnO and CdO added (separately) polycrystals of NaCl, KCl and (NaCl)_0.5(KCl)_0.5 were prepared by the melt method. Density, atomic absorption spectroscopic and X-ray diffraction measurements indicate that the ZnO and CdO have entered into the lattices of alkali halide crystals. The dielectric measurements indicate that the dielectric parameters increase with the increase in temperature. Also, the dielectric constant and dielectric loss factor values decreased whereas the electrical conductivities increased with the increase in frequency of the AC applied. Significant changes have been observed with the dielectric parameters caused by ZnO and CdO additions. Also, the depth profile study was carried out on CdO added crystals which indicates that the dopant addition creates different layers along the crystal with increase of dopant content from top to bottom.     

Optical and dielectric studies on succinic acid single crystals

Single crystals of ferroelectric succinic acid (SA) with very high degree of transparency were grown from aqueous solution by slow evaporation technique. Single crystal X‐ray diffraction analysis reveals that the crystal belongs to monoclinic system with the space group P2₁/c. Some physical parameters have been determined for grown crystal. The optical absorption study reveals the transparency of the crystal in the entire visible region and the cut off wave length was found to be 240 nm. The optical band gap is found to be 3.75 eV. The dependence of extinction coefficient (k) and refractive index (n) on the wavelength have also been reported. The presence of functional groups was determined qualitatively by using Fourier transform infrared spectrum (FTIR) from which force constant has been calculated. The dielectric constant was also studied as a function of frequency at room temperature and electrical conductivity has been calculated from the Cole‐Cole plot. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Electrochemistry of 4′-hydroxy and acetoxy flavones CV and NPP study

Electrochemical reduction behavior of 3-acetoxyflavone was compared with 3-hydroxyflavone on glassy carbon electrode with DMF and 60% DMF/Britton Robinson buffer at pH 3.8 & 10.1 using cyclic voltammetry (CV) and on dme using normal pulse polarography (NPP). Single irreversible reduction waves were observed due to the reduction of keto moiety. The effects of change in medium, pH and sweep rate were evaluated. The electrode process was found to be diffusion controlled and enhanced substituent effect was noticed due to extended conjugation. Kinetic parameters were calculated from CV & NPP measurements using R.S. Nicholson and I. Shain equation and Meites & Isreal equation, respectively. Paper presented at the 2nd International Conference on Ionic Devices, Anna University, Chennai, India, Nov. 28–30, 2003.