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By Noriaki Kurita, Norihiko Fulcatsu, Teruo Ohashi

"An electrochemical sensing device for hydrogen in molten metal has now been available owing to the development of the proton conducting solid electrolyte made of ceramics of metal oxide. The structure of the sensor and the theoretical limitations of its applications are discussed based on the electrochemical properties of the electrolyte used. The practical performance of the sensor is reviewed from the results of test measurements at the plants of aluminum and copper melting industries. The effectiveness of the sensor to the process control of continuous casting of copper is also discussed.IntroductionSince the in-line monitoring of the amount of oxygen dissolved in molten metal was realized by using the oxygen concentration cell based on zirconia solid electrolyte a similar method has been expected to be developed for sensing of hydrogen, which is a very important element of gas species in liquid metals, especially, in aluminum and copper. In 1981; Iwahara and coworkers found the dominant proton conduction at a high temperature in some perovskite-type oxide (1). Since then, the effort has been made to apply this proton conducting material as the electrolyte of the hydrogen concentration cell for high temperature use. The hydrogen sensor for liquid aluminum of this kind was first produced in 1991 (2) and released commercially from TYK Co., Ltd. Recently, we have developed the mother one usable at higher temperature such as copper and silver melting processes (3). In this note we discuss their structure, design and applicable limitations based on the electrochemical properties of this new type electrolyte. The performance of the sensor and benefit to use it to control the melting process is also discussed"

Jan 1, 2000

02, NaCI03, H202, Na0CI and Ce+4 have been examined as oxidants in an alkaline carbonate system for uranium in in situ leaching. The South Texas and New Mexico ores contained up to 2.6 meqJg of reducing compounds which consume oxidants in the leading operation. Leaching rates did not increase linearly with the oxidation potential of the oxidants. A mild oxidant can be used to maximize uranium oxidation selectively and oxidant efficiency. 02 can oxidize most of the uranium mineral with an adequate rate and high oxidant efficiency.

Jan 1, 1990

By Kandipati Sreenivasarao

Ion and precipitate flotation involve adding an appropriate collector to aqueous solutions containing metal ions, to form hydrophobic metal-collector complexes or precipitates that can be removed by flotation. With a better fundamental understanding of the effects of physical, engineering and chemical parameters on the performance, ion and precipitate flotation techniques could usefully complement techniques now available for removing metal ions from dilute solutions. The removal of Cu(II), Pb(II), Cd(II), Cr(III) and Cr(V1) has been studied, using different types of collector, according to the nature of the metal-bearing species. The effects of collector/metal ion ratio, and solution and froth height on the flotation kinetics, bubble coverage by the metal-collector complex, recovery of metal and effluent quality are reported. The observed behavior is related to the solubility products of the metal-collector complexes, which were also determined.

Jan 1, 1994

By Filipe de Menezes Torres, Augusto Pereira de Sa, Itavahn Alves da Silva, Eliana Ferreira Rodrigues, Carlos Antonio da Silva, Varadarajan Seshadri

Top slag eye opening which happens as a result of gas injection is a function of the gas flow rate in addition to other factors such as ladle geometry, porous plug location as well as slag properties. Slag eye opening leads to entrapment of atmospheric nitrogen, oxygen by the steel melt affecting adversely the steel quality. In this work aspects of mixing and eye formation in steel making ladles with inert gas injection have been analyzed through physical and mathematical modeling techniques. Influence of ladle, gas flow rate and distribution and slag properties has been assessed. A correlation for estimating eye opening has been developed. Results from PIV measurements and images of eye opening obtained using a camera have been utilized to validate results from CFD simulation.

Jan 1, 2015

By François Larouche

Since their commercialization in the early 1990s, lithium-ion batteries (LIBs) have become ubiquitous for powering a myriad of portable electronics. Their usage now extends to the automotive industry and stationary energy storage market. With an average life of 6.2 years and the strong demand, the volume of spent LIBs has increased exponentially, making recycling mandatory. Currently, recycling/ recovery of spent LIBs is limited in comparison to all other types of batteries. The current processes focus mainly on the recovery of the most valuable metals such as cobalt and nickel, leaving lithium and phosphate in a low value end-product. It is necessary that new advanced recycling technologies are developed for the recovery of spent LIBs both from an economic and environmental perspective. In this paper, the current R&D status of LIBs recycling is reviewed with the emphasis placed on hydrometallurgical processing opportunities for Li-ion and Li-solid state batteries.

By C. A. Pickles

Microwave processing is a relatively new technology that has been successfully applied in a number of industries. However, in the field of metal extraction, there is a paucity of success, despite considerable hype in the early years. Increased reaction rates, lowered reaction temperatures and higher energy efficiencies were some of the advantages claimed. Even with over almost two decades of research and some pilot plant studies, microwave metal extraction remains essentially a laboratory technique. In this paper, the research performed over the last few decades will be reviewed and some reasons for the lack of success in developing microwave metal extraction processes will be discussed. Based on the knowledge gained from these experiences, a more informed view of microwave heating can lead to the realization that there is still some untapped potential for this heating technique in metal extraction processes.

By R. A. Spitz, R. Leiby, M. Bricker

Electrochemistry plays a significant role in minimizing wastes at East Penn's secondary lead smelter. East Penn has been recovering spent battery acid for reuse in new batteries since 1992. East Penn also produces a fertilizer feedstock from sulfur dioxide in the smelter stack gases. The success of these processes is, in large part, due to the installation of electrochemical cells. The cells in the acid recovery plant allow the waste from this process to be concentrated into less that 10% of the original spent acid. The cells in the fertilizer plant treat the solution to remove dissolved metals prior to sale to fertilizer manufacturers.

Jan 1, 2000

By Anil Saigal, Mark H. Shooter, Michael A. Zimmerman

Liquid Crystalline Polymers (LCPs) provide favorable dielectric properties for extremely high frequency (30–100 GHz) radio frequency device packaging and printed circuit board substrates. The material studied in this work is a proprietary, thermotropic LCP composite developed and manufactured by iQLP (Woburn, MA, USA). Dielectric constants measured in the flow direction of the post-processed materials differ between the two processes, 3.51 in injection molded plaques, and 4.23 in cast films. This investigation sought to determine the cause of process-induced variation in the dielectric constant between injection molded and cast film extruded LCP. The complex thermomechanical environment present during processing of LCPs creates a through-thickness hierarchical structure, simplified in this study as a skin and core layer. The volume fraction of skin layer of the post-processed LCP was determined to be the differentiating factor, and responsible for the difference in dielectric constant between the injection molding and cast film extrusion processes. The resulting dielectric constant is a function of this volume fraction with a near linear relationship.

Mar 1, 2017

By S. Neogy, M. Gupta, D. Srivastava, V. Kain, S. Roychowdhury, R. C. Prasad, G. K. Dey

"Austenitic stainless steels are an important material of construction for Boiling Water Reactors (BWR). These stainless steels are amenable to strengthening by strain hardening. Various deformation modes at different test temperatures and strain become active. In the present investigation type 304LN stainless steel was used in the annealed and strain hardened condition. Thin foils were prepared from gauge section for transmission electron microscope (TEM) investigation after tensile testing at room temperature and at 288°C. TEM investigation reveals that twinning is the major mode of deformation for the tests done at room temperature while dislocation cross-slip is the major mode of deformation at higher temperature. Stacking faults were also observed to a limited extent. The extent of twinning was much higher for the tests done using the rolled material. The formation of martensite in the stainless steel due to straining was investigated by the analysis of selected area diffraction patterns.IntroductionAustenitic stainless steels (type 300 series) are an important material of construction in Boiling Water Reactors (BWR). These stainless steels cannot be heat treated but can be strengthened by cold working [1]. Nitrogen alloying of these stainless steels result in high strain hardening rates and higher strength without any loss in toughness [1]. Stress Corrosion Cracking (SCC) in BWR of these types of stainless steels have been attributed to surface strain hardening and strain hardening ofregions adjacent to constrained weldment [2].The test temperature [3, 4], prestrain [5] and nitrogen level [5] has been reported to affect the deformation mechanism during tensile testing. Byun et al. [3] have reported the formation of martensite, dislocations, stacking faults and twinning during tensile deformation, the extent of each depending on the test temperature. Strain localisation has been reported to occur during tensile deformation in irradiated stainless steels [ 6]. The behaviour of rolled material during tensile testing is similar to that of irradiated material to a large extent [3]. Austenitic stainless steels are low stacking fault energy (SFE) materials in which various types of microstructures have been reported to form during tensile deformation and the strain is also highly heterogeneous in nature in these stainless steels which aides SCC in BWR environment to a large extent [7]. During cold working of austenitic stainless steels second order twinning has also been reported [8]. Knowledge about the deformation mechanisms operative in the strain hardened austenitic stainless steels during tensile testing at different temperatures is essential to understand the material deformation behavior and the present study aims at enhancing the existing understanding."

Jan 1, 2011

By Liangying Wen, Zhehan Liao, Jian Xu, Chenguang Bai, Chengfeng Sun, Kaihui Ma, Yang Xu

The difference on particle density causes mass and size segregation in the blast furnace throat, causing poor permeability in radial and circumferential direction. Understanding the effect of density difference on particle spatial-temporal distribution helps stabilize smooth operation and improve energy ef ficiency of blast furnace iron-making process. Based on discrete element method simulation, the influence of density difference on particle segregation behaviors is quantitatively characterized by the proposed method when the binary-sized particles are charged from parallel-type hopper of blast furnace. The results show that increasing the 4 mm particle density aggravates the mass segregation in circumferential and radial direction, and the maximum standard deviation of each ring reaches as great as 0.415. For size segregation, the difference on average mass fraction of small particle between center and edge ring decreases from 0.373 to 0.301. When increasing the 6 mm particle density, the similar particle segregation behaviors could be obtained.

Mar 1, 2018

By P. M. Tyroler

Inco operates a hydrometallurgical plant to treat the residue from the pressure carbonylation process. The main constituent in the residue is cop¬per. The residue is leached under pressure in an acid sulphate solution in two stages and the copper is recovered via electrowinning. The electrowinning tankhouse is fully integrated into the overall plant flowsheet as spent elect¬rolyte is required in upstream leaching steps. In recent years, the amount of residue had increased and copper removal capacity became the rate limiting factor for the entire plant. Consequently, a major program was undertaken to upgrade the tankhouse with regards to capacity, efficiency, cathode quality, working environment and structual integrity and appearance. This paper will describe current facilities and operation, and detail progress in our up¬grading efforts.

Jan 1, 1987

By Dirk Bergmann

During the spray forming process, a continuous molten metal stream is atomized by impinging high speed inert gas jets. In the generated spray cone, the resulting metal droplets are rapidly cooled by the huge temperature difference to the surrounding gas phase and thereby partly solidified during flight. After a certain flight and residence time inside the spray cone, the droplets impinge onto the solid substrate and form the product (deposit) by compaction. Material properties of this preform strongly depend on several process parameters and especially on the thermal and kinetic state of the deposited droplets at the point of impingement. Smaller droplets may cool very fast due to their low mass and impinge onto the product in a completely solidified state as solid metal powder particles. Larger droplets with big mass contain a higher amount of thermal energy and impact during the state of phase change or still as completely liquid. It is obvious, that a certain amount of liquid content in the droplets is needed for forming a homogeneous deposit. Therefore, the thermal history of metal droplets during flight in the spray cone is of great importance for overall process modelling and control. Modelling the effects of the impinging droplet mass on the formation and heat balance of the deposit, the thermal conditions of the droplet stream need to be temporary and spatially averaged at different locations. Averaging may be achieved in different ways, giving alternative results. A first method is averaging over the droplets total enthalpy which consists of the thermal content and the remaining latent heat of fusion within the droplets. A second method may yield the average over the heat content and the solid fraction separately. Results of these two methods depend on the application and the kind of information which one wants to achieve and show some deviations, which will be discussed in terms of consolidation and energy conservation of the deposit.

Jan 1, 1999

By Arthur E. Morris

Fifty years ago when Professor Yazawa began his career, the field of process simulation and modeling was in its infancy. Since then, tremendous progress has been made in our ability to model metal production flowsheets from mine to refined metal. This progress has come about by parallel developments in basic understanding of process chemistry and in computational techniques, This paper will review the progress made in process understanding and modeling in lead, zinc, and copper metallurgy from its inception to the present, and the role of Professor Yazawa's work in furthering this progress. Specific examples will be given for the sintering of lead concentrates, slag fuming, zinc concentrate roasting, flash smelting of copper, and pyro-extraction of zinc. Factors limiting further progress will be described.

Jan 1, 2003

By Arthur E. Morris

Fifty years ago when Professor Yazawa began his career, the field of process simulation and modeling was in its infancy. Since then, tremendous progress has been made in our ability to model metal production flowsheets from mine to refined metal. This progress has come about by parallel developments in basic understanding of process chemistry and in computational techniques. This paper will review the progress made in process understanding and modeling in lead, zinc, and copper metallurgy from its inception to the present, and the role of Professor Yazawa's work in furthering this progress. Specific examples wi1\ be given for the sintering of lead concentrates, slag fuming, zinc concentrate roasting, flash smelting of copper, and pyro-extraction of zinc. Factors limiting further progress will be described.

Jan 1, 2003

By Jeffrey R. Taylor

The distribution of low concentrations of Cr, Mn, Rh, Co, Ni, Ag and Fe between copper matte and bullion phases has been measured at 1200oC. These results. together with values for nine other elements, have been used to develop a simple model to describe the distributions in terms of known thermodynamic properties?. The Temkin model for ionic melts was assumed to apply to the sulphide species in the Cu-S matte? phase and it is shown that the choice of sulphide species is particularly important for successful representation of the experimental .results?. In general, the lowest sulphlde (minimum sulphur :. metal ratio)? formed by the. metal is most suitable, although Ni, Co, Rh and Pd appear to associate with more sulphur in the melt than suggested by the? composition of their lowest sulphide. A correlation between the composition of the metal sulphide species formed in the ternary system and the? position of the minimum in the free energy of mixing curve in the metal-sulphur binary -system is? proposed.

Jan 1, 1983

By Theo Lehner

"The Boliden Rönnskär Smelter operates in the European Context of tight EH&S limits, with ever increasing regulations and tribulations. The near future promises to bring new burdens in the form of C02 trading, miners and pre-treaters increased appetite for a larger share of contained values, and changing compositions and competition in raw materials. On the other hand, European Smelters such as Rönnskär, Harjavalta have demonstrated an astonishing power of survival. This presentation lists and comments on current challenges but opportunities for increased survival power are also presented. One example of the latter is the ongoing investment into increased treatment capacity for e-scrap.UPDATE ON RÖNNSKÄR OPERATIONSThe Rönnskär Smelter has achieved 80 years of age with no signs of retirement. The smelter is most active in spite of its age! And it has undergone some face lift operations to maintain its attractiveness.Raw material, processing facilities and a market for the products are some essential prerequisites for a viable operation. To justify long term survival, economic terms such as return on investments and positive cash flow need to be considered. Below, we illustrate how the Rönnskär Smelter complies with these terms. To update the reader on current operations, our current flow sheet is depicted in Figure 1. The figure summarizes our current input and output."

Jan 1, 2012

By R. Hammen

Processes are needed to rapidly and cost-effectively produce highly pure lithium salts for the rechargeable battery sector. Lithium purification is a chemical engineering challenge, due to the low concentration of lithium compared to sodium, potassium, magnesium, calcium, and transition metal ions commonly occurring in lithium brine resources. We describe a Solid Phase Extraction (SPE) process that rejects sodium and potassium, while binding lithium and other higher valent ions. Lithium is then harvested by selective displacement from the SPE column. The rapid equilibration kinetics of SPE composites enables these ion separations to occur in a small SPE column and in one column stage. The chemical parameters of the process are described.

By Zhang Yongzhu

In hydrometallurgical processes of PGMs separation and refining, differences between 1-PGMs (Ru;Rh;Pd) and h-PGMs(Os;Ir;Pt) in thermodynamics and kinetics have been observed. The successful practice in the separation and refining of PGMs in China, is mainly based on the following two kinetically extraction sequences of: (1) for the extraction of PGMs complexes in different configurations with coordination mechanism (AuCI,) -> (MCl6)2-> (MCl4 )2-> (MCI6) 3- , and the substitution rate for h-PGMs complexes with higher effective nuclear charge Z' is much more slow than that of I-PGMs. and (2) for the extraction of PGMs in different configurations with oxonium (or ion -exchange) mechanism (AuCl4)-> (MCl4)2--> (MCl6)2-> (MCl6)3- and the extraction of h-PGMs complexes with low surface charge density is more fast than that of I-PGMs complexes. In view of atomic structure theory, the similarity of atomic radii and chemical properties and difficult separation of PGMs resulted from the Lanthanide Contruction between 5th period (1-PGMs) and 6th period (h-PGMs). The differences between h-PGMs and 1-PGMs are due to the loss shielding of 4f subshells on 5d electrons for h-PGMs with higher nuclear number, which makes h-PGMs have a higher Z' (effective nuclear charge) and strong attraction for outer space electrons. As a result, h-PGMs metals and complexes are thermodynamically more stable and kinetically more inert than the corresponding 1-PGMs. The differences between h-PGMs and 1 -PGMs in aspects of elements properties, complexes, hydration, substitution and redox reactions , are discussed.

Jan 1, 1993

By B. Mishra

Several reactive metal purification processes using molten salts generate effluent from which significant quantities of metal can be recovered prior to discardinglrecycling the salt. A Salt-scrub [SS] process has been applied where the reactive metals are recovered as a metal-gallium alloy by calciothermic reduction of the metal compounds. The SS alloy compositions were produced by mixing, pressing and sintering the metal-powders. Measurement of metal recovery has been studied for cerium, silver, tin and lead. The process has been optimized for variables such as the metal quantity per kg of effluent salt, amount of excess calcium over stoichiometry, stirring rate and time and holding time at reduction temperature. Over ninety-seven percent metal recovery has been obtained under optimized conditions. The development of an alloy for efficient Salt Scrub processing reduces a major contaminated waste disposal problem as well as recovering the valuable reactive metal. Surrogate metals have been used in this work to study the behavior of plutonium.

Jan 1, 1994

By Kazuyuki Kakegawa

The sintering characteristics and the change in the compositional distribution in the PbTiO3 PbZrO3-Pb(Mgl/3Nb2/3)O3 system during the sintering process by spark plasma sintering (SPS) method were examined. They were compared with those by a normal sintering method. The densification by the normal sintering was slow even at high temperatures, When SPS method was employed, much lower temperature and shorter period resulted in sintered bodies having almost the theoretical density. As expected in normal sintering, the compositional distribution decreased as the sintered density increased. On the contrary, the change in the compositional distribution by SPS was much smaller than that in the normal sintering. This sintering characteristic of SPS suggested a possibility of fabrication of sintered material having a desired compositional distribution.-

Jan 1, 2003