Search Documents

By Larry G. Twidwell, Jannette L. Chorney, Bryce D. Ruffier, Katelyn M. Lyons, Daniel W. Gaede, Ryan J. Foy, Jerome P. Downey

The Army Research Laboratory (ARL) has an interest in the recovery and processing of rare earth elements. At Montana Tech, elevated temperature chlorination of rare earth oxides is presently being investigated as a potential methods leading to the selective separation and recovery of rare earth elements from mineral ores and concentrates. After preliminary evaluation, ytterbium oxide was selected as a representative surrogate material for more extensive chlorination studies. Methods used to determine the conversion and recovery include X-ray diffraction (XRD) and inductively coupled plasma (ICP) analysis. These data have been used to establish and confirm process conditions that consistently yield high conversion efficiencies. Based on the promising results, further experimentation is underway to ascertain the metallurgical response of other rare earth oxides and carbonates to the roasting process. The end goal is to create a robust process for industrial application that has greater efficiency and reduced costs as compared to current practice.

Jan 1, 2015

By Ramasamy Santhanam

"India’s present annual marine fish catch is 2.9 million tonnes and its low value fishes such as sardines, sciaenids, goat fishes and leiognathids amount to 60%. The fish meal obtained from these resources is mainly used presently as an ingredient in live stock and aquaculture feeds. These fishes offer vast scope in the production of pet foods. Pet foods prepared with leiognathid fish meal (60%), maize flour (10%), wheat flour (5%), vitamin and mineral mixture (5%) and water (20%) and experimented with 50 cats and 50 dogs were found to be ideal. Depending on protein level, feeds are being formulated for experimenting with more number of pet animals. Training programmes are also planned for unemployed people to popularize pet foods for commercial purposes.IntroductionIndia’s present annual marine fish catch is 2.9 million tonnes and low-value fishes sucha s sardines (Sardinella albella, s. gibbosa, S. fimbriata and S. melanura); sciaenids (Otolithus spp. and Jhonius dussumieri); engraulids (Stolephorus indicus); and leiognathids Leiognathus bindus, L. equilus and Gazza achlamys) constitute 60% (Figure 1)[1]. The fish meal obtained from these resources is now mainly used as an ingredient in livestock, poultry and aquaculture feeds. Considering the rich nutritional status of these low-value fishes, it is felt that these resources could be converted into value-added products viz. pet foods."

Jan 1, 2008

By Pan Cao

The process of reduction roasting of nickel laterite with rotary hearth furnace combined with magnetic separation becomes a very potential way to prepare ferronickel alloy, especially for the low grade nickel laterite ore. In order to realize this new process, the effect of roasting temperature, time and additive on the reduction degree were investigated in the laboratory experimental. The results indicated that the recovery rate of Ni increased with the roasting temperature increasing to 1500°. Most of nickel and a spot of iron are selectively reduced with adding 25.19% SiO2, 6.42% coal, and roasting for 60min at 1500℃. Then conventional magnetic separation was carried out. The content of Ni and Fe are 7.50% and 59.08% in ferro-nickel nugget prepared by this method. And the recovery rate of Ni is 90.91%, which indicates that a high recovery of ferro-nickel from nickel laterite ore is achieved indeed.

Jan 1, 2014

By A. A. el-Geassy

High-grade iron ore fines rejected from the DRl plants (>96%Fe20) were isothermally reduced in 30-60%COIH2 gas mixtures at 973-1273K. The freshly reduced reaction products were then subsequently carburised in either H2/CO or H2/CO/S mixtures at 823-1073K for 30-120 min. The thermogarvimetric technique was used to follow up both of reduction and carburisation reactions as a function of time. The carburised samples were characterized by X-ray and Mossbauer techniques. Chemical and carbon analyses were also applied. The influence of temperature and gas composition on the reduction behavior was investigated. The calculated values of apparent activation energy, application of gas-solid mathematical formulations were correlated with the microstructures to predict the reduction mechanism, The influence of carburization time, temperature, CO contents in H2/CO or H2/CO/S were investigated. A conversion extent of Fe to Fe3C was taken as a measurable index for the efficiency of carburization reaction under the different experimental conditions.

Jan 1, 2003

By Liugen Sun, Xingming Jiang, Weijiao Yang, Yihang Hu, Yongqiang Yang, Hua Wang

During the past decades, cyclone electrowinning (CE) has been regarded as a novel separation technology, which can be used for direct electrowinning of metals from low concentration solution. Recently, CE was proven effective for the treatment of antimonic gold concentrates. The experimental results of cyclone electrowinning of antimony show the current efficiency increases from 43.8 to 72.2% with the increasing current density (from 254.8 to 647.3 A/m2), and on the other hand, power consumption per ton antimony decreases from 6100 to 4200 kWh with the aforementioned increasing current density. The grade of the obtained cathode antimony could reach 98.6%. Compared with the traditional electrowinning using parallel-board electrodes, the economic profit of CE was 33.1% higher attributed to the high current efficiency of CE. In addition, CE could adapt to high current density. All these characteristics indicate the CE method can be implemented commercially for processing antimonic gold concentrates.

Mar 1, 2018

By Nirlane Cristiane Silva, Leonardo Gonçalves Pedroti, Ana Augusta Passos Rezende, Anna Paula Sartori, Benício Costa Ribeiro, Andreiva Lauren Vital do Carmo, Wellington Emílio Hilarino Fernandes

The final disposal of sludge from recycled paper mill effluent treatment plants is costly and demands large areas for landfilling. Environmentally sound alternative uses of the sludge, enabling economic valoration of this material appear to be advantageous to industry and to the environment. This paper evaluates the feasibility of the incorporation of paper mill sludge in manufacturing of ceramic bodies. The combination of different proportions of weak clay, strong clay and sludge from recycled paper effluent treatment plant for the production of ceramic bodies was determined by using the Network Simplex method planning of mixtures. Samples were prepared and burnt in oven at temperatures of 750, 850 and 950 °C. Physical, mechanical and environmental tests were carried out, in addition to chemical, microscopic and thermic analysis. The results demonstrated that the flexion resistance increased with the increase in temperature, while the absorption decreased at higher temperatures. The mixture design is efficient combining sludge addition at small fractions with large amount of clay, which demonstrate the viability of sludge incorporation for ceramic bodies manufacture, since the desired characteristics are observed.

Mar 1, 2017

By Zhenyang Wang, Yiran LIU, Xiangdong Xing, Jianliang Zhang, Zhengjian Liu

Basic characteristics of marine placer were systematically studied by chemical analyze, scanning electron microscope and X-ray diffraction in this paper. It could be found that the marine placer mainly consists of titanomagnetite and titanohematite. A series of experiments were performed to investigate reduction-magnetic separation for Fe and Ti from the marine placer. Effects of reduction temperature, reduction time, carbon ratio, magnetic density, and grinding fineness on the reduction-magnetic separation process were investigated. And the optimal process parameters were obtained as follows: the reduction temperature 1300, the reduction time 30 min, the carbon ratio 1.1, the magnetic density 50mT, and the grinding fineness of 0.074μm 86.34%. Under such conditions, the metallization rate, iron grade of magnetic substance and iron recovery reached to 94.23%, 97.19% and 90.28% respectively, and the titanium grade in non-magnetic substance and recovery of was 57.94% and 87.22% respectively. The effective separation of iron and titanium could be achieved in reduction-magnetic separation process.

Jan 1, 2015

By Mingchun Lu, Zhe Wang, Mingming Cao, Xiangdong Xing, Shan Ren, Jianliang Zhang, Zhengjian Liu

"The effect of reduction temperature on the vanadium titano-magnetite carbon composite pellets was investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM), and the discussion has put emphasis upon the enhanced reduction mechanism of additives containing CaF2 and NaF in this paper. The results showed that the reduction temperature of 1350°C was needed for the generation, mergence and growing up of metallic iron as well as monomer dissociation between metallic iron particles and slag phase in the vanadium titano-magnetite metallization pellets. The iron compound was completely reduced into metal iron, and Fe2Ti04 was mainly transformed into metal iron, (Fe,Mg)Ti205 and FeTi03 at 1350°C. The maximum metallization ratio was only 88.5% at 13500 for 30 min without any additive. However, with the addition of 3.0% CaF2 or NaF, the metallization degree of pellets could reach up to 94.8% and 92.5%, respectively.IntroductionVanadium titano-magnetite which is mainly distributed in the area of Panxi, Chengde and Maanshan in China is a kind of complex iron ore which contains various valuable metal elements such as iron, vanadium, titanium, etc. Among the above areas, Panzhihua (Sichuan Province in China) area possesses the largest deposits of vanadium titano-magnetite and the future reserves are more than 100x108t, and the reserves of Ti existing as Ti02 reach to 8.7x108t which occupy over 91% of the whole nation and ranked No.1 in the world[1]. Lots of researches on the comprehensive utilization of vanadium titano-magnetite have been conducted in the world. And many technological processes have been applied successfully in industrial production. Among these processes, the process of rotary kiln-electric furnace is employed to recover iron and vanadium in South-Africa, while the process of blast furnace-rotary furnace is widely used in Russia and China. Besides, many researchers have made efforts on employing new direct reduction process to realize the effective comprehensive utilization of vanadium titano-magnetite[2-4]. However, the direct reduction process is only researched in laboratory and it has not been used in industry."

Jan 1, 2013

By Federica Paglietti

In this work is presented SEX (Structural & Elemental X-Ray Instrument), the first spectrometer completely portable which make non-destructive X-ray fluorescence and diffraction analysis, in contemporary and in real time. This instrument has been realized using miniaturized detectors, the same model installed on the mission Pathfinder NASA, and X-ray microtubes. SEX allows the chemical and mineplogical characterization of all kind of solid materials and allows to make chemical stratigraphy and liquids analysis.

Jan 1, 1998

By Ahmet Haxhiaj, Bajram Haxhiaj

Based on the placement of lead and its consumption in industry branches, the paper deals with the composition of lead in the massive of Kopaonik. Removal, tenuity and grinding of galenit. The paper in particular treats the flotation process, and also treats physico-chemical bases of reagents in the process, as well as decanting, drying, filtering and storage of concentrates. Verification of the chemical composition of Pb concentrates with Pb, Zn, Bi, As, Sb, In, Au, Ag, etc. It is special that in Kopaonik massive the ratio of Pb: Zn composition is 1.4:1.0 and during the flotation lead is inclined to go with pirotines concentrate more than is allowed. We are strongly focused to maximally decrease the Pb amount that goes with pirotine concentrates and wastes. The paper as such gave the first effects in optimizing of these parameters with positive effects in flotation process in Trepca.

Mar 1, 2018

By Marco Antônio Siqueira Rodrigues

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

Jan 1, 1999

By LuisW. Pommier

The industrial wastes generated by the plating industry, the circuit board manufacturing industries and other related industries normally contain high concentrations of metals, which make them hazardous. The extraction of the contained metals and their separation may be achieved by both pyro and hydro metallurgical processes. Some of the industrial wastes, those rich in some metals like nickel for instance, are being treated like mine ore concentrates and are being fed to smelting furnaces. The slags from these smelter operations are hazardous. They have, however, special environmental dispensations issued by the regulatory authorities. Hydro-metallurflcal processes have been reported. They also generate a residue which is hazardous because not all the valuable metals are leached out and also, because "non valuable" components, like chromium, are less readily leached. Residues from the plating industry, containing nickel, copper. zinc, iron and chromium as the major constituents and also sodium and calcium, together with cadmium, cobalt, lead. manganese, magnesium, molybdenum, and potassium, have been processed for the extraction of the valuable components. The generation of electrolytic nickel, copper and zinc and also of ferric chloride and chromium oxide is reported. The operation is achieved by a caustic leach for the extraction of zinc, followed by a sulfuric acid leach for the extraction of nickel and copper. This acid leach also extracts the iron and some chromium. The nickel copper and zinc are rendered pure by electrolysis, the iron is oxidized for the production of ferric chloride and the chromium is recovered as an oxide. The leaching operation is performed in two stages, first at a pH of 2.5 to generate an electrolyte for the partial recovery of the metals and then at a pH of 0.5 for the complete extraction of the metals. This leaching operation generates a residue, which although small in volume compared to the initial feed, still contains traces of the valuable metals and a portion of the chromium which makes it hazardous. Additional leaching with hydrochloric acid or nitric acid is required for its complete dissolution. The other minor constituents mentioned are present in concentrations each of less than 0.1% and are handled as impurities in the process. The metals which are soluble at a pH 0.5 and precipitate between 0.5 and 2.0 are bled off. Other impurities will concentrate on the raffinate from the solvent extraction operations from whence they are bled off. These bleeding streams are hazardous and the "impurity metals" are now present in concentrations which would make them valuable, however, the size of these streams is so small that they do not warrant their processing, however they could be marketed to specialized smelters. The extraction of the valuable metals, of the hazardous constituents, the generation of a marketable mixture of minor constituents and the production of a non-hazardous residue for declassification is profitably achieved.

Jan 1, 1998

By Dilek Kirgöz, Onuralp Yücel, Murat Alkan

"In this study, Mo containing Fe-based alloys, such as Fe-Ni-Cr-Mo, were synthesized using a mixture of Fe203-NiO-Cr203-Mo03 powders reducing with Al powders by metallothermic process which is a high energy efficient, fast and low-cost production technique for synthesis of cast alloys and advanced ceramics. Detailed thermochemical studies were simulated by using FactSage 6.2 Thermochemical software in order to calculate adiabatic temperature of the reactions and effects of initial molar composition on the final products. In the metallothermic processes, effects of stoichiometric Al addition and addition of the oxide powders (Alz03, Si02, CaO, MgO) on the metal recovery and compositions of final alloys were carried out. Final products were characterized by using chemical analysis (AAS), XRD, XRF and SEM/EDS techniques.IntroductionSelf Propagating High Temperature Synthesis (SHS) has significant advantages compared to the high technology furnace applications, such as very short processing time, simple operation, low energy requirement and low cost [l, 2]. In a SHS process, the ignition starts the combustion and propagates throughout the reactant mixture yielding the desired product. However, the disadvantages of the process such as inhomogeneous or unreacted products due to undesirable reaction rates needs to be overcome by changing some parameters such as ignition temperature, particle size, additive, atmosphere etc. [3, 4]. This work aims to establish a scientific and engineering background in the production of some cast Fe based alloys (Fe-Ni-Cr-Mo) which are used as surface coatings, wear-corrosion-oxidation resistive applications via SHS (Self Propagating High Temperature Synthesis) metallurgy which is attractive process technique regarding fast and low-cost production ability of cast alloys."

Jan 1, 2013

By Carlos Maurício. F. Vieira, Lázaro A. Rohen, Sérgio N. Monteiro, Rafael G. de Castro, Gustavo X. Borges, Maycon A. Gomes, Frederico M. Margem, Anna C. C. Neves

Economic and environmental benefits are motivating studies on natural fibers, especially lignocellulosic extracted from plants, have been studied to substitute synthetic fibers, such as glass fiber as reinforcement in polymer matrices. By contrast to synthetic fibers, natural fibers have the disadvantage of being heterogeneous in their dimensions specially the diameter. About the hemp fiber, little is known of their dimensional characteristics. The aim of the present work was to statistically characterize the distribution of the diameter of hemp fibers. Based on this characterization, diameter intervals were set and the dependence of the tensile strength of theses fibers with a corresponding diameter was analyzed by the Weibull method. The diameter was measured with precision using a profile projector. Tensile tests were conducted on each fiber obtain mechanical strength. The results interpreted by Weibull statistical showed a correlation between the resistances of the fiber to its diameter.

Jan 1, 2015

Many studies have been conducted over the past 3 decades on the leaching of gold in solutions containing thiosulfate, ammonia and copper. However, most of these studies have been carried out using ore samples, with very few fundamental studies of this system being attempted. The majority of the published studies have failed to acknowledge the undesirable side reaction between copper(H) and thiosulfate, let alone account for its effect. The fact that the solution chemistry is constantly changing makes it very difficult to perform a fundamental study of gold leaching. With the advent of the rotating electrochemical quartz crystal microbalance (REQCM), such fundamental studies are possible as this instrument measures mass in real time. This has allowed leach kinetics to be measured in a matter of minutes and hence at essentially constant solution conditions; The present paper highlights that a sufficient concentration of copper(II) and ammonia are required in order to achieve appreciable gold leach rates. However, the use of air (oxygen) to maintain the copper(Il) concentration catalyses the undesirable copper(II) reaction with thiosulfate. The presence of ammonium ions is shown to have an effect on this undesirable reaction as well as on the gold leaching ?reaction. Preliminary electrochemical studies into .gold electrowinning using the REQCM show that gold(I) thiosulfate cannot be readily reduced to metallic gold in the potential region at which cementation usually occurs. However, it is well known that gold cementation onto copper occurs rapidly. The current study addresses this discrepancy by studying the effect that copper and silver have on the reduction of gold thiosulfate. It has been found that the presence of both silver and copper enhance gold deposition, particularly at low over potentials. While this is beneficial in cementation, the presence of copper and silver in solution has been found to cause passivation of the cathode surface during electrowinning at 'higher overpotentials.

Jan 1, 1998

By N. B. Gray, I. F. Taylor

"Gas injection to promote chemical reactions or mixing is a feature of many metallurgical processes. Often the aim of gas injection is to bring about a chemical reaction between the gas and liquid but most of the past physical and mathematical modelling work has ignored the influence of such reactions. In the work reported here, cold model studies have been conducted in which gas reacts with the liquid into which it was injected. The rate of liquid mixing has been measured as an indication of the mechanical energy transfer. It has been found that gas generated chemically within the liquid is significantly less effective at promoting mixing than the equivalent volume of inert gas. The relative ineffectiveness of chemically produced gas is thought to be due to smaller bubble sizes in comparison to the inert gas case. Small bubbles characteristic of chemically generated gas move with low slip velocities relative to the liquid and lead to different turbulence generation mechanisms.IntroductionIn processes such as steelmaking, copper conversion, bath smelting and ladle steel finishing gas is injected into liquid metal where it reacts chemically or simply serves as a source of agitation. An understanding of fluid flow phenomena in such situations is an essential pre-requisite to the calculation of process intensity and the optimisation of vessel productivity. Traditional physical cold modelling approaches to prediction of liquid flow in such situations are now often augmented by the techniques of computational fluid dynamics. Even with the availability of numerical modelling techniques cold physical models continue to have an important role for validation because it is generally difficult to obtain quantitative data from high temperature processes.Almost all previous cold modelling work has been based on the injection of an inert gas into water or some other non-reactive liquid. Such models do not include the significant increase in gas volume inherent in some processes. For example the oxidation of carbon in steelmaking leads to a twofold increase in molar gas flux through the reaction:"

Jan 1, 1996

By R. Y. Wan

Low grade sulfidic-carbonaceous refractory ore from Newmont Gold Company's Carlin deposit was microbially pretreated. The biological pretreatment process gave partial oxidation of the sulfidic components of the refractory ore but the preg-robbing carbon continued to be active resulting in approximately zero cyanide gold extraction. A 495 ton pilot plant test heap was conducted using acidic thiourea leach following biooxidation. Activated carbon and cation exchange resin adsorption were tested for gold recovery from the thiourea pregnant solution. The results obtained from the test heap were not satisfactory. Gold extraction was low due to slow reaction kinetics which was caused by relatively large particles and very low winter temperatures. Problems existed in the thiourea-test heap and are discussed in this paper. An alternative heap leach process using thiosulfate has been successfUl at the pilot scale for gold extraction following biooxidation pretreatment of refractory sulfidic-carbonaceous ores.

Jan 1, 1995

By Maria D. Salazar-Villalpando, Anthony Cugini, Bryan Reyes

"The electrochemical reduction of CO2 was performed in a laboratory-made, divided Htype cell. A copper electrode was used as the cathode. An Aldrich Nafion 117-type ion exchange membrane (0.18mm thickness) was used as the diaphragm. NaHCO3 and KHCO3 were studied as the catholytes. Hydrogen evolution from water reduction and products from CO2 electrochemical conversion were recorded. Higher CO2 reduction enhancement was observed by KHCO3 as compared to NaHCO3. The main conclusion of this work is that in fact CO2 can be electrochemically reduced with copper electrodes.1.-INTRODUCTIONThe direct electrochemical reduction of CO2 may allow for a simple process and, by avoiding high temperature reactors, would enable the process production rate to be quickly varied to follow the time of day availability of surplus electricity [1]. Temperature has a major effect on the electrochemical conversion of CO2 since its solubility increases when temperature decreases [2]. The electrical potential applied to the electrochemical reacting system will have an influence on the product distribution, as well. For example, a narrow potential range during cyclo-voltagraphic studies will determine the detection of a lower number of products. A recommended potential range to study the electrochemical reduction of CO2 is -2V to 2V. Moreover, the reaction rate on the electrode is governed by various processes, such as the kinetics of electron transfer, adsorption/desorption at the electrode surface, and diffusion of CO2 to the Cu electrode. The availability of active species, CO2 for electro-reduction, is extremely low at the vicinity of the electrode surface and it seriously interferes with the rate of mass transfer. In batch type electrolytic reactors, depletion of CO2 at the surface takes place first. CO2 from the bulk then has to diffuse to the electrode surface, resulting in mass transfer controlled kinetic phenomena. During the above process, several other competitive side reactions could suppress the primary reaction even though the cathode has good electro catalytic properties for reduction of carbon dioxide. When the dynamic supply of specific active species is ensured to electrode surface, the mass transfer effects are minimized to certain extent. Hence it is envisaged that a continuous flow reactor is more efficient for the electro-reduction of CO2 in CO2 saturated aqueous electrolytes. The primary reactions that occur at the copper electrode during the reduction of CO2 are listed below (with the standard potentials calculated using formation energies [1] :"

Jan 1, 2010

By Xueqin Li, Xuewei Lv, Yu Zhang, Wenchao He

In order to make full use of the chromium-bearing vanadium titanium magnetite with chromium, a new process of “direct reduction-electric furnace smelting separation” has been developed for recovering the iron, vanadium, titanium and chromium in recent years. In this paper, FactSage, one of the most frequently-used thermodynamic calculation software, was used to calculate the reduction degree of Fe, V and Cr with different n C/nO (mole ratio of carbon and oxygen). It was found that the suitable operating conditions of direct reduction process were n C/nO > 1.07 and T > 1473 K. In addition, the direct reduction experiment of Hongge vanadium titanium magnetite was carried out and the obtained samples after direct reduction were analyzed by XRD and chemical composition. The result shows that the metallization rate of carbon-containing pellet is nearly 90%.

Mar 1, 2018

By P. Myllykoski, J. Nylander

"A commercial program package called Crownoff for the simulation of temper rolling in four high mills has been verified against measured data. The agreement between measured and calculated transversal strain distributions of the strip was found to be good. Effects of the strip crown and work roll bending force on the strain distribution were simulated. The results showed that when a single ground camber of work rolls is used for all strip widths; the strip crown should be parabolic, excluding the edge drop. An increase or decrease of the strip crown by 30 % during a coil can be compensated by a 2 to 5 t change in the work roll bending force. The ability to control the strip crown by work roll bending was insensitive to strip width. IntroductionCold rolled steel strips are usually temper rolled after recrystallization annealing, which follows cold rolling. The purpose of temper rolling is to suppress the yield point, finish the strip surface and correct possible flatness errors. The presence of a yield point might otherwise cause problems during subsequent forming processes. The in homogenous yielding in non-temper rolled steels leads to the formation of Lüders bands in the strip surface.The rolling force is influenced by the rolling speed and changes in frictional conditions in the roll bite. Therefore it is very important to plan carefully the mill settings and control algorithms during rolling. The purpose of mill control algorithms is to ensure constant reduction and the best possible strip flatness during the entire coil.Correctly predicting the rolling force is important for determining the mill presettings. Torque, forward slip and power requirements are not usually critical, if the reductions are small. However, the large elastic deformations occurring in the roll bite make the physical description of the process difficult. Physical rolling models developed for cold rolling contain assumptions that lose their validity as the reductions decrease to the level of one per cent."

Jan 1, 1994