Structural Dynamics in (ND4)2[Cu(D2O)6](SO4)2

The extended X-ray absorption fine structure spectroscopy (EXAFS) of (ND4)(2)[CU(D2O)(6)](SO4)(2) at 5, 14,100, 200, and 298 K is reported. This indicates that the Cu-O bond lengths of the Cu(D2O)(6)(2+) ion do not change significantly within this temperature range, which contrasts with EPR results and X-ray and neutron diffraction experiments, which imply that two of the Cu-(D2O) bonds converge in length as the temperature is raised. The EXAFS measurements thus confirm that the bond distances yielded by the diffraction experiments refer to the average positions of ligands involved in a dynamic equilibrium in which the directions of the long and intermediate bonds of the Jahn-Teller distorted Cu(D2O)(6)(2+) ion are interchanged in the crystal lattice. Analysis of the displacement parameters is consistent with this interpretation, as are the wave functions calculated using a model involving Jahn-Teller vibronic coupling and the influence of lattice strain interactions.

Eutectic solidification mode in sodium modified Al-7 mass %Si-3.5 mass %Cu-0.2 mass %Mg casting alloys

The influence of sodium (Na) on nucleation and growth of the Al-Si eutectic in a commercial hypoeutectic Al-Si-Cu-Mg foundry alloy has been investigated. The microstructural evolution during eutectic solidification was studied by a quenching technique. By comparing the orientation of the aluminium in the eutectic to that of the surrounding primary aluminium dendrites by EBSD, the eutectic solidification mode could be determined. The results show that the eutectic solidification starts near the mould wall and evolves with front growth opposite the thermal gradient on a macro-scale, and on a micro-scale with independent heterogeneous nucleation of eutectic grains in interdendritic spaces. Na-modified alloys therefore behave significantly differently from those modified by other elemental additions.

The effect of trace elements on the sintering of an Al-Zn-Mg-Cu alloy

Trace elements can have a significant effect on the processing and properties of aluminium alloys, including sintered alloys. As little as 0.07 wt% (100 ppm) lead, tin or indium promotes sintering in an Al-Zn-Mg-Cu alloy produced from mixed elemental powders. This is a liquid phase sintering system and thin liquid films form uniformly throughout the alloy in the presence of the trace elements, but liquid pools develop in their absence. Analytical transmission electron microscopy indicates that the trace elements are confined to the interparticle and grain boundary regions. The sintering enhancement is attributed to the segregation of the microalloying addition to the liquid-vapour interface. Because the microalloying elements have a low surface tension, they lower the effective surface tension of the liquid. This reduces the wetting angle and extends the spreading of the liquid through the matrix. An improvement in sintering results. (C) 2001 Acta Materialia Inc. Published by Elsevier Science Ltd. All rights reserved.

Precipitation hardening of Cu-Fe-Cr alloys - Part I - Mechanical and electrical properties

This research is part of a project whose scope was to investigate the engineering properties of new non-commercial alloy formulations based on the Cu rich corner of the Cu-Fe-Cr ternary system with the primary aim of exploring the development of a new cost-effective high-strength, high-conductivity copper alloy. The literature indicated that Cu rich Cu-Cr and Cu-Fe alloys have been thoroughly investigated. A number of commercial alloys have been developed and these are used for a variety of applications requiring combinations of high-strength, high-conductivity and resistance to softening. Little evidence was found in the literature that the Cu rich corner of the Cu-Fe-Cr system had previously been investigated for the purpose of developing high-strength, high-conductivity copper alloys resistant to softening. The aim of these present investigations was to explore the possibility that new alloys could be developed that combined the properties of both sets of alloys, ie large precipitation hardening response combined with the ability to stabilise cold worked microstructures to high temperatures while at the same maintain high electrical conductivity. To assess the feasibility of this goal the following alloys were chosen for investigation: Cu-0.7wt%Cr-0.3wt%Fe, Cu-0.7wt%Cr-0.8wt%Fe, Cu-0.7wt%Cr-2.0wt%Fe. This paper reports on the mechanical property investigation which indicated that the Cu-0.7wt%Cr-0.3wt%Fe, and Cu-0.7wt%Cr-2.0wt%Fe alloys were worthy of further investigation. (C) 2001 Kluwer Academic Publishers.

Precipitation hardening of Cu-Fe-Cr alloys - Part II - Microstructural characterisation

This research is part of a project whose scope was to investigate the engineering properties of new non-commercial alloy formulations based on the Cu rich corner of the Cu-Fe-Cr ternary system with the primary aim of exploring the development of a new cost-effective high-strength, high-conductivity copper alloy. Promising properties have been measured for the following alloys: Cu-0.7wt%Cr-0.3wt%Fe and Cu-0.7wt%Cr-2.0wt%Fe. This paper reports on the microstructural characterisation of these alloys and discusses the mechanical and electrical properties of these alloys in terms of their microstructure, particularly the formation of precipitates. These alloys have evinced properties that warrant further investigation. Cost modelling has shown that Cu-0.7wt%Cr-0.3wt%Fe is approximately 25% cheaper to produce than commercial Cu-1%Cr. It has also been shown to be more cost efficient on a yield stress and % IACS per dollar basis. The reason for the cost saving is that the Cu-0.7%Cr-0.3%Fe alloy can be made with low carbon ferro-chrome additions as the source of chromium rather than the more expensive Cu-Cr master-alloy. For applications in which cost is one of the primary materials selection criteria, it is envisaged that there would be numerous applications in both cast and wrought form, where the Cu-0.7%Cr-0.3%Fe alloy would be more suitable than Cu-1%Cr. (C) 2001 Kluwer Academic Publishers.

Cold worked Cu-Fe-Cr alloys

The aim of this project was to investigate the properties of copper rich Cu-Fe-Cr alloys for the purpose of developing a new cost effective, high-strength, high-conductivity copper alloy. This paper reports on the influence of cold work. The age hardening response of the Cu-0.7%Cr-2.0%Fe alloy was minimal, but the resistance to softening was superior to that reported for any commercial high-strength, high-conductivity (HSHC) copper alloy with comparable mechanical and electrical properties. For example, an excess of 85% of the original hardness of the 40% cold worked alloy is retained after holding at 700 degreesC for 1 hour, whereas commercial HSHC Cu-Fe-P alloys have been reported to soften significantly after 1 hours exposure at less than 500 degreesC. The Cu-0.7Cr-2.0Fe alloy would therefore be expected to be more suitable for applications with a significant risk of exposure to elevated temperatures. Optical microscope examination of cold worked and aged microstructures confirmed the high resistance to recrystallization for Cu-0.7%Cr-2.0%Fe. The Zener-Smith drag term, predicting the pinning effect of second phase particles on dislocations in cold worked microstructures, was calculated using the precipitate characteristics obtained from TEM, WDS and resistivity measurements. The pinning effect of the precipitate dispersions in the peak-aged condition was determined to be essentially equivalent for the Cu-0.7%Cr-0.3%Fe and Cu-0.7%Cr-2.0%Fe alloys. A lower recrystallisation temperature in the Cu-0.7%Cr-0.3%Fe alloy was therefore attributed to faster coarsening kinetics of the secondary precipitates resulting from a higher Cr concentration in the precipitates at lower iron content. (C) 2001 Kluwer Academic Publishers.

Investigations of growth processes in Y-Ba-Cu-O materials by microstructural examination of quenched samples

Y-Ba-Cu-O samples with additions of Y2O3 and CeO2 were quenched during seeded isothermal melt processing and examined by optical microscopy and scanning electron microscopy. Large YBa2Cu3O7-y (Y123) particles in the starting powder were found to form a distinct type of melt during heating, which was unaffected by the Y2O3 or CeO2 additives. This type of melt later formed regions with a low concentration of Y2BaCuO5 (Y211) particles in the Y123 matrix. The maximum growth rate of Y123 that could be sustained in the sample was found to be lower in the melt formed from large Y123 particles, and this may lead to growth accidents and subgrains in some samples.

Dynamic Behavior of the Jahn-Teller distorted Cu(H2O)(6)(2+) ion in Cu2+ doped Cs-2[Zn(H2O)(6)](ZrF6)(2) and the crystal structure of the host lattice

The temperature dependence of the X- and Q-band EPR spectra of Cs-2[Zn(H2O)(6)](ZrF6)(2) containing similar to1% Cu2+ is reported. All three molecular g-values vary with temperature, and their behavior is interpreted using a model in which the potential surface of the Jahn-Teller distorted Cu(H2O)(6)(2+) ion is perturbed by an orthorhombic strain induced by interactions with the surrounding lattice. The strain parameters are significantly smaller than those reported previously for the Cu(H2O)(6)(2+) ion in similar lattices. The temperature dependence of the two higher g-values suggests that in the present compound the lattice interactions change slightly with temperature. The crystal structure of the Cs-2[Zn(H2O)(6)](ZrF6)(2) host is reported, and the geometry of the Zn(H2O)(6)(2+) ion is correlated with lattice strain parameters derived from the EPR spectrum of the guest Cu2+ complex.

Copper transfer from the Cu(I) chaperone, CopZ, to the repressor, Zn(II)CopY: Metal coordination environments and protein interactions

Extracellular copper regulates the DNA binding activity of the CopY repressor of Enterococcus hirae and thereby controls expression of the copper homeostatic genes encoded by the cop operon. CopY has a CxCxxxxCxC metal binding motif. CopZ, a copper chaperone belonging to a family of metallochaperones characterized by a MxCxxC metal binding motif, transfers copper to CopY. The copper binding stoichiometries of CopZ and CopY were determined by in vitro metal reconstitutions. The stoichiometries were found to be one copper(l) per CopZ and two copper(l) per CopY monomer. X-ray absorption studies suggested a mixture of two- and three-coordinate copper in Cu(1)CopZ, but a purely three-coordinate copper coordination with a Cu-Cu interaction for Cu(1)(2)CopY. The latter coordination is consistent with the formation of a compact binuclear Cu(l)-thiolate core in the CxCxxxxCxC binding motif of CopY. Displacement of zinc, by copper. from CopY was monitored with 2,4-pyridylazoresorcinol. Two copper(l) ions were required to release the single zinc(II) ion bound per CopY monomer. The specificity of copper transfer between CopZ and CopY was dependent on electrostatic interactions. Relative copper binding affinities of the proteins were investigated using the chelator, diethyldithiocarbamic acid (DDC). These data suggest that CopY has a higher affinity for copper than CopZ. However, this affinity difference is not the sole factor in the copper exchange: a charge-based interaction between the two proteins is required for the transfer reaction to proceed. Gain-of-function mutation of a CopZ homologue demonstrated the necessity of four lysine residues on the chaperone for the interaction with CopY. Taken together, these results suggest a mechanism for copper exchange between CopZ and CopY.

Different mineralization styles in a volcanic-hosted ore deposit: the fluid and isotopic signatures of the Mt Morgan Au-Cu deposit, Australia

Quantitative laser ablation (LA)-ICP-MS analyses of fluid inclusions, trace element chemistry of sulfides, stable isotope (S), and Pb isotopes have been used to discriminate the formation of two contrasting mineralization styles and to evaluate the origin of the Cu and Au at Mt Morgan. The Mt Morgan Au-Cu deposit is hosted by Devonian felsic volcanic rocks that have been intruded by multiple phases of the Mt Morgan Tonalite, a low-K, low-Al2O3 tonalite-trondhjemite-dacite (TTD) complex. An early, barren massive sulfide mineralization with stringer veins is conforming to VHMS sub-seafloor replacement processes, whereas the high-grade Au-Cu. ore is associated with a later quartz-chalcopyrite-pyrite stock work mineralization that is related to intrusive phases of the Tonalite complex. LA-ICP-MS fluid inclusion analyses reveal high As (avg. 8850 ppm) and Sb (avg. 140 ppm) for the Au-Cu mineralization and 5 to 10 times higher Cu concentration than in the fluids associated with the massive pyrite mineralization. Overall, the hydrothermal system of Mt Morgan is characterized by low average fluid salinities in both mineralization styles (45-80% seawater salinity) and temperatures of 210 to 270 degreesC estimated from fluid inclusions. Laser Raman Spectroscopic analysis indicates a consistent and uniform array Of CO2-bearing fluids. Comparison with active submarine hydrothermal vents shows an enrichment of the Mt Morgan fluids in base metals. Therefore, a seawater-dominated fluid is assumed for the barren massive sulfide mineralization, whereas magmatic volatile contributions are implied for the intrusive related mineralization. Condensation of magmatic vapor into a seawater-dominated environment explains the CO2 occurrence, the low salinities, and the enriched base and precious metal fluid composition that is associated with the Au-Cu. mineralization. The sulfur isotope signature of pyrite and chalcopyrite is composed of fractionated Devonian seawater and oxidized magmatic fluids or remobilized sulfur from existing sulfides. Pb isotopes indicate that Au and Cu. originated from the Mt Morgan intrusions and a particular volcanic strata that shows elevated Cu background. (C) 2002 Elsevier Science B.V. All rights reserved.

Effect of soil composition and dissolved organic matter on pesticide sorption

The effect of the solid and dissolved organic matter fractions, mineral composition and ionic strength of the soil solution on the sorption behaviour of pesticides were studied. A number of soils, chosen so as to have different clay mineral and organic carbon content, were used to study the sorption of the pesticides atrazine (6-chloro-N-2-ethyl-N-4-isopropyl-1,3,5-triazine-2,4-diamine), 2,4-D ((2,4-dichlorophenoxy) acetic acid), isoproturon (3-(4-isopropylphenyl)1,1-dimethylurea) and paraquat (1,1'-dimethyl-4,4'-bipyridinium) in the presence of low and high levels of dissolved organic carbon and different background electrolytes. The sorption behaviour of atrazine, isoproturon and paraquat was dominated by the solid state soil components and the presence of dissolved organic matter had little effect. The sorption of 2,4-D was slightly affected by the soluble organic matter in the soil. However, this effect may be due to competition for adsorption sites between the pesticide and the soluble organic matter rather than due to a positive interaction between the pesticide and the soluble fraction of soil organic matter. It is concluded that the major factor governing the sorption of these pesticides is the solid state organic fraction with the clay mineral content also making a significant contribution. The dissolved organic carbon fraction of the total organic carbon in the soil and the ionic strength of the soil solution appear to have little or no effect on the sorption/transport characteristics of these pesticides over the range of concentrations studied. (C) 2002 Elsevier Science B.V. All rights reserved.