Geochemistry of Fe-Mn crusts in sediments of the Central Indian Ridge

Layered Fe-Mn crusts from the off-axis region of the first segment of the Central Indian Ridge north of the Rodrigues Triple Junction were studied geochemically and mineralogically. Vernadite (delta-MnO2) is the main mineral oxide phase. 230Thxs and Co concentrations suggest high growth rates of up to 29 mm/Myr and a maximum age of the basal crust layer of 1 Ma. Whereas most of the major and minor elements show concentrations which are typical of hydrogenetic formation, Co, Pb, Ni and Ti concentrations are strikingly lower. Concentrations and distribution of the strictly trivalent rare-earths and yttrium (REY) are typical of hydrogenetic ferromanganese oxide precipitates, but in marked contrast, the crusts are characterized by negative CeSN (shale normalized) anomalies and (Ce/Pr)SN ratios less than unity. Profiles through the crusts reveal only minor variations of the REY distribution and (Ce/Pr)SN ratios range from 0.45 to 0.68 (compared to ratios of up to 2 for typical hydrogenetic crusts from the Central Indian Basin). The apparent bulk partition coefficients between the crusts and seawater suggest that for the strictly trivalent REY the adsorption-desorption equilibrium has been reached. Positive Ce anomalies in the partition coefficient patterns reveal preferential uptake of Ce, but to a lesser extent than in normal hydrogenetic crusts. A new parameter (excess Ce, Cexs) to quantify the degree of decoupling of Ce from REY(III) is established on the basis of partition coefficients. Cexs/Cebulk ratios suggest that the CIR crusts formed by precipitation of Fe-Mn oxides from a hydrothermal plume and that in hydrothermal plumes and normal seawater the enrichment of Ce results from the same oxidative sorption process. The growth rates, calculated with 230Thxs data as well as with the Co formula, are inversely related to Cexs.

The effect of Cu addition and milling contaminations on the microstructure evolution of ball milled Al-Pb alloy during sintering

Al-10 wt.%Pb and Al-10 wt.%Pb-x wt.%Cu (x = 0-7.0) bulk alloys were prepared by sintering the mechanically alloyed powders at various temperatures. The microstructure changes of the as consolidated powders in the course of sintering were analyzed by differential scanning calorimetry, scanning electron microscopy, X-ray diffraction analysis and transmission electron microscopy. It has been found that, with respect to the Al-10 wt.%Pb-x wt.%Cu alloy, CuAl2 and Cu9Al4 phases formed in the milling process, and the amount of CuAl2 phase increased while the Cu9Al4 phase disappeared gradually in the sintering process. In both Al-10 wt.%Pb and Al-10 wt.%Pb-x wt.%Cu alloys, the sintering process results in the coarsening of Pb phase and the growth rate of Pb phase fulfills the Lifshitz-Slyozov-Wagner equation even though the size of the Pb phase was in nanometer range. The Pb particle exhibits cuboctahedral morphology and has a cubic to cubic orientation relationship with the Al matrix. The addition of Cu strongly depressed the growth rate of Pb. Contamination induced by milling has apparent influence on the microstructure of the sintered alloys. Al7Cu2Fe and aluminium oxide phases were identified in the sintered alloys. The cuboctahedral morphology of Pb particles was broken up by the presence of the oxide phase. (c) 2006 Elsevier B.V. All rights reserved.

Pole tip recession in linear tape systems

The tribology of linear tape storage system including Linear Tape Open (LTO) and Travan5 was investigated by combining X-ray Photoelectron Spectroscopy (XPS), Auger Electron Spectroscopy (AES), Optical Microscopy and Atomic Force Microscopy (AFM) technologies. The purpose of this study was to understand the tribology mechanism of linear tape systems then projected recording densities may be achieved in future systems. Water vapour pressure or Normalized Water Content (NWC) rather than the Relative Humidity (RH) values (as are used almost universally in this field) determined the extent of PTR and stain (if produced) in linear heads. Approximately linear dependencies were found for saturated PTR increasing with normalized water content increasing over the range studied using the same tape. Fe Stain (if produced) preferentially formed on the head surfaces at the lower water contents. The stain formation mechanism had been identified. Adhesive bond formation is a chemical process that is governed by temperature. Thus the higher the contact pressure, the higher the contact temperature in the interface of head and tape, was produced higher the probability of adhesive bond formation and the greater the amount of transferred material (stain). Water molecules at the interface saturate the surface bonds and makes adhesive junctions less likely. Tape polymeric binder formulation also has a significant role in stain formation, with the latest generation binders producing less transfer of material. This is almost certainly due to higher cohesive bonds within the body of the magnetic layer. TiC in the two-phase ceramic tape-bearing surface (AlTiC) was found to oxidise to form TiO2.The oxidation rate of TiC increased with water content increasing. The oxide was less dense than the underlying carbide; hence the interface between TiO2 oxide and TiC was stressed. Removals of the oxide phase results in the formation of three-body abrasive particles that were swept across the tape head, and gave rise to three-body abrasive wear, particularly in the pole regions. Hence, PTR and subsequent which signal loss and error growth. The lower contact pressure of the LTO system comparing with the Travan5 system ensures that fewer and smaller three-body abrasive particles were swept across the poles and insulator regions. Hence, lower contact pressure, as well as reducing stain in the same time significantly reduces PTR in the LTO system.

Annotated record and illustrations of Mn nodules retrieved during cruise KH-73-4 of the R/V Hakuho Maru and cruises GH76-1 and GH77-1 of the R/V Hakurei Maru

Deep sea manganese nodules from the Central Pacific Basin are mainly composed of 10Å manganite and d-MnO2 Two zones equivalent to the minerals are evidently distinguishable according to their optical properties. Microscopic and microprobe analyses revealed quite different chemical compositions and textnral characteristics of the two zones. These different feature of the two zones of nodules suggest the different conditions under which they were formed. Concentrations of 11 metal elements in the zones and inter-element relationships show that the 10Å manganite zone is a monomineralic oxide phase containing a large amount of manganese and minor amounts of useful metals, and that the d-MnO2 zone which is apparently homogeneous under the microscope is a mixture of three or more different minerals. The chemical characteristics of the two zones can explain the variation of bulk composition of deep sea manganese nodules and inter-element relationships previously reported, suggesting that the bulk compositions are attributable to the mixing of the 10Å manganite and d-MnO2 zones in various ratios. Characteristic morphology and surface structure of some types of nodules and their relationships to chemistry are also attribut able to the textural and chemical features of the above mentioned two phases. Synthesis of hydrated manganese oxides was carried out in terms of the formation of manganese minerals in the ocean. The primary product which is an equivalent to d-MnO2 was precipitated from Mn 2+ -bearing alkaline solution under oxigenated condition by air bubbling at one atmospheric pressure and room temperature. The primary product was converted to a l0Å manganite equivalent by contact with Ni 2+, Cu 2++ or CO2+ chloride solutions. This reaction caused the decrease of Ni2+, Cu2+ or CO2+ concentrations and the increase of Na+ concentration in the solution. The reaction also proceeded even in diluted solutions of nickel chloride and resulted in a complete removal of Ni2+ from the solution. Reaction products were exclusively 10Å manganite equivalents and their chemical compositions were very similar to those of 10Å manganite in manganese nodules. The maximum value of(Cu+Ni+Co)/Mn ratio of 10Å manganite zones in manganese nodules is 0.16, and the Ni/Mn ratio of synthetic 10Å manganite ranges from 0.15 to 0.18 with the average of 0.167.

(Table 1, Page 94) Elemental abundances in ferromanganese nodules and crusts from the Pernambuco Plateau and guyots off northeast Brazil

Ferromanganese deposits, mostly manganese crusts, are common in elevations along the northeastern Brazilian continental margin. Association of the deposits with more or less altered basaltic rock can be observed. On the Pernambuco Plateau and Ceara Guyot, ferromanganese deposits occur associated with phosphatic material and nodules. The mineralogical composition of the ferromanganese deposits indicates a predominance of the manganese oxide phase dMnO2. Low contents of Mn and Cu are characteristic of their chemical composition. Fe and Mn in the deposits probably precipitated from the sea water.

(Table 1, page 376), Composition of manganese deposits from the Gulf of Aden and the Carlsberg Ridge

Iron-manganese nodules from the ocean floor have been extensively studied. But, because of the fine grain size of the particles of the nodules, structural identification by X-ray and electron diffraction techniques is difficult and the mineralogy of the iron oxide phase has not been well characterized. The observation of the Mössbauer spectrum-in which each nucleus absorbs gamma-rays independently-is not limited by particle size in the same way as is the observation of Bragg peaks in diffraction measurements, in which radiation must be scattered coherently from a large number of atoms. The magnetic hyperfine splitting in the Mössbauer spectrum of magnetic materials is affected, however, when the particles are so small that they become superparamagnetic. We describe here an investigation using the 57Fe Mössbauer effect of two iron-manganese nodules in which the iron oxide phase could not be detected by X-ray or electron diffraction.

Geologia, petrologia, geocronologia e mineralizações sulfetadas do complexo ézio, província mineral de carajás, Brasil

Dissertação (mestrado)—Universidade de Brasília, Instituto de Geociências, Pós-Graduação em Geologia, 2015.

Electrocrystallization of phase I, CuTCNQ (TCNQ= 7, 7, 8, 8-tetracyanoquinodimethane), on indium tin oxide and boron-doped diamond electrodes

The electrochemical reduction of TCNQ to TCNQ•- in acetonitrile in the presence of [Cu(MeCN)4]+ has been undertaken at boron-doped diamond (BDD) and indium tin oxide (ITO) electrodes. The nucleation and growth process at BDD is similar to that reported previously at metal electrodes. At an ITO electrode, the electrocrystallization of more strongly adhered, larger, branched, needle-shaped phase I CuTCNQ crystals is detected under potential step conditions and also when the potential is cycled over the potential range of 0.7 to −0.1 V versus Ag/AgCl (3 M KCl). Video imaging can be used at optically transparent ITO electrodes to monitor the growth stage of the very large branched crystals formed during the course of electrochemical experiments. Both in situ video imaging and ex situ X-ray diffraction and scanning electron microscopy (SEM) data are consistent with the nucleation of CuTCNQ taking place at a discrete number of preferred sites on the ITO surface. At BDD electrodes, ex situ optical images show that the preferential growth of CuTCNQ occurs at the more highly conducting boron-rich areas of the electrode, within which there are preferred sites for CuTCNQ formation.

Electron capture of tetracyanoethylene oxide in the gas phase. Rearrangement of the parent radical anion to form [(NC)(3)C](-). A joint experimental and ab initio study

Capture of an electron by tetracyanoethylene oxide can initiate a number of decomposition pathways. One of these decompositions yields [(NC)3C]− as the ionic product. Ab initio calculations (at the B3LYP/6-31+G∗ level of theory) indicate that the formation of [(NC)3C]− is initiated by capture of an electron into the LUMO of tetracyanoethylene oxide to yield the anion radical [(NC)2C–O–C(CN)2]−· that undergoes internal nucleophilic substitution to form intermediate [(NC)3C–OCCN]−·. This intermediate dissociates to form [(NC)3C]− (m/z 90) as the ionic product. The radical (NC)3C· has an electron affinity of 4.0 eV (385 kJ mol−1). Ab initio calculations show that [(NC)3C]− is trigonal planar with the negative charge mainly on the nitrogens. A pictorial representation of this structure is the resonance structure formed from three degenerate contributing structures (NC)2–CCN−. The other product of the reaction is nominally (NCCO)·, but there is no definitive experimental evidence to indicate whether this radical survives intact, or decomposes to NC· and CO. The overall process [(NC)2C–O–C(CN)2]−· → [(NC)3C]− + (NCCO)· is calculated to be endothermic by 21 kJ mol−1 with an overall barrier of 268 kJ mol−1.

Plasma-produced phase-pure cuprous oxide nanowires for methane gas sensing

Phase-selective synthesis of copper oxide nanowires is warranted by several applications, yet it remains challenging because of the narrow windows of the suitable temperature and precursor gas composition in thermal processes. Here, we report on the room-temperature synthesis of small-diameter, large-area, uniform, and phase-pure Cu2O nanowires by exposing copper films to a custom-designed low-pressure, thermally non-equilibrium, high-density (typically, the electron number density is in the range of 10 11-1013cm-3) inductively coupled plasmas. The mechanism of the plasma-enabled phase selectivity is proposed. The gas sensors based on the synthesized Cu2O nanowires feature fast response and recovery for the low-temperature (∼140°C) detection of methane gas in comparison with polycrystalline Cu2O thin film-based gas sensors. Specifically, at a methane concentration of 4%, the response and the recovery times of the Cu2O nanowire-based gas sensors are 125 and 147s, respectively. The Cu2O nanowire-based gas sensors have a potential for applications in the environmental monitoring, chemical industry, mining industry, and several other emerging areas.

NMR spectrum of pyridine-N-oxide in a thermotropic nematic phase

Absract is not available.