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By A. H. Rosenberger, M. A. Tschopp, M. A. Groeber, K. N. Solanki, A. L. Oppedai, J. D. Miller

"Characterizing the spacing of primary dendrite arms in directionally-solidified microstructures is an important step for developing process-structure-property relationships by enabling the quantification of (i) the influence of processing on microstructure and (ii) the influence of microstructure on properties. The research objective herein is to evaluate the capability of various conventional approaches, as well as new or modified approaches, for spatial point pattern analysis with application to characterizing experimental dendritic microstructures. Both computer-generated and experimental dendritic microstructures are used for this analysis along with numerous techniques based on the nearest neighbor spacing, Voronoi tessellation, Delaunay triangulation, or graph theory. Comparison of new metrics with traditional primary dendrite arm spacing metrics will also be discussed for both local and global measures. The current methods investigated will supply information of local spacing and coordination number while addressing edge effects, parameter sensitivity, and correlation with interdendritic features, thus providing insight into how processing affects properties.IntroductionDeveloping an enhanced understanding of mechanical behavior in materials relies upon sufficiently characterizing microstructure details at the relevant length scales that contribute to this behavior. Moreover, to truly enhance the predictive capability of processing-structureproperty models that aim to improve material performance requires a quantitative description of the relevant microstructure features and, thereby, the material itself"

Jan 1, 2013

The reported values of the standard reduction potentials of the Au(NH3)2+/Au(0) and Au(S2O3)23-/Au(0) couples are reviewed to emphasise the experimental difficulties associated with the measurement of reliable values for these quantities. The standard reduction potential for Ag(I)/Ag(0) in ammonia and thiosulphate solutions measured at ionic strength 0.1 and 25oCis used to predict the following relevant stability constants () for gold complexes based on the linear free energy correlations: Au(NH3)2+2 = 1013, Au(S2O3)23-2 = 1024 and Au(NH3)43+4 = 1033. The equilibrium constant ( 10-11) for the reaction Au(S2O3)23- + 2NH3 = Au(NH3)2+ + 2S2O32- based on these stability constants is in reasonable agreement with the measured value (10-9) based on potentiometric and spectroscopic data when excess ammonia was added to a solution of Na3Au(S2O3)2. This also indicates that the stability constant of Au(NH3)2+ is 9 to11 orders of magnitude less than that of Au(S2O3)23-. Relevant species distribution and Eh-pH diagrams based on the revised data are presented.

Jan 1, 2003

By A. F. Otero

During the electrowinning (EW) of copper significant quantities of highly toxic vapors (acid mist) are produced due to the liberation of oxygen at the cathodes. Acid mist affects the health of operators, the environment and plant infrastructure. Acid mist can be decreased to acceptable levels by a combination of physical means (e.g. ventilation, plastic spheres over electrolyte) and chemical surfactants that decrease the surface tension of the electrolyte, modifying the way oxygen bubbles burst at the surface of the electrolyte. However, only few chemical surfactants are compatible with electrolytic applications, and they are not always used due to their high costs. This paper describes the application of a novel surfactant of natural origin (commercial name Mistop®) to suppress acid mist in copper EW process. Mistop® contains triterpenic saponins derived from the Chilean quillaja tree Quillaja saponaria Molina. The product is non-toxic, and poses no risks to the environment or to EW operators. Mistop® was tested at a laboratory, pilot plant and industrial scale in the world?s largest copper EW production plant at Radomiro Tomic (RT), CODELCO, Chile. At a Mistop® dosage of 8-9 ppm, acid mist decreased below the value accepted by Chilean regulations (< 0.5 mg/m3). At this dosage, Mistop® represents and economical alternative to chemical surfactants, and it is currently industrially used at RT.

Jan 1, 2003

By K. M. Parida

The kinetics of dissolution of manganese dioxide in dilute sulphuric acid solution have been investigated using iron pyrites as a reductant. The dissolution rate of manganese is independent of the speed stirring but depends upon temperature, particle size, specific surface area of manganese ore, acid concentration, Fe(II) concentration and amount of pyrite. The activation energy is 43.6 KJ/mol and the linear relationship between the rate of dissolution and lido indicates that the reaction is chemically-controlled. The redox reactions of MnO2 with iron pyrites and Fe(II) are the rate-controlling reactions.

Jan 1, 1990

By W. L. Cornell

Bulk sulfide concentrate produced from Missouri Pb ore concentrator tailings must be reground to liberate sulfide values for subsequent sepa-ration. Studies to determine grinding parameters for optimum liberation were carried out using optical microscopy coupled with image analysis. The major sulfide phases present in the ground mineral particulates are marca-site, pyrite, sphalerite, galena, chalcopyrite, siegenite. and bravoite. Results showed that the base metal minerals were liberated by grinding to 74 micrometers (200 mesh), but the siegenite and bravoite required grinding to 20 micrometers or less to achieve liberation. Both the experimental method and results are presented.

Jan 1, 1987

By Larry G. Stolarczyk

The development of geosteering technology for geothermal reservoirs is challenged by the integration of electrically small antennas in small-diameter metallic drill rods. To be useful, the antenna pattern must achieve sufficient back-lobe suppression, preferably with a forward-looking pattern. Forward-looking capability requires an antenna array with phase control. The phase-controlled antenna pattern enables imaging of geologic structures ahead of and surrounding the well bore. This paper describes the development of electric and magnetic dipole arrays for small-diameter drilling pipe.

Jan 1, 2006

By Hideaki Tokuyarna

Recovery of metal such as V, Ni and Fe from oil fly ash is important for efficient use of natural resources and protection of environment. Leaching of metals from fly ash followed by ion exchange of leached metals has been examined to develop a process which can selectively recover V and Ni from the fly ash. Experiment of leaching with water, HCI, H2S04 and NaOH leads us to propose a two-step leaching process as an effective and mild operation. The first step is leaching with water for removal of Ni, Mg, A1 and Zn and the second step is leaching with acidic solution for the recovery of V. The metals V and Ni are then separated from other metals in each leached liquor by ion exchange. Advantage of this separation process is that acidic leachant can be reused, which contribute to save separation energy.

Jan 1, 2002

By Keuncheol Choi, Yonghack Lee

"The new lead smelter based on the QSL technology was started operation from May 1992 at Onsan Refinery of Korea Zinc Co., Ltd. The smelter is designed to treat not only various types of lead concentrate but also secondary materials coming from the zinc plant without special pretreatment.Shortly after the start-up of the operation, it has demonstrated that the smelter have a capability to treat wide range of raw materials. Continuous modifications and improvements of the plant are still under way to increase the feed rate and also the ratio of secondary materials to the feed.In this paper, the operating experience and results of QSL smelter, especially the injection of gases and coal to the melt, will be presented with major operation parameters and data.INTRODUCTIONThe QSL lead smelter based on new injection technology was commissioned at the Korea Zinc's Onsan plant from May of 1992. After starting the operation, the QSL lead smelter faced various kinds of mechanical and metallurgical troubles. However, these were gradually worked out by the continuous improvements and efforts.At present, the QSL lead smelter is operated stably at the total feed rate of 57 tonnes per hour with an increased amount of secondary materials."

Jan 1, 1996

By Finn Olesen, Melina Garcia, Mark William Kennedy

"Furnace resistance is a function of the complex interrelationship between many factors including: operating practice, slag conductivity, temperature, power intensity, and geometry (electrode shape, diameter, spacing, immersion, slag depth, etc.).Accurate prediction of resistance is critical for success of the overall furnace design. The sizing of electrodes, columns, bus-bars, and transformers are all impacted. Estimation of minimum and maximum resistance or maximum operational current, as well as the maximum operating voltage are of fundamental importance.Various mathematical tools have been developed to assist designers with the selection of furnace dimensions and the prediction of resistance. Elkem found the methods of Downing and Urban 1965 and Westly 1975, to be particularly useful.In the current paper, comparisons are drawn between data from spent aluminum pot lining (SPL) demonstration testing at Elkem Bjolvefossen and predictions based on these classical tools and 3D finite element modeling (FEM) with COMSOL.®"

Jan 1, 2012

By Partha Patra

Extracellular bacterial protein (EBP) from Paenibacillus polymyxa was isolated. Adsorption of bacterial cells of Paenibacillus polymyxa as well as EBP onto pyrite, galena and sphalerite was studied. Both bacterial cells and EBP was found to have different adsorption density for different minerals. Protein from mineral surfaces were extrated and examined through SDS PAGE electrophoresis. Specific group of protein was found to be adsorbing, specific to respective minerals. EBP was fractionated through FPLC. Adsorption studies were carried out with each fractions. Difference in adsorption density was observed for individual minerals. Flocculation and flotation experiment were carried out with these mineral specific EBP. Pyrite was selectively removed from ternary mixture of galena and spharite through flocculation anf flotation using pyrite specific EBP. Mineral specific EBP was found to selectively separated remove pyrite from the complex sulphide mixture.Zetapotential studies were carried out to examine the surface chemical changes of the minerals on interaction with EBP. Hydrophobicity of the minerals were carried out on interaction with bacterial cells as well as mineral specific EBP.

Jan 1, 2006

By Toru H. Okabe

As part of a systematic study on the thermodynamic properties of complex nitrides, phase equilibria of the system Li-M-N (M Mg, AI, Ga) at 900 K were investigated. An attempt to determine the thermodynamic properties of complex nitrides was made by using the galvanic cell method, which utilizes LiMgN as an electrolyte under nitrogen atmosphere. The electromotive force (Emf) of ilie cell at temperatures between 800 and 1100 K was measured. Whilc the Emf of the cell at 900 K was measured to be 0.137 V, data discrepancies of ±0.03V were found. It was difficult to determine temperature dependence of ilie Emf. The Gibbs energy change for the reaction, 113 LbN (s) + 1/3 Mg3N2 (s) = LiMgN (s), at 900 K was determined to be tJ.Gor (LiMgN) -13.2 (±2.9) kJ/mol. Using thermodynamic information on ilie binary nitride from literature, the standard Gibbs energy of LiMgN was derived to be AGO f (LiMgN)= - 121 kJ at 900 K. The thermodynamic stability range of nitride was discussed by constructing isothermal chemical potential diagrams that provide a better understanding of ilie stability region of the LiMgN phase. The diagram was found to be in good agreement with the isoiliermal phase diagram determined by ilie alloy equilibration meiliod. Although the obtained data includes large uncertainties, the results provide a better understanding of the iliermodynamic stability of nitrides. The potential application of this complex nitride to nitrogen chemical sensors or a medium for controlling nitrogen potential is also shown.

Jan 1, 2003

By M. Huang

A conductivity-based sensor for on-line measurement of free acid was recently built. This sensor is suitable for high ionic strength solutions and its corrosion-free operation is based on induction currents. It has been tested against literature data and measurements made using a previous developed contact-type conductivity cell, with an average difference within 1%. The electrical conductivities of H2SO4?H2O, H2SO4?MgSO4?H2O and NaCl?Laterite-H2Osolutions at temperatures up to 250 °C were discussed. It was found that the solution conductivity depends on various factors, such as the electrolyte concentrations, the type of electrolytes, temperature and the amount of dispersions. A semi-empirical model was developed to account for all the factors discussed. This model was further tested on actual process solutions from the hydrometallurgy of nickel where sulphuric acid solutions containing a variety of metal sulphates and solids. The average difference between the estimated acid concentration from this model and the one from titration was generally less than 5%, which is excellent for industrial applications.

Jan 1, 2006

By Hande Cavus, Ibrahim Yusufoglu, Cem Kahruman

"In this study, ammonium tetramolybdate (ATM) was obtained as the intermediate product of ammonium heptamolybdate tetrahydrate (AHM). The thermal decomposition mechanism of ATM was investigated under nonisothermal and isothermal conditions in air and inert gas atmospheres. Nonisothermal experiments were carried out by TGA/DTA/MS while TG was used for isothermal conditions. Characterization of the decomposition products were carried out by XRD and FT-IR. The thermal decomposition of ATM in air proceeds in a single step and forms M0O3 while [(ÍÇ4)2è]ïïï83Ìïè3 and molybdenum suboxide (Ìïè3.÷, ÷=0.025) were obtained in the first and the second steps of thermal decomposition in He, respectively. Activation energies, frequency factors and kinetic model equations were determined for thermal decomposition reactions. Fractional conversion-time diagrams were compared with diagrams drawn according to kinetic model equation.IntroductionM0O3 is usually used as catalyst in industry [1]. AHM is the basic source to produce molybdenum containing catalysts used in petrochemistry [2]. The oxides of Li, V, W, Te, Bi and Sn are doped in M0O3 to produce catalysts, which find commercial applications in the industry. The properties of M0O3 are affected by dissolution, settling, calcination, drying and thermal decomposition processes [1]. There are several studies in the literature about the thermal decomposition of AHM and the characterization of the decomposition products in different gas atmospheres and at various heating rates [3-19]."

Jan 1, 2012

By Zvi Rivlin

Classical nucleation theory states that in first order phase transformations, such as liquid to solid transition, nucleation of the product phase starts with the formation of small, unstable clusters (embryos). When the thermodynamic barrier to nucleation is overcome, the embryos grow and attain a critical size, beyond which they are stable, i.e. they become nuclei. If nucle- ation does not occur, the parent, liquid phase remains in metastable equilibrium. At temperature lowers, undercooling increase and atomic mobility decreases. The viscosity change in the undercooled liquid may result in the formation of glassy state. As demonstrated in previous papers [I-21, in solidification involving surface nucleation of the product phase, as the case is in rapid quenching by melt-spinning, both nucleation temperature and nucleation time depend upon the number of atoms available at the isothermal surface in contact with the substrate. As a result of the thinness of the melt-spun ribbons, the embryo clusters that form at the freezing temperature may not be supplied by the amount of atoms necessary for their growth to critical nuclei sizes. In such extreme conditions, the liquid does not crystallize, it forms a metallic glass. A numerical simulation method is proposed for the reactions involved in embryo cluster formation and growth, at the atomic level. The simulation enables the caIcuIation of either the nucleation or the glass transition temperatures. Calculations made for the well-known glass forming CuZr and FeB systems afford prediction of the geometrical and thermodynamically conditions necessary for the formation of either crystalline or amorphous ribbons in melt-spun ribbons.

Jan 1, 1994

Lead removal has been problematic in nickel production by electrowinning from chloride solutions, as developed by Falconbridge. The C12 leach liquor needs to be diluted by electrolyte to allow precipitation of the lead prior to electrowinning. This results in higher solution purification costs and an aversion to consider lead contaminated (secondary) feeds. In this paper, the electrowinning of nickel chloride is carried out in a membrane equipped electrolytic cell. When lead containing nickel solutions are fed into the anode compartment and the anolyte is separated from the catholyte with a cation exchange membrane, lead remains in the anolyte due to the presence of a negatively charged chloride complex. The positive nickel ions migrate preferentially through the membrane to the catholyte, allowing a lower lead nickel cathode to be produced. Lead concentration in the catholyte and the cathode product has been tested as a function of lead concentration in the anolyte. Results are presented and discussed.

Jan 1, 1998

By Alain Jardy, Thibaut Quatravaux, Denis Ablitzer

"A numerical model of the Vacuum Arc Remelting process has been developed and applied to simulate remelting of various metallic materials, such as specialty steels, titanium and zirconium alloys. In practice, electromagnetic stirring is sometimes used, resulting in a complex 3D molten metal flow. After having validated the numerical model for different remelting conditions, we can use it to study the effect of applying a constant or alternated magnetic field on the thermohydrodynamic behaviour of the melt pool. The intensity of flow turbulence, computed with a classical k-E model, is shown to depend strongly on the nature of electromagnetic stirring.IntroductionThe principle of the Vacuum Arc Remelting (VAR) process, illustrated in figure I, consists in melting a consumable metallic electrode of the required grade under a high vacuum, in order to obtain a sound ingot of good structural quality.During remelting, an electric arc is maintained between the tip of the electrode and the top of the secondary ingot, in order to ensure melting of the electrode. The metal droplets fall through the arc plasma and progressively buid up the ingot, which solidifies in contact with the walls of a water-cooled copper crucible. The secondary ingot formed in this way contains three distinct zones, corresponding to the liquid pool, fully solidified metal and intermediate mushy zone. In order to stabilize the arc, it can be confined with the aid of a magnetic field created by an external induction coil. This field can also be used to stir the liquid metal, the rotation induced being in the orthoradial direction. By reversing periodically the coil current, stirring can be alternated."

Jan 1, 2004

By Ann M. Hagni

Electric arc furnace (EAF) dust from the secondary steel industry contains lead, cadmium, and chromium that causes it to be classified as a hazardous waste. Pyrometallurgical treatment of EAF dust is directed at recovering zinc and simultaneously rendering the dust non-hazardous. The mineralogy of the EAF dust is important in determining the occurrence and phase relationships of the zinc, lead, cadmium, and chromium contents. The principle phases in EAF dust as determined by reflected light microscopy, SEM-EDS, and XRD are solid solutions of the iron spinels (franklinite, magnetite, and jacobsite), zincite, hematite, and Ca-Fe-Si glass. Chromium is present in small amounts in solid solution in the spinels. Cyclone sizing of the minus 53 pm particles shows that more than 50% of this size fraction are less than 10 pm in diameter. The <I0 pm particles contain zinc as both franklinite in solid solution with magnetite and jacobsite, and zincite as determined by transmission electron microscopy and XRD. Auger electron spectroscopy did not detect coatings of volatile phases on the surfaces of EAF dust particles.

Jan 1, 1994

By Shoukun Wei, Cong Wang, Lin Cheng, Zhiyu Qiao, Jingkui Liang, Weidong Zhuang

"The subsolidus phase relations in the Sm2O3-CeO2-CuO ternary system sintered at 1000°C in air have been investigated by X-ray powder diffraction. The system can be divided into two ternary phase regions and three binary phase regions. Solid solution Sm2-xCexCuO4-y is the only ternary phase in the system. The maximum solid solubility was confirmed to be x = 0.2. The crystal structure, oxygen content and superconductivity of the solid solution Sm2-xCexCuO4-y have been investigated.I. INTRODUCTIONAfter the first discovery of the superconducting ceramic system La-Ba -Cu-O[l] with Tc = 30 to 40K, other families of cuprate-based ceramics have been synthesized with higher critical temperature. These oxides include the R-Ba-Cu-O (R: rare earth) systems (Tc=90K or so)[2,3], the Pb-Sr-(R,Ca)-Cu-O systems (T c = 50 to 100K), the Bi-Sr-Ca-Cu-O systems (Tc=80 to 105K)[4], the T1-Ba-Ca-Cu-O systems (Tc=85 to 125K)[5], the Hg-Ba-Ca-Cu-O systems (Tc=90 to 150K)[6,7], and some others. The improvement of Tc is very rapid. The measurement of the Hall and Seebeck coefficients shows that they all are p-type superconductors. In 1989, Tokura et al.[8] discovered the superconductors R2_XCexCU04_y(R = Nd, Pr, Sm) with Tc=20 to 24K (onset) and found that the charge carrier is electron in contrast to their hole doped counterparts. This discovery increases the fundamental understanding of the cuprate-based superconductors by comparing their characteristics and mechanisms to those of the p-type superconductors.One of the outstanding features of these n-type superconductors is the difficulty in obtaining samples in good charactors, such as the difficulty in obtaining zero resistivity state in single crystal or bulk samples; the semi-conductivity of bulk samples in ordinary state (opposite to the superconducting state) and a reducing reaction involved before the superconductivity has been found[9]. Therefore, it is necessary to optimize the sample preparation of the n-type superconductors. All the n-type superconductors have been found· considerable solid solubility. The compositional variations play a governing role in the carrier doping of the superconducting phases. Also, it is vital to the ceramic processing of superconductors to identify the compatible phases in the phase diagram. Finally, there is always the possibility of finding additional compounds, both superconducting and non-superconducting, in an unexplored system."

Jan 1, 1996

By P. N. Anyalebechi

"The effects of solidification rate, initial melt hydrogen concentration, and grain refining on porosity formation in aluminum alloy 2024 have been investigated with unidirectionally cooled laboratory-size ingots. The ingots were prepared from melts containing hydrogen concentration of 0.059-0.27 cm3/100 g and solidified at 0.2-37 °C/s. As expected, the amount of porosity, average pore size, and pore number density increased with increase in melt hydrogen concentration and decrease in solidification rate. However, the effect of solidification rate was greater at the very low melt hydrogen concentration (0.059 cm3/100 g). These results are consistent with reported effects of solidification rate and melt hydrogen content on porosity formation in other aluminum alloys. Interestingly, addition of grain refiner slightly increased the amount of porosity and the average pore size, especially at solidification rates above 1°C/s. IntroductionIn shaped castings and wrought products fabricated from ingots, billets, bars, or slabs of aluminum and its alloys porosity formation is a problem. This is because it compromises their tensile strength, fracture toughness, and fatigue properties [ 1-18]. The pores are usually the crack initiation and propagation sites [6,8,9] and the largest pores tend to dictate the fatigue life of the aluminum products [9,10,14]. Porous regions within an aluminum product probably yield first due to the reduced tensile load bearing capacity, causing the concentration of the strain near the voids which subsequently results in premature fracture. In aluminum alloy ingots, billets, bars and slabs porosity formation is particularly problematic because of its persistence through fabrication and potential for reappearance or exacerbation during subsequent thermal treatment processes before and/or after fabrication [19]. In fact, persistence of microporosity is a serious problem in large thick plates of wrought aluminum alloy products that must be rolled from correspondingly large direct-chill or electromagnetic cast ingots. Some of these thick plate products are machined into large aircraft components that are required in service to withstand multi-directional stresses and to possess high fatigue strength, fracture toughness, resistance to stress corrosion cracking, and strength in the short-transverse direction [1,20]."

Jan 1, 2011

By Stephen Chryssoulis, Stamen Dimov

Detection and quantification of precious metals (Au, Pd, Pt, and Rh) in spinels and silicate minerals is important for establishing the maximum attainable recovery by sulphide flotation. To achieve this goal subpart per billion (ppb) detection limits are required plus the ability to quantify results. Existing quantitative microbeam techniques (EPMA, PIXE, SIMS, TOFLIMS) have limits of detection in the O. l-200ppm range. Time-of-flight resonance ionization mass spectrometry (TOF-RIMS) is a microbeam analytical technique that allows for the identification and quantification of atomic species in very small quantities. It utilizes a tunable laser source for resonant excitation and ionization of a particular element of interest and has some unique features: elemental selectivity, linear response over a large dynamic range and very high sensitivity. The analysis consist of three steps: (i) the solid sample is vaporized by laser ablation to form a plume containing neutral atoms, (ii) the neutral atoms of a specific atomic element in the plume are resonantly excited and ionized by another tunable laser, and finally (iii) the ions created are mass analyzed in a time-of-flight mass spectrometer. A TOF-RIMS mass spectrometer was developed at AMTEL for trace element analysis of Au, Pd, and Rh in minerals. The spectrometer was calibrated using homogeneous CANMET and NIST reference samples covering three orders of magnitude in concentration. Attained minimum detection limits (MDL=2cr of the background) are in the low ppb range.

Jan 1, 1999