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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'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'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'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

By N. J. Themelis

In the last two decades, the Outokumpu flash smelting process has become the dominant new technology for copper smelting and has? also been applied to the smelting of other metal sulfides. The application of oxygen enrichment and improvements in concentrate burner and furnace design have resulted in ever increasing smelting rates per unit volume of the reaction shaft. This paper examines the. rate phenomena taking place in the reaction shaft of the Outokumpu furnace and compares information obtained from a mathematical model of heat and mass transfer rates to results obtained in pi1ot tests conducted at Pori, Finland, and to actual performance of a number of flash smelters around the world. 2?

Jan 1, 1985

By Jun Li

Rate processes of silver cyanidation were studied with the objective of understanding the reaction mechanism. The research was divided into three sections: anodic dissolution of silver in cyanide solutions, cathodic reduction of oxygen on silver surfaces and the direct leaching of silver in oxygenated cyanide solutions. The charge transfer steps plus the diffusion of reactants from bulk solutions to the silver surface were identified as rate-limiting and the rates of both anodic and cathodic reactions can be calculated using the Butler-Volmer equation and Fick's first law. Based on mixed potential theory and the results of electrochemical studies, a comparison of the rate obtained from direct leaching with that predicted from the calculation is made. Calculated results agree well with the experimental data.

Jan 1, 1992

By Miller, Geoffrey W.

The Ravensthorpe Nickel Project (RNP) flow sheet provides for the upgrading of Ni & Co in a size based beneficiation process prior to leaching. The upgrading effect on Ni and Co makes the beneticiation process a powerful addition to the flow sheet. Multiple linear regression (MLR) analysis based on 351 individual batch tests, 52 large scale composites and 21 pilot plant tests has been used to successfully model beneticiation product grade, recovery, upgrade and mass recovery. Statistically, 83% and 96% of the variability in nickel recovery and nickel product grade respectively was accounted for. Algorithms have been developed for Ni, Co, Mg, Al and Fe, which represents the revenue and operating cost factors for the process. The algorithms have subsequently been applied to the resource model, allowing prediction of elemental grade and recovery for the development of the mine schedules based upon these parameters and not head grades alone. This has allowed optimisation of the mine schedule for improvement to the project's NPV. Keywords: Ni Laterite, Prediction, Multiple Linear Regression, Beneficiation

Jan 1, 2004

By Alpagut Kara

Turkey is the fifth biggest ceramic tile exporter in the world. Considering the expectation that the Turkish tile sector continues to expand, further studies both on the improvement and the development of tile formulations are necessary in order to make the producers advantaged in the world market while maintaining the capital and running costs at reasonably competitive levels as well. In addition to such studies, waste management in tile manufacturing has also recently become an important issue. Accordingly, the industrial use of wastes in the traditional ceramic industry has been intensively investigated in the recent years. This work describes part of a detailed research project carried out jointly on the possible re-use of muds (raw production waste) from glazing and pressing lines of a local tile company in the development of new wall and floor tile formulations. In order to achieve this, the waste material was firstly investigated in function of chemical and mineralogical compositions. Then, the particular focus was given to the presence of the waste material in increasing amounts on the thermal behaviour and physico-mechanical properties of the re-formulated tile bodies. During the studies, SEM in combination with EDS, and thermal analysis techniques such as non-contact dilatometry were widely employed. The results indicated that it was possible to use the waste materials in the commercial tile production without deteriorating the relevant technological properties.

Jan 1, 2006

By Xiao Yang

Calcium oxide is one of the major fluxing agents used for steel refining. Because unreacted CaO remains in slag in most cases, discharged slag is difficult to be recycled smoothly. With the growth of environmental concerns, improving utilization efficiency of CaO is required to reduce the amount of discharged slag and energy consumption. The authors have reported a resource and energy-saving process by using multi-phase flux for dephosphorization. Reaction behavior of phosphorus in multi-phase CaO–FeOX–SiO2–P2O5 flux system was investigated. Formation mechanism of P2O5-rich phases was clarified at the interface between solid CaO or 2CaO, SiO2 and molten CaO–FeOx–SiO2–P2O5 slag. Phase relationship and thermodynamic properties of 2CaO, SiO2-3CaO, P2O5 solid solution were observed to confirm the condensation of P2O5 in solid phase. Based on these results, reduction of CaO consumption, discharged slag curtailment, and energy-saving effects in the novel refining process by using multi-phase flux were discussed.

By Xiaojie Gao, Jingshe Li, Chengsong Liu, Haiyan Tang

In order to clarify the reaction between MnO-SiO2 oxides with low FeO content and Fe-Mn-Si alloy, two diffusion couples were produced by the new method using confocal scanning laser microscopy (CSLM). The interface of the alloy and oxide, content of Mn and Si in the alloy near the interface, size distribution and composition of the particles which precipitated in the alloy were observed and analyzed using the electron probe microanalysis (EPMA). Results show that though the FeO content in the oxides decrease to 1% which is lower than the equilibrium with the molten steel at 1873K, the diffusion of oxygen from oxide to alloy still exists during the heat treatment at 1473K and causes shorter Particle Precipitated Zone (PPZ) and Manganese Depleted Zone (MDZ) normally for the reduction of diffusion flux of oxygen.

Jan 1, 2015

The kinetics of the oxidation of cyanide by manganese dioxide was studied using a rotation disc electrode system. The rate? of the half-cell reaction of cyanide oxidation is increased at higher hydroxide concentrations. An addition of copper up to 0.001 mole/l was found to enhance the diffusion current, especially at a high hydroxide concentration (0. 1M). A similar enhancement of the reaction rate is also achieved with nickel added at levels up to 0.01 mole/l. Manganese dioxide however requires a i:ow pH to achieve reasonable reduction rates. Leaching studies indicated that the initial reaction rate is strongly dependent on pH, initial concentration of cyanide. Using manganese dioxide cyanide could be oxidized at neutral pH's and ambient temperatures.

Jan 1, 1989