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By S. M. Copley, M. Yankova, E. Y. Yankov, J. A. Todd

"Nanophased coupled growth structures, with spacings of -10 nm, have been observed in banded microstructures produced by laser melting hypoeutectic Ag-Cu alloys. These coupled growth structures comprised a Cu-rich phase of width - 1 nm and a Ag-rich phase of width - 9 nm. In this paper, microstructural observations of nanophased coupled growth structures in hypo eutectic AgCu alloys are presented. Laser beam velocities for the transition from banded to microsegregation free microstructures are modelled and compared with experimental values. Models are presented to show that, at a critical undercooling, initial growth of a Ag-rich, metastable, extended solid solution is rapid but slows to a halt as copper is partitioned into the liquid at the solid/liquid interface. Following nucleation, the coupled growth structure then grows until the partitioned copper is consumed, at which point growth of the Ag-rich solid solution is again accelerated. This cycle then repeats resulting in banded microstructures comprised of 750 nm of the Ag-rich extended, metastable solid solution, followed by 250 nm of the coupled growth structure.1. Structural Studies of Laser Melted and Resolidified TrailsPresented here are observations of laser melted and resolidified trails in Ag-Cu alloys obtained at beam velocities ranging from 0.7 to 34 cm S·I. When the laser beam is scanned along the surface (positive x-direction) with a velocity Vb a melt pool with the shape given in Fig. 1a moves with the beam. The isotherms move with the velocity, Vi,. = Vb cos.p. Calculations employing the thermal analysis of Kou, Hsu and Mehrabian [1] for the beam velocities of this investigation and for the thermal properties of AgCu alloys, indicated that, .p, the angle between the isotherm velocity and beam velocity should be small at the surface where microstructural studies were made. This prediction was supported by observations of trail cross-sections. Based on these observations, and the calculations which include latent heat effects, the isotherm velocity for observations near the surface in our investigation was taken to be 27 cm S-I."

Jan 1, 1994

By Shadia J. Ikhmayies

SnO2:F/CdS:In bilayers were produced by the spray pyrolysis technique on glass substrates. The structures were characterized by recording and investigating their transmittance curves, I-V plots, X-ray difractograms (XRD) and by observing their scanning electron microscope (SEM) images. From the I-V plots it was found that the SnO2:F forms an ohmic or quasi-ohmic contact with CdS:In. XRD patterns show the polycrystalline nature of the films and show that there is a small shift in the position of the (200) line of SnO2:F without the appearance of new peaks. The morphology of the structures are compared with those of SnO2:F alone and CdS:In alone on glass substrates.

Jan 1, 2009

By P. D. Ferro

The direct oxide reduction (DOR) of plutonium oxide generates significant amounts of contaminated waste. This waste primarily consists of calcium oxide-saturated calcium chloride salt. This investigation explores the possibility of recycling the salt, by the electroreduction of the calcium oxide. Fused salt electrolysis of a simulated salt mix (CaC12 + ~10 wt. pct. CaO) is being carried out to electrowin calcium, and the process is being optimized in terms of the calcium solubility, cell temperature, current density and cell design to maximize the current efficiency. This work identifies the major concerns in the development of a process to electrowin calcium from this simulated salt mix.

Jan 1, 1992

By R. Boom, C. F. Balentina, J. H. L. Voncken

During vitrification of bottom ash generated from the combustion of municipal solid waste (MSW), a Fe-Cu based alloy phase with great value was formed. In order to find proper commercial use in metallurgical industry, it is necessary to separate Cu and Fe. The present study focuses on the sulfide treatment at temperatures of 1400 – 1500oC, in particular with FeS containing minerals. Various sulfide compounds such as Na2S, Al2S3 and Ni3S2 were added to promote the copper removal. Pyrite and zinc sludge (containing ZnS) as waste streams were studied with specific interests. The results showed that both zinc sludge and pyrite are effective for copper removal with the highest removal efficiency of 95% by using pyrite. The copper content drops from 12 wt% to about 2 wt%. However, it is still difficult to remove copper completely from the alloy in one step, and a multi-step operation is needed.

Jan 1, 2008

By Minge Zhao, Yuandong Pei, Zhixing Zhao, Zejun Ma, Lili Ban

"Confocal scanning laser microscope (CSLM) has been applied to carry out the in-situ observation of melting and solidifying characteristics during iron ore sintering process, accompanied with TG-DSC test. It can be found that apparent Liquid phase forming temperature(LFT) and ending solidifying temperature(EST) is about 1190? and 1160?, respectively. Forming liquid phase during sintering process goes through four courses, these are shrinking, expanding, shrinking and expanding coexisting and expanding totally. For Yandi fine, the corresponding temperature of these four courses is about 1120-1160?, 1190-1196?, 1218-1220? and 1233-1270?, respectively. Although CAJ fine has more difficulty in forming initial liquid phase, but when liquid phase expands, it may have better fluidity and easier for liquid phase formation. Adding enough CaO, CAJ fine takes on high fluidity like Yandi fine, because liquid phase during sintering process is formed mainly by reaction between CaO and Fe2O3.IntroductionConfocal scanning laser microscope (CSLM for short) has been applied to carry out the in-situ observation of metallurgical phenomena, especially in steelmaking process. Recently, many researches on ironmaking process were conducted with CLSM. While for high temperature properties during sintering process, there are limited reports on in situ observation1-2). In this paper, melting and solidifying characteristics of iron ore were observed with CLSM under simulated sintering temperature, and high temperature properties of iron ore during sintering process was clarified based on the in situ observation results and TG-DSC research."

Jan 1, 2012

By Pan Cao

The process of reduction roasting of nickel laterite with rotary hearth furnace combined with magnetic separation becomes a very potential way to prepare ferronickel alloy, especially for the low grade nickel laterite ore. In order to realize this new process, the effect of roasting temperature, time and additive on the reduction degree were investigated in the laboratory experimental. The results indicated that the recovery rate of Ni increased with the roasting temperature increasing to 1500°. Most of nickel and a spot of iron are selectively reduced with adding 25.19% SiO2, 6.42% coal, and roasting for 60min at 1500℃. Then conventional magnetic separation was carried out. The content of Ni and Fe are 7.50% and 59.08% in ferro-nickel nugget prepared by this method. And the recovery rate of Ni is 90.91%, which indicates that a high recovery of ferro-nickel from nickel laterite ore is achieved indeed.

Jan 1, 2014

By G. A. Irons, D. Guo

"The average spout height and width produced by bottom gas injection in a water model of a steel ladle were measured with an image processing technique. It was revealed that the spout height could be described by a Gaussian curve. A combined SIMPLE -VOF model was developed to simulate the liquid surface and flow. The results showed that, though the model produced reasonable velocity distributions and free surface positions, the spout height due to the dynamic head of the rising liquid was substantially lower than observed, indicating that the bubble dynamics at the bath surface play an important role in spout height.IntroductionDue to the enormous importance of gas injection and stirring in metallurgical processes, there have been numerous publications on water and numerical modeling of such vessels. The free surface of the bath has received considerably less attention, despite its importance. At the free surface there are often important chemical phenomena occurring that require a good understanding of the fluid flow; these would include reoxidation of steel, metal splash and fume formation. Furthermore, to understand the details of slag-metal interactions such as slag entrainment, metal losses to slag and the transport phenomena associated with refining reactions, it is necessary to understand the plume and spout interactions first.There have been few experimental studies of the free surface of liquid in gas-injected ladles [1- 3], and even fewer on numerical modeling. Brimacombe and co-workers [1] studied the gas void fraction in the spout region, using a double-tip electrical resistance probe. This sensor cannot distinguish between gas in bubbles about to break and gas in the freeboard. Thus, it is a matter of judgement as to the position of the free surface. Schwerdtfeger and co-workers [2] used a single probe configuration with a wire and a counter electrode in the liquid, so that the height of the continuous liquid phase was unambiguously determined. Irons and co-workers [3] measured the spout height by ultrasonic and electrical capacitance techniques. These techniques were as reliable as the resistance techniques, but were restricted to low flow rates."

Jan 1, 2001

By Santo Ranieri

We will briefly review the nickel market in 2003 and look forward to the supply demand balance for the next few years focusing in on the key factors influencing future price dynamics. On the supply side we will examine slated brownfield and greenfield expansions including the Norilsk factor and the small to mid-range 'supply creep'. We will also review the cost side of the industry and what to expect going forward. On the demand side, we will discuss the stainless steel and non-stainless demand, the China factor and the stainless steel scrap supply cycle. We will conclude by pinpinting where the market is on the current price cycle, and where we believe the mid-term direction is headed.

Jan 1, 2004

By Saskia Duyvesteyn

Small ion-exchange resin particles provide faster mass transport than conventional-sized beads. Unfortunately, high pressures are needed to pump solutions through columns containing small resin particles. It is preferable to disperse fine resins in the solution being treated. Screens have been used to separate the resin from the solution, but screens do not retain fines created by attrition of the resin particles. We have developed a separation process based on flotation, which relies on the surface characteristics of the resin, instead of size. The resin is conditioned with a surfactant before dispersing it in the solution to be treated; this increases the hydrophobicity of the resin sufficiently for froth flotation, without introducing surfactant directly into the solution. The surfactant adsorbed on the resin surface does not appear to impair the kinetics of metal ion removal. A flowsheet for an effluent treatment process is proposed; other applications are clearly possible.

Jan 1, 1998

By Ximena Diaz

Mercury is one of the most undesirable contaminants in gold bearing ores. During cyanidation mercury cyanide compounds accompany gold in all the extraction and recovery processes. Of course mercury in the carbon eluates creates environmental problems in subsequent refining steps. One possible process alternative for the separation of gold from mercury in such concentrated alkaline cyanide solutions is the selective solvent extraction of gold by undiluted Dibutyl Butyl Phosphonate (DBBP). In order to describe the behavior of mercury during extraction by DBBP, the results from a preliminary research program are presented. In this study, temperature and cyanide concentration have been found to be the most significant variables which influence the separation of gold from mercury by solvent extraction using DBBP. It was found, using plant eluate from a carbon strip, that excellent separation of gold from mercury can be obtained at 60' C with 98% gold recovery and complete mercury rejection in a single stage of extraction. The influence of pH is also discussed in terms of the extraction chemistry. These results complement previous research which described the DBBP solvation extraction of an aurocyanide ion pair. In addition, these results extend our understanding of the alkyl phosphorous ester extraction systems by illustrating that neutral ionic species such as Hg(cN)02sq, can be extracted at low cyanide concentrations, a phenomenon which had not been observed previously for other cyanoanions.

Jan 1, 1993

By Z. Zhang, Cuihuan Huang, Zongshu Zou, Nan Wang, Xueqian Xin

"Vitrification is considered as an attractive procedure for municipal solid waste incineration ash, which can realize the volume reduction and innocent treatment of incineration ash, as well as reuse of bottom ash. The main oxide components of molten ash slag are CaO, Al2O3, SiO2, Fe2O3, MgO, and Na2O, accounting for more than 90% of the total mass. The phase relations and thermodynamic properties of the CaO-Al2O3-SiO2-FeOx-MgO-Na2O oxide system is highly required, and is of great scientific significance for optimization of vitrification processing and sustainable resource utilization of melting slag. A study on the equilibria phase relations of CaO-SiO2-MgO-FeOx system was done by using CALPHAD method based on FactSage in this paper. The modeling parameters for the thermodynamic properties of liquid phase in CaO-SiO2-MgO-FeOx system were established and the equilibrium phase relations of MgO-SiO2-FeOx and CaO-SiO2-FeOx-MgO systems were calculated for different temperatures and oxygen partial pressures.IntroductionThe main oxide components of vitrified bottom ash slag are CaO, Al2O3, SiO2, Fe2O3, MgO, and Na2O, accounting for more than 90% of the bottom ash by weight [1]. During slag processing and modification, the knowledge of thermodynamic properties and liquidus temperature in the related slag system is highly required [2-5], which is not yet available. Through literature survey [6-9], it is clear that the systematic information on the concerned complex slag system is scarce. Most binary subsystems except FeOx-Na2O have been investigated well. Among ternary subsystems, few phase relations of the Na2O-MgO-SiO2 ternary system are available. For the phase relations of the system Na2O-MgO-Al2O3, all the studies are focused on the Al2O3-rich region. Investigation on the CaO-Al2O3-FeOx system is limited to Fe2O3-containing system with relatively higher oxygen potential. Most quaternary systems are not studied well except the CaO-MgO-Al2O3-SiO2 system, mainly due to their metallurgical importance. Figure 1 demonstrates the research status of the vitrified bottom ash slag with almost zero effort [10]. The effort here is defined based on the published literature by considering the number of publications, the investigated composition ranges, and the research details. So far the engineers in the field have to make assumptions of the thermodynamic properties of the simplified oxide system, without taking into consideration the interactions of the different oxide components, which hinders the development of the slag valorization and utilization. In order to provide thermodynamic properties for the application of the vitrified bottom ash, the six-component oxide system (CaO-MgO-Al2O3-SiO2-FeOx-Na2O) will be investigated through both experimental approach and computer modeling."

Jan 1, 2011

Many studies have been conducted over the past 3 decades on the leaching of gold in solutions containing thiosulfate, ammonia and copper. However, most of these studies have been carried out using ore samples, with very few fundamental studies of this system being attempted. The majority of the published studies have failed to acknowledge the undesirable side reaction between copper(H) and thiosulfate, let alone account for its effect. The fact that the solution chemistry is constantly changing makes it very difficult to perform a fundamental study of gold leaching. With the advent of the rotating electrochemical quartz crystal microbalance (REQCM), such fundamental studies are possible as this instrument measures mass in real time. This has allowed leach kinetics to be measured in a matter of minutes and hence at essentially constant solution conditions; The present paper highlights that a sufficient concentration of copper(II) and ammonia are required in order to achieve appreciable gold leach rates. However, the use of air (oxygen) to maintain the copper(Il) concentration catalyses the undesirable copper(II) reaction with thiosulfate. The presence of ammonium ions is shown to have an effect on this undesirable reaction as well as on the gold leaching ?reaction. Preliminary electrochemical studies into .gold electrowinning using the REQCM show that gold(I) thiosulfate cannot be readily reduced to metallic gold in the potential region at which cementation usually occurs. However, it is well known that gold cementation onto copper occurs rapidly. The current study addresses this discrepancy by studying the effect that copper and silver have on the reduction of gold thiosulfate. It has been found that the presence of both silver and copper enhance gold deposition, particularly at low over potentials. While this is beneficial in cementation, the presence of copper and silver in solution has been found to cause passivation of the cathode surface during electrowinning at 'higher overpotentials.

Jan 1, 1998

By J. S. Lee

A new high performance adsorbent is synthesized by the sol-gel method and applied to the removal of cadmium and mercury ions from aqueous solutions. Adsorbents based on metal oxides have been developed by immobilizing chelating molecules on the surface of the existing metal oxide networks and show ability for selective metal extraction from aqueous solutions. However, efficiencies of such adsorbents are limited due to low ligand density, and difficulty in pore accessibility. These difficulties are circumvented by synthesizing adsorbents using the sol-gel technique. In one example to be discussed, the sol-precursor possesses an organic moiety that binds cadmium, mercury, and copper ions. The capacities of 1.98mmol Cd(II-/gm and 6.40 mmol Hg/gm of this adsorbent are considerably higher than those of adsorbents prepared by the ligand immobilization technique. The scope of this paper is to discuss the development of the new adsorbent and its applications for cadmium and mercury removal from aqueous solutions.

Jan 1, 1999

By Walter Curlook

An improved process of hydrometallurgical treatment of laterite ores of the limonitic type for the recovery of nickel and cobalt using sulphuric acid has been developed and patented [I]. The major improvement is brought about by recycling a significant portion of the "mother liquor" emanating from the pressure leaching reaction back to the feed preparation stage thereby substituting for all or at least a major proportion of the fresh water that must be added. The amount of process effluent waters is correspondingly reduced. Concomitantly with the major savings in fresh water requirements, a degree of reduction in new sulphuric acid requirements is effected, along with a savings in limestone and lime required for subsequent neutralizations. Keywords: Acid pressure leaching; Nickel laterites

Jan 1, 2004

The kinetics of the oxidation of cyanide by manganese dioxide was studied using a rotation disc electrode system. The rate? of the half-cell reaction of cyanide oxidation is increased at higher hydroxide concentrations. An addition of copper up to 0.001 mole/l was found to enhance the diffusion current, especially at a high hydroxide concentration (0. 1M). A similar enhancement of the reaction rate is also achieved with nickel added at levels up to 0.01 mole/l. Manganese dioxide however requires a i:ow pH to achieve reasonable reduction rates. Leaching studies indicated that the initial reaction rate is strongly dependent on pH, initial concentration of cyanide. Using manganese dioxide cyanide could be oxidized at neutral pH's and ambient temperatures.

Jan 1, 1989

By Tamas Kekesi

Anion exchange in HCl media is considered an efficient alternative to the combination of the conventional purification methods. Anion-exchange distribution functions have been determined for cobalt and the main impurity elements by the technique of batch equilibration. Results were confirmed by spectrophotometric investigations and elution tests. Based on the new and the available distribution functions, combined with the assessment of thermodynamic stability, a procedure of anion exchange separation has been devised to eliminate virtually all the impurities from the cobalt-chloride solution. Separation of copper has been enhanced by the introduction of a preliminary step under reduced conditions. The rest of the impurities are eliminated in a second anion-exchange step applying rinsing and elution stages under oxidized conditions. The optimum parameters of the procedure have been determined according to performance characteristics (purification ratios, yields and volume efficiencies) derived from the analysis of elution curves obtained with laboratory scale ion-exchange columns. Special computer programs have been developed to facilitate thermodynamic simulation, analytical correction and data processing.

Jan 1, 2003

By Elli Nurminen

Sulphate decomposition was studied in the conditions of a typical copper flash smelting heat recovery boiler. The aim was to determine the kinetics of the copper sulphate decomposition reactions and to find out if they are likely to take place in the process conditions prevailing in an industrial HRB. The information is essential in CFD-modelling of the reactions taking place in the boiler and for optimising the process. Thermal decomposition of sulphates was studied by thermogravimetry. The experiments were conducted with a commercial copper sulphate, a partially sulphated copper oxide and an actual process flue dust. The main variables studied were temperature and gas composition of a N2-O2-SO2-mixture. The samples were characterized with SEM, optical microscope and XRD. Temperature affected the decomposition rate strongly but the gas composition had a minor effect on the kinetics. The decomposition was fastest in the partly sulphated oxide and slowest in commercial copper sulphate. Keywords: Sulphate decomposition, flash smelting, heat recovery boiler, flue dust

Jan 1, 2004

By Yuuki Yoshida

Electrolytic manganese dioxide, EMD, is the positive electrode material of primary batteries and the raw material of LMC used as the positive mass of lithium ion batteries and is currently produced by anodic deposition on and harvesting from a titanium anode in acidic manganese sulfate solutions prepared by dissolving high purity of manganese sulfate into sulfuric acid solutions. This paper presents an alternative method of EMD production using a novel anode, Mn2O3 coated titanium, at lower operating temperature than the current process to explore a possibility of manganese recovery from zinc electrowinning solutions. The Mn2O3/ Ti anode prepared by thermal decomposition of a precursor solution containing Mn (II) showed the anodic deposition of MnO2 by constant current electrolysis and the current efficiency was 95% in maximum, while the current efficiency and the crystallographic structure of deposited MnO2 depended on the current density, the electrolysis time, the bath temperature, and the concentration of Mn(II). The deposited MnO2 was successfully harvested from the anode and the recovery rate was 98%.

By William E. Frazier

The presence of minute amounts of sulfur (10ppm) in nickel-base superalloys has been associated with reduced oxidation resistance and the premature spallation of protective coatings. Removal of sulfur by annealing these alloys in a hydrogen atmosphere has been successfully attempted by several researchers. This paper examines the fundamental thermodynamics and kinetics governing hydrogen desulfurization of elemental nickel. Limiting conditions for successful desulfurization are delineated. Assuming that the diffusion of sulfur is the rate limiting process of desulfurization, the effectiveness as well as time associated with hydrogen desulfurization is explored.

Jan 1, 1994

By J. W. Matousek

In the flash smelting of copper sulfide concentrates, the course of reactions from the burner tip, through flame "burn-out" (the point of oxygen depletion), to settled matte and slag is of particular interest in understanding the mechanisms of the process. Numerous reaction sets can be proposed to describe the chemical changes that might be taking place, but from outside the furnace no one set offers an obvious advantage in explaining the actual processes involved. Only a combination of mathematical modeling and flame and bath sampling can achieve this result. This paper shows that flash smelting, while still reasonably orderly, is a more complex process than suggested by the technical literature.

Jan 1, 1993