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By Michael S. Moats, Scott C. Campin, J. Brent Hiskey

"Electrochemical techniques are a valuable means of analyzing the passivation of commercial copper anodes. Electrochemical impedance spectroscopy (EIS) provides information concerning transport and reaction phenomena occurring at an electrode surface. Commercial. copper anodes of varying compositions have been examined using EIS. Experiments were conducted in a flat cell with an electrolyte of 40 gil Cu2 + and 160 gil H2S04 maintained at 65 DC. Impedance spectra were obtained at the potentials characteristic of the open circuit voltage and passive region for each anode. The spectra of the passivating films exhibited a flattened resistive/capacitive loop at middle to high frequencies and an inductive loop at low frequencies. An equivalent· circuit utilizing an inductor-resistor series in parallel with the double layer capacitance and charge transfer resistance was adequate in modeling the impedance data. The influence of anodes impurities on the components of the equivalent circuit is discussed and correlated with a hi-layer passivation model.IntroductionPassivation of copper anodes during industrial electrorefining has received considerable attention in the past few decades. Great strides have been made in understanding the roles of anode impurities [1-25], electrolysis parameters [20,26], and electrolyte chemistries [20,26]. Even so, passivation still occurs even in the most modem of refineries. The exact cause of passivation is not fully understood. It is known that the anode surface becomes covered by a passivating film. This film has been proposed to be CuS04'&5H20, Cu20, or mixed oxides. The localized concentrations of Ft, Cu+, and Cu2+ ions determines which phase is more favorable. The presence of these ions is controlled by the reaction kinetics and diffusion of species through the slimes layer.Reaction kinetics between Cu, Cu +, and Cu2+ are based on the dissolution mechanism of copper. There exists four different models to describe the dissolution of pure copper. The classical model of Mattsson and Bockris [27] involves two single electron transfers with the cuprous-cupric reaction being the rate detennining step. More recently, Wong, Collier, and MacFarlane [28] used ac impedance to elucidate a more complex mechanism involving the affect of pH and anions. Their findings indicate that the formation of cuprous ions in solution, Cu(I)so~ is favored over Cu(1I) ions adsorbed to the electrode surface in the presence of sulfate and as pH increases from pH 1 to pH 5."

Jan 1, 1997

By Willy Persson

A common feature of the kinds and amounts of impurities present most pyrometallurgical, processes is injection of oxygen to, remove various in the feed. The degree of success of a specific process step relies critically on control of the instantaneous oxygen potential/oxidation stage, throughout the step as well as upon termination of the step. This will, for instance, determine the distribution of impurities between metal and slag. As long as the operation is perturbation free -detailed analysis of all additions and application of advanced models often yield satisfactory control means However, a pyrometallurgical process is seldom free from disturbances, which reduces the accuracy of the static models and leads to inconsistencies in scheduled route might be uncontrollable changes in quality and quantity of feed, operator interventions and shift changes, timing of cranes, lining wear and accretions etc. The implementation of dynamic, control to correct for disturbances and, more generally for process optimization, requires continuous on-line information on, the actual status of the process. The implementation of sensors for continuous process monitoring, e.g., as regards the instantaneously prevailing oxygen potential or oxidation stage, has been hampered by the highly aggressive environment in smelters; This is. where remote-sensing techniques based on optics and spectroscopy, have proven to form invaluable, tools towards the realization of dynamic production control. Since about 15 years Semtch has developed and industrialized a remote-sensing technology, based on ,optics and spectroscopy, for continuous on-line process monitoring and production control of various pyrometallurgical processes. The presentation will discuss applicability aspects with examples and experiences from installations and tests in ferrous and non-ferrous industry. Keywords: Applied spectroscopy, Metallurgy, Process monitoring, Production. Control

Jan 1, 2003

By Albert Wraith, Thomas Price, Wayne Boyd, Skip (I. E. ) Hills, Cameron Harris

Most Peirce-Smith converters inject air through tuyeres, with nitrogen representing the majority of gas passing through the process. The nitrogen controls the temperature of the vessel by carrying away heat from the reactions, both globally and locally at the tuyere tip. However, nitrogen adds energy to the bath and contributes to splashing and limits the blowing rate. High oxygen smelting has made streams of gas containing high concentrations of sulphur dioxide commonplace, which can be used to substitute SO2 for nitrogen and drastically changes Peirce- Smith converting (and all other smelting/converting processes as well). Less SO2 is required to carry away the same quantity of heat, which allows higher concentrations of oxygen and leads to the possibility of increased production. The paper investigates this substitution, its impact on converter productivity, and on the remainder of the plant. 181

Jan 1, 2009

By Marcelo B. Mourao

Interactions of carbonaceous materials with liquid Fe-C melts have been investigated experimentally by determining the volatile yield due to rapid devolatilization (Flash Pyrolysis) and rates of dissolution at temperatures ranging from 1623 to 1873 K. The volatile yield increased with increasing the temperature. The comparison of results of different types of carbonaceous materials was possible by expressing the volatile yield in terms of Enhancement Factor, fE. The rates of dissolution of spectroscopic graphite and an industrial coke seemed to obey the correlation for natural convection under turbulent conditions. The experimental data for the graphite suggested that the rate of dissolution was controlled by the mass-transfer in the liquid boundary layer adjacent to the solid sample. The value for the empirical parameter correlating the dissolution coefficient and the operating variables was found to be 0.19 which was close to that reported in the literature. The comparison of the results obtained for the coke samples with those for the graphite revealed that the impurities and the porosity of the samples can effect the dissolution rates.

Jan 1, 1992

By Heikki K. Jalkanen

Thermodynamic properties of copper-iron mattes and slag-matte distribution of copper and some minor matte constituents (Ni, Co, Mo, As, Sb and Bi) are discussed on? the basis of equilibrium measurements: a change from. oxidic to sulfidic solubility as the predominant form of dissolution of copper takes place as matte grade decreases. Distribution coefficients of minor matte constituents are complex functions of sulfur and/or oxygen potentials?. The distribution behaviour of different? metals can be qualitatively derived from their affinities to copper and stabilities. of their sulfides and oxides. The equilibrium results are compared with commercially observed values. from Outokumpu.Oy flash smelting furnace.

Jan 1, 1983

By Rainer Schmid-Fetzer

"Isothermal solidification can be used to form strong bonds at low temperature which remain solid at much higher temperatures. The exploitation of this principally known technique for new high temperature processing steps and applications in electronic assemblies is the aim of this study. Three basically different variants of this bonding process are given. A comprehensive metallurgical screening is performed and the feasibility of binary material systems is given on a quantitative scale. Very attractive systems are spotted that have never been studied before. Detailed examples for the realization of bonding with complex ternary and multilayer systems are given. A highly innovative example is the chip stack or wafer to wafer bonding of unmetallized Si or SiC at 250°C. The proposed bond remains stable above the melting point of Si and enables entirely new semiconductor manufacturing steps. An improved die bonding process was proposed and verified experimentally.1. IntroductionIsothermal solidification can be applied to form strong bonds at relatively low temperature which remain solid at higher temperatures. The general principle of this type of joining processes is illustrated in Fig. 1. An interlayer of a low melting component, Lo, is provided as a foil or a thin film coating between the high melting joint components, Hi. The assembly is heated under moderate pressure to the bonding temperature, T 8 , and a liquid filler forms, either because the melting point of Lo is exceeded or due to a eutectic reaction between Lo and Hi. This molten filler initiates a rapid interdiffusion or reaction diffusion between Lo and Hi and the subsequent approach to an equilibrium state results in isothermal solidification. The solid phases formed at T 8 in the joint region exhibit a remelt temperature above T8 •"

Jan 1, 1996

By J. E. Hoffman

The operation of the U .S Metals Refining Company, USMR Co. is defined below by the description of a variety of unit processes and operations the author encountered during his tenure with the operation, 1955 - 1978. The operations discussed include: sampling and sweating of radiators, processing of Indian Coin, treatment of insulated wire, baghouse and converter dust treatment, blast furnace and converter operation, the electric arc furnace, antimony control, selenium and tellurium products, electrolyte liberation with soluble anodes, and the precious metals refinery. These operations, although peripheral to the primary copper production circuit, were critical to the company's technological and economic base.

Jan 1, 2000

By Eulogio Velasco, Jose Nino, Marcos Cardoso

"Recycling of aluminum scrap for production of secondary alloys used for automotive applications is increasing continuously. Automotive alloys require a strict control to remove alloy impurities, inclusions and excess of magnesium. The advantage of aluminum is its recyclability with large energy and emission savings with minimal loss in material properties. The aim of this work is to study the magnesium removal from recycled aluminum by chlorine injection in a reverberatory furnace, and removal by an oxidation process at high temperature in an industrial rotary furnace.The magnesium removal by gas injection is carried out by the reaction between chlorine and magnesium, with its efficiency associated to kinetic factors. In the rotary rapid oxidation of aluminum and magnesium elements at high temperature is characterized by the formation of surface films composed of magnesium oxide. Additionally this work reviews the benefits of an efficient demagging process.IntroductionThe advantages of using light alloys for automotive applications include fuel economy improvement, greenhouse gas reductions and polluting emissions. These characteristics makes the aluminum alloys an attractive option for automotive components such as powertrain products and other critical parts like cylinder heads and blocks. [1]Aluminum alloys coming from recycled automotive components, used beverage cans (UBC) and wrought alloys have positive effects in the energy savings and current environmental trends. Producing a scrap recycled aluminum ingot consumes approximately 5% of the energy required to produce a primary aluminum ingot from bauxite ore. [2]"

Jan 1, 2011

By Y. Suzuki, J. Nagao, Y. Ueda, K. Shimokawa

"A Ti- Ni intermetallic compound could be formed rapidly from Ti and Ni powder compact with SHS process. Microgravity experiments using a drop shaft are carried out, This report shows the effect of microgravity or high gravity on formability of an intermetallic compound. It is concluded that the specimen forms a porous and nearly amorphous alloy by rapid cooling under microgravity but with rapid cooling under high gravity after microgravity, the specimen forms a uniform and dense structure with better crystallinity.IntroductionTi - Ni inter1etallic co1pounds have been produced and have beco1e si1ilar to the a1orphous and porous structure as a result of the SHS (Self Propagating High-te1perature Synthesis) process under 1icrogravity. SHS process is being applied to the synthesis of cera1ics and inter1etallic co1pounds (1). The technique is characterized by a large a1ount of heat being emitted within a very short ti1e interval as regards the sistering reaction. One SHS process, acco1panying 1elting by a reaction was observed, and that was due to the quick heating of a Ni-Ti co1pact containing 50 ato1ic percent of Ti under a low pressure (2-4). In this report, we have researched the use a drop shaft which is 1ore effective during a short ti1e under 1icrogravity and high-gravity, so as to obtain high dense speci1ens with the exception of porous specimens (5). Mechanical properties of each specimen were esti1ated from these 1icro-structures with a discussion about the effect of changing gravity regarding 1elting and solidification of the Ti-Ni intermetallic comounds."

Jan 1, 1996

By G. S. Victorovich

Technical progress in primary smelting has changed the face of the copper industry in the years since the Second World War. Much of this change has resulted from a wide acceptance of flash smelting technology. In addition, research has been directed toward devising converting processes to replace conventional Peirce-Smith converting technology. One major thrust has involved a revival of the old " ", idea of oxygen flash converting of comminuted mattes. This paper reviews the 60-year history of flash converting. Particular attention is paid to Inco's investigations into the processing of white metal containing significant amounts of nickel and, in some cases, iron. Thermodynamic analysis and laboratory experimental results are presented which throw light on the behaviour of nickel and other salient features of flash converting. The possible role of oxygen flash converting in the copper pyrometallurgy of the future is briefly discussed vis-a-vis direct production of copper.

Jan 1, 1993

By Sven Eck, Andreas Ludwig, Menghuai Wu

"Phase separation is a frequently occurring phenomenon during solidification accompanied by melt convection, sedimentation or, in the case of two unmixable liquids, a Marangoni driven motion. In order to describe these phase separation phenomena a two-phase volume-averaging model was employed for globular equiaxed solidification of binary alloys and decomposition and solidification of hypermonotectic alloys. The model considers nucleation and growth of equiaxed grains or second phase droplets, motion and sedimentation of grains or droplets, feeding flow and solute transport by diffusion and convection. It allows the prediction of macro segregations and the distributions of grain size or droplet size. Evaluations were made by comparing the numerical predictions with experimental results. For example it is shown that the numerically predicted grain size distribution in a plate casting (Al-4wt%Cu) agrees reasonably well with the experimental analyses.IntroductionModeling of metallurgical processes is a rapidly expanding field and the research activities in the last decades cover a wide range of areas including melt pre-treatment, solidification and subsequent manufacturing routes. Among those activities solidification stands in the central position, because the primary structure of the materials, and even many defects such as porosity, (macro or micro) segregation and inclusions form during solidification. Those primarily formed structures or defects once existing are difficult to be removed or modified by the subsequent material processing.Solidification is a multi-disciplinary field involving thermodynamics, fluid dynamics and solid mechanics, heat and mass transfer, and other disciplinesr1 -31• One of the most challenging problems in solidification modeling is the complex interactions between physical phenomena occurring on different length scales ranging from atomic rearrangement over single crystal-melt interactions to heat extraction, momentum and species transport at the system level. Modeling an industry process on atomic scale is umealistic, even on grain scale (e.g. phase field method) it would need another 40 years to be able to model the exact grain morphology in a casting space envelope of 10x10x10 cm3 [ 4]. Therefore, the realistic models for industry process are based on the solution of the macro transport equations (mass, momentum, enthalpy and species) on system scale. The microscopic phenomena such as thermodynamics, nucleation law, crystal growth kinetics and interactions at the liquid-solid interface are considered with simplified models, which are coupled with the macroscopic transport equations."

Jan 1, 2004

By R. Tunold, Y. J. Zhang

"The cathodic kinetics of aluminum deposition from aluminum chloridealkali chloride melts was studied by use of electro-cnemical transient techniques at 700 °C. Aluminum deposited as an insoluble product on a glassy carbon electrode and as a partly soluble product on a tungsten electrode. The deposition was found to be a simple diffusion controlled process involving the exchange of three electrons. The diffusion coefficient of aluminum chloride was calculated - 4.sx10-s cm2 ·S-I in AlCl3 -NaCl-LiCl melts and 2.6x10-s cm2 ·S-' in AlCl3 -NaCl-KCl melts. For AlCl3 -NaCl-CsCl system the diffusion coefficient exhibited some uncertainty due to nucleation. The determined rate constant of aluminum deposition reaction was on the order of 10-' -10-2 cm'S:' Constant potential electrolysis was carried out. TiB2 was well wetted by aluminum. The species of melts penetrated into graphite and glassy carbon but not into tungsten. The diffusion coefficient of species in glassy carbon was evaluated.IntroductionAluminum chloride electrolysis is attractive for its power saving of 30%. Different process to circumvent the conventional chlorization to obtain aluminum chloride economically, such as directly chlorizating mixture of Al~03 and C in a cell with A-shaped laminated bipolar electrodes by rising chlorine (1), or by use of a composite anode (2), will promote the electrolysis technology to be realized industrially. With the appearance of the Alcoa process periodically there are studies on the kinetics of aluminum deposition. Some discrepancies seem to exist on the mechanism of aluminum deposition. Borne studies (3,4,5) showed that the deposition of aluminum was hindered by diffusion process in the melts. M.Gabco et a1. (6) claimed a preceding dissociation of a complex being the rate controlled step. This paper presents our results on the mechanism of aluminum deposition from the study by use of transient techniques and some results from constant potential electrolysis."

Jan 1, 1988

By Mingming Zhang, Marshall S. Coe, Marcelo W. Andrade

To supply iron units and flux burden in blast furnaces, sinter basicity is one of the vital parameters for sinter plants. The sinter basicity also plays an important role in sinter quality since it imparts the formation of different mineral phases in sinter. Pot-grate sintering tests were carried out with low and high basicity to investigate the effects of sinter basicity on sinter mineralogy, properties and productivity. It was found that with an increase in sinter basicity, both sinter productivity and reducibility (RI) increased. Tumbler index (TI) and low temperature degradation index (LTD) of high basicity sinter were comparable to low basicity sinter. Softening and melting tests showed that sinter with 3.5 C/S basicity had slightly higher softening temperature comparing to lower basicity sinter with C/S 2.6, acid and fluxed pellets. XRD analyses confirmed the formation of silico-ferrite of calcium and alumina (SFCA) and calcium ferrite (CF) in the tested sinter samples.

Jan 1, 2015

By H. Yin, T. Emi

"Advantages of gas/flux injection technology as materialized in the main stay unit processes for steelmaking are depicted covering hot metal pretreatment through secondary refining. Current status of micro-kinetic issues involved in the injection technology are reviewed including gas-in- metal, gas-in-slag, flux-in-metal, metal-in-flux and three-phase dispersion systems with reference to macro-kinetics. Key problems are briefly addressed to further develop injection technology for steelmaking processes.1. FROM PAST TO PRESENTApplication of gas injection to steel industry started in early 1950's when inert gas bubbling via stopper rod, lance, or porous refractory plug was practiced to make the temperature of steel melt in ladle uniform The gas bubbling in ladle was then extended to slightly removing hydrogen ti'om the steel melt tapped from Electric Arc Furnace (EAF) and Basic Open Hearth Furnace (BOH) when vacuum processing facilities were not popular. Later, oxygen gas injection via calorized steel pipe into molten steel bath in BOH Furnace was also put into operation to promote the decarburization to increase the productivity of the process. This line of development has been made in parallel with more profound processes, i.e, top blowing Basic Oxygen Furnace (BOF) for primary steelmaking and side blowing Argon Oxygen Oecarburization (AOD) vessel for decarburizing stainless steels.On the other hand, injection of fluxes into steel bath was first industrialized in Germany in 1960's, Primary objective was to desulfurize steel melt in ladle by injecting CaC2 or CaCrCaO mixture via lance under neutral slag cover with good success. Difficulties in injecting fluxes without clogging and rippling at a desired flux/gas ratio, and durability of injection lance were resolved in due time to bring forth many injection facilities to flourish for versatile refining operation. Top injection of fluxes from main oxygen lance to BOF was also industrialized as LDAC to promote early slag formation. A new process then emerged which injects oxygen gas and fluxes together through concentric annular tuyere, installed at the bottom of the BOE into steel melt. This process, developed in Germany [Oxygen Bottom Maxhutte (OBM)] and brought into maturity in USA (Q-BOP) and Japan in a large scale operation, became the predecessor of the combined blowing (top and bottom blown) BOF which dominates modern steelmaking."

Jan 1, 1996

By H. Ikeda

The new Onahama N0.3 tankhouse was put into operation early in 1973. This new tankhouse, which has a capacity of 90,000 metric ton cathode per year, is distinct in many important respects from conventional tankhouses. The major objectives in design were to simplify the construction and ope- ration for reduction of the costs for labor, interest and depreciation and also to reduce the copper inventory in the tankhouse by the use of conti- nuously-cast anodes. As a result, the investment cost was decreased by approximately 30% and the inventory cost by approximately 600, while the production per unit area of the tankhouse was increased by 80 - 100% as compared with the existing conventional-type tankhouses at Onahama. By abolition of cell inspection and maximum mechanization of materials handling the labor cost was decreased by as much as 80%. On the other hand, the new system has some disadvantages, such as increase in anode scrap ratio and increased cost of anode casting. The No.3 tankhouse system is, however, still at its starting point, while conventional methods have been continuously improved over the past years of operation. It is expected that the innovational ideas behind this system will serve as bases for a more efficient electrolytic refining system in future.

Jan 1, 1976

By Paul C. Turner

In 1998, approximately 57,000 tons of titanium metal was consumed in the form of mill products (1). Only about 5% of the 4 million tons of titanium minerals consumed each year is used to produce titanium metal, with the remainder primarily used to produce titanium dioxide pigment. Titanium metal production is primarily based on the direct chlorination of rutile to produce titanium tetrachloride, which is then reduced to metal using the Kroll magnesium reduction process. The use of titanium is tied to its high strength-to-weight ratio and corrosion resistance. Aerospace is the largest application for titanium, and titanium cost has prevented its use in non-aerospace applications including the automotive and heavy vehicle industries.

Jan 1, 2001

By Jussi Vaamol

A commercial CFD-code was used to solve isothermal flow fields of gas and liquid in a Peirce-Smith converter. The model was validated with a 1/4 scale water model, and parametric study. Limits of the modeling technique used were recognized, but calculated results indicate that the present model predicts the general flow field with reasonable accuracy. The model was used to examine general flow conditions in an industrial scale PS-converter. Typical scaling factors of physical models were also evaluated with the aid of predicted bubble distribution, patterns of the flow fields and magnitude of flow velocities. The numerical simulations were found to open new viewpoints to the fluid dynamic related phenomena in the PS-process.

Jan 1, 1998

By H. Dong, J. J. Valencia, L. Nastac

"A comprehensive computer model was developed to understand and optimize the centrifugal casting process for manufacturing TiC/Al-bronze friction drums. Performance of these components requires proper distribution of TiC particles, which is shown by dimensional analysis to be dominated by centrifugal buoyancy effects and solidification kinetics.The model addresses the following: (1) a rheology-viscosity model of the interference between moving particles, (2) engulfment (entrapment) or pushing of particles in the mushy region by the advancing solid/liquid interface, (3) nucleation and growth of equiaxed and eutectic phases, (4) effects of particle size, particle concentration, and cooling rate on the final grain size, and (5) the impingement effect of particles on the nucleation and growth kinetics of solidifying microstructure.Parametric studies were conducted using the computer model to investigate the effects of various process and material parameters on the distribution of TiC particles. The effects of the volume fraction, size, and morphology of the particles (including clusters and agglomerates) on the particle distribution were evaluated in detail. The complex interaction between the solidifying structure and insoluble ceramic particles in centrifugally-cast metal-matrix-composites was also investigated.The model predictions of particle distribution and microstructure were validated with experimental data for centrifugally-cast A356/SiC and TiC/Al-bronze alloys.This work was conducted by the National Center for Excellence in Metalworking Technology, operated by Concurrent Technologies Corporation under contract No. N00140-92- C-BC49 to the U.S. Navy as part of the U.S. Navy Manufacturing Technology Program."

Jan 1, 2000

By R. D. Lrwin, W. M. Mullins, S. Venugopa, J. C. Malas

"Physical models for acoustic emission (AE) are introduced and expressions are derived to predict AE activity from such parameters as applied stress, strain and strain-rate. These models are then incorporated into a visco-plastic finite-element simulation program, and the acoustic emission event rate generated during metal forming operations are predicted. Simulation results are presented for upsetting operations on a typical C-Mn type steel for various friction and die geometry conditions. The AE model predictions compare well with the limited available experimental results reported in the literature and demonstrate that AE signatures can be reliably simulated. The signatures predicted for metal forging are fairly insensitive to processing parameter changes. This suggests that AE event rate monitoring may not be well suited to process monitoring for forging. However, the size of the features is conjectured to influence the frequency content of the AE signals. Thus, since current simulations include only the ability to predict the number of events for a set of processing conditions, future work is required to simulate the duration and magnitude of acoustic events. Fourier analysis techniques may then be applied to investigate correlation with microstructural features.IntroductionThe open loop control system method for deformation processing design, as described by Malas et al. [1 ], consists of several steps in series to achieve the final design. The first step uses microstructure development models to determine the optimum deformation path to achieve the desired final microstructure. The second step, the process model, calculates the processing parameters required to achieve this deformation path. Finally, the metal-working system uses the required processing parameters to produce the part. Figure 1 shows this in block diagram form"

Jan 1, 1997

By Youn-Bae Kang

Evaporation mechanism of S from liquid Fe–C–S alloys at 1873 K was proposed by analyzing available experimental data. It has been known that increasing C content in liquid alloy increases activity coefficient of S ðfSÞ, and it could raise driving force for the evaporation reaction S = S(g). However, experimental data of the evaporation of S in the Fe–C–S alloys could not be accounted for only by considering the increases of fS. In the present study, formation of carbosulfides, CS(g) and CS2(g), was additionally taken into account in order to explain role of C for the accelerated S evaporation. Surface adsorption of S was also taken into account, which retards the evaporation rate of S. An evaporation model equation was formulated. It can be applied to calculate the evaporation rate of S over wider C content (from zero to its saturation to liquid alloy).