Experimental study of phase equilibria in the PbO-ZnO-“Fe2O3”-CaO-SiO2 system in air for high lead smelting slags (CaO/SiO2=0.35 and PbO/(CaO + SiO2)=5.0 by weight)

Experimental studies on phase equilibria in the multicomponent system PbO-ZnO-CaO-SiO₂-FeO-Fe₂O₃ in air have been conducted to characterize the phase relations of a complex slag system used in commercial lead oxidation smelting. The liquidus in the pseudo-ternary section ZnO-“Fe₂O₃”-(PbO + CaO + SiO₂) with the CaO/SiO₂ weight ratio of 0.35 and the PbO/(CaO + SiO₂) weight ratio of 5.0 has been constructed using results of over 100 high-temperature equilibration and quenching experiments followed by electron probe X-ray microanalysis. The liquidus in this pseudoternary section contains primary phase fields of spinel (zinc ferrite) Zn _x Fe_3−x O_4+y , zincite Zn _u Fe_1−u O, melilite Pb _v Ca_2−v Zn _w Fe_1−w Si₂O₇, hematite Fe₂O₃, magneto-plumbite PbFe₁₀O₁₆, and dicalcium silicate Ca_2−t Pb _t SiO₄. The laboratory results are compared with the slags obtained from an industrial reactor.     

Adsorption–desorption noise in plasmonic chemical/biological sensors for multiple analyte environment

We investigated intrinsic noise in plasmonic sensors caused by adsorption and desorption of gaseous analytes on the sensor surface. We analyzed a general situation when there is a larger number of different analyte species. We applied our model to calculate various analyte mixtures, including some environmental pollutants, toxic and dangerous substances. The spectral density of mean square refractive index fluctuations follows a dependence similar to that of generation-recombination noise in photodetectors, flat at lower frequencies and sharply decreasing at higher. Some of the calculated noise levels are well within the detection range of conventional surface plasmon resonance sensors. An AD noise peak is observed in temperature dependence of mean square refractive index fluctuations, thus sensor operating temperature may be optimized to obtain larger signal to noise ratio. A significant property of AD noise is its rise with the decreasing plasmon sensor area, which means that it will be even more pronounced in modern nanoplasmonic devices. Our consideration is valid both for conventional surface plasmon resonance devices and for general nanoplasmonic devices.     

Investigation of Freeze Lining in Copper-Containing Slag Systems: Part III. High-Temperature Experimental Investigation of the Effect of Bath Agitation

Freeze-lining technologies have been employed to protect the cooling walls of reactors from chemically aggressive molten reactants. To date, the designs of freeze linings for pyrometallurgical reactors have been based on the basic assumption that the interface between the deposit and the bath remains at the liquidus temperature of the bulk liquid. There is, however, increasing evidence that interface temperature between stagnant deposit and bath is less than the liquidus of the bulk liquid. A previous study also demonstrated that the effects of bath chemistry need to be taken into account in freeze-lining designs. To investigate the fundamental processes involved in the formation and stability of the deposit, experimental laboratory studies have been undertaken in the Cu-Fe-Si-Al-O slag system in equilibrium with metallic copper using an air-cooled probe technique. In the current study, the effects of bath agitation on the microstructure, morphologies of the phases, and formation of various layers across the freeze-lining deposit were studied at steady-state conditions. It appears that the changes in the fluid flow pattern through changes in shear intensities result in corresponding changes in the deposit microstructure, formation of the sealing primary phase layer, thus influencing the interface temperature between freeze-lining deposit and the liquid bath.     

Experimental liquidus study of the binary PbO-ZnO and ternary PbO-ZnO-SiO2 systems

Phase equilibria of the binary PbO-ZnO and ternary PbO-ZnO-SiO₂ systems have been experimentally investigated at 1033–1898?K (760–1625?°C) for oxide liquid in equilibrium with air and solid oxide phases: tridymite or cristobalite (SiO₂), willemite (Zn₂SiO₄), zincite (ZnO), larsenite (PbZnSiO₄) and lead-zinc melilite (Pb₂ZnSi₂O₇) covering the ranges of concentrations not studied before. High-temperature equilibration on primary phase or inert metal (platinum) substrates, followed by quenching and direct measurement of the Pb, Zn and Si concentrations in the phases with the electron probe X-ray microanalysis (EPMA) has been used. Liquidus phase equilibrium data is essential for the development of the thermodynamic model.     

Experimental Study of Ferrous Calcium Silicate Slags: Phase Equilibria at {\text{P}}_{{{\text{O}}_{2} }} Between 10?5?atm and 10?7?atm

Ferrous calcium silicate slags, whose principal components are “FeO _x ”-CaO-SiO₂, are widely used in copper smelting and converting operations. In the current study, high-temperature equilibration and rapid quenching techniques were used to study the phase equilibria of the ferrous calcium silicate slags. The compositions of phases in the slags were measured accurately using electron probe X-ray microanalysis (EPMA). The phase equilibria of the system have been characterized at oxygen partial pressures between 10⁻⁵ atm and 10⁻⁷ atm at selected temperatures between 1473 K and 1623 K (1200 °C and 1350 °C). The effects of oxygen partial pressure and temperature on the compositions of phases in the slags are presented.     

Reaction of Aryl Iodides with (PCP)Pd(II)—Alkyl and Aryl Complexes: Mechanistic Aspects of Carbon—Carbon Bond Formation

The reaction of the PCP-type complex Pd(Me){2,6-(ⁱPr₂PCH₂)₂C₆H₃}( 3 ) with phenyl iodide results in the formation of Pd(I){2,6-(ⁱPr₂PCH₂)₂C₆H₃} ( 5 ), methyl iodide, toluene, and biphenyl. Formation of Pd(Ph){2,6-(ⁱPr₂PCH₂)₂C₆H₃}( 4 ) is observed during the reaction by ³¹P NMR. Reaction of 4 with aryl iodides results in the formation of 5 and Ph–Ph, Ph–Ar, and Ar–Ar, products indicative of a radical reaction. Under pseudo-first-order conditions, the rates of the reactions follow the order p-OMe > p-Me > H > p-NO₂ > m-Cl. The reaction is likely to involve electron transfer from 4 to the aryl iodide followed by fast decomposition of a postulated radical cation [Pd(Ph){2,6-(ⁱPr₂PCH₂)₂C₆H₃}]^+. ( 4 ^+.) to give a phenyl radical and [Pd{2,6-(ⁱPr₂PCH₂)₂C₆H₃}]⁺ ( 6 ⁺). Facile decomposition of the aryl iodide radical anion generates an aryl radical and I⁻. Recombination of aryl radicals gives rise to mixed biaryls, and 6 ⁺ combines with I⁻ to give 5 .     

Investigation of the Influence of Heat Balance Shifts on the Freeze Microstructure and Composition in Aluminum Smelting Bath System: Cryolite-CaF2-AlF3-Al2O3

Metallurgical and Materials Transactions B - In an aluminum electrolysis cell, the side ledge forms on side walls to protect it from the corrosive cryolitic bath. In this study, a series of...     

The effect of kinetic and hydrodynamic factors on current efficiency in the chlorate cell process

An equation has been derived which relates the current efficiency of chlorate production to the operational parameters of the process and the constants connected with the events in the diffusion layer of the anode. The latter have been estimated using available literature data and the equation has been tested for the temperature dependence of current efficiency by comparison with experimental results. A fair degree of agreement has been achieved.Partly presented at the XXth CITCE Meeting, Strasbourg 1969.     

Coupled experimental and thermodynamic study of the Zn-Fe-Si-O system

Experimental and thermodynamic modeling studies have been carried out on the Zn-Fe-Si-O system. This research is part of a wider program to characterize zinc/lead industrial slags and sinters in the PbO-ZnO-SiO₂-CaO-FeO-Fe₂O₃ system. Experimental investigations involve high-temperature equilibration and quenching techniques followed by electron probe X-ray microanalysis (EPMA). Liquidus temperatures and solid solubilities of the crystalline phases were measured in the temperature range from 1200 °C to 1450 °C (1473 to 1723 K) in the zinc ferrite, zincite, willemite, and tridymite primary-phase fields in the Zn-Fe-Si-O system in air. These equilibrium data for the Zn-Fe-Si-O system in air, combined with previously reported data for this system, were used to obtain an optimized self-consistent set of parameters of thermodynamic models for all phases.