Simulation and experimental study on compositional evolution of Li-Co in LiCoO(2) thin films during sputter deposition

The compositional evolution in sputter deposited LiCoO(2) thin films is influenced by process parameters involved during deposition. The electrochemical performance of these films strongly depends on their microstructure, preferential orientation and stoichiometry. The transport process of sputtered Li and Co atoms from the LiCoO(2) target to the substrate, through Ar plasma in a planar magnetron configuration, was investigated based on the Monte Carlo technique. The effect of sputtering gas pressure and the substrate-target distance (d(st)) on Li/Co ratio, as well as, energy and angular distribution of sputtered atoms on the substrate were examined. Stable Li/Co ratios have been obtained at 5 Pa pressure and d(st) in the range 5 11 cm. The kinetic energy and incident angular distribution of Li and Co atoms reaching the substrate have been found to be dependent on sputtering pressure. Simulations were extended to predict compositional variations in films prepared at various process conditions. These results were compared with the composition of films determined experimentally using x-ray photoelectron spectroscopy (XPS). Li/Co ratio calculated using XPS was in moderate agreement with that of the simulated value. The measured film thickness followed the same trend as predicted by simulation. These studies are shown to be useful in understanding the complexities in multicomponent sputtering. (C) 2011 American Institute of Physics. doi:10.1063/1.3597829]

Kinetics of hydrogen evolution on submicron size Co, Ni, Pd and CoNi alloy powder electrodes by d.c. polarization and a.c. impedance studies

Submicron size Co, Ni and Co-Ni alloy powders have been synthesized by the polyol method using the corresponding metal malonates and Pd powder by reduction of PdOx in methanol. The kinetics of the hydrogen evolution reaction ( HER) in 6 M KOH electrolyte have been studied on electrodes made from the pressed powders. The d.c. polarization measurements have resulted in a value close to 120 mV decade(-1) for the Tafel slope, suggesting that the HER follows the Volmer-Heyrovsky mechanism. The values of exchange current density (i(o)) are in the range 1-10 mA cm(-2) for electrodes fabricated in the study. The a.c. impedance spectra measured at several potentials in the HER region showed a single semicircle in the Nyquist plots. Exchange current density (i(o)) and energy transfer coefficient (alpha) have been calculated by employing a nonlinear least square-fitting program.

Self-assembled molecular films of tetraamino metal (Co, Cu, Fe) phthalocyanines on gold and silver. Electrochemical and spectroscopic characterization

The formation of molecular films of 2,9,16,23-tetraamino metal phthalocyanines [TAM(II)Pc; M (II) = Co, Cu, and TAM(III)Pc; M = Fe] by spontaneous adsorption on gold and silver surfaces is described. The properties of these films have been investigated by cyclic voltammetry, impedance, and FT-Raman spectroscopy. The charge associated with Co(II) and Co(I) redox couple in voltammetric data leads to a coverage of (0.35+/-0.05) x 10(-10) mol cm(-2), suggesting that the tetraamino cobalt phthalocyanine is adsorbed as a monolayer with an almost complete coverage. The blocking behavior of the films toward oxygen and Fe(CN)(6)(3-/4-) redox couple have been followed by cyclic voltammetry and impedance measurements. This leads to an estimate of the coverage of about 85 % in the case of copper and the iron analogs. FT-Raman studies show characteristic bands around 236 cm(-1) revealing the interaction between the metal substrate and the nitrogen of the -NH2 group on the phthalocyanine molecules.

Phase relations and activities in the Co Ni O system at 1373 K

The tie-lines delineating equilibria between CoO-NiO and Co-Ni solid solutions in the ternary Co-Ni-O system at 1373 K have been determined by electron microprobe andedax point count analysis of the oxide phase equilibrated with the alloy. The oxygen potentials corresponding to the tie-line compositions have been measured using a solid oxide galvanic cell with calcia-stabilized zirconia electrolyte and Ni + NiO reference electrode. Activities in the metallic and oxide solid solution have been derived using a new Gibbs-Duhem integration technique. Both phases exhibit small positive deviations from ideality; the values ofG E/X 1 X 2 are 2640 J mol−1 for the metallic phase and 2870 J mol−1 for the oxide solid solution.

Phase equilibria in the Co Ni F system and activities in (CoxNi1 x)F2 solid solutions at 1373 K

The tie-lines delineating equilibria between CoF2-NiF2 and Co-Ni solid solutions in the ternary Co-Ni-F system at 1373 K have been determined by electron microprobe and EDAX point count analysis of the equilibrated phases. Activities in the fluoride solid solution have been derived from the knowledge of activitycomposition relation in the metallic solid solution and tie-line data,using a modified form of the Gibbs-Duhem integration. The fluorine potentials corresponding to the tie-line compositions have been calculated.The excess Gibbs' energy of mixing for the fluoride solid solution derived from the present data can be represented by the expression

Simulation and experimental study on compositional evolution of Li-Co in LiCoO2 thin films during sputter deposition

The compositional evolution in sputter deposited LiCoO2 thin films is influenced by process parameters involved during deposition. The electrochemical performance of these films strongly depends on their microstructure, preferential orientation and stoichiometry. The transport process of sputtered Li and Co atoms from the LiCoO2 target to the substrate, through Ar plasma in a planar magnetron configuration, was investigated based on the Monte Carlo technique. The effect of sputtering gas pressure and the substrate-target distance (dst) on Li/Co ratio, as well as, energy and angular distribution of sputtered atoms on the substrate were examined. Stable Li/Co ratios have been obtained at 5 Pa pressure and dst in the range 5−11 cm. The kinetic energy and incident angular distribution of Li and Co atoms reaching the substrate have been found to be dependent on sputtering pressure. Simulations were extended to predict compositional variations in films prepared at various process conditions. These results were compared with the composition of films determined experimentally using x-ray photoelectron spectroscopy (XPS). Li/Co ratio calculated using XPS was in moderate agreement with that of the simulated value. The measured film thickness followed the same trend as predicted by simulation. These studies are shown to be useful in understanding the complexities in multicomponent sputtering.

Investigations on structural and optical properties of co-doped (Ag, Co) ZnO nanoparticles

Undoped and co-doped (Ag, Co) ZnO powders were synthesized by chemical co-precipitation method without using any capping agent. The X-ray diffraction results indicate that the undoped and co-doped ZnO powders have pure hexagonal structure and are consisting of nanosized single-crystalline particles. The size of the nanoparticles increases with increasing Ag concentration from 1 to 5 mol% as compared to that of undoped ZnO. The presence of substitution dopants of Ag and Co in the ZnO host material was confirmed by the Energy dispersive analysis of X-rays (EDAX). Optical absorption measurements indicate blue shift and red-shift in the absorption band edge upon doping concentration of Ag and blue emission was observed by photoluminescence (PL) studies.

Synthon identification in co-crystals and polymorphs with IR spectroscopy. Primary amides as a case study

IR spectroscopy has been widely employed to distinguish between different crystal forms such as polymorphs, clathrates, hydrates and co-crystals. IR has been used to monitor co-crystal formation and single synthon detection. In this work, we have developed a strategy to identify multiple supramolecular synthons in polymorphs and co-crystals with this technique. The identification of multiple synthons in co-crystals with IR is difficult for several reasons. In this paper, a four step method involving well assigned IR spectral markers that correspond to bonds in a synthon is used. IR spectra of three forms of the co-crystal system, 4-hydroxybenzoic acid: 4,4'-bipyridine (2 : 1), show clear differences that may be attributed to differences in the synthon combinations existing in the forms (synthon polymorphism). These differences were picked out from the three IR spectra and the bands analysed and assigned to synthons. Our method first identifies IR marker bands corresponding to (covalent) bonds in known/model crystals and then the markers are mapped in known co-crystals having single synthons. Thereafter, the IR markers are queried in known co-crystals with multiple synthons. Finally they are queried in unknown co-crystals with multiple synthons. In the last part of the study, the N-H stretching absorptions of primary amides that crystallize with the amide dimers linked in a ladder like chain show two specific absorptions which are used as marker absorptions and all variations of this band structure have been used to provide details on the environment around the dimer. The extended dimer can accordingly be easily distinguished from the isolated dimer.

Structural and magnetic properties of SmCo5/Co exchange coupled nanocomposite thin films

We investigated the structural and magnetic properties of SmCo5/Co exchange coupled nanocomposite thin films grown by magnetron sputtering from Sm and Co multitargets successively. The growth of the films was carried out at elevated substrate temperature followed by in situ annealing. On Si (100) substrate, X-ray diffraction confirms the formation of textured (110) SmCo5 hard phase, whereas on MgO (110) substrate, the diffraction pattern shows the epitaxial growth of SmCo5 phase with crystalline orientation along 100] direction. Secondary Ion Mass Spectroscopy reveals the structural transformation from multilayered (Sm/Co) to SmCo5/Co nano-composite films due to high reactivity of Sm at elevated temperature. Transmission electron microscopy indicates the existence of nanocrystalline phase of SmCo5 along with unreacted Co. Observed single phase behavior in magnetic hysteresis measurements indicates well exchange coupling between the soft and the hard phases in these nano-composite films. For samples with samarium layer thickness, t(sm)=3.2 nm and cobalt layer thickness, t(Co)= 11.4 nm, the values of (BH)(max) were obtained as 20.1 MGOe and 12.38 MGOe with H-c value similar to 3.0 kOe grown on MgO and Si substrates, respectively.

DRIFTS studies on CO and NO adsorption and NO plus CO reaction over Pd2+-substituted CeO2 and Ce0.75Sn0.25O2 catalysts

Sequential adsorption of CO and NO as well as equimolar NO + CO reaction with variation of temperature over Pd2+ ion-substituted CeO2 and Ce0.75Sn0.25O2 supports has been studied by DRIFTS technique. The results are compared with 2 at.% Pd/Al2O3 containing Pd-0. Both linear and bridging Pd-0-CO bands are observed over 2 at.% Pd/Al2O3. But, band positions are shifted to higher frequencies in Ce0.98Pd0.02O2-delta and Ce0.73Sn0.25Pd0.02O2-delta catalysts that could be associated with Pd delta+-CO species. In contrast, a Pd2+-CO band at 2160 cm(-1) is observed upon CO adsorption over Ce0.98Pd0.02O2-delta and Ce0.73Sn0.25Pd0.02O2-delta catalysts pre-adsorbed with NO and a Pd+-CO band at 2120 cm(-1) is slowly developed on Ce(0.73)Srl(0.25)Pd(0.02)O(2-delta) over time. An intense linear Pd-0-NO band at 1750 cm(-1) found upon NO exposure to CO pre-adsorbed 2 at.% Pd/Al2O3 indicates molecular adsorption of NO. On the other hand, a weak Pd2+-NO band at 1850 cm(-1) is noticed after NO exposure to Ce0.98Pd0.02O2-delta catalyst pre-adsorbed with CO indicating dissociative adsorption of NO which is crucial for NO reduction. Pd-0-NO band is initially formed over CO pre-adsorbed Ce0.73Sn0.25Pd0.02O2-delta which is red-shifted over time along with formation of Pd2+-NO band. Several intense bands related to nitrates and nitrites are observed after exposure of NO to fresh as well as CO pre-adsorbed Ce0.98Pd0.02O2-delta and Ce0.73Sn0.25Pd0.02O2-delta catalysts. Ramping the temperature in a DRIFTS cell upon NO and CO adsorption shows the formation of N2O and NCO surface species, and N2O-formation temperature is comparable with the reaction done in a reactor.

Aza-induced cardiomyocyte differentiation of P19 EC-cells by epigenetic co-regulation and ERK signaling

Stem cells in cell based therapy for cardiac injury is being potentially considered. However, genetic regulatory networks involved in cardiac differentiation are not clearly understood. Among stem cell differentiation models, mouse P19 embryonic carcinoma (EC) cells, are employed for studying (epi)genetic regulation of cardiomyocyte differentiation. Here, we comprehensively assessed cardiogenic differentiation potential of 5-azacytidine (Aza) on P19 EC-cells, associated gene expression profiles and the changes in DNA methylation, histone acetylation and activated-ERK signaling status during differentiation. Initial exposure of Aza to cultured EC-cells leads to an efficient (55%) differentiation to cardiomyocyte-rich embryoid bodies with a threefold (16.8%) increase in the cTnI(+) cardiomyocytes. Expression levels of cardiac-specific gene markers i.e., Isl-1, BMP-2, GATA-4, and alpha-MHC were up-regulated following Aza induction, accompanied by differential changes in their methylation status particularly that of BMP-2 and alpha-MHC. Additionally, increases in the levels of acetylated-H3 and pERK were observed during Aza-induced cardiac differentiation. These studies demonstrate that Aza is a potent cardiac inducer when treated during the initial phase of differentiation of mouse P19 EC-cells and its effect is brought about epigenetically and co-ordinatedly by hypo-methylation and histone acetylation-mediated hyper-expression of cardiogenesis-associated genes and involving activation of ERK signaling.

New rock salt-related oxides Li3M2RuO6 (M=Co, Ni): Synthesis, structure, magnetism and electrochemistry

We describe the synthesis, crystal structure, magnetic and electrochemical characterization of new rock salt-related oxides of formula, Li3M2RuO6 (M=Co, Ni). The M=Co oxide adopts the LiCoO2 (R-3m) structure, where sheets of LiO6 and (Co-2/Ru)O-6 octahedra are alternately stacked along the c-direction. The M=Ni oxide also adopts a similar layered structure related to Li2TiO3, where partial mixing of Li and Ni/Ru atoms lowers the symmetry to monoclinic (C2/c). Magnetic susceptibility measurements reveal that in Li3Co2RuO6, the oxidation states of transition metal ions are Co3+ (S=0), Co2+ (S=1/2) and Ru4+ (S=1), all of them in low-spin configuration and at 10 K, the material orders antiferromagnetically. Analogous Li3Ni2RuO6 presents a ferrimagnetic behavior with a Curie temperature of 100 K. The differences in the magnetic behavior have been explained in terms of differences in the crystal structure. Electrochemical studies correlate well with both magnetic properties and crystal structure. Li-transition metal intermixing may be at the origin of the more impeded oxidation of Li3Ni2RuO6 when compared to Li3CO2RuO6. Interestingly high first charge capacities (between ca. 160 and 180 mAh g(-1)) corresponding to ca. 2/3 of theoretical capacity are reached albeit, in both cases, capacity retention and cyclability are not satisfactory enough to consider these materials as alternatives to LiCoO2. (C) 2013 Elsevier Inc. All rights reserved.

Physical and magnetic properties of (Co, Ag) doped ZnO nanoparticles

Undoped and (Co, Ag) co-doped ZnO nanostructure powders are synthesized by chemical precipitation method without using any capping agent and annealed in air ambient at 500 A degrees C for 1 h. Here, the Ag concentration is fixed at 5 mol% and Co concentration is increased from 0 to 5 mol%. The X-ray diffraction studies reveal that undoped and doped ZnO powders consist of pure hexagonal structure and nano-sized crystallites. The novel Raman peak at 530 cm(-1) has corroborated with the Co doped ZnO nanoparticles. Moreover, the PL studies reveal that as the Co doping concentration increases and it enters into ZnO lattice as substitutional dopant, it leads to the increase of oxygen vacancies (Vo) and zinc interstitials (Zn-i). From the magnetization measurements, it is noticed that the co-doped ZnO nanostructures exhibit considerably robust ferromagnetism i.e. 4.29 emu g(-1) even at room temperature. These (Co, Ag) co-doped ZnO nanopowders can be used in the fabrication of spintronic and optoelectronic device applications.

What is... definitions and ideas in co-management

A discussion is presented on fisheries management and various strategies which may be operated and the problems involved. Topics such as access, property, and co-management are covered and an examination is made of the role that Fishery Departments can play in management. [PDF contains 19 pages]

Combustion of CSâ‚‚/Oâ‚‚ in a laminar mixing layer and processes in the CO chemical laser

The combustion of CSâ‚‚ and Oâ‚‚ in a free burning laminar mixing layer at low pressure was investigated using emission spectroscopy. The temperature fields, CO vibrational distributions, and CO concentrations were measured. The data indicate that vibration ally excited CO was produced in the mixing layer flames, but that there were no vibrational population inversions. In comparison with the CSâ‚‚/Oâ‚‚ premixed flames, the mixing layer flames favored greater production of COS and COâ‚‚. Computer modeling was used to study the mechanisms responsible for the production of COS and COâ‚‚, and to study how the branching chain mechanism responsible for production of CO affects the behavior of the mixing layer flame. The influences of the gas additives, Nâ‚‚O, COS, and CNBr, were also investigated.