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By R. Hurman Eric

Within the Ag-Pb-S ternary system, the boundaries of the immiscibility region together with the tie-line distributions were re-established at 925°C by the equilibrium-quenching technique where samples were kept in evacuated and sealed silica capsules. Activities of Pb were measured by the dew-point method along the Ag-Pb binary at 925°C, 1100° and 1200°C. positive deviations were observed and the results were modeled by the Krupkowski formalism. Activities of Ag, Pb, and S, along the ternary miscibility gap were calculated at 925°C by utilizing the boundaries binary thermodynamics, phase equilibria and tie-lines. Activities of PbS within the pseudobinary Ag2S-PbS mattes were also measured by the dew-point technique and the results were again modeled by the Krupkowski formation Where negative deviations were observed.

Jan 1, 2003

The results of laboratory, large-scale laboratory and commercial scale investigations regarding the process of slag melts cleaning by oxidizing-reduction gas mixtures with a wide range of Po2 and the use of matte of various compositions as an extracting phase are presented. The copper, nickel and cobalt behavior during the cleaning process has been studied based on SEM and x-ray Microprobe of the quenched slag melts. The general cleaning mechanisms have been found. On the basis of the obtained data the most efficient cleaning methods have been proposed.

Jan 1, 2003

By A. Deneys

An experimental technique has been devised for studying the reaction kinetics of the reaction: ZnO + 2Fe0 = Zn(g) + Fe203, by which zinc evolution can occur from a molten slag bath in the absence of a carbonaceous reductant. When studying the reaction kinetics by heating from room temperature, solid state reactions and poorly defined melting points may obscure the starting point of the reaction. In order to eliminate this problem, an experimental technique was devised whereby two molten slags could be melted independently, and then mixed, to provide a well defined starting point from which to begin taking measurements. Two crucibles were mounted in a vertical reaction cylinder. The upper, mild steel, crucible had a bottom pouring plug which was sealed by a steel stopper rod. A fayalite mixture was contained in this crucible. The lower crucible contained an A12O3-CaO-SiO2-ZnO solution. Once the two slags had been melted, the steel stopper rod was removed from the upper crucible. The upper, reduced slag (fayalite in equilibrium with the upper steel crucible), drained into the lower crucible where the two slags were mixed by submerged argon stirring. Dip samples were taken to measure the zinc content of the final mixture as a function of time. The experimental procedure will be described, as well as results of experiments which were conducted on synthetic slags. The system investigated was similar to the lead blast furnace slag which is produced by the primary lead smelters of Missouri, USA.

Jan 1, 1997

By R. Hurman Eric

Within the Ag-Pb-S ternary system, the boundaries of the immiscibility region together with the tie-line distributions were re-established at 925°C by the equilibrium-quenching technique where samples were kept in evacuated and sealed silica capsules. Activities of Pb were measured by the dew-point method along the Ag-Pb binary at 925°C, 1100° and l200°C, positive deviations were observed and the results were modeled by the Krupkowski formalism. Activities of Ag, Pb, and S, along the ternary miscibility gap were calculated at 925°C by utilizing the boundaries binary thermodynamics, phase equilibria and tie-lines. Activities of PbS within the pseudobinary Ag2S-PbS mattes were also measured by the dew-point technique and the results were again modeled by the Krupkowski formation where negative deviations were observed.

Jan 1, 2003

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 M. Pakala, Z. Fan, Ray Y. Lin

Deposition of hard chromium coatings using electrodeposition is accompanied by emission of hexavalent chromium mists which is a carcinogenic. Hence alternative chromium deposition technologies are being investigated. Sputter deposition is a strong candidate to economically deposit hard chromium coatings in an environmentally friendly way. Chromium coatings of 2-3 µ m thickness were deposited on plain carbon steel coupons using RF magnetron sputter deposition. Depositions were carried out with 0 to 22 vol% nitrogen in the plasma. Structure of the coatings was studied using x-ray diffraction analysis With increasing nitrogen contents, formation of the two nitride phases was observed. The pure chromium phase was detected in coatings with up to 7% nitrogen in the sputtering gas. The solid solution of nitrogen in the pure Cr phase coating was identified by shifts of Cr x-ray diffraction peaks to higher d-spacing. The microhardness of the coatings deposited at a substrate temperature of 200°C showed an increase in hardness with increasing nitrogen content from 600 kgf/mm2 (5.9 GPa) at 0% nitrogen to I250 kgf/mm2 (I2.25 GPa) at 9.5 % nitrogen and a subsequent decrease in hardness to I 100 kgf/mm2 (11 GPa) beyond 9.5 % nitrogen in the sputtering gas. This corresponds to the formation of the hard Cr2N phase, at 9.5 % nitrogen, and CrN phase, at I5.7 % nitrogen. The reported bulk hardness values of Cr2N and CrN are I600 kgf/mm2 (I5.7 GPa) and I 100 kgf/mm2 (11 GPa) respectively. For pure Cr phase coatings, there is a slight increase in hardness for coatings deposited at 7. I % nitrogen from that without nitrogen in the sputtering gas. This could possibly result from the solid solution strengthening of the Cr lattice by nitrogen. For films deposited at 200°C, phases of the deposited films seem to be the overwhelming factor in controlling the microhardness.

Jan 1, 1998

By Lenny Winkel

With the aim to develop a solar-driven process for the extraction of copper from sulfide concentrates research on the decomposition of copper sulfides under inert atmospheres has been initiated. Thermogravimetric measurements on chalcocite (CuzS) revealed that copper is formed already at 1823 K. Chalcopyrite (CuFeS2) also disintegrates at this temperature, although at a lower rate. Copper and iron have been identified in the solid residue. The results confirm the feasibility of copper extraction by direct decomposition of sulfides under atmospheric pressure. The decomposition under inert atmosphere prevents generation of SO2, it also alters the behavior of volatile impurities during decomposition of copper sulfide concentrates. Chemical eqUilibrium calculations for chalcopyrite contaminated with enargite (Cu3AsS4) have shown that the absence of an oxidic slag allows for a complete evaporation of arsenic and subsequent separation from intermediate sulfides. The need to better assess the potential of direct sulfide decomposition has prompted the development of an experimental setup for studying the decomposition reactions. The experiment has been devised such that data on the decomposition kinetics and on impurity removal can be obtained at temperatures up to 2500 K.

Jan 1, 2003

By Ho-Sang Sohn

The kinetic study on desulfurization of copper matte by gas bubbling was designed under the presumptions of lower FeO activity and of no slag formation, Copper matte with 59% Cu and 22.6% S in weight was oxidized at 1523K by bubbling of Ar + O2 gas through a submerged nozzle. The effects of oxygen partial pressure and flow rate of gas on the oxidation rate of matte were discussed. The desulfurization rate and the evolution rate of SO2 gas of copper matte were significantly influenced by the oxygen partial pressure, but the dependence on gas flow rate was rather complicated. The desulfurization rate and evolution rate of SO2 gas of copper matte were described by the mass transfer rate through the gas film around the rising gas bubbles. Thermodynamic correlation equations between the partial pressure of gaseous species and matte composition were incorporated to the kinetic calculation, The present model shows that the reaction path starts to transiently cross over an isobar line of PSO2 to asymptotically approach to the particular isobar line drawn in a matte composition plane of %S and %O.

Jan 1, 2003

By Jonkion M. Font

Due to the known disadvantages of the use of iron silicate slag in the nickel converting stage, i.e., high metal losses, high magnetite content, and low fixation of impurities in the slag, the development of the new proposed "ferrous calcium silicate slag" for smelting and converting processes of nickel is very promising. Hence, considering the successful experimental results of using CaO base slag for the nickel smelting process, a study based on a detailed comparison for the phase equilibrium, and the minor elements distribution between the Ni3S2-FeS matte with either FeOx-CaO or FeOX-Si02 base slag was investigated. The main results are summarized as: no difference in the nickel losses between both slags was found at high nickel content in the matte, and the fractional distribution analysis for arsenic and antimony pointed out their preferential fixation in the calcium ferrite slag rather than in the iron silicate slag. Considering the energy and pollution issues, the technical feasibility of using calcium ferrite slag in a converting process of the Bessemer matte will have a prominent future for the nickel industry.

Jan 1, 2003

By T. T. Chen

Canadian Electrolytic Zinc has developed the "cement-stabilization of jarosite residue" Garofix) process to stabilize zinc plant jarosite residues for disposal. The cement-jarosite mixtures cure quickly, have good mechanical strength and low hydraulic permeability; they possess good neutralizing capability and chemical stability. In the jarofix process, Portland cement partly decomposes jarosite to form (SO4MOH)12.nH2O, ferric hydroxide and an alkali sulphate. Approximately 40% of the jarosite reacts in mixtures containing 30% cement. The jarofix product also contains various Ca-Al-Fesilicate-sulphate-hydrate phases and gypsum, which bond the individual particles together imparting mechanical strength and reducing the permeability. Most of the reactions take place in the first few hours of curing. Ammonium jarosite is slightly more reactive than sodium jarosite but releases NH3 gas; water-soluble Zn in the jarosite residue is stabilized in the cement reaction products.

Jan 1, 1996

By A. González

Arsenic is one of the main contaminants present in Chilean copper concentrates and its abatement represents a challenge for the process metallurgy, particularly under the strong environmental requirements in the global community. The possibility to form ferric arsenate directly from a gas phase by means of a heterogeneous reaction between an arsenic gas bearing and iron oxide was studied at laboratory scale. A thermodynamical analysis for the system Fe-As-O-S has been initially made, in order to obtain the stability conditions for the ferric arsenate or other FexAs2O2 type compounds. Experiments were made using an hematite sample suspended in a thermogravimetric device. AS4O6 gas generated from solid AS203 that was passed through the iron oxide sample and its instantaneous weight change was recorded directly. A kinetic study for the AS4O6 volatilization was made to control the gas composition. A chemical control between 300 and 600°C with an apparent activation energy of around 14 Kcal/mol As2O3 was determined. The samples after the reactions were chemically and XRD analysed. Arsenates detected corresponds to complex compounds. Results shows a dependence on temperature and oxygen content in the gas phase. The kinetics for iron arsenates formation is slow, reaching an arsenic capture of 6% after 80 minutes of reaction when an oxygen content of 50% is fed continuously at 800°C and 3,56% As in the gas. Experiences made at the same temperature but under higher oxygen content in a closed reactor, allowed arsenic capture close to 60%. For higher temperatures the capture is considerably lower.

Jan 1, 2003

By Simon Lekakh, Von Richards, C. Hank Rawlins, Kent Peaslee

"Batch aqueous leaching and carbonation tests were conducted using industrial steelmaking slags to determine the effect of carbonic anhydrase enzyme as a catalyst. Calcium leaching is a strong function of particle surface area, and the extent can be expressed as a function of time and particle size. Carbonic anhydrase did not affect the calcium-leaching rate, however, it did catalyze calcium carbonate formation to achieve a neutralization time near the theoretical rate. Additionally, carbonic anhydrase modified the precipitate morphology due to accelerated particle nucleation. Time controlled tests in which the pH dropped to ~6 decreased the amount of carbonate produced, and this effect was exaggerated by carbonic anhydrase, while pH controlled tests (>8.5) exhibited the highest rate of carbonation. Because the leaching rate was ~50% faster than the carbonation rate, a further increase in the amount of carbonation may be realized by using carbonic anhydrase however pH must be >10.3.IntroductionSteelmaking slag contains high fractions of alkaline earth oxide based phases (i.e., CaO and MgO) that exothermically form carbonates. Thus, it is being considered as a means of permanent carbon dioxide sequestration. At current U.S. steel production rates, approximately 13-17 million tons/year of slag are generated from basic oxygen furnace (BOF), electric arc furnace (EAF), and ladle metallurgy furnace (LMF) processes [1]. BOF and EAF slag is used as high quality mineral aggregate or cement clinker, while LMF slag, produced at ~15% the rate of BOF and EAF slags, has limited use as blast furnace flux or acid mine neutralization with the majority going to landfill [2]. Based on slag’s chemical nature and immediate availability as a co-product from steel production, the steel industry initiated a project to investigate hydrous carbonate formation in steelmaking slag as a method of sequestering carbon dioxide emitted in steelmaking offgas [3]. The goal of this project is to determine the reactor parameters suitable for the design of an industrial system for treating steelmaking offgas with raw or minimally processed slag."

Jan 1, 2009

By J. R. Donald

Electric arc furnace (EAF) dust, which can be considered as a by-product of the steel recycling process, contains significant quantities of recoverable zinc and iron, as well as hazardous elements such as cadmium, lead and chromium, which can be leached by ground water. The zinc in the EAF dust is found almost entirely in the form of either zinc oxide or zinc ferrite, the latter accounting for 20 to 50 percent of the total zinc. It is important that an efficient process be developed which renders the dust inert, while reclaiming the valuable metals to off-set processing costs. During the conventional carbothermic reduction processes, iron is formed, and this iron can participate in the reduction of the zinc oxide in zinc ferrite. In the present work, the reduction of the zinc oxide in zinc ferrite by iron according to the following reaction: ZnO-Fe2O3(s,s) + 2 Fe(s) = Zn(g) + 4 FeO(s) was studied in an argon atmosphere using a thennogravimetric technique. First, a thermodynamic analysis was performed using the F*A*C*T computational system. Then, the effects of briquette aspect ratio (lid), temperature, zinc ferrite particle size, amount of iron added, as well as additions such as lime, sodium chloride, and calcium fluoride were investigated. It was found that, initially, the reaction was chemically controlled with an activation energy of 178.1 kJ/mol. Then, after a product layer had formed on the outer surface of the briquette, the reaction was restricted by the diffusion of zinc gas away from the reaction interface. The parabolic rate law was fitted to the experimental data, and the parabolic rate constant was found to be: = -6.2275 + 0.0054 T (K)

Jan 1, 1995

By M. Fujikawa, S. Goto, M. Nishikawa

"The semi-pilot scale plant for injection smelting of zinc calcine was operated under the committee of Joint Research Organization of Injection Metallurgy. The capacity of the plant is 10 ton metallic zinc per day. The plant was designed by the resul ts of basic and bench scale tests of the capacity of 1 ton metallic zinc per day which was published at ""Zinc '85"". The equipments of the plants, operational conditions, results of the operation such as recovery of zinc in injection furnace and condenser, combustion rate of powdered coke and consumption of energy in this process are presented in this paper. The results of the study of the feasibility of the commercial plant of 100,000 ton zinc per year by the injection smelting are also discussed in the paper. IntroductionThe research committee of new smelting process of zinc by injection was established in 1981 under the finantial support of Mining Promoting Foundation of Japan. Six zinc producing companies joined in this organization. The price of zinc was very low at that time and the energy cost, especially, cost of electric power in Japan was extremely high. Invention of a new economical process for zinc extraction had been stronglydesired. The author proposed a injection smelting of zinc as a economical process in energy saving after a calculation of thermodynamical equilibrium and heat balance(1 )(2).The research committee has been studying the injection process since 1981. The small basic experiment by using a crucible furnace was carried out from October 1981 to March 1983 and the reaction of reduction of calcine by injection smelting was ascertained (2). Vaporizatipon of zinc and behaviours of impurities were examined. After the basic experiment, the bench scale test with the production capacity of zinc of 1 ton per day was carried on from November 1983 to October 1984.The bench scale tests were carried out to obtain the proper design of feeding devices of calcines and coke into a furnace and also to obtain fundamental data for enlargement of this smelting process(3,4). The recovery of metallic zinc in this small equipments was about 50% and main loss of zinc was formation of dross in the condenser."

Jan 1, 1988

By G. Van Weert, A. van Sandwijk, O. W. J. S. Rutten

"Cathodic and anodic reactions in an acidic nitrate medium were studied in reference to the production of electrolytic manganese dioxide from pyrolusite' (Mn02) ores by reductive leaching. Two USA ores were investigated. The reductant for the pyrolusite ore is produced cathodically in an electrolytic cell and can either be nitrous acid (HN02) or nitric oxide gas (NO). In this work emphasis was placed on the nitrous acid leach. In a high-temperature leach in a nitrous/nitric acid medium, manganese and silver are solubilized and iron is not. Anodic electrowinning of manganese dioxide from the acidic manganese nitrate electrolyte yields flaky y-Mn02, similar to that produced from sulfate and chloride electrolytes. Cathodic regeneration of nitrorts acid was studied in a membrane cell in 1.0 M nitric acid and 0.0 to 0.1 M nitrous acid on a' platinized titanium cathode. At cathode potentials ranging from +950 to +700 mV (SHE), cathodic reduction to nitrous acid takes place, at cathode potentials < +700 mV, cathodic reduction of nitrous acid to nitric oxide takes place. A conceptual process is presented and discussed.IntroductionManganiferous-silver oresLarge reserves of manganiferous-silver ores are present in the Southwestern United States and Latin America. These ores are generally refractory to hydrometallurgical methods of treatment, due to the insolubility of the higher oxides of manganese (Mn 4+) in all common lixiviants such as cyanide solutions, dilute sulfuric acid, nitric acid, ammonia, salt solution, thiosulfates, etc. The silver is either bound by the insoluble manganese, or is rendered inaccessible to cyanide leach solution by the surrounding manganese mineralization.Higher oxides of manganese will dissolve if they are first reduced pyrometallurgically to manganous oxide (Mn2+). This is a widely used pretreatment for manganese dioxide ores and subsequent dissolution in sulfuric acid is common. In order to avoid the pyrometallurgical pretreatment with its large energy requirements and gaseous emissions, fully hydrometallurgical processes have been proposed. These processes are based on the presence of a reductant in solution, in order to reduce the insoluble higher oxides of manganese to soluble lower oxides. Aqueous S02 has been proposed and tested on industrial scale by the U.S. Bureau of Mines. After washing, silver could be extracted by cyanidation. The neutralization of the pulp prior to cyanidation however causes problems in filtration and the reagent consumptions are high [1]. More recently, acidified thiourea and bacteria were proposed for the solubilization of both manganese and silver in a single leach step. High extractions were obtained, but drawbacks of these methods are high reagent consumption or slow kinetics [2,3]. For the options of manganese recovery from the leach filtrate, precipitation with persulfate or ammonium carbonate and ion exchange have been proposed. The proposed options for silver reclaim are precipitation with either zinc or Na2S and adsorption onto activated carbon."

Jan 1, 1997

By Xie Zhang, Jiang Diao, Xin Qiu, Lu Jiang, Bing Xie, Hong-Yi Li

"Duplex converter process, in which the first converter is used for removing phosphorus from hot metal (De-P), is an important way to produce low P-content and ultra-low P-content steels. In order to improve phosphorization removal and formation of slag with high basicity at relatively low temperature during dephosphorization converter process, effects of temperature, silicon content in hot metal and varied compositions of the De-P converter slag on phosphorus distribution between the slag and hot metal were investigated with thermodynamic calculations and by laboratory scale experiments in present work. Results showed that phosphorus distribution ratio between slag and metal was varied in 10.6~26.6 when basicity of the slag was in the range of 1.5~2.1 at 1370, and the distribution ratio was increased with increasing basicity and Fe10 content in the slag.IntroductionIt is known that phosphorus exists in steel in the form of solid solution, which can significantly improve strength and hardness of steel at room temperature. However, the plasticity and toughness of steel, especially the low temperature plasticity is sharply reduced and leads to high ductile-brittle transition temperature. This phenomenon is commonly known as cold brittleness of steel [1~3]. Hence, phosphorus should be removed as much as possible in the steelmaking process, because it is generally harmful to the iron and steel products."

Jan 1, 2013

By Patrik Fredriksson

Thermodynamic data concerning FeO-containing slags is of importance in ladle refining of steel. With a view to generate a set of reliable and self-consistent thermodynamic data for these slags, experimental determination of the activities of FeO in binary and ternary slags was carried out using the gas equilibration method involving CO-C02-Ar gas mixtures at steelmaking temperatures. The slag samples in Pt crucibles were quenched after the equilibration and subjected to chemical analysis. The thermodynamic activities of "FeO" in the slags were calculated from the experimental data. The results are incorporated into a thermodynamic description of silicate melts in the present laboratory. The model is based on a Temkin-Lumsden approach and is able to compute the thermodynamics of higher order systems from the lower order ones.

Jan 1, 2003

By Ali Hasham

Reduction rates of FeO in CaO-SiO2-Al2O3 slags by Fe-C melts have been investigated experimentally at 1723 K. The rates were estimated using experimentally determined CO(g) evolution rates. Flash X-ray images were employed to visualize the behavior of the melt-slag interface during the reactions. The influence of melt interface was examined by conducting two types of experiments - (i) dropping one (or several) Fe-C droplet(s) weighing 2 g into the molten slag bath, and (ii) dropping a small amount (10-30 g) of slag onto a Fe-C melt weighing 400 g. The rates from both types of experiments were compared and analyzed to determine the rate limiting steps. It was established that neither the carbon transport in the Fe-C melt, nor the transport of gas species in the gas film adjacent to Fe-C melt was responsible in limiting the reaction rate. It is possible that the slag phase mass transport may be controlling the initial reduction rate in the droplet experiments. However, a, different mechanism was responsible in limiting the reduction reaction when the overall %C in the droplets fell to about 2-3.

Jan 1, 1992

By Courtney A. Young

Cyanide is a critically important chemical to the mining and metallurgical industry. It has a strong affinity for metals making it favorable as an agent for metal finishing and treatment as well as a lixiviant for metal leaching, particularly gold. These technologies are environmentally sound but, because cyanide is very toxic, safeguards are required to prevent accidental spills and treat effluents before being discharged. Various methods of cyanide remediation by separation and destruction for cyanide management purposes are therefore reviewed. The methods have been broadly categorized as physical, -adsorption. complexation and oxidation methods including photolysis and other advanced-oxidation processes. Reaction mechanisms for these methods are presented throughout this paper, Finally, the methods are compared in regards to their effectiveness in treating various cyanide species: free cyanide, thiocyanate, weak-acid dissociables, and strong-acid dissociables.

Jan 1, 1998

By Flavio Begazo, William A. Enrico

"Southern Peru Copper Corporation's Ilo Refinery, the largest in Peru, began operations in 1975 with a production capacity of 165,000 stpy. Southern Peru bought the Refinery from the state owned Minero Peru SA on June 1, 1994.The Refinery processes blister from Southern Peru's I/o Smelter. Blister copper is processed in an anode plant equipped with two 365 st tilting reverberatory furnaces, a 26 mold casting wheel and an anode press machine. Copper is electrorefined in a tank house equipped with 768 commercial cells, 44 stripper cells, and 40 liberator cells, utilizing two electrolyte circuits and a 21,000 Ampere rectifier.During 1989 through 1994 a program for improving productivity was carried out by increasing the number of cells and increasing current density to the total rectifier capacity. As a result, a capacity 215,000 stpy of refined copper, 2 million tr. oz silver and 6,000 tr. oz gold per year was achieved. In 1994 Southern Peru announced plans to increase capacity to 250,000 stpy of cathode with a US$ 18 million investment and a US$ 2 million investment in environmental improvement projects, as part of the purchase agreement with the Peruvian government.This paper outlines the scope of the SPCC lio Refinery modernization and environmental program. It describes the implementation of the Electrolytic Plant expansion based on instaliation of polymer concrete cells, a new rectifier, a new selenium roaster and a Precious Metal Plant upgrades."

Jan 1, 1997