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By S. M. McDeavitt

Waste form alloys are being developed at Argonne National Laboratory for the disposal of remnant metallic wastes from an electrometallurgical process developed to treat spent nuclear fuel. This metal waste form consists of the fuel cladding (stainless steel or Zircaloy), noble metal fission products (e.g., Ru, Pd, Mo and Tc), and other metallic wastes. The main constituents of the metal waste stream are the cladding hulls (85 to 90 wt%); using the hulls as the dominant alloying component minimizes the overall waste volume as compared to vitrification or metal encapsulation. Two nominal compositions for the waste form are being developed: (1) stainless steel-IS wt% zirconium for stainless steel-clad fuels and (2) zirconium-8 wt% stainless steel for Zircaloy-clad fuels. The noble metal fission products are the primary source of radiation in the metal waste form. However, inclusion of actinides in the metal waste form is being investigated as an option for interim or ultimate storage. Simulated waste form alloys were prepared and analyzed to determine the baseline alloy microstructures and the microstructural distribution of noble metals and actinides. Corrosion tests of the metal waste form alloys indicate that they are highly resistant to corrosion.

Jan 1, 1996

By F. J. J. van Loo, A. A. Kodentsov, J. A. van Beek, M. R. Rijnders

"A periodic layered morphology of the reaction zone has been observed in several annealed solid/solid diffusion couples, including metal/metal and metal/ceramic couples. This morphology is characterized by a regular array of alternating layers, which are either single-phase layers or bands of particles embedded in an intermetallic matrix phase. A description of several systems showing periodic layer formation is given. It is shown that the periodic layered structure with the single phase layers and the one with the bands of particles have a different mechanism of formation.IntroductionSolid state reactions in ternary systems can produce a variety of reaction zone morphologies if there are two or more reaction products. Three types of morphology have been described in detail: 1) simple layered; 2) isolated precipitates in a singlephase layer; 3) interpenetrating columnar (lamellar) or interwoven structure. Understanding the factors that govern the formation of different morphologies is of importance in many fields of engineering. For solid state displacement reactions the conditions governing the formation of these morphologies are well understood [1-4]. For example, the development of a layered or aggregate reaction zone depends on the relative diffusivities of the components through the reaction products.This paper is concerned with the periodic layered morphology which has been observed in various solid state systems. We consider this to be a fourth type of reaction layer morphology. Two manifestations of periodic layered morphology may be distinguished. One form consists of regularly spaced layers of particles of one reaction product embedded in a matrix phase (another reaction product). The other form consists of single-phase layers embedded in a matrix phase. It will be shown that each manifestation has its own mechanism of formation. In section A we consider a system (Ag/Ti-foil/Si) in which periodic layer formation will be explained as a special case of the Liesegang phenomenon. In section B we consider systems where the periodic layered structure has a different origin."

Jan 1, 1996

By Sung Tae Kim

The viscosity is one of the most critical properties of slags and thus its influence on the physicochemical phenomena in metallurgical processes has been issued for last decades. The viscosity of ferrous- and non-ferrous metallurgical slags can be understood via structural investigation with spectroscopic methodologies including x-ray photoelectron spectroscopy, infrared- and Raman spectroscopy, and solid state nuclear magnetic resonance spectroscopy, etc. Therefore, the reaction kinetics such as desulfurization in ladle metallurgical furnace, reduction of FeO and MnO in electric arc furnace is strongly dependent on the viscosity of the slags. The rates of oxide (inclusion and refractory) dissolution into the slags and fluxes are governed by the viscosity. Alternatively, the structure of aluminosilicate melts also affects the thermochemical properties such as sulfide capacity, etc. These diverse applications of the viscosity-structure relationship to ferrous- and non-ferrous metallurgical processes were reviewed.

By Wenbo Luo, Jilai Xue, Tiepeng Li, Jun Zhu

Sodium silicate solutions for producing silica have been ultrasound treated to enhance the precipitation process in laboratory scale. Higher precipitation rate was found with ultrasound treated solutions than those without ultrasound. The obtained SiO2 powder products were characterized using XRD, SEM, BET and laser particle size analyzer. The particle size distribution and the specific surface area of the powder products varied with the power input level and the processing time of the ultrasonic treatment. The results indicate that the efficiency of the precipitation process can be improved optimally when the ultrasound is conducted into the solutions before the nucleation stage.

Jan 1, 2015

By Gennady I. Gulyayev

A mathematical model of plastic deformation occurring in cold plug drawing of mother tubes with initial cross-sectional wall thickness variations (CSWTV) has been developed. The main provision of the model is that eccentricity em is of such value that projection of all forces acting upon the plug in the deformation zone along the axis perpendicular to the drawing axis equals to zero. Calculations have proven that with other conditions being equal increase in the die cone angle and the deformation cycle number reduces CSWTV. Theoretical findings were confirmed by practical results. Keywords: cold, drawing, plug, die cone, plastic deformation.

Jan 1, 2003

By Guilian Gao

TbFeCo is a common choice for many rare-earth transition metal films currently used as the magneto-optic layer for magneto-optical: recording devices. Since the environmental stability of RE-TM alloys is typically poor compared with traditional metal oxide particle media, such devices rely on multiple functional overlayers (metallic and/or dielectric) and organic coatings for durability. This paper presents an electrochemical evaluation of the degree of protection of several candidates for the reflective layer, Al, AlCr and AIPt and for the dielectric layer, SiN, AISIN and AIN. Cyclic voltammetry In 0.2M K2SO4 solutions at room temperature revealed that AIPt film offers superior corrosion protection compared to Al and AICr films. Of the three dielectric layers examined, SIN seems to be the most corrosion resistant. Examination by optical and scanning electron microscope confirm the findings of electrochemical experiments. The corrosion resistance of single layers of Al, AICr and AIPt has also been examined and factors affecting their performance are discussed.

Jan 1, 1992

By Zhangm Mingming

Three samples received from the EAF shop were characterized by chemical, X-ray diffraction (XRD), optical microscopy (OM) and scanning electron microscopy (SEM) methods. The objective of this characterization work was to investigate the occurrence of nickel, copper, zinc, sulfur and phosphorus and to identify their origin and associations with iron minerals in the concentrate samples from the mines. The samples were identified as MINERAL, PELLET, and HRD. The latter is the DRI product. All three samples were received as fine powders. The results indicate that, in the mineral sample, magnetite is the major iron oxide mineral with hematite as a second phase based on the OM and XRD studies. Pyrite [FeS2], chalcopyrite [CuFeS2] and bravoite [(Fe,Ni)S2] are the major sulfide minerals. Trace amounts of apatite [Ca5(PO4)3(F,Cl,OH)], wardite [Na4CaAli2(PO4)8(OH)8 6H2O], giniite [Fe;(PO4)4(OH)3 2H2O] and vivianite [Fe3(PO4)2 8H2O] were identified by SEM and XRD. Microscopic studies also indicated that most of the sulfide grains in the mineral sample are present either as liberated fine particles (about 10 microns) or as inclusions within the magnetite and hematite grains. XRD studies revealed magnetite as the major mineral with subordinate amounts of hematite and pyrite confirming the microscopic findings. Copper, nickel, and zinc are mainly present as chalcopyrite, bravoite, and franklinite [(Zn,Mn,Fe)(Fe,Mn)2O4] in trace amounts in the mineral samples, respectively. Impurities carry over to the pellet and HRD samples. Chemical analyses of the three iron-bearing samples indicate that sulfur and phosphorus in the pellet sample exceeded the specification. Since liberated pyrite and chalcopyrite particles were observed in both the mineral and pellet samples, magnetic and flotation processing routes should be effective for sulfide removal but at the cost of iron losses. The high phosphorus content of all three samples indicates that there are phosphates which are difficult to remove by the current concentrating processes (magnetic separation and flotation).

Jan 1, 2012

By Zongshu Zou, Qiang Li, Mingming Li, Mingxia Feng

The impingement onto the surface of bath by top-blown jets is a significant process characteristic in BOF and EAF steelmaking process. The cavity is one of the most important outcomes of the interaction and plays an important role on reaction kinetics and reactors performance. But to date, the understanding to cavity is still so limited. In present study, a water model for a BOF converter is established and the dimension of cavity profile is investigated. The effects of lance height, gas flow rate, nozzle inclination angle and the amounts of slag are discussed. The results show that penetration depth increases with the increase of gas flow rate and the amount of slag, and the decrease of lance height and nozzle inclination angle. Furthermore, a theoretical model of cavity dimension is proposed for multiply jets impinging liquid bath on the basis of energy balance at the stagnation point of cavity.

Jan 1, 2015

By K. H. Bech, S. T. Johansen

"The mass transfer at fluid-fluid interfaces due to turbulent agitation is investigated theoretically. In particular a theory is derived for interface stresses due to interface energy and surface renewal. This theory indicates that surface renewal may take place if the geometry is sufficiently large and if surface tension is sufficiently low.By using a model for a typical turbulent structure we compute the interface mass transfer for a stressless interface and a fully interface. Results for the general situation is not presently available. The computed results are used to derive analytical expressions for the mass transfer based on turbulent kinetic energy and free stream turbulent length scales.One important application of the theory is the mass transfer at the electrolyte side of the bath-metal interface in the Hall-Heroult process. For this process we show that mass transfer should be expected to be of the rigid surface type."

Jan 1, 1999

By Daniel Kim, Ari Rantala

Efficient on-line monitoring of electrolytic cell performance in copper electro-refining has been challenging due to the need for complex electrical measurement systems and the management of the enormous volume of data. Based on Kennecott Utah Copper's innovation Outotec has developed a novel and innovative electrolytic cell monitoring system called CellSense™ System. As the system is based on self-powering from bus bars, wireless communication, on-line adaptive modeling and easy to access information and alarming, traditional obstacles of electrolytic cell monitoring are eliminated. With cell voltage and electrolyte temperature measurements, CellSense System enables real-time cell performance discovery and early reaction to critical production or quality disturbances such as short-circuiting, flow blockages, cold cathodes or electrolyte temperature excursions. During the past few years the system has been delivered to over 3500 commercial cells. In this paper the largest CellSense™ System ever delivered and recently adapted by Kennecott Utah Copper with 1412 cells monitored on-line for high tankhouse performance, cathode quality and optimized operator work flow is presented. Early results and benefits are discussed.

Jan 1, 2012

By Nagy El-Kaddah, T. T. Natarajan

This paper describes a novel approach for modeling three-dimensional electromagnetically driven flow in inductively stirred systems, and its application to modeling electromagnetic and flow phenomena in sub-mold rotary stirring of billets. It is based on a new T-\jf potential formulation of electromagnetic field, which does not require the calculation of the field in free space. A finite element algorithm has been developed for solving the electromagnetic field and Navier-Stokes equations in the fluid flow domain. The computed results have shown that the electromagnetic force field generates a strong rotational flow within the vertical section covered by the stirrer, and a relatively strong secondary flow beyond the stirrer. It has also been shown that the rotational and secondary flows were driven primarily by the vorticity of the force field at the billet corners. The induced flow in the molten pool was found to be turbulent and the effective mixing region in the molten pool was about three times the length of the stirrer. The mathematical approach presented in this paper provides the theoretical framework for quantifying these effects for any given stirrer configuration and operating parameters.

Jan 1, 1999

By Y. Fukunaka, M. Niinae, E. Kusaka, T. Kuzuya, R. Ishii

"Samarium oxalattr particles was precipitated in oxalic acid aqueous solution from samarium-loaded D2EHPA solution emulsified with a conventional impeller. The calculated fractional precipitation of samarium oxalate was reasonably compared with the value determined by chemical analysis. Morphological variation of oxalate precipitate particles was then examined with H2C2O4 concentration in aqueous solution, Sm(III) and D2EHPA concentrations in organic phase. The needle-like precipitate was identified as Sm2(C2O4)3 10H2O by XRD. Precipitates obtained at higher H2C2O4· or Sm(III) concentration greatly decreased the length of major axis of precipitate, while those at higher D2EHPA concentration increased it. The oxalate was further precipitated under ultrasonic irradiation. However, the morphological variation caused by theses processing variables was not so evident under ultrasonic irradiation as in an impeller or shaking mixer.IntroductionThe materials processing of the rare earth elements must be reviewed from the scope of industrial ecology, since they have the potential applications of magnetic materials as well as secondary battery in developing programs of the electric vehicle. The technological trend to develop the electric vehicle may greatly influence the concept of materials processing, since the global· environmental problem must accommodate with the sustainable development for mankind. The recycle design must be a key issue in the materials science and engineering.Solvent extraction provides a unique separation technology -in this sense. Doyle (1)(2) reported the integrating solvent extraction with processing of advanced ceramic materials, whose chemical composition and microstructure must be precisely controlled. In her paper, the higher productivity inherent to the present process superior to hydrolyzing metal alkoxides was emphasized. Oxalic acid has been used as precipitant for rare earth purification process, since rare earth oxalate has a very small solubility in water and can be easily decomposed to oxide. It is thus suitable for precipitation stripping agent in cationic exchange type extracting system (i.e. D2EHPA, VA-10, PC-88A and so on)."

Jan 1, 2000

By Christopher Solnordal

A mathematical model was developed to simulate the performance of the reaction shaft at BHP-Billiton?s Olympic Dam copper flash smelter. In order to have confidence in the predictions of the mathematical model, validation was performed by comparing and reconciling the predictions from the model with the results from a campaign of sampling and plant measurements. The model was based on the computational code CFX4.4 utilizing a combustion sub-model purpose-built by CSIRO. The combustion sub-model employed the concept of a composite particle which contained the three components of the solid charge: concentrate, flux and returned dust. Plant measurements were made and samples taken immediately below the burner and through a port halfway down the reaction shaft. Parameters measured included temperature, solid loading and SO2 concentration in the gas. Comparison of the measured and predicted values then showed that: predicted far field gas temperatures were within ±50C of measured values; predicted temperatures in the central plume were lower than measured, and, the predicted plume width was slightly smaller than measured. An optimum composite particle size of 19 m was identified for use in future modeling work at Olympic Dam.

Jan 1, 2006

By Luis W. Pommier

Large quantities of sea sludge containing halogenated organic compounds, such as PCB, oils and metals like arsenic and lead have accumulated throughout the years at the bottom of sea channels and harbors and are obstructing navigation and creating environmental problems which need to be resolved. A sludge from a California port would be dredged by suction pumps, it would be processed in a plant which would be built either on firm soil or on floating platforms. The sludge shows contents of up to 1 ppm of PCB, 15 % oil and 10 ppm of arsenic, which generates a very fetid odor. Bench scale work indicates that most of the contamination concentrates on the solid phase, in fact, only minor amounts of oil report to the sea water and can be readily removed by physical means. After separation of the sea water from the solids of the sludge by decantation, it is possible to solubilize the PCB, the oil and the metals into an organic solvent leaving a non-hazardous soil for disposal near the harbor. The PCB is dehalogenated during the solubilization process leaving a liquor solution containing the oil and metals. The oil is extracted leaving an aqueous solution containing the arsenic. Further process extracts the arsenic from this solution rendering the liquid non-hazardous. Transportation and disposal of the sludge is impractical. There are hundreds of thousands of tons of hazardous soils accumulated in each harbor, which would fill the hazardous waste disposal sites available and it would be, prohibitively expensive to do so. It is not possible to compare the costs of decontamination with a competitive method. If it were, the proposed process would be less expensive than transportation and disposal and it has the advantage of removing the liabilities from the Responsible party. After a full scale continuous pilot project is run to decontaminate a small, 500 cubic yards accumulation of this type of sludge in a California harbor, a full scale environmental project would be initiated. The decontamination of one million tons of sludge would be completed in five years.

Jan 1, 1995

By Hongmin Zhu, Guihua Wang, Xiangsheng Wang

"The anode process of carbon electrode in fluoride melt was studied by voltammetry and chronoamperometry. Anode gases were analyzed by gas chromatography on-line during controlled-potential electrolysis. Two peaks were observed on the cyclic voltammograms. According to the results of gas chromatography, the first peak was corresponded to the discharge of residual oxide ions, with the formation of CO and CO2. Discharge of fluoride ions occurred at 4.1 V vs. Li+/Li, and leading to the anode effect. With the occurrence of anode effect, small amount of CF4 was detected. As the potential reached 4.5 V, CF4 and C2F6 gas evolution occurred, and the current increased to form the second peak.1.IntroductionIn the primary production of Aluminum and some rare earth metals like neodymium, a departure from normal cell operation known as anode effect results in the generation of perfluorocarbons (PFCs), which have high global warming potentials [1]. Owing to the pressure of environmental protection, considerable research has been carried out to clarify the mechanism of anode effect and PFC generation of industry and laboratory cells in the aluminum electrolysis system [2-9]. The common result on PFC generation is that the PFCs are emitted from Hall-Heroult cells only when they are on anode effect. In this article, we selected LiF, the main electrolyte for the neodymium electrolysis [10-11], to perform further investigation on the underlying kinetics of PFC generation and the nature of the reactions at the electrode.2. ExperimentalAll experiments were carried out in an alumina tube reactor, which was filled with high purity helium atmosphere. Spectrographic graphite crucibles were used, which played the dual role of molten fluoride container and the counter electrode. Lithium fluoride was analytical grade. The experiments were carried out at 900 °C."

Jan 1, 2011

By LeoJ. Miller

Exploration for an ore deposit commences with an outline of the regional ore controlling environment and is followed by the application of tools to focus the target area. One of the most essential focusing is the mapping of the mineral assemblages within the area of the ore. Key elements of mineralizing fluids, either epigenetic or syngenetic, enter into mineral assemblages that extend far beyond ore deposits. Portions of these assemblages may consist of new matrix minerals or alteration of previously existing minerals. Today, ore deposits are divided into genetic classes and each class is d8fined by a specific geological environment. Ore deposits within a given class are associated with a mineralogy, that is characteristic of the ore deposit class. So faithful is the mineral assemblage surrounding, or within an ore deposit, that recognition of the assemblage may be sufficient to define the class. Porphyry copper deposits have long been noted for their halos of alter-ation minerals. The outermost ring of chlorite, epidote and calcite extend thousands of feet away from the main ore zone. The mineral associated with porphyry copper deposits have been well documented by our distinguished speaker Paul Kerr, at Santa Rita (1), and Silver Bell' (2), and by excellent papers from S. C. Creasey, 1959 (3), Sales, 1948 (4), T. S. Lovering, 1949 (5), our Co-Chairman John Guilbert, 1970 (6), and many others. Several recent porphyry copper mines have been discovered in recent years by utilizing the mineral assemblage model described by Lowell and Guilbert, 1970 (6). Dave Lowell applied his own model of mineral halos for the discovery of Kalamazoo at San Manuel (7), Arizona, and Casa Grande West, Arizona. The purpose of this paper is to outline the application of mineralogy for discoveries of deposits other than porphyry copper mines and in particular, to ore discoveries in which mineralogy has played a key roll.

Jan 1, 1981

By Luis Velazquez, Andrea Zavala, Nora Munguia

"This paper is aimed at describing the evolutive strategy in which the University of Sonora is following for optimizing the organic and inorganic material life cycle in the products used on campus. The institutional strategy has be oriented towards new patterns of behaviors in order to integrate the principles of sustainability as a guideline for preventing, eliminating, and/or reducing the negative environmental and occupational impacts generated when performing university substantive functions of teaching, research, and outreaching and partnership as well as its management operation tasks.IntroductionThe University of Sonora is the largest and most important university among several other universities in both the city and the state. It is a public university with a 29,792 students in three campuses in the state. The main campus of the University of Sonora is located in the capital city of Hermosillo, which has a population of more than 609,829, in the state of Sonora in the northwestern region of Mexico [1].Despite the fact that in the University of Sonora there were, in the eighties, some projects dealing with environmental issues, there was not until 1992 that the sustainability efforts were really initiated. It happened when the Sustainable Development Group was created in the Department of Industrial and Systems Engineering as a response to the need for adapting the industrial engineering curricula to the challenge of sustainable development [2]. In order to promote sustainability, it has been necessary to cope and break with several university paradigms. For this reason, the strategy for becoming a sustainable university has continuously evolved throughout the years from a simple structure composed by individual and isolated projects to a systematic and integrative Sustainability Management System. Thanks to this evolution, the University of Sonora has won a respectable reputation in the greater community and it is seen in the region as an icon of sustainability promoter. In this sense, the substantives functions of education, research, and outreach and partnership, which are considered supportive and integrative, have also evolved to play a key role for the success of sustainability initiatives.The institution has followed four avenues for becoming a sustainable university; education, research, outreaching and partnership and greening the campus [3]."

Jan 1, 2008

By Toshihiro Kuzuya

A hydro metallurgical process has been developed for the recovery of metal values such as Co, Ni and rare earths from the electrode materials of spent nickel metal-hydride(Ni-MH) secondary battery. MmNis_xCo. (Mm : Misch metal) intermetallic compound could be separated from the electrode materials mixture by sedimentation. A typical chemical composition of MmN5-xCox was approximately, in mass%, 56.0%Ni, 13.4%Ce, 10.6%La and 7.9%Co. The time dependency of leaching intermetallic compound with sulfuric acid solution was examined with processing factors such as sulfuric acid concentration, temperature and agitation intensity, The leaching of rare earth metals proceeded very rapidly, reaching completion in less than 1.8ks. On the other hand, the slow leaching of nickel was observed. The percent of nickel leached at 328K could only reach about 70%.

Jan 1, 2003

By T. T. Chen

A mineralogical study of copper anodes and copper anode slimes was carried out to elucidate the silver phases present and the behaviour of silver during copper electrorefining. Most of the silver in the anodes is in metastable solid solution in the copper metal. As the copper dissolves, silver also dissolves, but is rapidly removed from solution by a variety of reactions. Some of the silver is precipitated as Ag by cuprous ions and some is precipitated as a complex CU-Ag-Pb-As-Se oxidate phase. Much of the silver, however, reacts with copper selenides to form, progressively, (CU,Ag) 2se, AgCuSe and Ag2se. The reaction commences at the periphery of the selenide grains and progresses inward; the result is commonly a silver-rich species on the outside of a silver-deficient core. Slimes collected periodically throughout the electrorefining cycle show a progressive silver enrichment of the selenides. Traces of Ag2Te also may be present, but the telluride seems to J:ie a rare constituent of most raw anode slimes.

Jan 1, 1989

By Line Hallgren

The fluid flow in the mold during up-hill teeming is of great importance for the quality of the cast ingot and therefore the quality of the final steel products. At the early stage of the filling of an up-hill teeming mold, steel enters, with high velocity, through the nozzle into the mold and the turbulence on the meniscus could lead to entrainment of mold flux. The entrained mold flux might subsequently end up as defects in the final product. It is therefore very important to get a mild and stable inlet flow in the entrance region of the mold. It has been acknowledged recently that swirling motion induced using a twist tape swirl blade, in the submerged entry nozzle is remarkably effective to control the fluid flow pattern in both the slab and billet type continuous casting molds, resulting in increased productivity and quality of the produced steel. From the above result, we propose, swirling flow generated through a swirl blade inserted into the entry nozzle, as a new method of reducing the deformation of the rising surface and the unevenness of the flow during filling of the up-hill teeming mold. The swirling blade has two features: (1) to generate a swirling flow in the entrance nozzle and (2) to suppress the uneven flow, generated/developed after flowing through the elbow. The effect of the use of a twist tape swirl blade was studied using both numerical calculations and physical modeling. Water modeling was used to assert the effect of the swirling blade on rectifying of tangential and axial velocities in the filling tube for the up-hill teeming and also to verify the results from the numerical calculations.

Jan 1, 2006