Liquidus temperatures in calcium ferrite slags in equilibrium with molten copper

Experimental laboratory methods have been developed that enable phase-equilibria studies to be carried out on slags in the system Ca-Cu-Fe-O in equilibrium with metallic copper. These techniques involve equilibration at temperature, rapid quenching, and chemical analysis of the phases using electron-probe X-ray microanalysis (EPNIA). Equilibration experiments have been carried out in the temperature range of 1150 degreesC to 1250 degreesC (1423 to 1523 K) and in the composition range of 4 to 80 wt pct "Cu2O," 0 to 25 wt pct CaO, and 20 to 75 wt pct "Fe2O3" in equilibrium with metallic copper. Liquidus and solidus data are reported for the primary-phase fields of spinel (magnetite) and dicalcium ferrite. The resulting data have been used to construct liquidus isotherms of the CaO-"Cu2O"-"Fe2O3" system at metallic copper saturation.

Phase equilibria in the ZnO-rich area of the Fe-Zn-O system in air

The phase equilibria in the Fe-Zn-O system in the range 900-1580degreesC in air have been experimentally studied using equilibration and quenching techniques. The compositions of the phases at equilibrium were determined using electron probe X-ray microanalysis (EPMA). The ferrous and ferric bulk iron concentrations were measured with a wet chemical analysis using the ammonium metavanadate technique. X-ray powder diffraction analysis (XRD) was used to characterise the phases. Iron oxide dissolved in zincite was found to be present principally in the ferric form. The XRD analysis and the composition measurements both indicate that zincite is the only phase stable in the ZnO-rich area in the range of conditions investigated. The solubility of the iron oxide in zincite rapidly increases at temperatures above 1200degreesC; the morphology of the zincite crystals also sharply changes between 1200 and 1300degreesC from rounded to plate-like crystals. The plate-like zincite forms a refractory network-the type of microstructure beneficial to the Imperial Smelting Process (ISP) sinter performance. The software program FactSage with a thermodynamically optimised database was used to predict phase equilibria in the Fe-Zn-O system.

Phase equilibria in the Fe-Zn-O system at conditions relevant to zinc sintering and smelting

Zincite and spinel phases are present in the complex slag systems encountered in zinc/lead sintering and zinc smelting processes. These phases form extensive solid solutions and are stable over a wide range of compositions, temperatures and oxygen partial pressures. Accurate information on the stability of these phases is required in order to develop thermodynamic models of these slag systems. Phase equilibria in the Fe–Zn–O system have been experimentally studied for a range of conditions, between 900°C and 1580°C and oxygen partial pressures (pO2) between air and metallic iron saturation, using equilibration and quenching techniques. The compositions of the phases were measured using Electron probe X-ray microanalysis (EPMA). The ferrous and ferric bulk iron concentrations were determined using a specially developed wet-chemical analysis procedure based on the use of ammonium metavanadate. XRD was used to confirm phase identification. A procedure was developed to overcome the problems associated with evaporation of zinc at low pO2 values and to ensure the achievement of equilibria. An isothermal section of the system FeO–Fe2O3–ZnO at high ZnO concentrations at 1200°C was constructed. The maximum solubilities of iron and zinc in zincite and spinel phases in equilibrium were determined at pO2 = 1 × 10-6 atm at 1200°C and 1300°C. The morphology of the zincite crystals sharply changes in air between 1200–1300°C from rounded to plate-like. This is shown to be associated with significant increase in total iron concentration, the additional iron being principally in the form of ferric iron. Calculations performed by FactSage with a thermodynamically optimised database have been compared with the experimental results.

Iron-rich intermetallic phases and their role in casting defect formation in hypoeutectic Al-Si alloys

Iron is the most common and detrimental impurity in aluminum casting alloys and has long been associated with an increase in casting defects. While the negative effects of iron are clear, the mechanism involved is not fully understood. It is generally believed to be associated with the formation of Fe-rich intermetallic phases. Many factors, including alloy composition, melt superheating, Sr modification, cooling, rate, and oxide bifilms, could play a role. In the present investigation, the interactions between iron and each individual element commonly present in aluminum casting alloys, were investigated using a combination of thermal analysis and interrupted quenching tests. The Fe-rich intermetallic phases were characterized using optical microscope, scanning electron microscope, and electron probe microanalysis (EPMA), and the results were compared with the predictions by Thermocalc. It was found that increasing the iron content changes the precipitation sequence of the beta phase, leading to the precipitation of coarse binary beta platelets at a higher temperature. In contrast, manganese, silicon, and strontium appear to suppress the coarse binary beta platelets, and Mn further promotes the formation of a more compact and less harmful a phase. They are therefore expected to reduce the negative effects of the phase. While reported in the literature, no effect of P on the amount of beta platelets was observed. Finally, attempts are made to correlate the Fe-rich intermetallic phases to the formation of casting defects. The role of the beta phase as a nucleation site for eutectic Si and the role of the oxide bifilms and AIP as a heterogeneous substrate of Fe intermetallics are also discussed.

Experimental study of phase equilibria in the Fe-Sn-Zn-O system in air

The four-component Fe-Sn-Zn-O system was studied experimentally in the range of temperatures from 1100 to 1400 degrees C in air using high temperature equilibration and quenching techniques followed by electron probe X-ray microanalysis (EPMA). Phase equilibrium relations and the extent of solid solutions among the phases cassiterite (Sn,Zn)O-2, hematite (Fe,Sn,Zn)(2)O-3, spinel (Fe,Sn,Zn)(3)O-4 and zincite (Zn,Fe,Sn)O are reported. Phase equilibria in the pseudo-binary systems Fe2O3-SnO2 and SnO2-ZnO are reported in air in the temperature ranges from 1100 to 1400 degrees C and 1200 to 1400 degrees C, respectively.

Experimental study of phase equilibria in the Al-Fe-Zn-O system in air

The phase equilibria in the Al-Fe-Zn-O system in the range 1250 °C to 1695 °C in air have been experimentally studied using equilibration and quenching techniques followed by electron probe X-ray microanalysis. The phase diagram of the binary Al2O3-ZnO system and isothermal sections of the Al2O3-“Fe2O3”-ZnO system at 1250 °C, 1400 °C, and 1550 °C have been constructed and reported for the first time. The extents of solid solutions in the corundum (Al,Fe)2O3, hematite (Fe,Al)2O3, Al2O3*Fe2O3 phase (Al,Fe)2O3, spinel (Al,Fe,Zn)O4, and zincite (Al,Zn,Fe)O primary phase fields have been measured. Corundum, hematite, and Al2O3*Fe2O3 phases dissolve less than 1 mol pct zinc oxide. The limiting compositions of Al2O3*Fe2O3 phase measured in this study at 1400 °C are slightly nonstoichiometric, containing more Al2O3 then previously reported. Spinel forms an extensive solid solution in the Al2O3-“Fe2O3”-ZnO system in air with increasing temperature. Zincite was found to dissolve up to 7 mole pct of aluminum in the presence of iron at 1550 °C in air. A meta-stable Al2O3-rich phase of the approximate composition Al8FeZnO14+x was observed at all of the conditions investigated. Aluminum dissolved in the zincite in the presence of iron appears to suppress the transformation from a round to platelike morphology.

Phase equilibria at sub-solidus conditions in the Fe-Mg-Zn-O system in air

The phase equilibria in the Fe-Mg-Zn-O system in the temperature range 1100-1550degreesC in air have been experimentally studied using equilibration and quenching followed by electron probe X-ray microanalysis. The compositions of condensed phases in equilibrium in the binary MgO-ZnO system and the ternary Fe-Mg-O system have been reported at sub-solidus in air. Pseudo-ternary sections of the quaternary Fe-Mg-Zn-O system at 1100, 1250 and 1400degreesC in air were constructed using the experimental data. The solid solution of iron oxide, MgO and ZnO in the periclase (Mg, Zn, Fe)O, spinel (Mg2+, Fe2+, Zn2+)(x)Fe(2+y)3+O4 and zincite (Zn, Mg, Fe)O phases were found to be extensive under the conditions investigated. A continuous spinel solid solution is formed between the magnesioferrite (Mg2+, Fe2+)(x)Fe(2+y)3+O4 and franklinite (Zn2+, Fe2+)(x)Fe(2+y)3+O4 end-members at 1100 and 1250degreesC, extending to magnetite (Fe2+)(x)Fe(2+y)3+O4 at 1400degreesC in air. The compositions along the spinel boundaries were found to be non-stoichiometric, the magnitude of the non-stoichiometry being a function of composition and temperature in air. It was found that hematite dissolves neither MgO nor ZnO in air.

Distribution of calcium phosphate in the exoskeleton of larval Exeretonevra angustifrons Hardy (Diptera : Xylophagidae)

Distribution and organisation of the mineral, amorphous calcium phosphate (ACP), has been investigated in the exoskeleton of the xylophagid fly larva Exeretonevra angustifrons Hardy. While head capsule and anal plate are smooth with a thin epicuticle, the epicuticle of the body is thicker and shows unusual micro-architecture comprised of minute hemispherical (dome-shaped) protrusions. Electron microprobe analysis and energy dispersive spectroscopy revealed heterogeneity of mineral elements across body cuticle and a concentration of ACP in the epicuticle, especially associated with the hemispherical structures. Further imaging and analysis showed the bulk of the ACP to be present in nano-sized granules. It is hypothesised that the specific distribution of ACP may enhance cuticular hardness or durability without reducing flexibility. (c) 2004 Elsevier Ltd. All rights reserved.

A reinvestigation of phase equilibria in the system Al2O3-SiO2-ZnO

The phase equilibria and liquidus temperatures in the binary SiO2-ZnO system and in the ternary Al2O3-SiO2-ZnO system at low Al2O3 concentrations have been experimentally determined using the equilibration and quenching technique followed by electron probe X-ray microanalysis. In the SiO2-ZnO system, two binary eutectics involving the congruently melting willemite (Zn2SiO4) were found at 1448 +/- 5 degrees C and 0.52 +/- 0.01 mole fraction ZnO and at 1502 +/- 5 degrees C and 0.71 +/- 0.01 mole fraction ZnO, respectively. The two ternary eutectics involving willemite previously reported in the Al2O3SiO2-ZnO system were found to be at 1315 +/- 5 degrees C and 1425 +/- 25 T, respectively. The compositions of the eutectics are 0.07, 0.52, and 0.41 and 0.05, 0.28, and 0.67 mole fraction Al2O3, SiO2, and ZnO, respectively. The results of the present investigation are significantly different from the results of previous studies.

Phase equilibria in the system Fe-Zn-O at intermediate conditions between metallic-iron saturation and air

The phase equilibria in the FeO-Fe2O3-ZnO system have been experimentally investigated at oxygen partial pressures between metallic iron saturation and air using a specially developed quenching technique, followed by electron probe X-ray microanalysis (EPMA) and then wet chemistry for determination of ferrous and ferric iron concentrations. Gas mixtures of H-2, N-2, and CO2 or CO and CO2 controlled the atmosphere in the furnace. The determined metal cation ratios in phases at equilibrium were used for the construction of the 1200 degrees C isothermal section of the Fe-Zn-O system. The univariant equilibria between the gas phase, spinel, wustite, and zincite was found to be close to pO(2) = 1 center dot 10(-8) atm at 1200 degrees C. The ferric and ferrous iron concentrations in zincite and spinel at equilibrium were also determined at temperatures from 1200 degrees C to 1400 degrees C at pO(2) = 1 center dot 10(-6) atm and at 1200 degrees C at pO(2) values ranging from 1 center dot 10(-4) to 1 center dot 10(-8) atm. Implications of the phase equilibria in the Fe-Zn-O system for the formation of the platelike zincite, especially important for the Imperial Smelting Process (ISP), are discussed.

Effect of Al2O3 and Cr2O3 on loquidus temperatures in the cristobalite and tridymite primary phase fields of the MgO-"FeO"-SiO2 ststem in equilibrium with metallic iron

The effects of alumina and chromite impurities on the liquidus temperatures in the cristobalite/tridymite (SiO2) primary phase fields in the MgO-FeO-SiO, system in equilibrium with metallic iron have been investigated experimentally. Using high temperature equilibration and quenching followed by electron probe X-ray microanalysis (EPMA), liquiclus isotherms have been determined in the temperatures range 1 673 to 1 898 K. The results are presented in the form of pseudo-ternary sections of the MgO-FeO-SiO, system at 2, 3 and 5 wt% Al2O3, 2 wt% Cr2O3, and 2 wt% Cr2O3+2 wt% Al2O3. The study enables the liquidus to be described for a range of SiO2/MgO and MgO/FeO ratios. It was found that liquiclus temperatures in the cristobalite and tridymite primary phase fields, decrease significantly with the addition of Al2O3 and Cr2O3.

The number, morphology, and distribution of retinal ganglion cells and optic axons in the Australian lungfish Neoceratodus forsteri (Krefft 1870)

Australian lungfish Neoceratodus forsteri may be the closest living relative to the first tetrapods and yet little is known about their retinal ganglion cells. This study reveals that lungfish possess a heterogeneous population of ganglion cells distributed in a horizontal streak across the retinal meridian, which is formed early in development and maintained through to adult stages. The number and complement of both ganglion cells and a population of putative amacrine cells within the ganglion cell layer are examined using retrograde labelling from the optic nerve and transmission electron-microscopic analysis of axons within the optic nerve. At least four types of retinal ganglion cells are present and lie predominantly within a thin ganglion cell layer, although two subpopulations are identified, one within the inner plexiform and the other within the inner nuclear layer. A subpopulation of retinal ganglion cells comprising up to 7% or the total population are significantly larger (> 400 mu m(2)) and are characterized as giant or alpha-like cells. Up to 44% of cells within the retinal ganglion cell layer represent a population of presumed amacrine cells. The optic nerve is heavily fasciculated and the proportion of myelinated axons increases with body length from 17% in subadults to 74% in adults. Spatial resolving power, based on ganglion cell spacing, is low (1.6-1.9 cycles deg(-1), n = 2) and does not significantly increase with growth. This represents the first detailed study of retinal ganglion cells in sarcopterygian fish, and reveals that, despite variation amongst animal groups, trends in ganglion cell density distribution and characteristics of cell types were defined early in vertebrate evolution.

Use of stable-isotope probing, full-cycle rRNA analysis, and fluorescence in situ hybridization-microautoradiography to study a methanol-fed denitrifying microbial community

A denitrifying microbial consortium was enriched in an anoxically operated, methanol-fed sequencing batch reactor (SBR) fed with a mineral salts medium containing methanol as the sole carbon source and nitrate as the electron acceptor. The SBR was inoculated with sludge from a biological nutrient removal activated sludge plant exhibiting good denitrification. The SBR denitrification rate improved from less than 0.02 mg of NO3-.N mg of mixed-liquor volatile suspended solids (MLVSS)(-1) h(-1) to a steady-state value of 0.06 mg of NO3-.N mg of MLVSS-1 h(-1) over a 7-month operational period. At this time, the enriched microbial community was subjected to stable-isotope probing (SIP) with [C-13] methanol to biomark the DNA of the denitrifiers. The extracted [C-13]DNA and [C-12]DNA from the SIP experiment were separately subjected to full-cycle rRNA analysis. The dominant 16S rRNA gene phylotype (group A clones) in the [C-13]DNA clone library was closely related to those of the obligate methylotrophs Methylobacillus and Methylophilus in the order Methylophilales of the Betaproteobacteria (96 to 97% sequence identities), while the most abundant clone groups in the [C-12]DNA clone library mostly belonged to the family Saprospiraceae in the Bacteroidetes phylum. Oligonucleotide probes for use in fluorescence in situ hybridization (FISH) were designed to specifically target the group A clones and Methylophilales (probes DEN67 and MET1216, respectively) and the Saprospiraceae clones (probe SAP553). Application of these probes to the SBR biomass over the enrichment period demonstrated a strong correlation between the level of SBR denitrification and relative abundance of DEN67-targeted bacteria in the SBR community. By contrast, there was no correlation between the denitrification rate and the relative abundances of the well-known denitrifying genera Hyphomicrobium and Paracoccus or the Saprospiraceae clones visualized by FISH in the SBR biomass. FISH combined with microautoradiography independently confirmed that the DEN67-targeted cells were the dominant bacterial group capable of anoxic [C-14] methanol uptake in the enriched biomass. The well-known denitrification lag period in the methanol-fed SBR was shown to coincide with a lag phase in growth of the DEN67-targeted denitrifying population. We conclude that Methylophilales bacteria are the dominant denitrifiers in our SBR system and likely are important denitrifiers in full-scale methanol-fed denitrifying sludges.

XSophe, a computer simulation software suite for the analysis of electron paramagnetic resonance spectra

The XSophe computer simulation software suite consisting of a daemon, the XSophe interface and the computational program Sophe is a state of the art package for the simulation of electron paramagnetic resonance spectra. The Sophe program performs the computer simulation and includes a number of new technologies including; the SOPHE partition and interpolation schemes, a field segmentation algorithm, homotopy, parallelisation and spectral optimisation. The SOPHE partition and interpolation scheme along with a field segmentation algorithm greatly increases the speed of simulations for most systems. Multidimensional homotopy provides an efficient method for accurately tracing energy levels and hence tracing transitions in the presence of energy level anticrossings and looping transitions and allowing computer simulations in frequency space. Recent enhancements to Sophe include the generalised treatment of distributions of orientational parameters, termed the mosaic misorientation linewidth model and a faster more efficient algorithm for the calculation of resonant field positions and transition probabilities. For complex systems the parallelisation enables the simulation of these systems on a parallel computer and the optimisation algorithms in the suite provide the experimentalist with the possibility of finding the spin Hamiltonian parameters in a systematic manner rather than a trial-and-error process. The XSophe software suite has been used to simulate multifrequency EPR spectra (200 MHz to 6 00 GHz) from isolated spin systems (S > ~½) and coupled centres (Si, Sj _> I/2). Griffin, M.; Muys, A.; Noble, C.; Wang, D.; Eldershaw, C.; Gates, K.E.; Burrage, K.; Hanson, G.R."XSophe, a Computer Simulation Software Suite for the Analysis of Electron Paramagnetic Resonance Spectra", 1999, Mol. Phys. Rep., 26, 60-84.