A study of cubic bismuth oxides of the type bi(26-X)m(X)O(40-delta) (m=ti, mn, fe, co, ni or pb) related to gamma-bi2O3

A structural investigation of cubic oxides (space group I23) of the formula Bi(26-x)M(x)O(40-delta) (M = Ti, Mn, Fe, Co, Ni and Pb) related to the Y-Bi2O3 phase has been carried out by the Rietveld profile analysis of high-resolution X-ray powder diffraction data in order to establish the cation distributions. Compositional dependence of the cation distribution has been examined in the case of Bi26-xCoxO40-delta (1 < x < 16). The study reveals that in Bi(26-X)M(X)O(40-delta) with M = Ti, Mn, Fe, Co or Pb, the M cations tend to occupy tetrahedral (2a) sites when x < 2 while the octahedral (24f) sites are shared by the excess Co or Ni cations with Bi atoms when x > 2. Also experimental magnetic moments of Mn, Co and Ni derivatives have been used to establish the valence state and distribution of these cations.

Stabilized alpha-Ni(OH)2 as electrode material for for alkaline secondary cells

Hydrotalcite-like compounds of formula Ni1-xAl(x)(OH)2(CO3)x/2 . nH2O (x = 0.1 to 0.25), having the same structure as that of alpha-Ni(OH)2, have been synthesized by substituting nickel hydroxide with aluminum. Of these, the compounds of compositions x greater-than-or-equal-to 0.2 are found to have prolonged stability in strong alkaline medium. The electrodes comprising stabilized alpha-Ni(OH)2 of x = 0.2 composition are rechargeable with discharge-capacity values of 240 (+/- 15) mAh-g-1 and are attractive for applications in various alkaline secondary cells employing nickel-positive electrodes.

EXAFS investigations of Ni/gamma-Al2O3 and Ni/AlPO4 catalysts and their precursors

In-situ EXAFS investigations have been carried out on Ni/gamma-Al2O3 catalysts with different metal loadings and prepared from different precursors. When the calcined precursors are reduced in hydrogen, the proportion of nickel metal formed varies with the nature of the precursor employed; NiAl2O4 is the unreduced product. The metal loading does not have any significant effect on the proportion of metal formed except in the case of the catalyst prepared by wet-impregnation, where appreciable metal is obtained only when the loading is greater than 10wt%. Ni/AlPO4 catalysts do not show the formation of NiAl2O4 and reduction to metal is complate, unlike with the Ni/gamma-Al2O3 catalysts which show only partial reduction to metal.

Coadsorption of Dioxygen and Water on the Ni(110) Surface: Role of O1--Type Species in the Dissociation of Water

While the adsorption of dioxygen at a clean Ni(110) surface gives rise to two O(1s) features at 531 and 530 eV assigned to O-(a) and O2-(a) type species respectively, coadsorption of dioxygen and water mixtures result in the additional formation of hydroxyl species characterized by an O(1s) peak at 532.3 eV. The latter is attributed to the oxygen induced dissociation of water via a low energy pathway involving the O-(a)-type species. The proportions of the O-(a) and the hydroxyl species are greater for small O-2/H2O ratios and lower temperatures (120 K). With increase in temperature, the relative surface concentrations of the O-(a) and the hydroxyl species decrease while there is an increase in the concentration of the oxidic O2-(a) species. Thus, the surface concentrations of both the hydroxyl and the O2-(a) species depend critically on the presence of O- type species. Above 300K the surface chemistry in the main involves the conversion of O- to O2- species via the hydroxyl species.

Differences in the glass-forming ability of rapidly solidified and mechanically alloyed Ti-Ni-Cu alloys

Melt spinning of Ti50Ni50 ? xCux (x = 10, 25, 40) alloys showed that the glass-forming ability is good for Cu-rich compositions and poor for Ni-rich compositions. The results of mechanical alloying experiments in the same system showed a reverse trend as far as the glass-forming ability is concerned. These contradictory results are explained in the light of thermodynamic and kinetic considerations. Crystallization results of the melt spun alloys are also presented.

Solid state amorphization in binary Ti---Ni, Ti---Cu and ternary Ti---Ni---Cu system by mechanical alloying

An amorphous phase has been synthesized by mechanical alloying in a planetary mill over a nickel content range of 10�70 at.% in the Ti---Ni system and a copper content range of 10�50 at.% in the Ti---Cu system. In the case of ternary Ti---Ni---Cu alloys the glass-forming composition range has been found to be given by x = 10�20 for Ti60Ni40 ? xCux, x = 10 � 30 for Ti50Ni50 ? xCux and x = 10 � 40 for Ti40Ni60 ? xCux alloys. The difficulty in the amorphization of copper-rich compositions is explained in the light of enthalpy composition diagrams calculated for the ternary solid solution and the amorphous phase.

Microstructural stability and nanoindentation of an electrodeposited nanocrystalline Ni-1.5wt.%P alloy

Microstructural stability of nanocrystalline Ni-1.5wt.%P alloy with an initial grain size of 3 nm processed by pulsed electrodeposition was studied using differential scanning calorimetry (DSC) and annealing. Microstructural characterization suggests that the observed exothermic peak during heating in DSC is related to both concurrent grain growth and Ni3P formation. Nanoindentation on samples with grain sizes from 3 to 50 nm revealed a breakdown in Hall-Petch strengthening in nano Ni-P alloy at grain sizes <= 10 nm, consistent with some previous observations. It is concluded that there is a grain boundary weakening regime for grain sizes < 10 nm, based on analysis which show that the data cannot be rationalized in terms of microstrain relaxation, variation in elastic modulus, texture evolution and duplex structure formation.

Electron microscopy and diffraction of ordering in Ni---W alloys

Electron microscopy and diffraction studies of ordering in stoichiometric Ni-20%W and off-stoichiometric Ni-15%W alloys have been carried out. The specimens of Ni-20%W were first disordered at 1398 K for 4 h and then quenched rapidly into water. Short range order (SRO) spots were observed at {1 1/2 0}* positions. Two hitherto unknown metastable phases: D-2h(25)-Ni2W and DO22-Ni3W were observed in the diffraction patterns. Long range order (LRO) transformations were studied at 1103 and 1213 K. Kinetics and mechanism of transformations have been identified. Ni-15%W specimens were solution treated at 1523 K for 1 h followed by quenching in water. SRO spots similar to those found in Ni-20%W were observed in this alloy as well. The transition to LRO was studied at 1093 K. Distinct Ni4W precipitates could be observed after 5 h of annealing at this temperature. After 100 h of annealing precipitates were found to grow into faceted shape coherent with the disordered matrix. After prolonged annealing for over 150 h the Ni4W precipitates began to lose coherency by the generation of misfit dislocations. The microstructural observations have been compared for the stoichiometric and off-stoichiometric alloys.

Superconductivity of La2?ySryCu1?xNixO4+? (y = 0.1, 0.2; 0less-than-or-equals, slantxless-than-or-equals, slant0.5) The hole-compensating effect of Ni

Magnetization measurements below 50 K on ceramic La2?ySryCu1?xNixO4+? (y = 0.1, 0.2; 0less-than-or-equals, slantxless-than-or-equals, slant0.5) show a progressive diminution of superconducting properties with increasing x. The larger suppressive action of Ni in the y=0.1 system than that for y=0.2 is attributed to the hole-compensating effect of Ni3+. The assumption that nickel is in the 3+ state satisfactorily explains: (1) the reduction in hole concentration, (2) a right-shift of the Tc versus y curve with x, and (3) the low magnetic moment carried by Ni atoms, in the La2?ySryCu1?xNixO4+? system.

Synthesis of new transition metal nitrides, MWN2 (Mtriple bond; length as m-dashMn, Co, Ni)

We report the synthesis of ternary transition metal nitrides of the formula MWN(2) for M=Mn, Co, Ni by reaction of the corresponding MWO(4) with NH3 gas at 600-700 degrees C. MnWN2 is isostructural with the already-known FeWN2, crystallizing in a hexagonal structure (a=2.901(2), b=16.48(5) Angstrom) related to LiMoN2. CoWN2 and NiWN2 (which are isostructural amongst themselves) adopt a different hexagonal structure with a smaller c parameter. While the Mn and Fe nitrides are semiconducting, the Co and Ni nitrides are semimetallic.

Nature of the Oxygen Species at Ni(110) and Ni(100) Surfaces Revealed by Exposure to Oxygen and Oxygen-Ammonia Mixtures: Evidence for the Surface Reactivity of O- Type Species

Adsorption of dioxygen at clean Ni(110) and Ni(100) surfaces gives rise to two prominent features in the O(1s) spectra at 530 and 531 eV due to O2- and O- type species, respectively. Interaction of ammonia with a Ni(100)-O surface where theta(oxygen) < 0.1 ML favors the dissociation of NH3 giving NHn, (n = 1, 2) and N(a) species. This is accompanied by a decrease in the intensity of the 531 eV feature. On the other hand. a Ni(100)-O surface where the oxygen species are mainly of the O2- type is unreactive, Coadsorption studies of NH3-O-2 mixtures show that at Ni(110) surfaces the uptake of both oxygen and ammonia increase with the proportion of oxygen in the NH3-O-2 mixture. The surface concentrations of the O- species and the NHn species also increase with the increase in the O-2/NH3 ratio while the slope of the plot of sigma(N) versus sigma(O-) is around unity. The results demonstrate the high surface reactivity of the O- species and its role in the dissociation of ammonia. Based on these observations, the possibility of the formation of a surface complex between ammonia and oxygen (specifically O-) is suggested. Results from vibrational spectroscopic studies of the coadsorption of NH3-O-2 mixtures are consistent with those from core-level spectroscopic studies.

Photoemission study of pyrite-type transition-metal chalcogenides MS2-xSex (M=Fe, Co, Ni)

The electronic structures of pyrite-type transition-metal chalcogenides MS2-xSex (M = Fe, Co, Ni) has been investigated by photoemission and inverse-photoemission spectroscopy. The valence-band spectrum of ferromagnetic CoS2 does not show exchange splitting of the Co 3d peak, in disagreement with band-structure calculations. High-resolution photoemission spectra of NiS1.55Se0.45 shows spectral weight transfer from low (similar or equal to 50 meV) to high (0.2-0.5 eV) binding energies, in going from the metallic to the insulating phase.

Synthesis of Co(II), Ni(II) and Cu(II) Complexes from Schiff base Ligand and Reactivity Studies with Thermosetting Epoxy Resin

A hybrid thermosetting maleimido epoxy compound 4-(N-maleimidophenyl) glycidylether (N-MPGE) containing Co(II), Ni(II) and Cu(II) ions was prepared by curing N-MPGE and tetradentate Schiff base Co(II), Ni(II) and Cu(II) complexes. The curing polymerization reaction of N-MPGE with metal complexes as curing agents was studied. The cured samples were studied for thermal stability, chemical (acid/alkali/solvent) and water absorption resistance and homogeneity of the cured systems. The tetradentate Schiff base, 3-(Z)-2-piperazin-1-yl-ethylimino]-1,3-dihydro indol-2-one was synthesized by the condensation of Isatin (Indole-2, 3-dione) with 1-(2-aminoethyl)piperazine (AEP). Its complexes with Co(II), Ni(II) and Cu(II) have been synthesized and characterized by microanalysis, conductivity, Uv-Visible, FT-IR, TGA and magnetic susceptibility measurements. The spectral data revealed that the ligand acts as a neutral tetradentate Schiff base and coordinating through the azomethine nitrogen, two piperazine nitrogen atoms and carbonyl oxygen.

Microstructural stability and superplasticity in an electrodeposited nanocrystalline Ni-P alloy

Stabilization of nanocrystalline grain sizes by second phase particles can facilitate superplasticity at high strain rates and/or low temperatures. A metastable single phase nano-Ni-P alloy prepared by electrodeposition, with a grain size of similar to 6 nm, transforms to a nanoduplex structure at T> 673 K, with similar to 4 vol.% Ni3P particles at triple junctions and within Ni grains. The nanoduplex microstructure is reasonably stable up to 777 K, and the growth of Ni grains occurs in a coupled manner with the growth of Ni3P particles such that the ratio of the two mean sizes (Z) is essentially constant. High temperature tests for a grain size of 290 nm reveal superplastic behavior with an optimum elongation to failure of 810% at a strain rate of 7 x 10(-4) s(-1) and a relatively low temperature of 777 K. Superplastic deformation enhances both grain growth and the ratio Z, implying that grain boundary sliding (GBS) significantly influences the microstructural dynamics. Analysis of the deformation processes suggests that superplasticity is associated with GBS controlled by the overcoming of intragranular particles by dislocations, so that deformation is independent of the grain size. The nano-Ni-P alloy exhibits lower ductility than nano-Ni due to concurrent cavitation caused by higher stresses. (C) 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.