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By Bora Derin

This work deals with the recovery of valuable metals from the ancient copper smelting slags located in Küre-Turkey. In this process, copper and cobalt were recovered in metallic form and/or as their compounds, whereas iron was recovered as magnetic oxide or pigment. Abrasive grit material was produced using reduced final slag. The process stages involved carbothermal reduction in a DC arc furnace, granulation, leaching, chemical precipitation, selective sulfidizing roasting and product preparations. In this paper, the process stages were described as theoretically and experimentally whereas slag and products were characterized in detail.

Jan 1, 2003

By J. Grogan

Leaching of galvanized steel coatings allows the steel substrate to be used as a zinc-free scrap source to steel and iron furnaces. In this study the behaviors of sulfuric acid leaching solutions are investigated. The ranked significance of the variables are shown to be acid concentration > temperature > zinc concentration. Examination of the leaching mechanism finds the rate-limiting step to be the cathodic hydrogen reduction reaction. This rate is not only influenced by acid concentration, but also by the hydrogen reduction exchange current density. Dezincing leaching rates are improved by taking advantage of the higher exchange current density of the iron substrate versus the zinc coating. This is accomplished in practice by increasing the exposed interfacial zinc:iron surface area through shredding. Also, a leach control mechanism is proposed through online monitoring of the zinc-iron couple mixed potential.

By J. S. Pitsillos

A new furnace tapping technique involving the simulation of a control valve at the exit to a furnace is being investigated. The purpose of this new tapping technique is to regulate the flowrate of liquid furnace products( slags, metals and mattes). Numerical modelling and experimental work has been carried out on tapping of slags leaving a SIROSMELT reactor and the results found to be in good agreement. Numerical modelling has also enabled prediction of the important industrial conditions for the onset of blockage from the shape of the pressure versus flowrate curves. Slag launder experiments have been carried out and a one-dimensional heat transfer model was used to evaluate the effectiveness of launder covers and different coolants. From the experimental results and mathematical model some launder design guidelines such as inclination angle, covers and coolants have been developed.

Jan 1, 1991

By Musa Karakus

In an attempt to explain the phenomena of lead entrainment during Cu drossing of lead bullion, two different synthetic lead bullions were heated to 1050°C, cooled slowly to various temperatures, and then quenched. The morphology and composition of dross particles that form when Mn is used to desulphurize bullion also were examined. Polished sections of these pyrometallurgical products were examined by process mineralogical techniques to identify the impurity phases, determine their chemical compositions, examine the morphology of the impurity phases and evaluate the potential for lead entrainment in such crystals, and characterize pre-quench and quench-generated phases. The phases crystallized were metallic lead, metallic copper, galena, chalcocite, albandite, Cu14.4Pb2S9. and 5.5Pb2S3.5. Metallic copper formed isometric skeletal crystals, chalcocite formed platy and skeletal crystals, and 1formed crystals and eutectic intergrowth with chalcocite and Cu14.4Pb2S9 or Cu5.5Ph2S3.5. The pre-quench crystals are larger and usually exhibit skeletal forms; the quench-generated phases are only a few micrometers across and disseminated throughout the lead matrix. Skeletal crystals of metallic copper and chalcocite form three dimensional networks that entrain large amounts of metallic lead.

Jan 1, 1989

By H. Matsuda, T. Iwashita, H. Awata, H. Liwei, D. Hirabayashi, Y. Saito, S. Ozawa, Y. Goto

"The present study is concerned with investigating the effect of chemical treatment on enhancing the HCl absorption capacities of coal burnt ash and slag. It was found that the HCl absorption capacity of coal burnt ash discharged from fluidized bed combustor was improved by hydration with water and 5% polyethylene glycol solution. This phenomenon was based on an increase of the specific surface area of treated coal burnt ash. The HCl absorption capacity of hydrated ash with polyethylene glycol solution was almost equivalent to that of standard CaO and Ca(OH)2. In particular, the specific surface area of hydrated ash with polyethylene glycol solution was found to be 19 m2/g, which was more than over eight times larger than that of raw sample. Hydrated slag treated with lON sodium hydroxide solution also showed high HCl absorption capacity, with highly improved surface area. It was found that the absorption capacity of slag for HCl depended on the treatment time, showing the maximum absorption capacity for 12 hours of hydration treatment.IntroductionA large amount of coal burnt ash, slag and dust are discharged from such industrial processes as coal combustion and metal refinery etc., and it becomes an serious problem to recover and diminish these solid wastes because of the shortage of dump sites and subsequent metal elution to the environment. Figure 1 shows the present situation of reutilization of coal burnt ash and slag in Japan [1,2]. It is shown in this figure that these solid wastes are recycled as materials in the fields of earthwork, agriculture and forestry etc. A part of these solid wastes, however, is still dumped to landfill. To decrease this dumped amount, the development of environmentally friendly reutilization technique for these solid wastes is of great importance."

Jan 1, 2000

By R. Steven Izatt

Green chemistry principles will be discussed, and examples will be given of the use of Molecular Recognition Technology (MRT) to selectively separate specialty metals such as cobalt, nickel, bismuth, rhenium, molybdenum, indium and germanium from various primary and secondary feed streams. Recovery of these metals has numerous advantages including (i) conservation of valuable resources, (ii) prevention of environmental damage, and (iii) elimination of capital and operating expenses due to re-processing or disposal of metal-bearing streams.

By S. E. Khalafalla

A method for preparing ferrochromium alloys containing less than 2 pct carbon has been devised in a single vacuum furnace reactor. This method can conserve chromium and should reduce the capital and energy requirements relative to chromite electrothermal reduction. Reduced products containing less than 2 and as low as 0.01 wt pct carbon were obtained by reacting pellets of chromite and carbonaceous reductant mixtures at pressures of 0.1 to 1 ton and temperatures of 1,230° to 1,320° C. The extent of reduction increased with increased temperature and decreased pressure; however, operating conditions were limited due to the onset of significant chromium vaporization at higher temperatures and lower pressures. Foundry coke, anthracite, and carbon black were found to be superior to graphite as reductants. The reduction of chromite to metallics was found to proceed via the carbide intermediates Fe3C or Cr3C2. Lime accelerates the. rate of solid state reduction of chromite and can shorten the furnacin1r time at 1,3000 C under vacuum from 13 hours to less than three hours. Additional lime and silica are added to the hot reduced chromite after releasing the vacuum and raising the furnace. temperature to 1, 700° C. Soaking the charge for about 20 minutes gave a button of low carbon ferrochromium alloy beneath a well-defined slag layer.

Jan 1, 1985

By KNona C. Liddell

The ion interaction model Pitzer proposed twenty years ago is today the most widely used method for calculation of osmotic coefficients and electrolyte and single ion activity coefficients in aqueous solutions. This is due in part to the accuracy of the results that have been obtained for many concentrated electrolytes. An additional factor is that, compared to alternative activity coefficient models, there are many more parameter values available for the Pitzer equations. The important features of this model are reviewed. Published parameter values for Co, Ni, Cu, Zn and Fe are tabulated, and applications of interest in the aqueous processing of these metals are described.

Jan 1, 1993

By Yiling Zhang, Paul A. Salvador, Gregory S. Rohrer

"Photocatalysis utilizes solar energy to produce hydrogen by splitting H2O. When a thin film of photocatalyst TiO2 is supported on a ferroelectric BiFeO3 substrate (band gap ~2.5 eV), the TiO2/BiFeO3 heterostructure is capable of photochemically reducing Ag+ to Ag0 in aqueous solutions under blue light with enhanced efficiency. The observation of spatially selective silver patterns on surface of the heterostructure after reaction suggests that photogenerated electrons and holes in ferroelectric BiFeO3 are driven in opposite directions to reduce their chance of recombination. Comparisons of the amounts of reduced silver on TiO2 film grains with distinct phases/orientations show that the reactivity is mildly preferential on anatase TiO2 phase and does not strongly depend on crystallographic orientation of BiFeO3.IntroductionTitania (TiO2) is capable of photocatalytically converting H2O to hydrogen and oxygen under the irradiation of ultraviolet light. [1, 2] One of the limiting factors for titania to be used as an effective photocatalyst is its band gap. Because the absorption edges of rutile and anatase titania are at 3.0 eV and 3.2 eV, respectively, they can only absorb light in the UV portion of the spectrum, which is about 3% of the available solar energy. [3-5] This limitation has motivated attempts to modify the absorption edge of titania so that it can absorb visible light.One strategy is to substitute a portion of the titanium and/or the oxygen with other atoms. There are numerous reports on visible light absorption of titania by doping and co-doping of Cr, V, Mo, Sb, Fe, N, S, C, and F. [6-34] Another strategy is to add an adsorbed molecular species that absorb visible light and donate an electron or hole to the titania, such as organic dyes [33, 35, 36] and Ce3+/Ce4+. [37, 38]The strategy in the present work takes the approach of depositing a pure titania thin film on a visible light absorbing substrate BiFeO3 to induce visible light activity of the heterostructure. BiFeO3 is a semiconductor with a band gap of about 2.5 eV [39-41] and is photocatalytically active in visible light. [42, 43] It is also ferroelectric with spontaneous polarization along pseudo-cubic <111> directions of 6.1 µC cm-2. [44] The spontaneous polarization gives rise to internal electric fields that drive photogenerated charge carriers, namely electrons and holes, in opposite directions to reduce their chance of recombination. [45-47] Additionally, the separation of electrons and holes leads to the spatial separation of reduction and oxidation half reactions so that the back reaction of intermediates is also suppressed. Such charge carrier separation has been reported in TiO2/BaTiO3 heterostructures with UV light illumination. [48-51] The TiO2/BiFeO3 heterostructures in this work combine both advantages of the relatively narrow band gap and the internal fields in BiFeO3 to enhance the overall photocatalytic activity."

Jan 1, 2014

By Kuniaki Murase, Tetsuji Hirato, Koji Nitta, Yasuhiro Awakura

"The redox behavior of copper species in an ""ammonium imide"" room temperature molten salt was examined in order to clarify the applicability of the salt to the electroplating media of various metals. Trimethyl-n-hexylammonium bis(trifluoromethanesulfonyl)- amide (TMHA-Tf2N), having an electrochemical window of 5.6 V (50 °C), and corresponding copper(II) salt were synthesized. In TMHA-Tf2N media monovalent copper ion, Cu(I), was stable and Cu metal was oxidized, or corroded, in the presence of Cu(II) species. Cathodic electrodeposition of copper metal and anodic dissolution of it were, thus, one-electron reaction and their current efficiencies were almost 100%.IntroductionElectrodeposition of metals from aqueous solutions is an important soft process for manufacturing thin-film materials, surface finishing, and extractive metallurgy. However, the electrodeposition of base metals, such as zinc, chromium, and nickel, from aqueous media inevitably accompanies hydrogen evolution, which lowers the cathodic current efficiency of metal deposition. Since the electrodeposition of aluminium, titanium, and rare earths from aqueous media is actually impossible due to their largely negative redox potentials, nonaqueous media such as aprotic organic solvent and high-temperature molten salts have been employed for the electrodeposition of these metals. Room temperature molten salts (RTMS),1, 2) or room temperature ionic liquids, have also been developed as a promising electrolytes for the electrodeposition of base metals. In this field, chloroaluminates of alkylpyridinium or alkylimidazolium cation have been well investigated for aluminium3) or alluminium-alloy4-5) electroplating media. On the other hand, in order to avoid high hygroscopicity arising from the use of aluminium chloride, attempts have been made to combine the alkylimidazolium cations with fluorine-containing hydrophobic anions, e.g. BF4-,6) CF3SO3- (TfO-),7) (CF3SO2)2N- (Tf2N-),8) and H(HF)n-ions,9) and investigated for electrodeposition media.'°) Recently, a new series of RTMS consisting of tetraalkylammonium cations and Tf2N- anion, sometimes abbreviated as TFSI- anion, was found independently by MacFarlane et al.11, 12) and Matsumoto et al. 13) This type of RTMS, which is commonly named ""ammoniumimide"" salt, has a wide electrochemical window of ca. 5 V and, thus, the RTMS seems to be suited for practical application as a solvent for the electrodeposition process. In this paper, we report the electrochemical behavior of copper species in an ammoniumimide RTMS, trimethyl-n-hexylammonium bis(trifluoromethanesulfonyl)amide (TMHA-Tf2N)."

Jan 1, 2000

By William Petrul

Image analysis studies were performed on mill products from laboratory flotation tests of the Zn-Pb ore from the Faro deposit in Yukon, Canada, to determine mineral liberations at specific grinds and to predict recoveries at optimum flotation conditions. The minimum and optimum grinds for liberating sphalerite and galena were predicted from size analysis data for the minerals in large ore pieces, and determined by image analysis studies of the mill products. The determined optimum grinds are about 2 Tyler mesh sizes larger than predicted because sane of the fine grained sphalerite and galena occurs in interstices between coarser grained pyrite and is liberated when the pyrite grains are broken apart. Materials balance calculations were performed on the analyzed values for the liberated and unliberated sphalerite and galenaa to determine their distributions in the mill products. The laboratory flotation tests recovered 74% of the sphalerite and 83% of the galena in Zn and Pb concentrates respectively. The mineral evaluation study indicates that the optimum recovery for sphalerite and galena are 85 and 83% respectively. The company is currently recovering 80% &apos;of the sphalerite and 82% of the galena.

Jan 1, 1989

By Takeshi Nagano

Copper pyrometallurgy in Japan has experienced quite fundamental changes in last fifteen years. The severe environmental restriction coupled with increase of energy costs accelerated the development work of the new continuous process in Mitsubishi Metal Corporation. After several years of pilot plant test work the commercial plant was put into operation at Naoshima Smelter in 1974, the design capacity of which was 4,000 tonnes of copper per month. Many modifications and improvements have been incorporated into the process and 7,200 tonnes per month of copper production was achieved in 1983, proving that continuous process was much more economical than conventional process. It is now possible to design and operate the continuous process in wide range of capacity. This paper will review the process and describe the progress of the process in these 10 years. 311

Jan 1, 1985

By Jagdish C. Agarwal

Although copper ranks very low in the order of abundance of elements in the crust of the earth, it has been one of the first metals utilized by mar, at his emergence from the Stone Age, about 10,000 years ago. Use of copper for weapons, tools, utensils and ornaments dates back to the twilight of history, 6,000-5,000 B.C. Native copper outcrops and the malleability of the metal explain its very early use by the cave-dwellers. The working, melting and extraction of copper from its minerals are among the oldest metallurgical achievements of the human race. The oldest complete smelting installations for the extraction of copper from its minerals, dated about the fourth millenium B.C., were recently discovered in the Timna Valley, Wadi Arabah, Israel. (1) The history of the developments of the extractive metallurgy of copper has been adequately reviewed recently. (2,3) The center of copper production migrated from the Eastern Mediterranean to Northern Europe (Mansfeld, Germany, Swansea, Wales) towards the end of the Middle Ages (1500 A.D.). The production of the metal was boosted tremendously in North America since the end of the nineteenth century (Fig. 1).

Jan 1, 1976

By Zhang Hengzhong

Based on thermodynamics of surfaces and a proposed two-dimensional state equation for surfaces, the relationship between the surface tension (Y) of a solution and the activity (a1) of its component (i) was derived: (1/Y)r2-.¬E (ai/Yl) The derived equation was verified with reported experimental data of water-alcohol systems and water-acetone system, the calculated results showed astonishing coincidence with experimental. Applications of the equation to the five matte systems Cu2S-FeS, Ni3S2-FeS, FeS-PbS, Cu2S-PbS and FeS-Cu22S-PbS also demonstrated that at given matte compositions the calculated surface tensions agreed with experimental fairy well.

Jan 1, 1993

By Neng-Wen Yu, Miao Wang, Ji-He Wei

The mass transfer characteristic between powder particles and liquid steel in the RH-PTB (Powder Top Blowing) refining has been investigated in a water model of 1/5 scale for a 90t RH degasser. The sodium chloride powder with analytical purity has been used as the flux for blowing. The mass transfer coefficient of the liquid side has been determined under the conditions of RH-PTB process. The influences of the main technological and structural parameters on the mass transfer rate have been examined. The results indicated that under the conditions of the present work, the mass transfer coefficient on the liquid side increases with raising the lifting gas blowing rate, inner diameter of the up-snorkel, circulation rate of the liquid and particle size of powder flux. And it decreases with an increase in the inner diameter of the down-snorkel. It is in the range of (l.36-7.30) x 10·4 mis, the appropriate dimensionless relationships have been obtained as follows:

Jan 1, 2000

By S. P. Ball

A major limitation to maximising the rate of gold extraction in commercial operations occurs as a consequence of the limited solubility of oxygen in cyanide liquors. The use of additions of solid inorganic peroxides as an in-situ supply of oxygen to the lixiviant has been studied, in particular in its application to heap leaching. Experimental studies showed-that the release of oxygen into solution from these peroxides is very sensitive to solution pH. Agitated leaching tests showed that, when either Ba, Ca or Sr peroxides were used as the-sole source of oxygen, both the rate and extent of gold extraccion was enhanced. Column leach tests were used to simulate heap leach conditions. These showed that significant increases in the rate of gold extraction could be achieved by additions of calcium peroxide, made to the ore, prior to it being loaded into the columns.

Jan 1, 1989

By T. DebRoy

In recent years rapid technological advances have been achieved in the application of high energy density heat sources such as lasers and electron beams in diverse metals processing operations such as metal refining, fabrication, coating, surface modification and alloying. However, our phenomenological understanding of these new and emerging processes has not kept pace with the technological achievements. Inadequate understanding of plasma-metal interactions, the complexity of the component physical processes, and the scarcity of thermophysical data at temperatures much higher than the melting points of metals are the main difficulties in the comprehensive analysis of these processes. Several unique contemporary issues related to metals processing with high energy density beams such as rapid evaporation of alloying elements during processing and the role of plasma in influencing vaporization rate interfacial tension and species solubility in metals are discussed in this paper.

Jan 1, 1993

By John R. FitzPatrick

The separation and purification of uranium from either nitric acid or hydrochloric acid media tan be accomplished by using either solvent extraction or ion-exchange. Over the past two years at Los Alamos, emerging programs are focused on recapturing the expertise required to do limited, small-quantity processing of enriched uranium. During this period of time, we have been investigating ion-exchange as a method for extraction/purification of uranium from acidic media. In addition, waste stream polishing is associated with this effort in order to achieve more complete removal of the uranium prior to recycle of the acid. Extraction chromatography has been demonstrated&apos; to further polish the uranium from both nitric and hydrochloric acid media thus allowing for a more complete recovery of the actinide material and creation of less waste during the processing steps. We will discuss contact experiments for evaluation of eleven different resins for uranium removal from nitric acid, the evaluation (again by contact experiments) of uranium elution from the ion-exchange media by various chemicals, and small-scale experiments for the removal of 235U from nitric acid. Larger-scale (100-gram) flow experiments using depleted uranium, were done after the small-scale evaluation Of the selected resin. A discussion is also included concerning the shortcomings of the contact experiments and how the flow experiments were modified in order to overcome these problems. We will also discuss the application of ion-exchange for some specific process needs at Los Alamos Contact experiments were used to evaluate some commercially available solvent-impregnated resins in addition to evaluation of several resins of this type synthesized in our laboratory. These experiments&apos; involved both nitric and hydrochloric acid media. The data from these experiments will be used to determine the column size and&apos; amount of resin required to polish the waste stream produced by the ion-exchange process described above. Small-scale flow experiments will be described and data given on the mass balances achieved using this two step process. Future work for evaluation of new ion-exchange and solvent-impregnated resins as well as the search for new eluants will be discussed. Other future experiments for both processes, including large-scale experiments, will be discussed in detail.

Jan 1, 1996

By J. Etay, S. Daugan, Y. Fautrelle

"New type of electromagnetic parametric instabilities arising at the free surface of liquid metal in the presence of a low frequency magnetic field are presented. First, the mechanism of the instability is analysed in an idealised case. Then, the experimental device working with mercury is described. Various shapes, both regular and irregular, of free surface are found. A experimental stability diagram is obtained. Measurements of the deformation performed on photographs are compared with physical orders of magnitude.IntroductionWhen a liquid metal pool of electroconductivity a is submitted to an A.C. magnetic field B = B0 cos mt, electrical currents j are induced in the liquid metal and interact with the applied magnetic field to create electromagnetic body forces F = j x B. Those Lorentz forces comprise both a mean value (time average) and an oscillating part. Those forces are widely used in many metallurgical processes to stirr a liquid metal or to control its free surface, e. g., in aluminium continuous casting or electromagnetic levitation problems (1-3). When liquid metal free surfaces are submitted to AC. magnetic fields, the shape of those interfaces may interact with the applied field and leads to a various instabilities. A review of these instabilities may be found in Fautrelle (4). That instabilities may be a problem for the control of processing as electromagnetic levitation or quasi-levitation."

Jan 1, 1999

By Yichi Lu, Haydn N. G. Wadley, Douglas T. Queheillalt

"Using a 3-D ray tracing methodology combined with laser ultrasonically measured elastic constant data near the melting point, ultrasonic propagation in cylindrical single crystal bodies containing either a convex or a concave solid-liquid interface have been simulated and used to design new sensing concepts. Ray paths, wavefronts and time-of-flight (TOF) of rays that travel from a source to an arbitrarily positioned receiver have been calculated. Experimentally measured TOF data have been collected using laser generated/detected ultrasound on model systems with independently known interface shapes. Both numerically simulated data and experimental results have shown that the solidification (interfacial) region can be identified from ultrasonic transmission TOF data. Since convex and concave solid-liquid interfaces result in distinctively different TOF data. When TOF data collected in the diametral plane are used in a nonlinear least squares algorithm, the interface curvature has been successfully reconstructed and ultrasonic velocities of both the solid and liquid obtained. The reconstruction errors were found to be less than 5%.IntroductionMany of today's single crystal semiconductors are grown by variants of a vertical Bridgman technique in which a cylindrical ampoule of a molten semiconductor is translated through a thermal gradient, resulting in directional solidification and the growth of a single crystal, Fig. 1.1 It has long been recognized that during crystal growth the velocity and the shape of the solid-liquid interface, together with the local temperature gradient, control the mechanism of solidification (i.e. planar, cellular or dendritic), the likelihood of secondary grain nucleation/ twin formation (i.e. the loss of single crystallinity), solute (dopant) segregation, dislocation generation, etc. They thus determine the crystals' resulting quality.2-4 The solidification rate and the solid-liquid interface shape are also sensitive functions of the internal temperature gradient (both axial and radial) during solidification.5•6 This in turn is governed by the heat flux distribution incident upon the ampoule, the latent heat release at the interface, and heat transport (by a combination of conduction, buoyancy and surface tension driven convection, and radiation) within the ampoule. The solid-liquid interface's instantaneous position, velocity and shape during crystal growth are therefore difficult to predict and uncontrolled during growth, especially for those semiconductor materials with low thermal conductivity (e.g. CdTe).4-6 The development of technologies to non-invasively sense the interface position and shape throughout the vertical Bridgman crystal growth process has therefore become a key step toward developing a better understanding of the growth process, for enabling sensor-based process control, and thus ultimately for improving the yield and quality of difficult to grow semiconductor materials like CdTe."

Jan 1, 1997