Search Documents

By Gökhan Demirci, Ishak Karakaya

"Energy consumption in electrolytic magnesium cells is well above the theoretical values. However, the mechanism of the back reaction, the main cause of the current losses, has not been fully understood yet. Magnesium dissolution into the melt is generally regarded as the limiting step for the back reaction. Accordingly, present cell designs are made with priority given to fast magnesium removal from the cell. However, experimental data and modeling results in this study indicate that the limiting step for the back reaction between magnesium and chlorine is the chlorine dissolution into the electrolyte when physical contact between electrolysis products was eliminated. Effects of chlorine bubbles on the current efficiency and the cell potential were investigated. Results show that the extent of back reaction is proportional to the chlorine surface area in contact with the electrolyte per unit time, and the cell potential increases with the amount of chlorine bubbles inside the electrolyte.1. IntroductionMagnesium is less dense than the electrolyte in electrolytic magnesium production. Therefore, both electrode products, magnesium and the chlorine gas, move upwards inside the molten salt electrolyte during electrolysis. The upward motion of electrode products promotes the most important current loss mechanism, the ""back reaction"". Separation of the highly reactive species; liquid magnesium and the chlorine gas in the cell, to prevent their recombination is one of the main concerns in cell designs. The employment of large inter-electrode distance or a separation wall in early cell designs; decreased the extent of recombination, but increased the cell voltage and energy consumption. Recent cell designs, on the other hand, make use of lifting action of chlorine gas [1,2] by utilizing smaller inter electrode distances to separate the magnesium and chlorine gas faster. Although energy consumption was reduced, but more physical interactions between electrode products make electrolytic magnesium cells still highly inefficient when energy consumptions are compared with the theoretical values. Today, the most efficient industrial cells utilizing high purity feed operate at 10.5-11.5 kWh kg-1 Mg [3-5] and it is considerably higher than the theoretically attainable value of about 6.0 kWh kg-1 [6]. This large gap demonstrates the necessity of more research on physics and chemistry of magnesium cell electrolysis."

Jan 1, 2011

By Carlos G. Levi

"The principles involved in the rapid solidification of supercooled metal droplets and existing numerical models are reviewed. The limitations of these models for studying alloy solidification are discussed in terms of the effects of alloying elements on the relevant heat transfer, thermodynamic and kinetic parameters. Analysis of the enthalpy-temperature diagram reveals how the extent of rapid solidification is hindered by the addition of solute. A solidification model incorporating thermodynamic and kinetic relationships into a Newtonian heat transfer formulation is used to analyze the thermal history and concurrent solute redistribution during recalescence. IntroductionIt is well acknowledged that microstructural evolution during solidification is intimately associated with the thermal history of the liquid-solid interface. Structural parameters like chemical homogeneity, morphology and size scale of the phases can be related to the interfacial temperature and velocity. These in turn change by the interaction of the interface with the thermal and solutal fields in its neighboring environment.The thermal history of powder solidification can be conveniently described on the enthalpy-temperature diagram for a pure metal shown in Figure 1 and discussed in detail elsewhere [1). A system can conceivably follow any path of decreasing enthalpy in the supercooled region of Figure 1 (~ < 1), starting at the nucleation temperature (oN < 0) on the liquid line, and ending at some point on the solid line. A vertical path represents an isothermal transformation, of which a limiting case is solidification without significant barriers to nucleation and growth, with the interface at the equilibrium temperature TM (path one in Figure 1). A horizontal path represents isenthalpic (or adiabatic) solidification whereby the system could form an amount of solid proportional to the initial supercooling of the liquid without further heat loss to the environment. A liquid that can completely transform to solid under adiabatic conditions is said to be ""hypercooled""."

Jan 1, 1986

By Wenbin Liu

A novel route for rapid synthesis of ultrafine WC-Co cemented carbides with homogeneous binder phase distribution is reported. The composite powder is produced by in situ reduction-carbonization reactions by using WO2.9, Co3O4 and carbon black as raw powders. The reaction equilibrium and phase stability are studied by thermodynamic calculations. The WC-Co composite powder is condensed by spark plasma sintering (SPS) to obtain the cemented carbides bulk. The sintering temperature is lower than that in the conventional sintering methods by 1500C, while the sintering time is remarkably reduced by 3-5 times. The high performances of the hardness and the fracture toughness are obtained. The experimental results confirm that the present processing scheme of in situ reduction-carbonization reactions and subsequent SPS sintering is an efficient way to prepare WC-Co cemented carbides, and is apparently superior to the conventional long-period techniques of preparing composite powder and cemented carbides bulk.

Jan 1, 2008

By L. Y. Zhang

The current status of metal hydride alloys for NiMH batteries was systematically reviewed. Extensive application-oriented research and development has successfully made the NiMH battery an important part, with growing potential, among rechargeable batteries. The rare earth based metal hydrides (AB5) have been considered the best alloy material for use in the negative electrode in NiMH batteries. However, being in demand for high performance electronic markets, the still young NiMH industry is facing serious technical challenges in developing better products. Among all the efforts to respond to the challenges, advanced AF3, alloys are in great demand: the capacity enhancement race requires new or improved alloys possessing higher volumetric capacity; price competition mandates MH materials with low cost; high performance under severe service environments calls for alloys with high corrosion resistance when subjected to electrochemical cycling; and finally, high power service requires the negative electrode to deliver current at high rates.

Jan 1, 1997

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 Thenepalli Thriveni, Ch. Ramakrishna, Yujin Jegal, Ji Whan Ahn, Jyothi Rajesh Kumar

In alumina production or alumina refining, bauxite is converted to alumina (aluminium oxide) The rare-earth elements (REEs) are a group of 17 chemically similar metallic elements (15 lanthanides, including scandium and yttrium). Rare earth elements play a key role in many industrial applications, petroleum refining, clean energy, automobile, electronics, and defense applications. These rare earths are essential to the success of green technologies. China today controls more than 95 percent of the rare-earth supplies and nearly all rare-earth refining and after 2009 year rare earths crisis raises due to China’s export restrictions and growing internal demand for rare earth elements. The extraction of gallium and yttrium from Korean red mud (KC red mud) by selective acid leaching was explored. The recovery of gallium and yttrium from a leach solution of the Korean red mud using solvent extraction was studied. A number of extractants were investigated for the extraction of those mentioned two rare earth elements and also we proposed a flow sheet of rare earth elements respectively. The toxic heavy metals presented in KC red mud were removed by CO2 stabilization.

Jan 1, 2015

By D. A. R. Kay

Phase stability diagrams are used to predict the abilities of lanthanum and cerium oxides to desulfurize coal gasification products in the temperature range 800-1000 C. Results of desulfurization studies in laboratory fixed bed reactors illustrate the effects of i) sorbent preparation, ii) input gas quality and iii) temperature, on the desulfurization reaction. 2CeO(2-x)(s) + H2S(g) + (1-2x)H2 = Ce2O2S(s) + 2(1x)H2O(g) The results of desulfurization/oxidation regeneration cycles are also reported.

Jan 1, 1989

By J. M. Tourre

1995 have seen a continuation of a positive trend in the Rare Earth industry The availability of a greater diversity of Raw Material has brought additional flexibility to the Producers permitting better economics China remains the major raw material source; Chinese concentrate producers have increased capacity in 1995 (Baotou, Sichuan, etc) China&apos;s role in the Rare Earth industry will continue to evolve; the acquisition of a majority equity position by San Huan/CNNC will have a significant impact on both the Rare Earth and Magnet markets Chinese producers are increasing the quality of their products and realize their true values Chinese market, itself, is also changing as the internal needs for separated rare earth&apos;s grow Already already producer of Lamps, Loudspeakers, Magnets, and TV tubes, China is in an unique position where the potential of its internal market might be more promising than the prospects outside China 1995 has also seen the application market become more diverse and complex. There are new applications growing at a very strong pace (such as battery alloy), applications that are now penetrating their target markets with significantly increased growth rates (such as bonded NdFeB), and some applications that became more complex requiring much more sophisticated products (such as catalysis). Rare Earth producers have to spend significant ressources in order to monitor the market trends in order to predict the demand and then adjust their raw material mix. Even though there is a greater diversity of raw material available, there is still some Rare Earth elements that are in excess, while other are just in balance. As a consequence rare earth producers invest heavily in R&D in order to develop new applications for these excess elements.

Jan 1, 1997

By James D. Navratil

Although liquid membranes have several advantages over conventional liquid-liquid extraction, problems such as membrane instability remain. In order to solve these problems, we have combined an electrostatic field with the principle of liquid membranes and developed a novel reactor system for rare earth recovery. Our cylindrical reactor, filled with extractant and diluent, is divided by means of a perforated cylinder into an outer annular extraction cell and an inner stripping cell. Below the extraction and stripping cells are two settlers for the aqueous solutions. The design of the reactor permits the organic solution to flow freely through the special perforated cylinder and the added feed and strip solutions, outside and inside the perforation, respectively, to be completely separated.

Jan 1, 1990

By Tetsuya Uda

Our recent achievements of rare earth separation technique[1,2] and new process idea for rare earth magnet recycling[3] are reviewed, (1) Binary chloride mixtures of rare earths were separated by a new selective reduction-vacuum distillation process. According to our experimental results, apparent separation factors were 8.1 for the Pr-Nd chloride mixture and 570 for the Nd-Sm chloride mixture. These values are much higher than conventional solvent extraction methods. (2) A study of recycling process of magnet sludge was carried out. The rare earths in the neodymium magnet sludge were extracted by chlorination with FeCI2, An activated carbon was used as a de-oxidation reagent Metallic iron in the sludge was not chlorinated because the iron monochloride is not stable, The extracted rare earth chlorides were easily separated from Fe-alloy and the excess of FeCh by vacuum distillation, 96 % of neodymium and 94 % of dysprosium in the sludge were extraeted into chloride phase, By the vacuum distillation, a mixture of neodymium and dysprosium trichlorides of 99.2 % purity was recovered, On the other hand, the rare earth chlorides can be converted to the corresponding oxides by a pyrohydrolysis reaction accompanied by a formation of HCl gas, The HCI gas can chlorinate metallic iron to FeCh, Therefore, a new recycling process for rare earth magnet waste can be realized as a chlorine circulation type process. During the process, only carbon and water are consumed and there are no toxic pollutants, Moreover, the obtained rare earth oxide can be directly used as raw material in the conventional oxide electrolysis process,

Jan 1, 2003

By James D. Navratil

Advances in hydrometallurgy require the introduction of new separation and purification processes, but they can be complex, costly and energy intensive. Chromatographic processes have low energy requirements and possess very high separation efficiencies. However, they have not yet made the great industrial impact that might be expected from their benefits. The large-scale and difficult separation of rare earths would greatly benefit from an improved continuous chromatographic operational device. Truly continuous, multicomponent chromatographic separations may be achieved by means of the continuous annular chromatograph. Work has been Initiated at The University of New South Wales involving the improvement and development of such equipment for the separation and purification of rare earths.

Jan 1, 1990

By G. D. Sandrock

The science and technology of roan temperature rechargeable metal hydrides began about 1969 with the discoveries that the intermetallic Compounds LaNi5 and TiFe could be, conveniently hydrided and dehydrided at roan temperature and modest H2 pressures. Subsequently, this lead to the development of a broad family of REE-containing AB5 hydrides and numerous applications that make use of the extraordinary H2-absorption and reaction-heat properties of these materials. Some of the applications include H2 storage, compression and separation, as well as heat pumping, heat to mechanical energy conversion and electric energy storage. This paper briefly reviews the fundamental phenomenology of metal hydrides, the history of the use of REE&apos;s in rechargeable metal hydrides, the practical engineering properties of these materials and the applications that have evolved around them. The rechargeable nickel metal hydride battery, a new vial alternative to NiCd cells, stands at the forefront of the applications.

Jan 1, 1992

By Neil E. Ryan

Because of their chemical reactivity and affinity for oxygen, rare-earth elements are difficult to extract, and due to their close chemical similarity, it is an exacting task to separate one from the other. Nevertheless, these same characteristics can be used to benefit other metals by enhancing their resistance to high-temperture oxidation/corrosion and by inhibiting their corrosion in aqueous environments. This paper gives an overview of the use of rare-earths: [a] as alloy additions, [b] in coatings, and [c] when added to hostile environments, to retard rates of high- temperature oxidation and inhibit aqueous corrosion.

Jan 1, 1992

By Haydar Güneş

In this study, a hydrometallurgical process was evaluated for the recovery of Nd from a Nd-Fe-B magnet. Each leaching test was performed at the solid (weight) to liquid (volume) ratio of 1:50 and was mixed at 400 rpm at ambient temperature. The effects of 3 different acids (HCl, HNO3, and H2SO4) on the extraction of Nd were investigated and H2SO4 was found to be more effective than other acid solutions. Under the optimal conditions, pregnant leach solution was produced with H2SO4 for subsequent Nd precipitation testing. Each precipitation test was carried out using 100 mL of feed solution mixed at 600 rpm at 25°C. NaOH and H2C2O4 were used for Nd precipitation. The highest Nd was precipitated as Nd2(C2O4)3, 10H2O with C2H2O4 at 20 min.

By Itsuki Uehara, Hiroyuki T. Takeshita, Tetsuo Sakai, Nobuhiro Kuriyama, Hideaki Tanaka

"AB5 type hydrogen storage alloys (A: rare earths, B: transition metals) are extensively applied to a negative electrode of a nickel metal hydride (Ni-MH) rechargeable battery for portable electric equipments, electric vehicles, hybrid vehicles etc. Performance of a hydrogen storage alloy electrode is affected by various factors, microstructure and surface composition of the alloy and structure of the electrode as well as composition of the alloy. Control of those factors enables us to commercialize the Ni-MH battery in various field.IntroductionA Nickel-metal hydride (Ni-MH) battery has been extensively developed because of (1) good compatibility with a nickel cadmium (Ni-Cd) battery, (2) high energy density (1.5-2 times higher per unit volume than a Ni-Cd battery) and high dischargeability, and (3) low environmental pollution. The charge/ discharge reactions can be written as [l, 2,3]:(+) Ni(OH)2+OH- = NiOOH+H2O+e· (E=+0.490V NHE),(-) l/6LaNi5+H2O+e-· = 1/6LaNi5H6+OH- (E=-0.828V NHE),where E° is a standard potential of an electrode vs. normal hydrogen electrode (NHE). Because of the above advantages of a Ni-MH battery, the battery have been widely used as a power source of portable computers, cellular phones, electric vehicles (Toyota ""LAV4L EV"", Honda ""EV Plus"" etc.) etc. Some hybride vehicles (Toyota ""Prius"" and Honda ""INSIGHT"") and fuel cell vhehicles (Toyota ""FCEV"") are power-assisted by a high-power Ni-MH battery. In 1999, the production of Ni-MH batteries reached 870 million cells in Japan. Most of commercialized NiMH batteries are incorporated with rare-earth-based AB5-type hydrogen storage alloy as a negative_ electrode. The production of rare-earth-based alloy is estimated to be approximately 8000 tons.The battery performances of the Ni-MH battery, for example, capacity, durability (cycle life), dischargeability (kinetics) and selfdischarge, ate closely related to the metal hydride· (MH) electrode, especially, the hydrogen storage alloy in the electrode. Substitution of alloy components, heat treatment, and surface treatment in order to change surface and bulk structure of hydrogen storage alloys have been examined by us and many reseachers in order to improve the performances of MH electrodes. This paper is a review of our and their efforts to improve performances of MH electrodes."

Jan 1, 2000

By S. F. Cheng

Among the many extraordinary features of the rare earths are their magnetic and magnetoelastic properties. The rare earths, e.g. Tb, Dy, Nd, Sm, are known worldwide for their large magnetocrystalline anisotropy and magnetization, which has led to the importance of magnetic rare earths as vital ingredients of modem permanent magnets. In this paper, we focus on the strain dependence of these giant effects which gives rise to huge magnetostrictions, magnetomechanical couplings, and ?E effects. Magnetostrictions greater than 10-3 have been measured at temperatures as high as 500 K. At low temperatures magnetostrictions reaches -1%. ?E effects - 10. No other solid state material has matched these values. A proper balance of magnetic anisotropy and magnetostriction, plus a proper choice of crystal axes lead to alloys which can switch large quantities of energy between the internal (magnetic) and external (mechanical) states with the application of small triggering magnetic fields. In addition to the traditional use of these materials in transduction, they are particularly valuable for smart systems where reliability and robustness are needed such as active structure stiffening and active vibration control.

Jan 1, 1997

By D. E. Woolley

The rate of reduction of iron oxide from calcia-silica-alumina slag by carbon in liquid iron has been measured over the temperature range 1400-1600°C by monitoring the rate of carbon monoxide (CO) evolution. Slags containing ferric iron have been used in order to study the reduction of both ferric and ferrous cations. Results show that ferric iron is reduced before ferrous iron, so that the ferrous iron concentration increases initially. It is also shown that the rate constant, k, decreases at low reaction rates, or, equivalently, at low concentrations. The authors conclude that the reaction occurs in two periods. During the first period, ferric iron is reduced to ferrous iron. During the second period, ferrous iron is reduced to metallic iron, and the rate-limiting step during the second period is the mass transfer of ferrous cations in the slag phase to the slag-metal interface.

Jan 1, 1998

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 Renato G. Bautista

The chemistry of the separation of metals from each other and from the other undesirable components involve multiple simultaneous chemical reactions. In the case of leaching, the heterogeneous chemical reactions between the solid and the liquid phase may be limited to a few reactions. In the homogeneous liquid phase, the number of simultaneous chemical reactions could be double or triple that of the number of heterogeneous reactions:. The rate of dissolution becomes very dependent on the changing concentrations of the significant chemical species taking part in the multiple reactions in both the heterogenous and homogeneous phase. The rate expression developed for the process must take into account the mechanism of chemical reactions in order to best represent the actual process. This paper also examine the role of mass transfer with chemical reaction in the develpoment of the rate equations for dissolution, liquid-liquid extraction, membrane separation, precipitation, and electrodeposition.

Jan 1, 1996

By Renato G. Bautista

"The chemistry of the separation of metals from each other and from the other undesirable components involve multiple simultaneous chemical reactions. In the case of leaching, the heterogeneous chemical reactions between the solid and the liquid phase may be limited to a few reactions. In the homogeneous liquid phase, the number of simultaneous chemical reactions could be double or triple that of the number of heterogeneous reactions. The rate of dissolution becomes very dependent on the changing concentrations of the significant chemical species taking part in the multiple reactions in both the heterogenous and homogeneous phase. The rate expression developed for the process must take into account the mechanism of chemical reactions in order to best represent the actual process. This paper also examine the role of mass transfer with chemical reaction in the develpoment of the rate equations for dissolution, liquid-liquid extraction, membrane separation, precipitation, and electrodeposition.IntroductionThe understanding and the elucidation of the mechanism of the rate phenomena for a specific chemical reaction system is of prime importance in the development of a successful chemical process. The development of successful emerging technologies for metals separation will depend on the accurate interpretation of the intrinsic chemical reaction kinetics and the rate of mass transfer of the desired metal species during its separation from the undesirable chemical species. This is the case whether the process application is for separation, concentration, and /or purification.The chemical processes that will be examined in this presentation will include leaching, solvent extraction, membrane separation, precipitation, and electrodeposition."

Jan 1, 1996