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By Asmo Vartiainen

The viscosity of liquid Fe-O-SiO2 -slag at copper smelting conditions was investigated using a rotational viscometer. The studied parameters were oxygen partial pressure (10" °-10"6 bar ); composition of slag (Fe/SiO2 ratio), and temperature (1250-1400°C). The viscosity values are presented as a function of Fe/SiO2 ratio and as isoviscosity curves in ternary FeO-Fe2O3-SiO2 diagrams. The increase in viscosity at high silica contents can be accounted for the polymerisation effect of SiO4/4- -anions. At high ferric iron contents, higher oxygen partial pressure, the viscosity values increase especially near the magnetite saturation. The viscosity values are highest at the double saturation of silica and magnetite. At lower silica and ferric iron contents the viscosity values are more uniform in the homogenous liquid slag area. The viscosity values were lowest at high temperatures and highest at low temperatures.

Jan 1, 1998

By R. Padilla, M. C. Ruiz

Arsenic, antimony and bismuth are commonly found in copper concentrates usually as the minerals enargite, stibnite and bismuthinite, respectively. Concentrates having high levels of arsenic and antimony must be pretreated before smelting. Roasting is the preferred method for removing these toxic impurities from concentrates; However, the removal of As, Sb and Bi in oxidizing roasting by volatilization may not be complete due to the slow reaction rates at 500- 700 °C. Oxidizing/volatilization data were obtained from pure mineral mixtures and from arsenic rich copper concentrate. The reaction mechanism for the volatilization of arsenic and antimony were discussed. Near 100% As and over 95% Sb volatilized in the oxidation of a mixture of pure minerals at 700 °C, 1% oxygen, while over 95% As, and 35% Sb volatilized at 600 °C in 1% oxygen atmosphere when using a copper concentrate containing 3.51% As, 0.14% Sb, and 0.01% Bi. Bismuth did not volatilize.

Jan 1, 2015

By Dong Liu, Zejian Yang, Yong Li, Tao Jiang, Xiangxin Xue, He Yang

"The structure, composition, morphology, and adsorption property of UV-vis light of as-prepared samples were characterized using XRD, SEM, FTIR-EDS, and UV-vis DRS. UV-visible light induced photocatalytic degradation of methylene blue ~) over Ti02-doped diopside was investigated. Experimental results show that doping Fe + induced the formation of Ti-0 or Ti-0-Si in diopside, and promoted the light adsorption property of diopside. Photocatalytic reactivity of Ti02-doped diopside obviously depended on content of doping Ti02. The diopside with 3% Ti02 exhibited the superior photocatalytic activity with 76% degradation of methylene blue under light irradiation for 3 h.IntroductionPhotocatalytic technology has been extensively studied in the process of dealing with inorganic and organic pollutants. Ti02, with its own non-toxic, stable, low-cost and other advantages, has become the most widely studied photocatalytic materials[l-SJ_ The low utilization quantum made it restricted in the practical application. SrTi03 as the representative of the perovskite[9·121, Bi2W06 for the composite oxide[13,141, also attracted wide interest in the photocatalytic studies. However, these photocatalytic material has been mostly prepared in relatively strict experimental conditions with chemical reagents, they had small production, high cost, which made them difficult for practical applications.In our country, there has 400 million tonnes of ti-bearing blast furnace slag (TBBFS) each year in the process of smelting pig iron, which has lead to waste of titanium resources and pollution of the surrounding environment. In recent years, studies have shown that TBBFS instead of pure Ti02 to be photocatalytic materials is feasible[ 151. TBBFS has not only been higher photocatalytic degradation activity for the o-nitrophenol, methyl orange, nitrobenzene and other organic matter[16-191,but also exhibited excellent in the process of dealing with inorganic heavy metals in waste water (containing Cr6+i201. If TBBFS can be successfully applied to photocatalytic technology, the will make large accumulation of titanium-bearing slag reasonable used, so as promote the re-use of energy. At present, our understanding of the photocatalytic activity of TBBFS is steadily deepening. Photocatalytic activity ofCaTi03 has been reported as one of the main minerals ofTBBFS [21'21J, However, there were few studies for Another major mineral of TBBFS - diopside which had the content of9-15%. diopside would doped with Ti02 In the process of smelting pig iron, therefore, Ti02-doped diopside's photocatalytic activity in the UV-Vis was mainly studied in this paper."

Jan 1, 2013

By Edouard Asselin, Guikuan Yue

"In the present study, electrochemical measurements, especially cathodic potentiodynamic polarization (CPC) and cyclic potentiodynamic polarization (CPP), have been employed to study the kinetics of ferric reduction on chalcopyrite in aqueous Fe( II )-Fe(III)-H2S04 solution at 25°C and 70 °C. Results from the calculation ofspeciation in the above solution reveal that, at both 25 °C and 70 °C, the real Fe3+/Fe2+ ratio is much lower than the nominal ratio, which leads to smaller values for the reversible potential of the ferric/ferrous couple based on the Nemst equation. Exchange current densities of the ferric/ferrous couple were obtained by extrapolating the cathodic linear Tafel line to the reversible potential and are on the order of 10-7·10-6 A/cm2 at 25°C and 10·6-10-5 A/cm2 at 70 °C, respectively. The transfer coefficients were about 0.35-0.38 at 25°C and 0.35-0.45 at 70 °C. Polarization plots of CPC and CPP under different nominal Fe3+/Fe2+ ratios are in good agreement at 25 ·c and at 70 °C. Based on the obtained exchange current densities, the rate constant k, was calculated and is on the order of 10-1 cm/s at 25 °C and 10 1 cm/s at 70 °C.IntroductionChalcopyrite is the most abundant copper mineral in nature, accounting for about 70% of copper reserves in the world [I]. In recent years, the metallurgical industry has been searching for a hydrometallurgical process as an alternative to pyrometallurgical treatment due to high emissions of S02 and capital costs associated with smelting. Activity in this area has increased recently due to some inherent advantages associated with hydrometallurgical processing, such as the possibility of treating low-grade ores (increasingly more abundant in the case of copper) and easier control of waste, with the attendant benefits to the environment [I]. Chalcopyrite is highly refractory under most hydrometallurgical conditions, owing to the formation of an anodic passivation layer on the chalcopyrite surface which renders the process kinetics very slow. Most of the currently proposed processes are based on sulfuric acid with ferric ions and/or dissolved oxygen as oxidants. Sulfuric acid is preferred over all other leaching reagents in terms of cost, environmental friendliness, and ease of its regeneration during electro-winning. Some of these processes have been piloted in attempts to implement these technologies on an industrial scale,"

Jan 1, 2012

By Jian Li, S. Penttilä, P. Liu, W. Zheng, C. Bibby

"The materials selection for Gen IV supercritical water reactor in-core components faces major challenges due to severe operating condition. The current Canadian pressure-tube supercritical water (SCW) concept design requires core outlet temperature of 650 °C at 25 MPa with peak cladding temperature reaching as high as 850 °C. Aside from oilier challenges, there is currently very limited data on candidate stainless steels' corrosion resistance under this operating condition. Austenite stainless steels that include 316L, 304H, AL6XN and 3 l0S that cover a wide range of Cr contents are promising candidates for either direct in core applications or as base coating materials. However, their corrosion resistance has not been tested systematically under this stringent condition. In this study, these types of stainless steels are tested, and their corrosion resistances are compared.IntroductionThe Canadian pressure-tube supercritical water (SCW) concept will operate at a core outlet temperature of 650 °C at a pressure of 25 MPa, with potential peak cladding temperature reaching as high as 850 °C. High-temperature corrosion resistance is one of the key design requirements for fuel cladding components. As summarized by Allen [1 ], most testing to date has been carried out at temperatures below 730 °C. To date, SCW corrosion data above 600 °C is very limited. Even at relatively low temperature exposure to SCW (e.g. 500 °C), F/M steels develop a thick oxide layer rapidly, while some austenitic stainless steels develop thinner surface oxide. Ni based alloys appear to form very thin surface oxide, however pitting was observed in the vicinity of intermetallic precipitates [2-5]. Dissolution of major alloying components from all of these alloys could also pose significant problems for downstream piping [6]. Kaneda et al. [7] suggested some modified stainless steels provide better SCW general corrosion resistance, with no sign of SCC under the slow-strain rate test.Cho [8] suggested that as the Cr content increase, general corrosion resistance improved at 510 °C and 25 MPa. However, similar to Cho's work, most of the SCW corrosion resistance assessments were based on weight change measurement. This can be unreliable due to potential exfoliation of thick oxide film. Besides, there have been no systematic SCW corrosion resistance tests for candidate stainless steels under higher temperatures. SCW corrosion rate increase dramatically for alloys tested at 600 °C [1]. It is also important to understand the role of major alloying elements under this stringent operating condition, not only for fuel cladding components' materials selection, but also for coating materials development."

Jan 1, 2013

By R. K. F. Lam

Unacceptable levels of impurity were noted in high purity chromium melting. Analysis of recent melting data determined that oxygen content in chromium is the critical parameter. Thermodynamics studies identify zirconia to be the most stable oxide in the presence of liquid chromium, followed by alumina and silica. Iron oxide reacts readily with liquid Cr. A certain degree of chemical reaction between liquid chromium and oxides does occur, contamination by the crucible is therefore unavoidable. Equilibrium constants indicate that a chromium oxide addition decreases 'ceramic dissolution and reduces impurity contamination. Safe operating conditions with oxygen content between 1190 ppm and 2500 ppm were identified. Additions of chromium oxide (Cr2O3) of 161 grams and 264 grams to liquid chromium yielded acceptable levels of impurity, and oxygen content was respectively increased to 1624 ppm and 2 179 ppm. A new process of melting high purity chromium with chromium oxide addition for controlling the activity of Cr2O3 is recommended.

Jan 1, 1997

By C. J. Beyke

Slags and/or mattes from three secondary lead producers were studied as part of an effort to develop treatment methods for these lead-bearing residues. Each company used a somewhat different production process. Company A used a reverberatory furnace followed by a blast furnace. Company B used only a blast furnace. Company C used both a reverberatory and a blast furnace, and the scrap material was desulfurized with sodium carbonate prior to smelting. The slag matrix produced from sulfur-bearing scrap consisted mainly of iron-calcium silicates; the slag from desulfurized material was similar, but also contained sodium. In all the slags most lead was present in metallic form, often alloyed with tin, antimony, arsenic, and/or iron. Slag from Company B contained the most alloying elements, often as discrete subparticles within the lead droplets. Mattes were produced at Companies A and B; predominant phases were pyrrhotite and magnetite, while lead was present in metallic form and as galena.

Jan 1, 1995

By Murray Hughes, Neil Brown, John Carran

"A control system architecture has been developed using the Ward-Mellor structured analysis techniques for real-time applications. This approach has produced several advantages over traditional control system implementation methods including:•,partitioning of the control system into discrete control functions.•,easy identification of the interaction between individual control functions and the rest of the system including the impact of changes at the control system boundary (i.e. additional inputs or outputs).•,simplified control software testing.•,a closed loop design, implementation and documentation process.This paper describes a generic control application in which the process specification and control system design are logically linked. Both components are used by process engineers for on-going development.IntroductionAluminium is reduced from alumina in multiple electrochemical semi-batch reactors. Raw material additions and molten metal withdrawal are made at discrete intervals ranging from seconds to days. The electrolytic reduction process is continuous, despite the semi-batch nature of the material inputs and outputs. The chemical and physical processes that occur within each reactor are complex and interdependent, therefore simple methods used for the control of many chemical processes are impractical. The process control system is required to optimise operating efficiencies within the safe operating zone.The process control of aluminium reduction cells is heavily biased towards calculation of process variables with relatively few measured sensors. Each cell is controlled independently of the other cells, although changes to process conditions and raw material . quality will affect all cells. The process responds relatively slowly and with significant time lags. Measurements and process variable calculations occur each second, however the accuracy and precision of actuator response and sensor sampling are measured 111 milliseconds. Time-based scheduling is a significant component of reduction cell control."

Jan 1, 1994

By A. V. Tarasov, V. M. Paretsky

"Based on theoretical and experimental studies into the specific features of the mechanism, kinetics, aerodynamics and heat transfer parameters of the flame-type oxidation of metal sulfides in a stream of technical-grade oxygen, a three-dimensional deterministic mathematical model of an oxygen-flame smelting furnace has been developed on the basis of the zonal method for computation of heat exchange. The model is presented in the form of equations taking into consideration the radiation component of the selective radiation, the convection component of mass transfer between the space and surface zones, heating of charge particles due to heat conductivity, accretions formation on a multi-layer refractory lining with inserted cooling elements. The adaptation of the model for a full-scale furnace has demonstrated the possibility for its use for computation of main smelting process parameters. Multifactor model investigations were conducted and the results obtained were applied using statistical methods for development of a simplified computational regression model describing the interrelation of the main output parameters: temperatures of flame, lining, slag and off-gas; heat fluxes to the lining; thickness of accretions; heat removed by cooling elements; copper content of matte. On the basis of this model, a block diagram of the algorithm was developed for control of the thermal conditions of the furnace, as well as the control algorithm itself.IntroductionThis paper presents the results of an integrated modeling and development of principles for control of copper smelting process using as an example the oxygen-flame smelting process (KFP) for treatment of sulfide concentrates at the Kovoguty Krompahy copper smelter (Slovakia) with a capacity of 20,000 tpy of copper."

Jan 1, 2001

By I. C. Knight

The current levels of copper smelter by-product acid production are reviewed on a regional basis, together with the possible changes in the future. There will be increasing pressure for all smelters to achieve a sulphur capture level of at least 95% by the end of the decade.

Jan 1, 1996

By Klaus-Markus Peters, James G. Hemrick, John Damiano

"Work was performed by Oak Ridge National Laboratory (ORNL), in collaboration with industrial refractory manufacturers, refractory users, and academic institutions, to employ novel refractory systems and techniques to reduce energy consumption of molten material processing vessels found in industries such as aluminum, glass and pulp and paper. The energy savings strategies discussed are achieved through reduction of chemical reactions, elimination of mechanical degradation caused by the service environment, reduction of temperature limitations of materials, and elimination of costly installation and repair needs. Key results of several case studies resulting from US Department of Energy (DOE) funded research programs are discussed with emphasis on applicability of these results to high temperature processing industries.IntroductionRefractory materials are limited in their application by many factors including chemical reactions between the service environment and the refractory material, mechanical degradation of the refractory material by the service environment, temperature limitations on the use of a particular refractory material, and the inability to install or repair the refractory material in a cost effective manner or while the vessel is in service. All of these limitations reduce the energy efficiency of the process as degraded refractory materials lead to loss of process heat (reduced insulation by refractories) and the need for maintenance through repair or replacement of refractory linings.This situation is conceptualized in Figure 1 which shows that when the thickness of the refractory wall is reduced by chemical or mechanical degradation, the heat losses through the wall increase exponentially. The subsequent maintenance to repair such conditions often requires cooling of the furnace or refractory lined vessel which entails loss of energy due to cooling and consumption of energy due to reheating. Additionally, production time and capability are sacrificed.Additionally, in most applications where refractories are used (metal melting furnaces, glass furnaces, steel making furnaces, gasifiers, etc.) wear of the refractory lining is not uniform. Very often, specific areas will wear (become thinner) more rapidly due to exposure to more corrosive or erosive conditions. This concept is illustrated in Figure 2, through the example of excessive metal line corrosion."

Jan 1, 2009

By Akira Kaneda

Mitsubishi continuous process employs an electric furnace for settling matte from slag. Electrodes are immersed into the slag layer in the slag-cleaning furnace and the temperature of the melt is maintained at a predetermined level by Joule's heat. Electrodes are immersed to the depth where the current of each electrode is kept at a set value, and they are raised or lowered automatically to compensate for the deviation from it. Because electric resistance of the bath is varied with the matte level in the furnace and the composition and temperature of the slag, the immersion depth of the electrodes is affected by them. Therefore by monitoring the immersion depth and its change with time, abnormal situations in the furnace, such a~ rise of matte level or local abnormal state of melt, can be detected. In this paper, relations between state of the furnace and electrode behavior are discussed based on the plant data, and then a new and simple monitoring method of the condition of the furnace is proposed.

Jan 1, 2001

By Merete Tangstad, Ragnar Tronstad

Ferromanganese production in electrical furnaces is quite an old process. However, as the furnaces are getting bigger, the requirements of cost, yield, product quality, emissions and security are raised. With the increased expectations, the fundamental knowledge must follow. Within the last 25 years there has been a great effort both in the industry as well as the academic environment to push the limits of this process. This article will show some examples of improvements within fundamental data, reaction mechanisms and emissions over this time period.

Jan 1, 2014

By J. M. Floyd

"Top submerged lance furnace developments started in CSIRO in the early 1970s and was given the name Sirosmelt. In the early work the technology was developed for tin smelting and processing tin slags but once a small pilot plant was established other slag processing applications were soon recognised and evaluated for various copper, nickel, zinc and cobalt-containing slags. The process was tried for copper smelting and converting, which was proven in the small pilot plant in 1978. In the same year the first commercial application of the technology was established for the recovery of tin from slags at Associated Tin Smelters, Sydney. Work on lead smelting was initiated by the CSIRO team in the late 1970s and laboratory work led to pilot plant trials by Mount Isa Mines.In the second decade of the technology the focus of development became commercial acceptance of the technology through marketing, development and application by Ausmelt and Mount Isa Mines; the former commercialising and developing the technology for a wide range of applications, while the latter concentrated on its own commercial needs of copper and lead smelting. This decade saw a number of commercial plants built in Australia, with considerable interest becoming evident from other parts of the world. Towards the end of this decade Mount Isa also entered into the business of marketing of the technology through rights dating to the joint work with CSIRO in the late 1970s.So far, after five years, the third decade of the technology has been characterised by diversification of applications of the technology to areas outside the non-ferrous and precious metals production industry. The waste processing and recycle industry and the iron and steel industry have recognised that the top submerged lancing system is a new type of reactor with many significant features which provide new opportunities for processing a range of materials under good environmental controls in a cost effective manner.I hope this audience will excuse my boldness in talking about the third decade of the technology when we are only half way through! I am aiming in this paper to not only talk about the past, but to try illustrate the future directions which I envision."

Jan 1, 1996

By Norihiko Fukatsu, Takashi Iwamoto, Noriaki Kurita, Koji Katahira, Kunihiro Koide, Teruo Ohashi

"The galvanic cell-type hydrogen sensor employing CaZro.9Ino.t03-a. as the solid electrolyte was designed for the measurement of hydrogen activities in molten copper under industrial .conditions. The sensor probe consists of the cap-shaped solid electrolyte with porous platinum electrode on the inside and alumina refractory tube. The gas mixture of the composition 4%H2-0.5%02-Ar was made to flow on the inside electrode. The hydrogen sensor probe was inserted directly into molten copper and the melt was used as the outer electrode. The effect of oxygen activity gradient to EMF was eliminated theoretically by measuring the oxygen activity in the melt simultaneously with an oxygen sensor. The high stability of output and excellent response to the change of hydrogen activity were obtained over the wide range of industrial copper melting conditions.IntroductionIn the metal casting process, hydrogen easily dissolves in molten metals from water vapor in the surrounding atmosphere. Owing to the large difference in hydrogen solubility between liquid and solid metal, dissolved hydrogen becomes a cause of the defects of blowholes in castings or ingots. It is necessary to control the hydrogen content in the molten metals [l]. Using proton-conducting ceramics as a solid electrolyte, high temperature-type hydrogen sensor can be constructed [2]. SrCe03- and BaCe03-based perovskite-type oxides exhibit appreciable proton conduction under hydrogen containing atmosphere at high temperature [3-5]. A hydrogen sensor for molten aluminum using CaZro.91no.103-a. has been developed and widely used in the ·process control in the aluminum melting industry [6,7]. The same type of hydrogen sensor has also been expected in the copper melting industry. .. However, CaZro.91no.103-a shows ·not only proton but also oxide ion conduction in the high temperature and at low oxygen activies like the copper melting· conditions. Then we studied the oxide ion conduction in CaZro.91no.103-a. iit · detail [8]. From the consideration on the EMF of the galvanic cell employing this material as electrolyte, it was shown that the unknown hydrogen activity may be precisely determined from cell potential which is corrected for the effect of oxygen potential gradient And the hydrogen sensor based in this principle was constructed and tested in laboratory-scale [9,10]. We repeated the similar tests in factory-scale and developed the sensor system for practical uses [11, 12]. In this report, the structure and system of the hydrogen sensor for molten copper will be introduced first. The reliability of the sensor will then be demonstrated from the results of experiments for sensor probes carried out in TYK's laboratory."

Jan 1, 2000

By Mingming Zhang, Ramana G. Reddy

"Carbon dioxide (CO2) is one of the most common by-products produced during light metals production. It is considered to be the cause of greenhouse effects. Efficient reduction of CO2 can help minimize the rate of global warming and improving energy sufficiency. In this paper, a novel light metal production process was developed using ionic liquid electrolytes. This process has significant advantages compared to the traditional high temperature processes such as zero CO2 and CF4 emission, low energy consumption due to the low temperature operation and nonconsumable electrodes. Two types of anode materials (graphite, extruded carbon) were tested in electrolysis experiment. The results showed that both anode materials were stable (negligible weight loss). However, the extruded carbon was found to be superior to graphite in terms of current density and current efficiency. The calculated energy consumption for aluminum production was less than 10 kWh/kg at current densities up to 300 A/m2.IntroductionGlobal demand for ultra-light, ultra-strong, recyclable metals is growing as the world switches to low-emission vehicles, energy-saving devices and sustainable products. Aluminum demand is forecast to climb by 30 percent; magnesium demand by 200 percent, while for the emerging industrial light metal, titanium, the demand is expected to be at least double in the next decade. However smelting of light metals is the most energy intensive among all the steps of light metals production. For example, on an average it takes about 15.7 kWh of electricity to produce one kilogram of aluminum from alumina [1, 2, 3]. Advancements in energy efficiency have been steady, but slow, and most U.S. aluminum smelting production operates at 95% current efficiency. Besides high energy consumption, another major concern of the light metals smelting process is the emissions of greenhouse gases (GHG). Electrolysis green house gas emissions in the Hall-Héroult process can be split into three groups: 1) reduction reaction emissions, carbon dioxide (CO2) and carbon monoxide (CO); 2) process upset perfluorocarbons emissions; and 3) hydrogen fluoride (HF) formed from the moisture (H2O) present in the raw materials [2, 3]. Hydrogen fluoride gas can be captured and returned to the cells by the alumina dry scrubbing system used in modern facilities. A total of 5.31 kilograms of CO2 is generated from the reduction process for each kilogram of aluminum produced in the average U.S. primary facility. The perfluorocarbon emissions are related to the “anode effect.” If the concentration of alumina in the bath becomes too low, other reactions between the carbon anode and the bath occur and tetrafluoromethane (CF4) and hexafluoroethane (C2F6) are generated. These gases have high global warming potentials (GWP), which is a ratio developed to compare the ability of each greenhouse gas to trap heat in the atmosphere relative to carbon dioxide"

Jan 1, 2008

By David G. Dixon, Ahmad Ghahremaninezhad, Edouard Asselin

"In this study pertaining to the electrochemistry of chalcopyrite, the active/passive behavior of a chalcopyrite electrode in 0.5M sulfuric acid solution was investigated. Potentiostatic and potentiodynamic polarization and multi-cyclic voltanunetry were conducted to analyze the electrodissolution parameters of the electrode.The potentiodynamic and potentiostatic polarizations of chalcopyrite revealed the formation of a passive film on the surface of chalcopyrite. From the potentiostatic study in the passive potential region, a decrease in the dissolution current density by increasing the potential was observed. From this, it was concluded that the passive film is an n-type semiconductor and cation interstitial defects or anion vacancies are the charge carriers. From multi-cyclic voltammetry studies, four cathodic peaks at - 0.37, 0.30, -0.10 and-0.20 YsHE were detected on the surface of a passivated chalcopyrite electrode. The cathodic peaks at 0.37 and 0.30 V were connected to ferric to ferrous reduction and copper sulfide formation, respectively. The peaks at -0.10 and - 0.20 were related to chalcopyrite reduction. The products of the chalcopyrite reduction reactions were suggested to be Cu2S, Cu9fesS16 and Cu5feS4 and evolution of hydrogen sulfide gas (H2S).IntroductionChalcopyrite is the most abundant copper bearing mineral in the world and its dissolution behavior represents the most important technological consideration in the hydrometallurgical extraction of copper [I]. Since the current pyrometallurgical methods for copper extraction from chalcopyrite have environmental issues, many studies have considered the leaching and dissolution of CuFeS2 in different aqueous media [2-5]. The main problem associated with leaching processes is the slow dissolution rate of the mineral [6]. During the dissolution process, increasing the potential of the chalcopyrite in the anodic direction will cause the formation of surface layers which hinder the dissolution rate of the mineral [7]. The precise composition of the layers is in dispute. Previous studies have concluded that these layers could be sulfur [8-9], precipitated iron compounds [8], a solid electrolyte interphase (SEI) - which slows the rate of electron transfer- [10], a metal deficient sulfide [ll], or polysulfidic in nature [12-13]. In order to increase the leaching kinetics of chalcopyrite, the characterization of the layers formed during dissolution is essential and electrochemical methods are important to this end. Studies by Biegler [14] show nucleation and growth of a thin two-dimensional sulfide phase on the surface of chalcopyrite during the exposure of a polished sample in HzS04 solution or air. More studies by Biegler and Swift [15] have shown evidence for nucleation and growth of a 3-dimensional phase at low anodic potentials (around 200 mV vs. OCP). The current-time behavior of the dissolution process in this potential area has the characteristics of expansion and overlap of localized dissolution centers."

Jan 1, 2012

By K. S. Han, M. Yoshimuura, H. Fujita, Y. Sato, S. W. Song

"Film of LlCoO2 as cathode material for rechargeable lithium microbatteries has been fabricated on the platinum metal substrate by electrochemical-hydrothermal method in concentrated LiOH solution at 200 °C as Soft Solution-Processing. The film fabrication has been understood in terms of dissolution of cobalt metal powders and subsequent oxidative deposition on the substrate. The film structure was characterized using scanning electron microscope, X-ray diffraction analysis; X-ray photoelectron spectroscopy and micro-Raman spectroscopy.IntroductionRapid growth of wireless communications and emerging integrated optoelectronic circuits caused the miniaturization· cif electronic devices, thus the demand for high energy density microbatteries as a power source for the microelectronics increases. In this regard, all solid-state lithium microbatteries including LiCoO2 and LlMn2O 4 [l-4], the most promising intercalation cathode material, have been developed. However, major difficulty of .fabrication of a lithium microbattery arose from the preparation of cathode film, according to a· recent report on Rare Metal News [5]. Although many attempts have been made to deposit the cathode films, all those methods are mostly chemical vapor deposiiton (CVD), various evaporation, sputtering techniques and spray pyrolysis. These methods require preparation of bulk cathode materials cir its precursor, then deposition with complicated instruments including high· vacuum system, and even postsynthesis annealing to obtain desire electrochemical 'properties. It is clear that all of these techniques are neither economic nor environmentally friendly. Compared to those methods, film form.ation from an aqueous solution is thought to be simpler and more economical, and requires much· less energy consumption. Our .group has demonstrated the utility of Soft SolutionProcessing [6,7], which is defined as environmentally friendly processing using (aqueous) solutions, to produce films of a variety of functional solid materials. According to the Pourvaix's diagram [8], some metal can be dissolved in an alkaline solution and consequently combined with hydroxyl group or oxygen anion forming metalate or metalite. Cobalt also seemed to form cobaltite, HCoOi in strong alkaline solution in the Pourvaix's pH-potential diagram. Based on this information, it was expected that LiCoO2 could be prepared using the cobalt metal in Li OH solution by Soft Solution-Processing. Recently, we reported the successful single step fabrication of electrochemically active LlCoO2 films on the cobalt metal substrate by hydrothermal methods without any post-synthesis annealing as Soft SolutionProcessing [9,10]. Film formation mechanism could be elucidated by the following evidences. . As expected from Pourvaix's diagram, cobalt metal was dissolved in concentrated LiOH solution forming dissolved cobalt species which was detected by an observation of absorption band in UV-VIS absorption spectrum [10]. Thus the reaction was assumed to be started from dissolution. Time dependent potential of Co electrode exhibited only one-step evolution with 0.6 eV from Co metal to LiCoO2 [10]. Another strong evidence was the finding of LiCoO2 powder precipitates at the bottom of tetlon beaker after the reaction [11]. Based on those experimental findings, it was understood that film is formed by dissolution-precipitation mechanism [9-11]."

Jan 1, 2000

By M. F. Hochella

Transmission electron microscopy (TEM) and energy dispersive X-ray (EDX) analysis have been used to study the mode of occurrence and mineral associations of gold in partially oxidized high grade gold ore from the Carlin sediment-hosted deposit. Rounded.gold particles have been observed that range in size from 0.03 to 0.1 p.m (300 to 1000 A) in diameter. The gold is associated with maghemite h-Fep3l and a K-Al-Si-bearing phase that is suspected to be illite. Detailed descriptions of gold and its mineral associations in 'Carlin-type' gold deposits are critical not only to understanding the mechanism of fluid transport and precipitation of gold, but also to developing improved metallurgical techniques for the recovery of gold from refractory ore. Direct observation of gold in unoxidized ore is rare due to its relatively high degree of dissemination and low average bulk concentration which averages 9 ppm according to Radtke (1). Hausen and Kerr (2) observed 1 to 5 p.m grains of gold directly in oxidized ore but these microscopically visible particles account for only a small percentage of gold present in the ore. The samples used in this study were selected from individual beds of high grade, partially oxidized ore (4.55 oz/ton or 156 ppm gold) that were collected in the Main pit of the Carlin mine. The samples were collected from several thinly laminated carbonate micrite beds within the top 50 meters of the Roberts Mountains Formation. The carbonate micrite has been altered by hydrothermal fluids to a calcite-absent, moderately silicified rock referred to as alteration zone #3 by Bakken and Einaudi (3). Based on petrographic and SEM studies, the samples contain carbonaceous matter, and both pyrite and iron oxide pseudomorphs after pyrite. The oxidation of pyrite may be a pro-duct of deep weathering, in which case limited remobilization of gold may have occurred. TEM sections of the rock were prepared by first embedding small chips in low viscosity epoxy. The epoxy blocks were cut with a Reichert Ultracut E ultramicrotome, producing thin sections less than 0.1 p.m thick. The sections were examined with a Phil-lips 400ST TEM at 120 keV in both imaging and selected area diffraction modes. Native golci*was easily detected in TEM bright field images due to the large electron density contrast between gold and all other phases that are present (Figs. 1 and 2), Gold was positively identified with high spatial resolution EDX analysis in the transmission electron microscope, although selected area diffraction of individual grains was not successful EDX analyses of the platy and massive minerals immediately surrounding the gold particles typically indicate the presence of Si, AI, K, and Fe, However, the d-spacings derived from selected area diffraction of these polycrystalline masses (as, for example, in Fig. 2) give an exact match for maghemite. As a result, there is no diffraction information to identify the K-AI-Si-bearing phase(s). The lack of a diffraction pattern could be due to either electron beam damage or to a poorly crystalline phase(s).

Jan 1, 1987

By John Nauman

Liquid ferrous silicates that are related to cop- per slags have been studied as media for the transfer of heat in pyrometallurgical processes. The effective thermal diffusivities have been measured from 1025Oto 1400°C, and values in the range of 0.004 to 0.007 cm2/ sec have been obtained. The heat-transfer characteristics of these slags have been determined by measuring the rise of temperature of a cold nickel sphere immersed in the liquid slag. The sphere is spun about its vertical axis to obtain a well characterized flow of liquid about the sphere. The principal barrier to the transfer of heat from the bulk slag to the metal sphere is a solid shell of slag that forms around the sphere and subsequently melts. It appears that the detailed nature of this shell is important to theheat- transfer process. A mathematical model is used to predict the rate of heating of the sphere, and to evaluate various aspects of the system that can influence the transfer of heat.

Jan 1, 1976