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By Alessandro Blasi, Massimo Morgana, Corradino Sposato, Pietro Garzone, Giuseppe Devincenzis

A comparison among (2-ethylhexyl)-mono (2-ethylhexyl) ester Phosphonic acid (P507), Secondary-octyl phenoxy acetic acid (CA-12) and Bis(2,4,4-trimethylpentyl) phosphinic acid (Cyanex272), in heavy rare earths separation via hydrometallurgical processes has been investigated. The separation coefficients, , were obtained and the extraction selectivity has been evaluated using a mixture of heavy rare earths from Samarium to Ytterbium. The experimental results indicated that P507 and Cyanex 272 display a greater affinity for heavier rare earths while CA12 proved to be more effective for the lighter rare earth metals.

Jan 1, 2014

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 Jeong-Soo Sohn

Physical treatment and chemical treatment of spent lithium-ion battery were studied in our research team. Especially we developed two types of acidic leaching for crushed powders containing LiCoO2 of spent lithium ion battery. One of them is sulfuric acid leaching with H2O2 as a reducing agent. The leaching rates of cobalt, lithium and the other metals were above 99 % at the condition of 2 M H2SO4, 10 vol. % H2O2, 75 °C, 300 rpm agitation speed, 250 g/5L solid liquid ratio and 75 minutes reaction time. And the other leaching process is the oxalic acid leaching. In this process more than 99% of Li and less than 1% of Co were dissolved at the condition of 3M oxalic acid, 80°C reaction temperature, 300rpm agitation speed, 50g/L initial solid/liquid ratio and 90min extraction time. Each process has its advantage and disadvantage. In sulfuric acid leaching, leaching reagent is very cheap and cobalt could be recovered into cobalt hydroxide. On the other hand, oxalic acid is more expensive than sulfuric acid but lithium could be dissolved selectively. Also cobalt could be recovered into cobalt oxalate and it could be changed into cobalt oxide after heat treatment. In order to select the effective recycling process, recovery rate and purity of cobalt hydroxide and cobalt oxalate were compared and it was investigated which process was more environment-friendly and economical.

Jan 1, 2006

By J. D. Ecuyer, L&apos

he microstructure of galvanneal coatings formed on extra low carbon and interstitial free steel substrates has been characterized using electron microscopy (TEM and SEM) and x-ray diffraction. The coatings are found to consist of a mixture of gamma, delta and zeta phases, of which delta is the main constituent. The amounts of each phase influences the powdering resistance of the coating which was evaluated using reverse Olsen testing and 60" bending. For the three heat input conditions considered, IF coatings were always found to contain a significant amount of gamma and only those which retained zeta phase on the surface exhibited a satisfactory powdering resistance. In much the same way, ELC coatings with relatively thick gamma layers performed satisfactorily only when some zeta was retained. It was also found, however, that coatings with minimal zeta and gamma had an excellent powdering resistance. The latter coatings were produced under galvannealing conditions of lower relative heat input. These results indicate that in addition to the zinc bath composition, coating weight and galvanneal thermal cycle, the base steel chemistry also has an effect on the coating microstructure. Knowledge and control of all aspects of galvannealing is therefore essential to consistently produce acceptable coatings.

Jan 1, 1992

By Sadegh Safarzadeh, Anne-Marie Suriano, Stanley Howard

The electrodeposition of metal ions from aqueous electrolyte solutions has been a well-known process for the last half century. With numerous industrial applications such as electroplating, electrowinning and electrorefining, the kinetics of electrochemical reactions involved in the process has been extensively researched. Arrhenius-type rate equations, the Butler-Volmer equation, and the empirical Tafel equation are among the most important models to explain the rate of electrochemical reactions. The study of the kinetics of metal deposition is critical to understanding the underlying mechanisms through which a certain morphology of metal deposit is formed on the cathode. The purpose of this paper is to elucidate the influence of experimental parameters such as pH and additives on the rate and the reaction mechanism determining the rate limiting step of the electrodeposition reactions.

Jan 1, 2015

By Marco Antônio Siqueira Rodrigues

The possibilities for treating rinse waters fiom chromating bath by electrodialysis are discussed together with the possibilities of optimizing the treatment process for waste reduction and reuse of water and chemical products. An industrial effluent with 4600 ppm of Cr(VI), besides other metallic contamination, was used as work solution. This solution has been recirculated on an electrodialysis cell of three compartments, using exchange membranes Selemiom AMT and CMT. A migration of dichromate ions into the anodic compartment was obtained, so that an extraction of circa 99.9 % of Cr(VI) present on the solution was observed, resulting in water with a Cr(V[) concentration of 4 rnd. These results show that electrodialysis can be used to treat these effluents, and this water could be reused as rinse water. The solution of the anodic compartment, consisting at the beginning of the experiment of H2S04, 0.1 N, reached 7200 mg/l of Cr(VI). This concentrate could be reused on the chromating bath itself.

Jan 1, 1999

By Yuanbo Zhang, Yingming Chen, Zijian Su, Bingbing Liu, Jun Chen

Iron, tin-bearing tailings is a kind of hazardous solid waste generated from cassiterite dressing operation. It is difficult to utilize the tailings by present mineral processing methods due to the complex dissemination characteristics. In this study, a process of gas-based magnetizing roasting followed by magnetic separation was studied for separating and recovering iron from the tailings. The effects of roasting and magnetic separation parameters on the recovery of iron were systematically investigated. The optimum parameters were proposed as follows: CO/(CO+CO2) content of 5%, roasting temperature of 850 C, roasting time of 60 min, grinding particle size of 90% less than 45 μm and magnetic field intensity of 800 Gs. Under these conditions, the magnetic concentrate containing 68.5% Fe and 0.06% Sn was achieved, which can be used as high-quality raw materials for direct reduction iron production.

Jan 1, 2016

By L. Yin, R. B. Haber, N. Sobh, D. A. Tortorelli, R. W. Hyland Jr.

"We optimize continuous quench process parameters to produce a desired precipitate distribution in aluminum alloy extrudates. To perform this task, an optimization problem is defined and solved using a standard nonlinear programming algorithm. Ingredients of this algorithm include a cost function, constraint functions and their sensitivities with respect to the process parameters. These functions are dependent on the temperature and precipitate size which are obtained by balancing energy to determine the temperature distribution and by using a reaction-rate theory to determine a discrete precipitate particle size distribution. Both the temperature and the precipitate models are solved via the finite element method. Since we use a discrete particle size model, there are as many as 105 degrees-of-freedom per finite element node. After we compute the temperature and precipitate size distributions, we must also compute their sensitivities. This seemingly intractable computational task is resolved by using an element-by-element discontinuous Galerkin finite element formulation and a direct differentiation sensitivity analysis which allows us to perform all of the computations on a PC.1 IntroductionThis work addresses the need for an integrated design capability that links microstructure evolution to the process parameters. It is motivated by the manufacture of lightweight aluminum-alloy extrusions for use in automotive structures. Aluminum alloys offer obvious benefits, however, care must be taken to manufacture favorable microstructures that ensure acceptable structural performance. For example, the manufacturing process for 6000-series components involves hot extrusion of cast aluminum billets followed by either an air or water quench process. The bill~t's initial grain structure is dramatically altered during extrusion by massive mechanical deformations and recrystallization processes. The microstructure continues to evolve during the quench, as complex chemical processes determine the formation of precipitates. The control of the precipit'ate size distribution is vital. Indeed, large precipitates located on grain boundaries serve as crack initiation sites which adversely effect structural crash· worthiness."

Jan 1, 2000

By Hong Yong Sohn, Miguel Olivas-Martinez

"Different approaches are used for calculating the ‘energy requirement’ of a process. The determination of energy requirement becomes confusing for a process in which a fuel is also a reactant. The key issue is which heat of chemical reaction should be included in the ‘energy requirement’ value. We will use the example of ironmaking processes to illustrate the problem. The different approaches essentially boil down to the question: does one include the combustion heat of the reductant used in the reduction reaction or just the heat of the reduction reaction? Depending on the viewpoint, either approach can be accepted; it is a matter of convention. There is a need, however, to select a standard approach because the absolute value of ‘energy requirement’ of a process depends on the choice. The energy requirement of a novel flash ironmaking process will be compared with that of an average blast furnace operation.IntroductionDifferent approaches are used for performing energy balance calculations and perhaps more significantly in presenting the ‘energy requirement’ of a process. The question becomes more involved for a process in which one or more reactants are also used to generate the process heat by combustion. Often the key issue is which heat of chemical reaction to include in presenting the ‘energy requirement’ of the process.It is worthwhile to note at the outset that the difference in energy requirements between different processes for converting similar raw materials to the same desired product is largely unaffected by the choice of chemical reactions to be included. However, the absolute value presented as the ‘energy requirement’ of a process can be different by a large amount depending on the approach. We use the example of ironmaking processes to illustrate the problem. In these processes, as currently practiced or under development, carbon and/or hydrocarbons (including hydrogen) are used as the fuel as well as the reactant for reducing the iron oxide mineral.The different approaches in this case essentially boil down to the following question: does one include the combustion heat of the reductant used in the reduction reaction or treat the reductant portion as just a reactant? Depending on the viewpoint, either approach can be considered acceptable. It is a matter of convention. There is a need, however, to select a standard approach because the absolute value of ‘energy requirement’ of an ironmaking process (e.g., the currently dominant blast furnace process) depends on such a choice. It is particularly important to clearly state the specific approach used when the energy requirement of ironmaking is compared with those of other industrial processes such as petrochemicals production."

Jan 1, 2014

By Xiangru Chen, Honggang Zhong, Qijie Zhai, Qingqing Sun

"A horizontal directional solidification equipment, with an in-situ pouring system, was employed to physically simulate the solidification behavior of continuous casting. In this paper, the 2304 duplex stainless steel (DSS 2304) was investigated using this equipment due to its microstructure produced by continuous casting process was usually not satisfied. The grain size combined with the position of columnar to equiaxed transition (CET) of DSS 2304 were observed and the results showed these microstructure characteristics were very close to those of the continuous casting slabs. In addition, the influences of pouring temperatures and cooling conditions on the CET behavior were investigated. The results revealed that the length of the columnar grains decreased with decreasing the pouring temperatures and flow rates of the cooling water. Besides, the content of austenite decreases with increasing the distance from the chilled sidewall.IntroductionDuplex Stainless Steels (DSSs) have been widely used in industry for their excellent mechanical strength and superior corrosion resistance in Cl- environments when compared with other stainless steels [1,2]. Their good performances are mostly on account of the duplex phase structure-ferrite (d) and austenite (?) and the high proportion of alloying elements. Although, DSSs have good ductility, but worse formability compared to the austenitics, and this is the key to restrict DSSs application [3]. This is due to the differences properties between the two phases. The hot workability of ferrite (d) is better than austenite (?) and exhibits a lower flow stress during hot rolling processing [4]. The early workers had revealed that coalescent force of phase interface, microstructure, difference of mechanical property between two phases and the precipitations are the main factors affecting the formability of DSSs [5,6]. Another important reason that affects the alloy’s mechanical properties is columnar to equiaxed transition (CET) [7]. It often occurs during continuous casting solidification process and induces inhomogeneous mechanical properties and the microstructure varies with different processing parameters, such as pouring temperatures, cooling conditions (water flow rates in the cooling zones) and casting speed [8]."

Jan 1, 2012

By Larry Twidwell, Ed Rosenberg, Courtney Young, Sean Dudley, William Gleason, Maureen Chorney

Experimental and industrially produced polystyrene and silica resins are tested for recovery capabilities of Rare Earth Elements (REE). Testing regimes being used are typical of resin analysis. Inductively Coupled Plasma-AES results indicate that preferential separation and recovery is possible in the adjusted pH range of2 to 10, solution conditions, and resin type. Testing conditions are resulting in structure modification of the composite resin as indicated by X-Ray Diffraction, Differential Scanning Calorimetry, Scanning Electron Microscopy, Mercury Porisometry, and density analysis. Resin modification indicates both surface and internal structure alteration outside of reported standard behavior of resins. Structural changes have ramification for both Rare Earth Recovery RER and traditional resin operations. Analysis shows that the resin uptake of REE can be manipulated for concentration. Further analysis with SEM work indicates that widespread surface and interior modification is taking place as resins load with REE. This modification is leading to pore rupture and particle breakage. Further investigation is being performed to determine the mode of breakage.

Jan 1, 2015

By J. Murphy

The economics of microbial coal desulfurization are affected significantly by the proper selection of the plant site and by maintenance of variables at suitable levels. High sulfur coal particles below 200 mesh show sulfate production rates triple those with 150 mesh coal but grinding costs are greater. Slurry solids density increases from 5% to 20% reduced the rate constant by a factor of 10. Coal added to a batch reactor in the stationary phase resulted in a sudden second exponential sulfate production phase indicating feasibility of lower cost continuous operation. Successful operation in the absence of beef broth, yeast or added nutrients at non-sterile conditions enhanced projected economics. Finally, the need for adequate agitation and aeration was well established.

Jan 1, 1985

By QinGuo, Shenghui Guo, Jinhui Peng, Linqing Dai, Libo Zhang

This paper adopts a simple and novel preparation. Taking cellulose as a template, a tubular morphology structure of micro/nano ZnO crystals was obtained by microwave roasting at high temperature. The higher the microwave roasting temperature, the larger the degree of crystallization. The experiments indicate that the best photo catalytic effect can be obtained at 850 : At this temperature, the oxidation of cellulose is complete. Large quantities of hexagonal shaped ZnO crystal can be observed, specifically the (0001) crystal face. Under ultraviolet-visible irradiation, taking long arc mercury lamp as light source, the material had good photocatalytic activity. The decomposing efficiency of methylene blue reaches 97% in 60min, which is superior to that of preparations without templates at the same temperature.

Jan 1, 2016

By A. E. Isaacson

The U.S. Bureau of Mines is studying the effect of supercritical water, at 400' C and 3,500 psi, and subcritical water, at lower temperatures and pressures, on mixtures of minerals and metals to determine the possible applications of water at high temperature and pressure for processing these materials. This research was conducted using a flow-through bench-scale system. Copper-bearing minerals studied were chalcocite, chalcopyrite, covellite, and cuprite. In general, mixtures of copper minerals and pyrite reacted to form bornite. Intermediate phases formed were chalcopyrite and digenite. Similar reactions occurred between pyrite and metallic copper. A mixture of chalcopyrite and pyrite was inert in supercritical water'. The reaction between cuprite and metallic zinc yielded metallic copper. The cuprite was reduced by hydrogen generated by the reaction between metallic zinc and water. None of the reactions occurred exclusively in supercritical water, but also occurred in water at high temperature and pressure below the critical point. 'Experimental results did show that a dual-reaction process, consisting of solid-state diffusion and fluid transport, was occurring.

Jan 1, 1989

By Cledwyn Mangunda

Mining operations generate Acid Mine Drainage (AMD) that poses a significant threat to the natural environment. AMD treatment using Ca(OH)2 leads to the precipitation of a sludge dominated by a mixture of ferri-oxyhydroxides. This sludge has poor dewatering tendencies and is deposited in landfills with potential for metal remobilization. This study investigated the dewatering behaviour of a precipitate formed during elevated temperature treatment of a primary, pre-settled sludge from the neutralisation of aqueous acidic Fe2(SO4)3 and Ca(OH)2 solutions in an MSMPR reactor. The resulting treated precipitates were analysed for micro-properties, with results showing that an increase in the secondary reactor temperature from 25 °C up to 50 °C led to an increase in mean particle size, a decrease in the number of particles and improved dewatering behaviour at a ferric concentration of 300 mg/L. This was ascribed to the attainment of a circum-neutral surface charge that favoured agglomeration and a change in micro and nano-structure that allowed for better water passage.

By Byung-Su Kim

The recovery of elemental sulfur from sulfur dioxide has important implications for coal- burning power plants and nonferrous metal smelters. The thermodynamic analyses showed calcium sulfide to be suitable for recovering elemental sulfur from sulfur dioxide. At the temperatures of 1023 to 1153 K under the sulfur dioxide partial pressures of 5.0 - 60.1 kPa, elemental sulfur from sulfur dioxide was recovered by its reaction with calcium sulfide. The kinetics of this reaction were measured at the same conditions using a thermogravimetric analysis technique. This reaction scheme would be attractive if the coproduct calcium sulfate can be reduced to regenerate calcium sulfide. This is the topic of another paper. At 1073 K under the sulfur dioxide partial pressure of 25.8 kPa, 48 % of the original calcium sulfide was converted to calcium sulfate in an hour. Under the same conditions, 55 % of the regenerated calcium sulfide were converted to calcium sulfate in an hour even after third regeneration.

Jan 1, 1999

By R. Lanza, M. Hytros, N. Saka, I. Jureidini, J. H. Chun, D. Kim

"A novel method for delineating the solidification front in metal casting has been developed using the attenuation phenomenon of electromagnetic radiation (y-rays or x-rays) and computed tomography (CT). The densities of the liquid and solid phases that exist during metal casting may differ anywhere from 4 to 12 % depending on the metal. As in the medical imaging field, CT provides an excellent means of mapping this density variation in a solidifying casting into two-or three-dimensional images.In an effort to develop an industrial-scale sensor, laboratory-scale experiments have been conducted using a cobalt-60 (Co60) radioisotope and a sodium-iodide (Nal) scintillation detector. The CT image reconstruction was performed on a crucible containing pure tin in a two-phase state. Although the spatial resolution and data acquisition speed were not optimum, the CT images clearly differentiate the liquid and solid phases of the tin in the crucible. To maximize resolution and minimize data acquisition time, a linear accelerator (linac)-based CT sensor is being developed and tested for application in the continuous casting of steel and aluminum alloys.IntroductionIn all casting processes, the quality of a finished product and its production rate depend upon the shape and movement of the solidification front. From a quality perspective, it is well documented that solidification kinetics (heat and mass transfer, fluid flow, microstructure evolution) greatly influence the final properties of castings [l,2,3]. Product shortcomings, such as surface defects, cracks, macro-and microsegregation, and inclusions are directly controlled by the solidification process. By understanding the role the solidification front plays in the casting process, product quality may be dramatically increased through the reduction of defects."

Jan 1, 1997

By S. P. Vanka, B. G. Thomas, S. Sivaramakrishnan

"During the continuous casting of steel, transient 'flow events can be very important to the generation of quality problems, such as shear entrainment, surface level fluctuations and bubble entrainment. These phenomena can be better predicted using Large Eddy Simulation (LES) models than the K-E models, which have been extensively studied. In this work the turbulent transient flow in a water model of a continuous caster has been both simulated using LES models and measured using Particle Image Velocimetry (PIV). The results of PIV and LES have been compared to validate the LES model and also to enhance the understanding of the prominent transient features of the flow field. The flow near the top surface in PIV was found to contain periods of 5-1 Os when the velocities were three to four times their mean values, which is of importance to the shear entrainment of the liquid flux. In both simulation and PIV the upper roll structure is found to change chaotically from a single large recirculation structure to a set of distinct vortices. The inlet swirl in PIV is seen to persist more than halfway across the mold, causing a characteristic staircase velocity vector pattern when viewed in a plane parallel to the wide faces. The lower rolls in PIV are significantly asymmetric for very long periods of time (- I-hour) and go through a repeating sequence of features. One of these features involving a short circuit between the upward and downward flow in the lower roll is also seen in the simulation and is of significance to bubble entrapment.IntroductionThe turbulent flow through the nozzle and in the mold of the continuous caster has been studied extensively using computational Reynolds Averaged Navier Stokes (RANS) models of turbulent flow [1,2]. Defects, such as internal inclusion of liquid fl4x through surface shear, pencil pipe defects due to bubble entrapment, surface defects due to level fluctuations are caused by transient flow phenomena oc'curring in the mold. These phenomena can be better predicted using transient Large Eddy Simulation [3] or ""LES"" models."

Jan 1, 2000

By Junwei Han, Wenqing Qin, Dawei Wang, Fen Jiao, Wei Liu

The removal of iron impurity from zinc calcine was studied by magnetization roasting and magnetic separation. The effects of roasting temperature, magnetic intensity, ore grinding, and leaching pretreatment on iron grade and recovery were investigated. The results indicated that iron recovery increased with the increase of roasting temperature or magnetic intensity, while iron grade was always less than 22%, depending on the fact that the magnetite were not liberated completely. The good liberation was difficult to be achieved by ore grinding but was easier by acid leaching, since the magnetite grains were very fine. After the leaching pretreatment, the recovery of 76.31% with iron grade of 53.24% was obtained by one roughing and cleaning. The SEM/EDS analysis showed that a part of sphalerite, zinc ferrite and other gangues were mixed into the iron concentrate, while some of fine magnetite was reported to the tailing.

Jan 1, 2016

By Fumio Hashiuchi, Yushiro Hirai, Masatoshi Maeda, Toshihiro Nagata

"Increase in the copper smelting capacity at Saganoseki Smelter & Refinery was attained through various improvements in the PSconverters and the flash furnace. Two of the major innovations in the converting process were: a new operational technology which avoids increase in the copper content in the converter slag even when higher copper grade matte (65%) are treated in the slag making stage and a technology which shortens the operational interruption time which is caused by coolant charging. The latter was realized by introducing a new automated coolant charging system with which it was made possible to charge the coolant without stopping the blowing into the converter. These improvements brought about a remarkable increase in · the production capacity per converter and an annual production of 450,000 tons of copper without adding new furnaces was made possible. In addition, good results have been obtained of the tests with modified tuyeres to further increase the production.IntroductionIn a bid to renovate its Saganoseki Smelter & Refinery and to establish a leading production unit in terms of global competitiveness, Nippon Mining & Metals undertook major restructuring efforts since 1994. One of its themes was the shift from· a two-flash furnaces operation to a single-flash furnace operation. The shift was successfully completed in 1996 while maintaining the production at the same level (330,000 tons per annum of copper). Then, the productivity was enhanced to 450,000 mtpy without adding new furnaces through technological and operational improvements. It is now planned to increase the smelting capacity further to 470,000 mtpy this year.Some technological and operational improvements in the matte converting process and the new plan resulted from the tests with modified tuyeres are presented in this paper."

Jan 1, 2000