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By Michal Rzyman, Nakamura Takashi, Shibata Etsuro, Grabda Mariusz, Oleszek-Kudlak Sylwia

"Thermodynamic considerations indicate that heavy metal oxides should easily react with HBr, the main gaseous product from the thermal decomposition of tetrabromobisphenol A (TBBPA), forming low boiling point metallic bromides suitable for volatile separation. Mechanisms and kinetics of the bromination reactions must be well recognized prior to developing of a new treatment for the simultaneous recycling of plastic waste containing brominated flame retardants (BFRs) and metal oxides (printed circuit boards, automotive shredder residue, plating sludge, metallurgical dusts). In this work, a differential scanning calorimeter and laboratory-scale furnace were used to investigate the possibility and conditions of the bromination of ZnO by product of thermal decomposition of TBBPA. The formed solid, condensed and gaseous products were analyzed by X-ray diffraction analysis, electron probe microanalysis, inductively coupled plasma analysis, ion chromatography and gas chromatography coupled with mass spectrometry. Introduction Tetrabromobisphenol A (TBBPA) is the largest volume brominated flame retardant (BFR) in production today and is used in more than 70% of the world’s electronic and electric (E&E) appliances [1]. The growth in the production of E&E products and the fact they become obsolete so quickly cause significant problems in the safe disposal and recycling of the electrical and electric waste (E-waste) and other BFR-containing waste [2]. Among various treatment processes, thermal methods are most useful since they allow the recycling and recovery of both the organic and inorganic fractions of the waste. However, incineration of the BFR-containing wastes results in the emission of hazardous organobromine compounds, while the main portion of bromine released from decomposed BFRs is present in flue gas as hydrogen bromide (HBr) [3]. HBr, which is known to damage incineration systems, seems to be a very effective bromination agent for many metallic oxides present in waste. The concept of this study is to take advantage this of its property."

Jan 1, 2008

By Olga A. Gomon, Alexey N. Lozhko

The technology of heat treatment for metal frequently includes multiple fast heating and cooling of the products surface. If the product is heavy-weight or long-size, its moving from a zone of cooling to a zone of heating and return require a long time. Other important condition of ensuring qualitative surface at heat treatment is intensification of cooling phase. It is known that turbulization of a flow activates heat exchange and increases efficacy of cooling without increasing volume flow rate of water. Additional difficulty is to ensure the regularity of heating and cooling on length of a product. The technology of cyclic heat treatment of rolling products, at which mobile zone of turbulent heat exchange is formed on the surface of a product, was developed and realized. The submission of water occurs through to face spray systems. Each of the systems has six long-range atomizers, which are located circularly. Two flows of water move towards one another along a surface of a product. When they collide, the right zone of turbulent heat exchange creates heat transfer in this zone of 10-15 time more intensive than on other surface of a product. The effect of moving turbulent zone on length of a product is reached by changing the proportion of volume flow rate of water, which is created by face sprays. The speed of movement for turbulent zone along a surface of a product is chosen so, that the cooling takes place on a small depth only. Then after passing the turbulent zone over a determined site of a surface, its temperature recovers fast owing to hot internal layers. The parameters of process were determined by mathematical simulation of cooling in an installation. The equations for dynamics of movement of collision point of flows, which were received this way, are interesting supplementary products of research. The experiments show that frequency of movement of turbulent zone is an important technological parameter. It defines mechanical properties of a surface and should be chosen depending on a profile of product and metal grade. The results of comparison of mechanical properties of a surface of various rolling products, which were received by developed and conventional technologies, are described in this report. Dependence of regularity of mechanical properties on frequency of movement of turbulent zone is adduced.

Jan 1, 1998

By Nozomu Hasegawa

The phase diagrams and microstructures of the slags in the Mitsubishi Continuous Copper Smelting and Converting Process were studied for the prevention of the magnetite troubles such as accretion build-up on furnace hearths and launders, blockages at the melt outlet, slag viscosity increases and so on. According to the results of those studies, the silica and lime contents in the silicate slag at the smelting furnace, and the lime content in the lime-ferrite slag at the converting furnace were changed, resulting in lower and more consistent copper levels in the discard slag, with much less need for operators to clean melt outlets and launders. However, these changes may decrease the desirable amount of accretion-coating inside the furnaces and thereby reduce furnace campaign lives. Therefore, a method of estimating the magnetite level in the melts was developed, and slag compositions and temperatures have been controlled within the appropriate ranges to prolong furnace lives and also prevent magnetite troubles.

Jan 1, 2003

By Wei-ling Wang, Ryosuke O. Suzuki, Xiang-ning Meng, Miao-yong Zhu

"A finite-element thermal-stress model of continuous casting mold is conducted to predict deformation of copper plates and its change with different cooling structure. The results show that deformation behavior of copper plates is mainly governed by cooling structure and thermal- mechanical conditions, deformation amount is related to structure geometry, and a small deformation mutation occurs in cooper-nickel boundary due to different properties. The maximum deformation of hot surface centricities of wide face locate at 100 mm below meniscus and that of narrow face locate at meniscus and terminal of water slots and significant curvature fluctuations on both sides of copper-nickel boundary. The maximum deformation of centricities is increased up to 0.05 mm with thickness increment 5 mm of copper plates, and maximum deformations are only depressed 0.01 mm and 0.02 mm with increments of 1 mm nickel layer thickness and 2 mm water slot depth respectively.IntroductionIn conventional continuous casting of steel, a large amount of sensible and latent heat of molten steel dissipate in primary cooling zone and make continuous casting mold under enormous heating load giving rise to thermal stress, deformation, high-temperature fatigue and creep not only depress mold life-span, but reduce casting stability [1] Many studies focused more on heat transfer, solidification and shrinkage of solidifying shell to provide inverse proposals for optimizing cooling system and even designing new taper of mold [2,3], but it is generally useless to those of having been manufactured or being put into production. Therefore, mold-related forward problems show necessity to be discussed deeply, and stress and deformation distributions based on special thermal conditions in mold should be analyzed in order to explore suitable cooling structure of mold directly. Samarasekera et al. [4] examined heat flow and distortion of two-dimensional longitudinal sections and investigated effect of cooling water velocity, copper plates thickness and carbon content on formation of rhomboidity and longitudinal comer cracks. O'Connor et al. [5] developed a three-dimensional mathematical model to compute thermo-mechanical state in thin-slab mold and calculated temperature and deformation of mold wall to assess roles of various process parameters on impacting mold life. Thomas et al. [6] predicted temperature, distortion and residual stress in mold and indicated increased distortion requires increased remachining, which reduces mold life and increased residual stress increases the probability of a catastrophic crack failure. Park et al. [7l determined heat-flux profiles in funnel-shaped and parallel thin-slab molds based on an inverse heat conduction model and thermocouple temperature measured in-plant and put them into three- dimensional finite-element thermal-stress model to predict temperature, distortion and residual stress of mold wall. Korie et al. [SJ focused on prediction of temperature, distortion and residual stress in mold and in particular to clarify that mold life is significantly affected by temperature and its rigidity, but little effect by mechanical including clamping force, bolt prestress, friction and ferrostatic pressure. Meng et al. [9l predicted temperature and thermal stress in a slab mold and analyzed effect by cooling system geometry and casting speed quantitatively. In present study, a three-dimensional finite-element thermo-mechanical model with type-switched element is transformed from previous heat-transfer finite-element model [9l, and mold deformation is simulated in order to shed light on thermo-mechanical behavior with special thermal conditions and different mold geometry at high casting speed."

Jan 1, 2013

By Stanko Nikolic

Ferrous calcium silicate slags are potentially important for future practice in copper converting operations and processes and can be described by the ?Cu2O?-FeO-Fe2O3-CaO-SiO2 system. Despite its industrial importance the phase equilibria in this system have not been fully investigated. Characterization of this slag system is necessary to improve the design and optimization parameters of new processes, including fluxing and operating temperatures. Experimental methods have been developed to investigate the phase equilibria of these slags at copper saturation and without copper. This technique involved equilibration of samples at a fixed oxygen partial pressure, rapid quenching, and analysis of the compositions of phases using electron probe x-ray microanalysis (EPMA). Liquidus and solidus data are reported for the primary phase fields of spinel, wollastonite and tridymite at 1250oC and an oxygen partial pressure of 10-6atm. The resulting data has been used to construct liquidus isotherms in the ?FeO?-CaO-SiO2 system both in equilibrium with and without molten copper. The experimental results were compared with the predictions of a thermodynamic computer package utilizing a self consistent thermodynamic database. The predictions of the model were in good agreement with the experimental isotherms when projected onto the FeO-CaO-SiO2 section, however the copper concentrations in the liquid phase at copper saturation were lower than predicted using the current database of the model.

Jan 1, 2006

By Debbie Marshall

Process water is an important consideration in the development of a nickel laterite project. Depending on the location of the ore body, sufficient fresh water may not be available and it may be necessary to use seawater (or saline groundwater) for ore preparation. This introduces various species, which have major effects on materials of construction and leaching chemistry. This paper summarizes batch testwork completed at the Falconbridge Technology Center. The leaching behaviour of eleven different laterite ore samples were compared using seawater and fresh water. For brevity, six of the eleven samples are reported here-the other five samples showed similar results. Each ore type was leached under identical conditions in both freshwater and seawater and the leaching chemistry compared. The batch test results were confirmed in a continuous pilot plant, and leach kinetics for the two systems were compared. Keywords: high pressure acid leaching, laterites

Jan 1, 2004

By Dinesh Agrawal

Microwave energy has been in use for variety of applications for over 50 years. These applications include communication, food processing, wood drying, rubber vulcanization, medical therapy, polymers, etc. In the last two decades microwave heating has been also applied very effectively and efficiently to heat and sinter ceramic materials. Microwave heating is recognized for its various advantages, such as: time and energy saving, very rapid heating rates, considerably reduced processing cycle time and temperature, fine microstructures and improved mechanical properties, better product performance, etc. The most recent application of microwaves has been in the field of metallic materials for sintering, brazing/joining and melting. Several common steel compositions, pure metals and refractory metals have been sintered in microwaves to nearly full density with improved mechanical properties. Many commercial powder-metal components of various alloy compositions including iron and steel, copper, aluminum, nickel, Mo, Co, Ti, W, Sn, etc., and their alloys have also been sintered in microwaves producing better properties than their conventional counterparts by using a 2.45 GHz multimode microwave system. This work has been further extended to join and braze bulk metal pieces, especially super alloy based turbine blades. Further, in a specially designed microwave cavity, even the bulk metals can be made to couple with the microwave field and melted. The implications of these findings are obvious in the field of powder metal technology.

Jan 1, 2006

The entrainment of copper matte in the slag during the slag skimming stage of a Peirce-Smith converter was studied with a dam break model. Experiments were carried out with a range of fluid pairs where the lighter fluid was allowed to overflow a weir and the amount of entrained heavier fluid measured. The resulting entrainment is measured as the ratio of the heavy to light fluid withdrawn. The fluids include oil-water, water- glycerol and salt solutions-water pairs to cover a wide range of densities and viscosities. It was found that the Richardson number, Ri, correlates the entrainment well. For the case of the liquid-liquid interface initially at the same height as the weir, the entrainment was found to vary with Ri-1/3. The transient flow was simulated with a volume of fluid (VOF) code written in-house and used a stairstep approach to represent flow obstacles. The code was validated against the experimental results with good agreement for the variation of the heights of the two fluid with time. The simulation showed that the prevailing mechanism for entrainment is due to a pressure differential created across the liquid in the converter during pouring resulting in the heavier liquid being rotated upwards and over the weir.

Jan 1, 1999

By M. J. Collins

Pressure leaching of zinc sulphide concentrates has been practiced commercially for nearly two decades. The process, which includes direct leaching of concentrate with spent electrolyte in an autoclave, has been commercialized at four separate locations to date. In pilot studies carried out in the Dynatec lab in Fort Saskatchewan, dozens of additional zinc concentrates have been shown to be amenable to pressure leaching. This paper highlights recent improvements in zinc pressure leaching that have been identified through process development studies, and how the experience gained in these studies has been utilized in the development of a new copper pressure leach process.

Jan 1, 2000

By B. Balamurugan, D. J. Sellmyer, J. E. Shield, G. C. Hadjipanayis, Damien Le Ror, R. Skomski

"Rare-earth transition-metal (R-TM) alloys show superior permanent magnetic properties in the bulk, but the synthesis and application ofR-TM nanoparticles remains a challenge due to the requirement of high-temperature annealing above about 800 °C for alloy formation and subsequent crystalline ordering. Here we report a single-step method to produce highly ordered R-TM nanoparticles such as YCO5 and SmCO5, without high-temperature thermal annealing by employing a cluster-deposition system, and we investigate their structural and magnetic properties. Nanoparticles of size = 10 nm are monodispersed (s /d ~ 0.15) and have Hc values at T = 300 K of 8.0 and 4.5 kOe for YC05 and SmC05, respectively. Alignment of the easy axes is performed via a field applied to the clusters before deposition. These processing steps are highly desirable to create and assemble R-TM nanoparticle composites for future permanentmagnet applications.IntroductionMagnetic nanoparticles with high magnetocrystalline anisotropies (Ki > 1 MJ/m3) are required for permanent-magnet, recording-media, and other significant applications [1-3]. In this regard, bulk rare-earth transition metal alloys (R-TM) especially RC05 (R = Y and Sm) crystallized in the hexagonal CaCu5-type structure have shown a large Ki = 5 MJ/m3 (YC05) and 22 MJ/m3 (SmCo5) along with an appreciable saturation-magnetic polarization (Js, > 10 kG) and high curie temperatures (Tc > 1000 K) [2]. The challenges in controlling the size, sizedistribution, phase purity and crystalline ordering, however, limit the research on RCo5 nanoparticles [4,5]. The conventional arc-melting technique requires high-temperature annealing for alloy formation and subsequent crystalline ordering, which causes excess growth and thus results in nanocrystalline powders of particles sizes larger than 30 nm [6, 7]. Low-temperature wet-chemical techniques yield SmC05 nanoparticles of sizes smaller than 20 nm [5], but the control of phase purity is challenging due to the presence of surfactants and formation of other secondary phases [8]."

Jan 1, 2012

By Chikabumi Yamauchi, Masami Tashiro, Toshiharu Fujisawa, Hiroyuki Snano

"Rare earth metals usually contain large amount of oxygen because of their reactiveness, and therefore oxygen removal is one of the major problems on the purification of rare earth metals. In the present research work, halide flux treatment at high temperature under inert gas atmosphere was applied to the oxygen removal from neodymium. NdF3 was used as a halide flux. Deoxidation reaction and its mechanism were discussed based on the experimental results. Halide flux treatment is very effective for oxygen removal from rare earth metals.IntroductionSolid Sate Electrotransport (SSE) process has been successfully applied for the elimination of interstitial gaseous impurities from chemically active metals[l]-[5]. However, to achieve a higher effectiveness of the SSE process, it is required a very low initial impurity content in the metal. In case of rare earth metals, it is known that they usually contain large amount of oxygen that should be lowered as much as possible before applying the SSE process. In addition, if effective oxygen removal is achieved by simple process, it is significant also from the industrial viewpoint. In the present work, the application of a halide flux treatment is investigated to remove oxygen from neodymium by using NdF3 as a flux. At first, deoxidation reaction and its mechanism were discussed based on the phase diagram of the Nd-NdF3-Ndp3 quasi-ternary system. Based on the results, oxygen content in deoxidized neodymium was calculated theoretically and it was verified by deoxidation experiments."

Jan 1, 1998

By K. G. F. Janssens

In the process of annealing a deformed metal the microstructure changes due to concurrent recrystallization, grain growth and precipitation. It is common knowledge that all three of these microstructural transformations show a strong dependence on each other, and that an overall model must take the relevant interactions into account. Aiming at the development of an approach which is useful in the more general case, a computational model is being developed which allows the prediction of the three dimensional grain topology and orientation distribution function of any metal submitted to subsequent deformation and annealing, taking into account concurrent recrystallization, grain growth and precipitation and starting from a statistical representation of the deformed microstructure. In this contribution a case study is presented which illustrates the potential and limits of the state of the art in the field. Keywords: Microstructure Evolution Modeling, Irregular Cellular Automata, Deformation, Precipitation, Recrystallization, Grain Growth

Jan 1, 2003

By Munetaka Iwasaki

Nitrogen strongly affects mechanical properties of steel and therefore we may sometimes modify the various processes for its content. Numerous studies based on the results of chemical analysis of quenched samples were reported with a few exceptions of Hot Sievert method. The technique always poses a risk of uncertainty whether the true content of nitrogen in liquid metal is measured or not. In this study vacuum remelting under relatively low pressure was done to enhance gas phase mass transfer. Total pressure of the melt chamber was about 10-3 pa and electron beam heating was used. Mass spectroscopy was used for the direct observation of the rate of denitrization. Nitrogen molecules or atoms were detected by a mass spectrometer set above the melt. Continuous monitoring of the intensity of the fixed mass number may reflect the transfer of nitrogen from the melt to the vacuum. The results of the new and conventional techniques agree, both technique can be verified.

Jan 1, 1999

By S. Redik, C. Wenzl, D. Gregurek, A. Spanring

Zinc is a component of many input materials used in various pyrometallurgical processes, for example primary lead and zinc production from Pb/Zn ores and recycling processes dealing with zinc-containing residues (e.g., copper recycling, WAELZ process). Hence, zinc and its compounds are present in the respective metallurgical vessels and interact with the refractory lining. In the present work the zinc attack on the refractories out of various primary and secondary furnaces is briefly introduced and discussed. At the prevailing processing temperatures in the metallurgical vessels, zinc oxide is highly corrosive for the brick components. The knowledge of the wear behavior is based not only on a detailed chemical and mineralogical characterization carried out on provided post mortem samples, but also on FactSage calculations. This together with results obtained by practical testing in the RHI pilot plant represents an important prerequisite for product development and brick selection for the individual customer application.

Jan 1, 2016

By D. S. Barr

The Freeport McMoRan chlorination circuit is comprised of four related processes: ore chlorination, gas scrubbing, chlorine supply and excess hypochlorite removal ("hypo kill"). Each of these processes are described, and related to the pertinent mineralogic components in the carbonaceous ore feed to the plant. The chlorination system in use at Jerritt Canyon to passivate forms of preg-robbing organic carbon has proven to be a cost effective and efficient means to recover gold from low sulfide carbonaceous refractory ores, where gold may not be specifically associated with either the sulfides or the carbon.

Jan 1, 1987

By Dieter Offenthaler

Catalysts used in petroleum industry often contain valuable amounts of PGMs. The typical recycling route for those materials is the pyrometallurgical one, but this treatment way offers limited flexibility with respect to small charge weights. A new process, combining a pyrometallurgical pre-treatment step of the ceramic carriers with a hydrometallurgical leaching procedure overcomes this disadvantage. It not only allows the economical treatment of even very small charge weights, but also gives the possibility to maximize the PGM yield by individually adapting the process to the different charge materials. Due to an ingenious process design, where all leaching agents and effluents are recycled in a closed loop and therefore no waste waters leave the process, process operation becomes very economical. However, the temperature-time-regime in the pyrometallurgical pre-treatment step is of major importance for the success of the whole process. Therefore various investigations have been done to identify how the different process variables in the pyrometallurgical pre-treatment influence the subsequent leaching procedure. It turned out, that the adjustment of the correct phase-modification in the ceramic carrier materials during the pyrometallurgical treatment is the key factor of this process step. Although it is a troublesome issue to exactly adjust the correct phase modifications, it is the prerequisite to take advantage of the benefits of this new process concept.

Jan 1, 2006

By F. K. Letowski

Leaching in froth is a particular case of a three phase (liquid-solid-gaseous) process which combines flotation with leaching by using a reactive gaseous reagent as a flotation carrier and a leaching solution as the reactive liquid medium to fonn the foam (froth) in' which the solid particles are suspended. Some physico-chemical and engineering aspects of leaching in froth are discussed and illustrated by its application for cleaning the mineral graphite. Leaching of the graphite concentrate containing 4L4% of the elemental carbon and 3.16% of the sulphidic 'sulphur was canied out in the froth fonned by: (a) a concentrated chloride solution, with a small addition of nitric acid, in the foam state; (b) a mixture of gaseous O2, NO., and H20 encapsulated in the foam; and (c) notable particles of graphite suspended in the foam. The laboratory experiments werecanied out in a "flotation column"-type reactor ala temperature from 80 to !08°C and under total pressure of 100 to 200kPa. In the 3-stage leaching-flotation process, the non-flotable fraction of particles was separated three times from the notable fraction. The concentration of carbon and elemental sulphur in the final flotable fraction was 96% C and 0.38% S respectively. The expected advantages and possible application in hydrometallurgy are suggested.

Jan 1, 1995

By J. E. Klein

Bench scale tests using a stack of ten whole SAES St909 pellets, 6 grams, to crack methane have been completed with pure methane feed. Test conditions ranged from 600 to 800°C at 101 kPa (760 ton) with a methane feed rate of ten sccm. Methane reformation tests, test where hydrogen was passed through a St909 bed after cracking methane, were performed to determine if and how much methane can be generated under "reformation" conditions. Phase structure determinations of St909, composed of a ZrMnFe alloy with aluminum used as a pellet binder, after methane cracking were complicated by the number of materials that can be formed by the elements in the St909 and the carbon from methane cracking. It was determined that the aluminum not only alloys with the Zr, Mn, and Fe in the St909 alloy, but also forms aluminum transition metal carbides in addition to ZrC as the carbon content and the temperature of the St909 increases. Some A14C3 was also found in some pellets. Passing hydrogen over St909 pellets after methane cracking formed methane at various rates in the temperature range of 600 to 800°C. Temperatures of 800°C gave the best methane cracking performance and efficiencies decreased rapidly with temperature.

Jan 1, 2002

By Raj P. Singh

Lewatit TP207, a chelating resin with iminodiacetate functional group, is used for the purification of cobalt hexammine chloride solution for divalent cationic impurities (US Patent No. 5,154,757). The method is employed at commercial scale in OSRAM SYLVANIA Inc. cobalt chemical production since 1992. It is observed that after long use in the purification of cobalt hexammine chloride solution, a large number of resin beads tum black from their original beige color. The purpose of this paper was to characterize these black-colored resin beads for their ion exchange behavior. The resin sample used in this work was an exhausted production TP207 resin containing large number of black-colored beads. The results indicated that blackened resin beads can be regenerated to almost full capacity and' their ion exchange behavior for the purification of cobalt hexammine chloride solution was comparable to the new resin.

Jan 1, 2001

By Jr. Loper, M. H. Kim, H. H. Jo, C. S. Kang, T. S. Song

"An investigation has been conducted to describe the effect of grain refiner (e.g.,Ti) or modifier (e.g., Sr) on the microstructure of an Al-11.3wt%Si alloy produced by the Ohno horizontal continuous casting process using a heated mold so as to obtain directional solidification at high cooling rate of 300 to 2000°C/s. Experimental results demonstrated that the directionality of the primary a grain was promoted by the addition of0.2 to 0.4%Ti or by the addition of0.02%Sr, whereas the addition of0.6%Ti suppressed this directionality. Feathery a grains were promoted by the addition of 0.2%Ti, while these feathery a grains were suppressed when over 0.4%Ti (grain refinement) or when 0.02%Sr was added. The addition of Ti also resulted in increased coarsening of the eutectic Si in these Al-1 l.3wt%Si alloys.IntroductionThe mechanical properties of conventionally cast Al-Si alloys can be enhanced through judicious control of the casting parameters, by the addition of grain refiners (e.g., Ti) and by the addition of eutectic modifiers (e.g., Sr).[1-3] The Ohno continuous casting process[4-5] uses a heated mold (maintained at a temperature above the alloy liquidus temperature) to produce a casting with a mirror surface free of shrinkage defects. The process is especially suitable for the production of high quality and non-deformable rods of small diameter. This study was conducted at investigate the effects of Ti and Sr on the microstructure of Al-1 l .3wt%Si rods cast by the 01).no process."

Jan 1, 1998