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By Xu Zhang, Xuewei Lv, Guibao Qiu

Slag foaming phenomenon is of vital importance to the mass and energy transfer in metallurgical processes. A considerable extensively studies carried out via out-gas in the past cannot simulate well the foaming phenomenon formed in the blast furnace where high TiO2 iron ore is used. A gas reaction was designed in the water-glycerol system to simulate the inner-gas system. This study investigated the influences of solution viscosity, particle concentration and particle size on foaming caused by endogenetic gas. The results show that the foaming height decreases with the increase of solution viscosity, which means reduced foaming ability, more difficult foaming elimination process and prolonged time for natural defoaming. With increasing the solid particle content, the foam height presents a trend which increases firstly and then decreases. Under a certain solid particle content, foaming height decreases with the increase of solid particle size, indicating a weak foaming ability.

Jan 1, 2015

By Frederick T. Wallenberger

"Laser assisted chemical vapor deposition (LCVD) is a new containerless fiber process whereby growth of small diameter fibers or microstructures (microsprings, microsolenoids) occurs directly from the vapor phase. The laser beam has a focal point adjusted to coincide with the tip of the growing fiber inside the reaction chamber. Since the growing fiber is not in contact with reactor walls or foreign materials, it is chemically pure, and suitable for optical uses and uses requiring high structural uniformity. Continuous fibers and multifilament yams are possible. The use -of high reaction chamber pressures (1-10 bar) and a small wavelength Nd-YAG laser made it possible to fabricate small diameter fibers at growth rates >1 mm/s. This paper describes the synthesis of single crystal, polycrystalline and amorphous fibers by LCVD, and provides a comprehensive analysis of phase transformations occurring during their fabrication.IntroductionLaser assisted chemical vapor deposition (LCVD) is a new containerless fiber process [1-10] whereby growth of small diameter fibers or microstructures occurs directly from the vapor phase. The laser beam has a focal point adjusted to coincide with the tip of the growing fiber in the reaction chamber (Figure 1). The diameter of the growing fiber corresponds to that of the laser focus. Depending primarily on the laser energy (Le., the temperature at the growing fiber tip), it is possible to obtain single crystal, poly crystalline or amorphous fibers by this method.Since the growing fiber is not in contact with reactor walls or foreign materials, it is chemically pure, and suitable for optical uses and uses requiring high structural uniformity. Laser assisted CVD is a potentially continuous process; continuous fibers and multifilament yams are possible."

Jan 1, 1994

By cheng Peng-fei, TANG Hai-yan, guo Xiao-chen, LI Jing-she, Liang Yong-cang, Zhao Baojun

The origin and evolution of non-metallic inclusions for Al-killed casing steel during EAF-LFVD- CC process were studied by industrial tracer experiments. The formations of Al2O3 and MgO·Al2O3 micro- and macro-inclusions from ladle slag were analyzed by theoretical calculations. The results show that micro-inclusions were formed during deoxidation and temperature decreasing in the process of casting, most of the macro-inclusions come from entrapped ladle and mold slags. In addition, most of the Al2O3 formed were modified into 12CaO·7Al2O3 and 3CaO·Al2O3 inclusions which are liquid at steelmaking temperature. MnS cannot be fully modified to CaS and it was only wrapped outside the alumina or calcium aluminate in the form of (Ca,Mn)S with the amount of Ca-Si wire fed during the test.

Jan 1, 2016

By Bin Zhu, Mingmei Zhu, Hong Zhou, Xiaofei Dou, Bin Xie, Yu Wang, Tiancheng Lin

In this study, the formation of 2CaO·SiO2 and 3CaO·P2O5 solid solution (nC2S-C3P) in hot metal dephosphorization process is discussed. The variations of CaO and SiO2 mass, both in nC2S-C3P solid solution phase and liquid slag phase with increasing P2O5 mass in CaO-SiO2-FetO-P2O5 slags were calculated using Factsage software. CaO-SiO2-FeOt-P2O5 slag containing up to 18 % P2O5 was melted at 1823 K then cooled to 1673 K. The contents of CaO and SiO2 both in the solid solution phase and liquid slag phase of quenched samples were observed and analyzed by SEM/EDS. Both the calculated and experimental results show that the contents of CaO and SiO2 in the solid solution phase decreased, just opposite in the liquid slag phase, with increasing P2O5 content in the slags. Formation mechanism of nC2S-C3P solid solution in the slags was derived based on the ionic structure theory of molten slag. The SiO4 4- in the nC2S-C3P solid solution can be replaced by PO4 3- in the liquid phase resulting in the increasing of free Ca2+ and SiO4 4- in liquid phase.

Jan 1, 2015

By M. R. Barkhudarov

Semi-solid metal can be formed into useful products of near net shape and high quality. Use of this method has been limited, however, because of the difficulty of working with metal in the semi-solid state, which has strong shear rate, temperature and time-dependent properties. In this paper we describe a thixotropic model and apply it to the problem of small metal droplets impacting on a flat plate.

Jan 1, 1997

By Dao-Wu Yang, Ju-Lan Zeng, Li-Xian Sun, Yan Yao

"The hydration heat of the pure cement, the fly ash single-dopped cement, as well as the fly ash and fluorgypsum co-dopped cement were investigated by means of micro-calorimety with an eight-channel micro-calorimeter (TAM Air). The results showed that the hydration heat and the hydration rate could be reduced significantly by fly ash and fluorgypsum. However, the reduction was not proportional to the loading of dopant. The exothermic peak of the fly ash and fluorgypsum co-doped cement was appeared earlier than the fly ash single-doped cement. As the temperature decreased, the hydration heat and the hydration rate of the doped cement were reduced, and the exothermic peak appeared later. The effects of fly ash and fluorgypsum on the compressive strength of cement were also investigated. The results revealed that the early compressive strength of concrete made up of the co-doped cement was largely higher than that of the fly ash single-doped cement. Based on the experiment results obtained in this paper, we could conclude that fluorgypsum is a suitable additive for fly ash-doped cement.IntroductionFly ash and fluorgypsum are industrial waste. In 2008, nearly 400 million tons of fly ash has been produced by coal-burning power plants in China. And it is estimated that this number would exceed 500 million at the year of 2015. Besides, every year the fluoride salt factories in China discharge more than 100 million tons of fluorgypsum. Tremendous of fly ash and fluorgypsum occupy considerable land and contaminate air and water sources [1]. As a result, comprehensive utilization of this two industrial waste has draw great attention from all over the world.Cement is the most-used construction material on earth. But the production of cement consumes huge energy and destroys the environment. This problem might can be partly solved by applying fly ash and fluorgypsum as additive for cement [2-4]. During the last decade, some papers that focused on applying fly ash and fluorgypsum as additive for cement have been published [5, 6]. However, to the best of our knowledge, none of these papers investigated the hydration heat of the fly ash and fluorgypsum co-doped cement.The hydration of cement is an exothermic reaction, which can result in serious problem for mass concrete: The interior of the concrete could reach very high temperature as the hydration proceeded [7-9]. As a result, the great temperature difference between the interior and the outer of the concrete would exist and cause serious thermal stresses. Thus, the concrete would be destroyed by the cracks which in tum are resulted from the thermal stresses [10, 11]. The heat released by the cement hydration and the hydration rate is commonly regulated by adding mixed materials or transferring additive such as fly ash and fluorgypsum [12-14]."

Jan 1, 2011

By G. G. Richards

"The slag fuming process has operated for close to 70 years to recover zinc from lead blast furnace slag. The process is normally carried out through the batch treatment of slag by submerged injection of coal and air. Within the bath the coal acts as both a reductant, to reduce Zno to zinc vapour, and a fuel, to maintain bath temperature during the endothermic reduction process. The partition of coal between the slag, combustion and bypass is dependent on factors such as bath depth and injection pressure. The option of continuous fuming has been pursued at the D. Blagoev smelter in Bulgaria using heavy fuel oil as reductant/fuel. There has, however, been little attempt at commercial continuous fuming with coal. This paper presents an analysis of a coal-based continuous slag fuming furnace. The data on the Plovdiv fumer is used as a reference point. Critical design criteria for continuous fuming include the slag feed rate, degree of coal combustion and furnace size. Mathematical modelling analysis suggests that continuous fuming with coal can achieve respectable zinc/coal ratios.IntroductionThe slag fuming process was developed in the early part of this century to recover zinc from non-ferrous smelting slags [1-3]. The majority of installed furnaces were put in place to fume zinc from lead blast furnace slag on a batch basis. In most cases coal is used to effect reduction of zinc oxide, but one furnace uses natural gas [4] and, in a curious twist, a continuous fumer was developed based on fuel oil [5].Given the general nature of blast furnace lead smelting, it is not surprising that slag fuming has remained a batch process, in spite of the advantages that could be gained by moving to continuous fuming. Blast furnaces are usually operated as relatively independent units, and tapping has traditionally been done into ladles. The presence of a crane aisle makes direct coupling of the blast furnace to a slag fumer difficult, especially in a retrofit situation. Furthermore, steady-state blast furnace operation is not easy to achieve. The size of these furnaces and the nature of their feed make it difficult to guarantee constant operation."

Jan 1, 1996

By Torn H. Okabe

A fundamental study was conducted with the purpose of establishing an environmentally sound recovery process for recycling of valuable metals, by combining scraps containing such metals. As an example, direct extraction and recovery of neodymium (Nd) in magnet scraps was investigated by utilizing liquid metal as an extraction medium. It was found that liquid magnesium (Mg) is a suitable extraction medium and can extract Nd from iron alloys with high efficiency at around I 100 K. The newly developed extraction apparatus for Nd is a mechanically simple and static device without moving parts, where the Mg extraction medium circulates due to differences in the temperature inside the reaction vessel. This developed device can simultaneously accomplish continuous extraction of metal Nd from scraps, re-extraction of Mg from Mg-Nd alloy and the eventual recovery of pure Mg. As a result, metal Nd with 98 % purity was directly recovered from magnet scraps under certain conditions. It was also shown that the extraction agent Mg could be reused. The results of this investigation show the possibility of establishing a new process for the direct extraction of Nd in pure metal form without oxidization.

Jan 1, 2003

By Arpad E. Torma

The identification and characterization of lithographic iron and sulfur oxidizing bacteria in the 1940' s. opened up new possibilities and challenges for the mining and metallurgical industries. These were exploited during the 1950's and' 1960's, when it was demonstrated' that mining wastes and complex unused mineral resources could be economically treated by bacterially assisted heap and dump leaching processes?. During the 1970's this technology grew into a more structured discipline called "biohydrometallurgy". In the l980's efforts were devoted to the identification of a variety of organisms involved in naturally occurring leaching processes. Further efforts dealt with the elucidation, of leaching mechanisms; the leach ability of nickel, coban, zinc, and precious metals; the desulfurization of coal; and diverse biosorpion phenomena. The application of genetic engineering techniques for the improvement of microbial performance was also initiated?. Current trends in biohydrometallurgy include improvement of many of the techniques noted above, as well as application of leaching. technolog.ies to. environmental remediation scenarios. These activities afford considerable opportunities for research in the 1990's. For example, bioremectiation of abandoned mining and processing sites requires development of new and economically viable technologies capable of removing low concentrations of toxic metals from high volumes of solid and/or liquid wastes.

Jan 1, 1991

By Yousef Mohassab, Manoranjan Misra, Monalisa Panda, Eman Wahbah

This work studies the removal of arsenic (V), arsenate, and arsenic (III), arsenite, from aqueous solution using calcined Quintinite-3T. The two adsorbents Quintinite-3T was prepared, calcined at different temperatures, and characterized by XRD, BET, and SEM. The surface area of the calcined Quintinite-3T was 193.4 m2/g. The particles size ranged from 12 to 56 nm for the uncalcined Quintinite-3T and from 24 to 42 nm for the calcined Quintinite-3T. Kinetic analysis, adsorption isotherm, and factors affecting the adsorption were investigated. Calcined Quintinite- 3T retained As(v) and did not release it back to water even after an entire month.

Jan 1, 2016

By Srinath Viswanathan, Adrian Sabau

"In general, the occurrence of microporosity during metal casting is due to the combined effects of solidification shrinkage and gas precipitation. The governing equations for fluid flow and hydrogen evolution indicate that porosity formation and fluid flow are strongly coupled. However, in most studies on microporosity, it is considered that the porosity formation does not influence the fluid flow in the mushy zone. In this study, a computational methodology is presented for the numerical simulation of interdendritic fluid flow and microporosity evolution. The solution algorithm presented includes a fully coupled, implicit treatment of microporosity and local pressure in the mushy zone. The effects of microporosity evolution due to the local pressure drop in the mushy zone, and pore expansion in casting regions where liquid feeding alone cannot compensate for the solidification shrinkage are also considered. It is shown that neglecting the effect of porosity formation on the pressure in the mushy zone yields higher pressure drops. By its growth, microporosity partially compensates for the solidification shrinkage, reducing the feeding demand. A reduced feeding demand requires less fluid flow to compensate for solidification shrinkage, and results in smaller pressure drops in the mushy zone. Therefore, in order to accurately describe casting defects, comprehensive models of fluid flow, heat transfer, and solidification must include the effect of microporosity as well.IntroductionIn the terminology commonly used by foundrymen, porosity is usually considered to be either ""hydrogen"" or ""shrinkage"" porosity. Hydrogen porosity is the term given to porosity that is generally rounded, isolated, and well distributed. Porosity that is interconnected or clustered, and of an irregular shape corresponding to the shape of the interdendritic region, is usually termed shrinkage. In general, the occurrence of microporosity in aluminum alloys is due to the combined effects of solidification shrinkage and gas precipitation [1]. Continuum models [1, 2- 7] have been used to predict the level of porosity in castings. A number of other studies have also attempted to understand the phenomena of porosity formation and pore growth [8-10] and pore morphology [11].The governing equations for fluid flow and hydrogen evolution indicate that porosity formation and fluid flow are strongly coupled. However, in most studies [4, 9, 10], it is considered that the porosity formation does not influence the fluid flow in the mushy zone. Kubo and Pehlke [3] presented a methodology for the prediction of microporosity distribution in shaped castings by considering the effects of both the hydrogen precipitation during solidification and the pressure drop in the mushy zone. In their approach, the local pressure and porosity were computed in an uncoupled manner based on a ""flux of interdendritic liquid"" criterion, i.e., either pressure or porosity was first computed using the other variable at the previous time step. Their approach has been used with little change in numerous studies [6, 12, 13]. Recently, Kuznetsov and Vafai [14] presented a fully coupled, one-dimensional model for the computation of pressure and porosity. They showed that neglecting the effect of porosity formation on the pressure in the mushy zone yields higher pressure drops and an over-prediction of final porosity. They also showed that the influence of porosity formation on the pressure is larger at lower pressures in the mushy zone."

Jan 1, 2001

By Jafar Safarian, Merete Tangstad, Leiv Kolbeinsen

"Silicon and its binary alloys have several applications in metallurgical, chemical, photovoltaic and semiconductor industries. Silicon goes to its liquid state within its production, refining and when it is alloyed with other elements. Therefore, the characterization of silicon melts thermodynamics is important and useful. The liquidus and activities in several silicon binary systems have been recently calculated by the application of two liquidus constants, which were established using the experimentally determined liquidus data. In the present study, the thermodynamic properties of six silicon binary melts, which are simple eutectics, are calculated by analytical approaches. In this case, the changes in the partial and integral Gibbs free energies and enthalpies of mixing are calculated and compared with the experimental data in literature. The enthalpies are calculated by two methods and the calculation results are compared to the data from the literature. It is shown that thermodynamic properties of silicon binary melts can be accurately predicted without the use of complicated thermodynamic software.IntroductionSilicon and its alloys have several industrial applications. Silicon is used for making aluminium-silicon alloys to produce cast parts, mainly for automotive industry. Silicon in the form of ferro-silicon is used to deoxidize and alloy steel and cast iron. The photovoltaic (PV) industry has had a rapid growth in the recent years and silicon is the dominant material used for the fabrication of solar cells. Silicon is primarily produced through carbothermic reduction of quartz in electric arc furnaces and the produced metallurgical grade silicon (MG-Si) contains around 1 wt% impurities. It is further refined to produce solar grade silicon (SoG-Si) with above 99.9999 wt% Si to fulfil the chemical requirement for PV application. Since molten silicon is processed all along the metallurgical route, obtaining fundamental thermodynamics knowledge about silicon melts is valuable for the related industries."

Jan 1, 2012

By H. V. R. von Rhaden

Systematic quantitative X-ray diffraction analyses performed on diamond-drill cores originating from the Aandenk formation at the Loraine Gold Mine, located in the Welkom goldfield, Orange Free State, South Africa, have revealed the presence of a number of phyllosilicate mineral assemblages which have not hitherto been reported from this region. Rectorite, a regularly interstratified 1:1 mica-montmorillonite "swelling clay", is found to occur together with paragonite, muscovite, pyrophyllite, kaolinite, and chlorite in highly-altered friable rocks. The presence of rectorite in mill feeds may have potentially serious implications with respect to gold recovery. Quantitative X-ray diffraction analysis for phyllosilicates can be used as an aid to correlation, and also to guide the widths of stopes in underground mining. Rectorite has a unique mode of origin, which is discussed.

Jan 1, 1991

By D. E. Larson

The U. S. Bureau of Mines has developed a image analysis methodology to correlate the energy consumed during the grinding of an ore to the mineral liberation achieved. Energy consumption values are obtained using a laboratory-scale ball mill equipped with a torque sensor, and an automated image analyzer is used to determine the liberation present in ground products. By combining liberation information with energy consumption data an appraisal can be made of the energy required to liberate the mineral(s) of interest. Results of tests performed on a complex sulfide material determined the effects of grind duration on the liberation achieved and the energy efficiency.

Jan 1, 1995

By Masatoshi Ogasawara

Saganoseki smelter & refinery operated two flash smelting furnaces, producing a combined 330,000 metric tons per year (hereinafter mtpy) of copper. In 1996, however, it successfully shifted to a single furnace operation while maintaining production at the same level. Since then, the production capacity has been further increased to the present 470,000 mtpy by technological improvements. Also, in order to reduce the converter load which represents a bottleneck in efforts to increase production, the matte grade was gradually increased and currently runs at 65 to 66% attaining the low copper content in the slag (hereinafter slag loss) of 0.7 to 0.8%. This paper introduces some improvements, recent operation results and thermodynamic analyses.

Jan 1, 2003

By Zhengjie Chen, Wenhui Ma, Jijun Wu, Kuixian Wei

The gasification reactivity of PC (petroleum coke), strengthened by addition of different potassium carbonate proportions using different grinding medium, was investigated by using thermogravimetric analysis (TGA). Results showed that the gasification reactivity of PC not only increased with the increase of catalyst-loaded, but also showed the effective improvement by anhydrous alcohol. The PC was mixed with potassium carbonate [K2CO3] catalyst at 0.5%, 0.8%, 1.0% and 1.5%, and then ground wet with distilled water. The CO2-gasification rate of PC was only 77.35%, 80.55%, 84.07% and 85.88% under the gasification temperature 1100 °C and holding time 120 min, at different K2CO3 respectively. However, when the PC was ground in anhydrous alcohol at the same condition of catalyst-loading, the gasification rate of PC reached 95.43%, 96.63%, 95.50% and 95.61% at the holding time of 108 min, 101 min, 74 min and 35 min, respectively. It was shown by FTIR, SEM and EDX determinations that the anhydrous alcohol used as the grinding medium can further improve the gasification reactivity of PC when compared with the distilled water.

Jan 1, 2016

By Marcelo Mourao, Adolfo Pillihuaman, Alberto Nogueira, Cyro Takano

"The self-reduction is an alternative and promising process for production of pig iron because offers decisive benefits such as enhancing the reaction kinetic with decrease in fuel consumption and C02 emissions. The self-reduction mixture of iron ore fines, carbonaceous reducer and additives for slag forming components, without agglomeration, was tested in a laboratory rotary kiln. The additives for slag were defined for presenting two different estimated liquidus temperatures (1623 Kand 1773 K) to verify the effect of these temperatures on the iron-carbon nuggets coalescence process. These mixtures were tested at 1673 and 1773 Kin an experimental rotary kiln. After reduction-melting and coalescence processes the samples were disaggregated and the iron nuggets were classified by size. It was considered that nuggets larger than 7,93mm would be a good reference for coalescence index. Low liquidus temperature slag presented 37% of this larger fraction against only 13.5% for high liquidus temperature one. The low liquidus temperature slag would facilitate contact between the particles of iron-carbon in a rotary kiln, enhancing the coalescence.IntroductionThe slag composition usually depends on the reducer ash composition, the ore gangue, the binder composition and any fluxing material [l], and the mechanism of carbon transportation in slag that contains iron oxide reducible by carbon can be explained by the oxide reduction and the metal carburization. During carbon transportation, the carburized particle is transported to slag-metal interphases by the gravity effect, being assimilated by the metallic phase [2]. When the slag's iron oxide comes in contact with the solid carbon, it is immediately reduced, forming Fe particles and CO bubbles as it is shown in the figure l(a). The Fe particles are carburized by carbon particles; they are liquefied simultaneously in the carbon-slag interphase. The Fe-C liquid particles are transported from the slag-carbon interphase to iron-slag interphase as a result of slag flow, based on the surface tension difference (Marangoni effect), figure l(b). The Fe-C liquid particles coalesce on the iron surface and the carbon is immediately diffused in the iron as it is shown in figure l(c). The reduced iron is carburized continuously by repeated sequences [3]."

Jan 1, 2013

By J. R. Parga

A shortage of landfill space and growing environmental concerns in Mexico are renewing interest in the recyclability of scrap from automobiles. This work describes a pyroumetallurgical process for the recovery of metallic lead from waste lead paste. Argentopyrite concentrate is commingled with lead paste residue and smelted in a fuming process thereby transferring the precious metals into lead bullion. The process consists of smelting lead paste and argentopyrite, sodium carbonate, and metallic iron at smelting temperatures of about 1100 T. The reaction products are slag and molten lead bullion enriched with precious metals. A major feature of this process is the removal of precious metals from the bullion by means of zinc, whereby a silver-zinc intermetallic compound is formed and floats out of the lead. The recoveries of precious metals are about 98%.

Jan 1, 1996

By K. Adham

"Fluidized beds are utilized in a wide range of high-temperature applications throughout the metals and materials industry. Their main advantage is the fast and uniform heat and mass transfer between the hot combustion gases and the particulate solid feed. A further benefit can be the lowering of the processing plant's energy consumption, through heat recovery from the fluid bed processes used for solids heating. Here, the enhanced energy efficiency of fluidized systems is investigated and the modeling results are discussed for three configurations: the flash tube, the single bubbling bed and the multi-stage fluid bed. Key thermal design aspects of each system are identified based on results from process simulations, in order to benchmark their main operating features and overall energy efficiency. Suitability and applicability of each configuration is also discussed based on a number of process and material property considerations.IntroductionCombustion based heating of particulate solids is commonly done using three different types of fluidized beds. The flash tube (FT) is similar to a hot pneumatic transport system. The single-stage fluidized bed (FB) typically uses in-bed combustion. The multi-stage fluidized bed (MSFB) can have two or more stages stacked into a tower.Flash tube (FT) suspends the incoming solid charge in a high-velocity stream of hot combustion gases. To maintain the solids suspension in the FT, two parameters are required: high velocity for elutriation of the particles and adequate solid-to-gas ratio for avoiding high pressure drops and solids drop-out [l].The fluid bed (FB) works at much lower velocities than the flash tube. Therefore, most of the solids are not conveyed in the gas stream, but are only suspended in a liquid-like manner. At minimum fluidization velocity (Umr), the gas flow exerts just enough force on the solids to keep them suspended in place [2].Multi-stage fluid bed (MSFB) heats up the solids as they are transferred from an upper bed level to a lower one, counter-current to the rising flow of hot gases generated at the lowest stage. As the temperature and volumetric flow of the gases decrease from bottom to the top stage, smaller bed diameters can be used in the energy recovery stages [3]."

Jan 1, 2014

By W. W. Albrecht

I. Introduction Refractory metals like tungsten, molybdenum, rhenium, tantalum and niobium and their compounds are essential ingredients of our modern technology. Especially in purified form, they are used in special alloys, electronics, optics and ceramics. The processing route from raw material to high purity refractory metals and their compounds includes, as a prime option, the following steps: - dissolution of raw materials. - liquid liquid extraction. - precipitation of high purity intermediate compounds. - calcination/reduction to high purity oxides/metals. Especially in the first three steps, major amounts of chemicals like acids or sodium hydroxide are used and, as by-products, substantial quantities of residues and effluents are generated. The impact of environmental regulations on these by-products and the attempt to reduce or minimize the amount of residues and effluents produced will be discussed in this presentation using Ta/Nb chemistry as the example. The basis of our considerations will be the way these by-products are handled at HCST, a major, and in some cases, the biggest producer of refractory metals (tungsten, molybdenum, rhenium, tantalum, and niobium).

Jan 1, 1992