Development of a clean bioelectrochemical process for leaching of ocean manganese nodules

Through the application of negative reduction potential significant reduction of manganic and iron oxides in the ocean manganese nodules can be achieved, liberating the occluded copper, nickel and cobalt for easy dissolution in an acid medium. Electroleaching and electrobioleaching of ocean manganese nodules in the presence of Thiobacillus ferrooxidans and Thiobacillus thiooxidans at the above negative applied dc potentials resulted in significant dissolution of copper, nickel and cobalt in 1 M H2SO4. The role of galvanic interactions in the bioleaching of ocean manganese nodules in the presence of T thiooxidans is also discussed, (C) 2002 Published by Elsevier Science Ltd.

Electrochemical aspects of leaching of ocean nodules in the presence and absence of microorganisms

instead of using chemical-reducing agents to facilitate the reduction and dissolution of manganese and iron oxide in the ocean nodule, electrochemical reduction based on two approaches, namely, cathodic polarization and galvanic interaction, can also be considered as attractive alternatives. Galvanic leaching of ocean nodules in the presence of pyrite and pyrolusite for complete recovery of Cu, Ni and Co has been discussed. The key for successful and efficient dissolution of copper, nickel and cobalt from ocean nodules depends on prior reduction of the manganese and ferric oxides with which the above valuable nonferrous metals are interlocked. Polarization studies using a slurry electrode system indicated that maximum dissolution of iron and manganese due to electrochemical reduction occurred at negative DC potentials of -600 mV (SCE) and -1400 mV (SCE). The present work is also relevant to galvanic bioleaching of ocean nodules using autotrophic microorganisms, such as Thiobacillus ferrooxidans and T thiooxidans, which resulted in significant dissolution of copper, nickel and cobalt at the expense of microbiologically generated acids. Various electrochemical and biochemical mechanisms are outlined and the electroleaching and galvanic processes so developed are shown to yield almost complete dissolution of all metal values. (C) 2002 Elsevier Science B.V. All rights reserved.

First-principles electronic structure of the delafossites ABO(2) (A=Cu, Ag, Au; B=Al, Ga, Sc, In, Y): evolution of d(10)-d(10) interactions

While bonding between d(10) atoms and ions in molecular systems has been well studied, less attention has been paid to interactions between such seemingly closed shell species in extended inorganic solids. In this contribution, we present visualizations of the electronic structures of the delafossites ABO(2) (A = Cu, Ag, Au) with particular emphasis on the nature of d(10)-d(10) interactions in the close packed plane of the coinage metal ion. We find that on going from Cu to Ag to Au, the extent of bonding between A and A increases. However, the structures (in terms of distances) of these compounds are largely determined by the strongly ionic 13,11 0 interaction and for the larger B ions Sc, In and Y, the A atoms are sufficiently well-separated that A-A bonding is almost negligible. We also analyze some interesting differences between Ag and Au, including the larger A-O covalency of the Au. The trends in electronic structure suggest that the Ag and Au compounds are not good candidate transparent conducting oxides. (C) 2002 Editions scientifiques et medicales Elsevier SAS. All rights reserved.

High temperature phase chemistry of system Eu-Pd-O

An isothermal section of the phase diagram for the system Eu - Pd - O at 1223 K has been established by equilibration of samples representing 20 different compositions, and phase identification after quenching by optical and scanning electron microscopy, X-ray powder diffraction, and energy dispersive spectroscopy. Three ternary oxides, Eu4PdO7, Eu2PdO4, and Eu2Pd2O5, were identified. Liquid alloys and the intermetallic compounds EuPd2 and EuPd3 were found to be in equilibrium with EuO. The compound EuPd3 was also found to coexist separately with Eu3O4 and Eu2O3. The oxide phase in equilibrium with EuPd5 and Pd rich solid solution was Eu2O3. Based on the phase relations, four solid state cells were designed to measure the Gibbs energies of formation of the three ternary oxides in the temperature range from 925 to 1350 K. Although three cells are sufficient to obtain the properties of the three compounds, the fourth cell was deployed to crosscheck the data. An advanced version of the solid state cell incorporating a buffer electrode with yttria stabilised zirconia solid electrolyte and pure oxygen gas at a pressure of 0.1 MPa as the reference electrode was used for high temperature thermodynamic measurements. Equations for the standard Gibbs energy of formation of the interoxide compounds from their component binary oxides Eu2O3 with C type structure and PdO have been established. Based on the thermodynamic information, isothermal chemical potential diagrams and isobaric phase diagrams for the system Eu - Pd - O have been developed.

Measurement of 1/f noise and its application in materials science

This is a review of the measurement of I If noise in certain classes of materials which have a wide range of potential applications. This includes metal films, semi-conductors, metallic oxides and inhomogeneous systems such as composites. The review contains a basic introduction to this field, the theories and models and follows it up with a discussion on measurement methods. There are discussions on specific examples of the application of noise spectroscopy in the field of materials science. (C) 2002 Elsevier Science Ltd. All rights reserved.

Nanotubes of the disulfides of groups 4 and 5 metals

The layered chalcogenides, having structures analogous to graphite, are known to be unstable toward bending and show high propensity to form curved structures, thus eliminating dangling bonds at the edges. Since the discovery of fullerene and nanotube structures of WS2 and MoS2 by Tenne et al. [1-3], there have been attempts to prepare and characterize nanotubes of other layered dichalcogenides with structures analogous to MoS2. Nanotubes of MoS2 and WS2 were prepared by Tenne et al. by reducing the corresponding oxides to the suboxides followed by heating in an atmosphere of forming gas (5 % H-2 + 95 % N-2) and H2S at 700-900 degreesC [1-3]. Alternative methods of synthesis of MoS2 and WS2 nanotubes have since been proposed by employing the decomposition of the ammonium thiometallates or the corresponding trisulfide precursors. This alternative procedure was based on the observation that the trisulfide seems to be formed as an intermediate in the synthesis of the MoS2 and WS2 nanotubes [4]. Accordingly, the decomposition of the trisulfides of MoS2 and W in a reducing atmosphere directly yielded nanotubes of the disulfides MoS2 and WS2 [5]. In this article, we describe the synthesis, structure, and characterization of a few novel nanotubes of the disulfides of groups 4 and 5 metals. These include nanotubes of NbS2, TaS2, ZrS2, and HfS2. The study enlarges the scope of the inorganic nanotubes significantly and promises other interesting possibilities, including the synthesis of the diselenide nanotubes of these metals.