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By G. Coryell, S. Blaskovich

"A computer model has been developed to simulate the flash furnace and converter operations at the ASARCO Hayden Copper Smelter. The focus of the modeling was to optimize the converter operation to eliminate high matte level episodes in the flash furnace. These episodes (reducing feed to the furnace) resulted from the lack of converter operation scheduling. The model provided ""what if?"" scheduling scenarios that led to increased efficiency of the converter and flash furnace operations.This paper discusses alternatives studied to optimize the converter operation and the development of the computer modeling program, including implementation of the project. The discussion details the results of the project including the conversion from batch to a real time converter scheduling process. IntroductionASARCO's Hayden Smelter consists of a fluid bed drying system, an Inco oxygen flash smelting furnace, Peirce Smith converters, two anode furnaces and two casting wheels, gas cleaning plant, 2800 stpd sulfuric acid plant, 650 stpd oxygen plant and 200 gpm water treatment plant. The process flow sheet of the plant is shown in Figure 1.Over the past several years, the Hayden smelter has been involved in productivity improvement and cost reduction programs. This has been necessary to become a low cost copper producer in today's market. Part of the productivity improvement program was the use of process control to streamline the flash furnace and converter operations. Process control, through the use of computers and electronic controllers, has played an increasingly important role in optimizing processes in the Hayden Plant since the startup of the Inco flash furnace in 1983."

Jan 1, 1989

By Volker Uhlenwinkel

The design of a free fall atomizer as well as the process parameters affect the particle mass flux distribution in the spray cone. The mass flux distribution is important in spray forming because of its influence on the deposit shape and enthalpy input into the deposit. In this article the effect of different process parameters on the mass flux distribution is shown. Furthermore, different melts were atomized with the same atomizer. An empirical correlation will be introduced to predict the mass flux in the spray cone. This correlation will be compared with experimental results.

Jan 1, 1999

By Wenbin Liu

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

Jan 1, 2008

By K. Morsi, S. K. Kassegne, K. S. Moon, A. Numula

"Current Activated Tip-based Sintering (CATS) is a new process for the powder-based manufacturing of macro, micro and possibly nano-scale features and shapes. CATS enables the selective sintering of powders by localizing current activation conditions through an electrically conducting small tip (either in the stationary or moving mode). This paper presents preliminary experimental results on the CATS of reactive mixtures of Ni/Al powder to form nickel aluminide intermetallics. Preliminary investigations on the effect of current on the reaction characteristics are discussed.IntroductionSpark Plasma Sintering (SPS) has been the subject of intense research over the past decade [1,2, 3,4,5,6]. The process boasts remarkable advantages which include ultra fast heating rates (hence by-passing low temperature non-densifying sintering mechanisms), considerably lower sintering temperatures and shorter sintering times than achieved in conventional sintering. The process is however limited to the generation of simple geometries on the macro-scale. Recently three of the authors conducted work on a novel process ""Current-activated tip-based sintering (CATS)"" [7], where electric current is passed through a conducting tip that is placed or allowed to travel over a powder bed/compact to locally sinter powders. lD, 2D and 3D micro-scale sintered shapes can be generated with the possibility of 3D rapid prototyping on the macro/micro or nano-scale. Although CA TS of single phase powders has been conducted, the CATS of reactive powders has not yet been investigated.The Ni-Al phase diagram contains five intermetallic compounds, AhNi, AhNh, AlNi, AhNi5 and NhAl. Out of these intermetallics, NiAl and NhAl have received the vast majority of scientific and industrial interest [8]. NhAl can be formed by reaction synthesis, where nickel and aluminum reactant powders are heated to a reaction ignition temperature at which the reactant powders are converted to the intended intermetallic product. The reaction is exothermic which gives rise to considerable compact self heating, thus instantaneously raising the compact temperature by several hundred degrees which facilitates sintering [8]. Applying and electric current locally would not only provide for a rapid local reactive sintering, but would generate a number of intriguing scientific investigations. For example, of interest would be, how would the reaction propagation and microstructural/phase evolution be affected by the temporal and spatial temperature and current distributions."

Jan 1, 2011

By Mototsugu Matsuno

A new process has been developed to treat fly ash generated from municipal incinerators, which contains not only toxic metals such as lead and cadmium, but also dioxins. The process includes the following steps; fly ash is formed into green pellets with some additives and the pellets are then roasted to eliminate or stabilize the toxic metals and to decompose dioxins. A pilot plant with a capacity of approximately 100 kg/hr was used to test the process, The tests verified that heavy metals were either volatilized or stabilized and dioxins were decomposed by high-temperature roasting. The pelletized ash was found to be non-toxic, so that it can be recycled as artificial lightweight aggregate. It was also found that volatilized metals collected as secondary ash can be recycled as smelting resources.

Jan 1, 2003

By Patrick R. Taylor

Keywords: Thermal Plasma, Electroreduction, Electrolysis, Transition metals, Waste treatment, Molten oxides, Chromium oxide. An innovative process to treat transition metal oxide waste materials from diverse sources is presented. This technology involves using reverse-polarity DC plasma driven electrolysis in molten oxides. The process results in the recovery of the transition metal and other heavy metals from waste. By-products generated throughout the processing was converted to environmentally acceptable slag. The significance of this technology is that the treatment of the waste is accomplished in one step which in turn lowers the cost of remediation. Moreover, this process uses high temperature properties of thermal plasmas, which makes it possible to use molten oxides instead of halides as electrolytes. Chromium was successfully reduced from chromium oxide through the plasma driven electro-reduction process. It was shown that the selection of the appropriate ionic conducting oxides was critical for the formation of a slag that would enhance the reduction of chromium oxide.

Jan 1, 2004

By R. M. Lamya

A considerable part of gold encapsulated in some refractory sulphides can be dissolved during sulphide matrix decomposition in non-complexing aqueous media. This has been concluded from laboratory results of gold extraction from pyritic and arsenopyritic concentrate containing 172.8ppm Au, into 10% hydrochloric, sulphuric and nitric acids. The degree of sulphides decomposition in the non-oxidative acids limits the gold extraction from this specific concentrate to about 10%. In the case of nitric acid, the gold dissolution follows the rapid decomposition of sulphides, reaching 32 to 42% of extraction at almost total decomposition of the sulphidic minerals. Accumulation of gold in this acidic and non-complexing solution to several ppm was not affected by the soluble products of the sulphides decomposition. An attempt to explain this gold behaviour is undertaken and some practical implications are discussed. In the investigated concentrate the "soluble gold" is mostly associated with arsenopyrite. This is consistent with the latest findings of other authors that gold disseminated in arsenopyrite can occur as cation Au3+. In a comparative test the gold extraction into highly concentrated chloride solution, in the same oxidative conditions, amounted to 92.34%.

Jan 1, 1995

By H. Y. Sohn, S. PalDey

"Fine particles of nickel aluminides and Ni4Mo were synthesized by reducing mixtures of, respectively, A1Cl3 + NiC12 and NiC12 + MoC12 vapors with hydrogen. Though thermodynamically favorable, the coreduction of NiC12 and A1Cl3 by H2 to form Ni3Al did not readily happen experimentally. The addition of a small amount of aluminum vapor was needed to initiate the coreduction reaction. The product particles as observed by TEM were very fine but usually agglomerated. The electron diffraction pattern of particles identified NiAl and NiA13 along with Ni3Al and metallic Ni. The content of Ni3Al was maximized at 52 mol% at 1050°C under the partial pressures ofH2, A1Cl3, and NiC12 at 57, 1.4, and 0.5 kPa, respectively. When a mixture of NiC12 + MoC15 was reduced by hydrogen, Ni4Mo particles with some Ni or Mo particles were obtained, the maximum content of Ni4Mo obtained being 93 mol % . The particle size was in the range of 100 to 200 nm. An Ni4Mo coating of 700 nm thickness on an Ni substrate was also prepared.IntroductionThe search for new high-temperature structural materials has stimulated much research on intermetallic compounds. Nickel aluminides have low densities, relatively high melting points, and good high-temperature strength properties. They show an increase, rather than a decrease, in yield strength with increasing temperature (1). Ni4Mo is also of interest as a high-temperature structural material. The major shortcomings of these intermetallics are their inherent brittleness at room temperature when they are in polycrystalline form. For much the same reason, the conventional casting of intermetallics is difficult. Ingot metallurgy and powder metallurgy are two other processing techniques. The first technique is quite energy consuming. In powder metallurgy, the powders of metals and alloys are consolidated in near net shape and then subjected to secondary processing. It would, therefore, be advantageous if intermetallic compounds can be produced in fine powder form from inexpensive raw materials, using less energy."

Jan 1, 1998

By A. Patti, S. Reutzel, D. M. Herlach, L. Ratke, I. Egry

Cu-Co shows a metastable miscibility gap in the region of the undercooled melt. Undercooling of the melt below the binodal leads to separation of the melt into a Co-rich LI-phase and a Curich L2-phase. Experimentally, undercooling into the metastable miscibility gap is realised by means of electromagnetic levitation (EML), processing in drop tube (DT) and by melt flux embedding. As undercooling is large in these experiments, the velocity of the solidification front is high and the microstructure is frozen in instantaneously. Samples have been undercooled and solidified in the TEMPUS-facility (container less electromagnetic processing under weightlessness) during parabolic flight under reduced gravity conditions. Microstructures of solidified samples have been analysed and compared to those processed under gravitational conditions. The influence of convection on phase growth is much lower in reduced gravity. The microstructure shows spherical droplets of the minority phase, statistically dispersed in the majority phase.

Jan 1, 2004

By Tuula Mäkinen

One of the latest applications of the Outokumpu Flash Smelting Technology is the direct smelting ,of nickel concentrates to metallised low-iron nickel mattes. Compared to the conventional nickel smelting, the new DON process needs a lower number of smelting vessels resulting in considerable economic and environmental benefits. Fundamentals of smelting nickel concentrates in one stage to low-iron mattes are presented. Properties of nickel. smelting slags with an emphasis of the slag fluidity at high MgO-levels are also discussed. Conditions prevailing in DON mattes at high oxidation degrees are presented as well as their influence on the behaviour of such mattes in the settler and on tapping the furnace. Distributions of elements in the direct smelting are presented and compared with the conventional process. A further comparison is made with pilot-plant data and the industrial scale.

Jan 1, 1998

By Achilles J. B. Dutra, Carlos M. Juarez

"The use of thiourea as a gold leaching reagent has been extensively studied by many researchers, and it has proved to be promising for some cases as refractory ores. Otherwise, the recovery of gold from these solutions did not receive so much attention. In this paper the electrowinning of gold in acidic thiourea solutions was studied by voltarnmetry and chronopotentiometry. An adsorption step was detected prior to Au(I) reduction and the diffusion coefficients at 25°C for Au-TU complex and FD were found to be 1.00 x 10.5 cm2 S-I and 1.98 x 10-5 cm2 S-I respectively. At -0.350 V (SCE) a passivation probably due to TU adsorption was observed. For higher overpotentials hydrogen evolution was the main reaction.IntroductionThe use of acidic thiourea solutions for the extraction of gold and silver has shown to be a promising alternative to the traditional process of cyanidation, specially for certain refractory ores (1-3) and electronic scrap (4). In some cases, the industrial scale was reached (1,5). The thiourea leaching of precious metals presents advantages over cyanidation, as faster kinetics, lower toxicity and lower sensibility to base metals; however the costs due to high thiourea consumption impairs its use.The majority of the publications on thiourea processing of gold is on leaching. Many are review papers (5-7). Recently, the adsorption and desorption of the gold-thiourea complex on activated carbon and ion exchange resins have been studied (8-11).Little research has been done on the electrowinning of gold from acidic thiourea solutions, most of it has been carried on the seventies and beginning of the eighties in the former USSR (12-17) and concerned the eletrolytic extraction of gold in tridimensional cathode cells.The present paper concerns the cathodic behavior of the gold-thiourea complex in the presence of formamidine disulfide in order to provide information on the electrowinning of gold from solutions obtained directly from leaching or from an elution process."

Jan 1, 1997

By A. Niedbalska

A technique was developed for low pressure diamond synthesis using a specially prepared glassy carbon. The glassy carbon is produced in the form of solid plates by slow carbonization process of phenol formaldehyde resin interrupted at temperatures of 1273° K, 1073° K, and 923° K. The diamond synthesis is performed using cobalt plates as a catalyst-solvent. Synthesis was carried out at applied pressures of 6.0 and 3.8 GPa and a temperature of 1970° K and 2170° K. The products were analyzed by the x-ray powder dyffraction method and by microprobe to identify the diamond crystallites. The samples were taken from the place of contact between the glassy carbon and the cobalt catalyst. They were separated from the charge by a chemical method. Diamonds of the best form and the largest size were obtained at pressures that were much lower than those used in the traditional graphite method of diamond synthesis.

Jan 1, 1989

By Lawrence D. May, Harry Mudgett

"In the course of developing a new industrial process, information produced at the Research and Development (R&D) stage is critical to determining the technical and economic feasibility of the project. Understanding the fundamental operating parameters for each unit operation in a flowsheet typically comes from historical knowledge of similar systems or by technical development through a robust research program. This approach holds true for processes incorporating fluidized-bed technology. In this paper, the authors will present a practical approach for performing a research study that will allow a process owner to determine if the concept of using a fluidized-bed system can become a reality. Included are discussions of key steps required at each level of the R&D program, and the critical information required for advancing the project to the next stage.IntroductionThe conduct of a research and development program typically starts with a process owner identifying a new industrial need or modification to an existing operation. The owner can pursue this need through multiple routes, including initial in-house development, coordination through an engineering firm, contacting suppliers of key equipment envisioned for the process, or through direct contact with research and development organizations. Where and when the project is conducted is as variable as the number and types of owners who pursue them. Factors that can influence the decision of where to conduct a research program can include the type of process desired, the scale and scope of the project, the location of the project site relative to the R&D options, the experience, capability, and availability of the potential research sources, and the costs to conduct the program. Often, the owner may choose a combination of the available resources to achieve their objectives. In the end, the owner's choice should be based on a thorough understanding of their goals and objectives for the program, and a good understanding of how to measure success while achieving those objectives. Herein, the authors will describe the methods we have typically used to develop the information an owner needs to make an educated decision for investing in a new or modified process."

Jan 1, 2014

By Kimiaki Utsunomiya, Yasumasa Hattori, Yoshiaki Mori, Toyokazu Okubo

"The effect of various operating conditions on splashing behavior in a Peirce-Smith converter has been investigated with a 1/5.7 scale cold model. Dynamic similarity between the model and a commercial converter was attained by setting the modified Froude number in the model experiments in· the range for normal converter operation. It is known that for a given modified Froude number the dimensionless penetration length of gas into the liquid phase increases as the liquid density decreases. Moreover, penetration· length has a large effect on splashing behavior. Therefore, a heavy liquid, a mixture of water and lead concentrate was used as the liquid phase. It was concluded that the amount of splash dramatically decreases with a reduction in the buoyancy energy per, unit liquid mass and an increase in the horizontal distance between the tuyere tip and the edge of the mouth.IntroductionSubmerged gas injection is widely used in practice in ferrous and nonferrous pyrometallurgical operations to achieve large gas-liquid contact areas and good agitation of liquid for rapid chemical reaction. The common application in ·nonferrous industry is the Peirce-Smith converter with multi-tuyere for copper and nickel matte converting. This process has been used for over 100 years because of its effectiveness in mixing of the molten bath, as well as its merits of the engineering simplicity. However, the mechanisms which · determine the blowing performance is poorly understood, and the design and operating conditions of the Peirce-Smith converter varies widely from plant to plant, such as by diameter, length, mouth angle, tuyere position and level of molten matte. Smelters have continuously made an effort to increase converter productivity, implying maximum tuyere blowing rate. Above a certain critical blowing rate, splash of molten matte from the converter mouth becomes unacceptable because of dangerous ejection and accretion buildup around the converter mouth, which results in interference with effective hood sealing. In fact, a 1993 converter survey[!] reported that splash was a major limiting factor for blowing rate and 54% of responding plants from around the world regard it as a limiting condition[2]. In order to increase tuyere blowing rate a study of the effect of various operating conditions on splashing behavior is expected."

Jan 1, 2000

By Kuniaki Murase, Tetsuji Hirato, Koji Nitta, Yasuhiro Awakura

"The redox behavior of copper species in an ""ammonium imide"" room temperature molten salt was examined in order to clarify the applicability of the salt to the electroplating media of various metals. Trimethyl-n-hexylammonium bis(trifluoromethanesulfonyl)- amide (TMHA-Tf2N), having an electrochemical window of 5.6 V (50 °C), and corresponding copper(II) salt were synthesized. In TMHA-Tf2N media monovalent copper ion, Cu(I), was stable and Cu metal was oxidized, or corroded, in the presence of Cu(II) species. Cathodic electrodeposition of copper metal and anodic dissolution of it were, thus, one-electron reaction and their current efficiencies were almost 100%.IntroductionElectrodeposition of metals from aqueous solutions is an important soft process for manufacturing thin-film materials, surface finishing, and extractive metallurgy. However, the electrodeposition of base metals, such as zinc, chromium, and nickel, from aqueous media inevitably accompanies hydrogen evolution, which lowers the cathodic current efficiency of metal deposition. Since the electrodeposition of aluminium, titanium, and rare earths from aqueous media is actually impossible due to their largely negative redox potentials, nonaqueous media such as aprotic organic solvent and high-temperature molten salts have been employed for the electrodeposition of these metals. Room temperature molten salts (RTMS),1, 2) or room temperature ionic liquids, have also been developed as a promising electrolytes for the electrodeposition of base metals. In this field, chloroaluminates of alkylpyridinium or alkylimidazolium cation have been well investigated for aluminium3) or alluminium-alloy4-5) electroplating media. On the other hand, in order to avoid high hygroscopicity arising from the use of aluminium chloride, attempts have been made to combine the alkylimidazolium cations with fluorine-containing hydrophobic anions, e.g. BF4-,6) CF3SO3- (TfO-),7) (CF3SO2)2N- (Tf2N-),8) and H(HF)n-ions,9) and investigated for electrodeposition media.'°) Recently, a new series of RTMS consisting of tetraalkylammonium cations and Tf2N- anion, sometimes abbreviated as TFSI- anion, was found independently by MacFarlane et al.11, 12) and Matsumoto et al. 13) This type of RTMS, which is commonly named ""ammoniumimide"" salt, has a wide electrochemical window of ca. 5 V and, thus, the RTMS seems to be suited for practical application as a solvent for the electrodeposition process. In this paper, we report the electrochemical behavior of copper species in an ammoniumimide RTMS, trimethyl-n-hexylammonium bis(trifluoromethanesulfonyl)amide (TMHA-Tf2N)."

Jan 1, 2000

By Kazuhiro Asai

Hitachi Refinery of Nippon Mining & Metals Co., Ltd. installed a reverberatory type recycling fumace in 1978 in order to treat the industrial wastes which contain metal elements such as copper, gold and silver. Pyrite and industrial waste materials such as galvanizing sludge, hydroxide slime and dust are smelted. Sulfidized copper, iron and precious metals are transformed into matte and other metallic elements are oxidized into slag This copper matte is transported to Saganoseki smelter and copper and precious metals in the matte are recovered. Recently it is difficult to obtain pyrite economically because of the decrease of pyrite production. Therefore, a new treating process of the liquid waste has been investigated at Hitachi Refinery. In this process, the sulfide or sulfate from the liquid waste are smelted as a source of sulfur.

Jan 1, 1997

By Aiyuan Ma, Tu Hu, Chenyu Sun, Yonggang Zuo, Hongying Xia, Jinhui Peng, Libo Zhang, Yongguang Luo

"In this study, the adsorption characteristics of tannin acid in aqueous solution were investigated using regenerated activated carbon (AC), with the aim to remove the tannin acid organic matter from the solution after zinc hydrometallurgy and Ge precipitation. Results showed the temperature has little effect on the adsorption ability (q.) of the regenerated activated carbon. The experimental equilibrium data were tested for the Langmuir and Freundlich isotherms. The adsorption equilibrium was better described by the Langmuir isotherm (R2 > 0.99). Pseudo first- and second-order kinetic models were used for describing kinetic data. It was determined that the kinetics of tannin acid removal was well fitted by second-order reaction.IntroductionGermanium recovery is a complex processes [1]. Hydrometallurgical processes are favoured and these are based on the precipitation of germanium as hydroxide or sulphide or alternately with tannic acid [2]. However, in the germanium recovery process, too much tannin is consumed by the germanium-tannins complexation process, and results in a high content of tannic acid remaining in solution, which is harmful to the valuable metal recovery [3]."

Jan 1, 2014

By W. Kunda

A laboratory study was carried out on the treatment of sulphidic copper concentrates in aqueous chloride systems under elevated temperatures and oxygen overpressure. Exploratory tests showed that chalcopyriteoxidizes with various chloride salts to form, depending upon the pH of the system, soluble copper chloride or insoluble copper oxychloride salts; the copper can then readily be recovered from the solution or residues respectively. During the leaching, iron was oxidized to iron oxide and remained in the leach residue while the bulk of the sulphide sulphur was oxidized to the elemental form with a minor portion oxidized further to sulphate. The presence of metal chloride salts in the system increased the oxidation rates of chalcopyrite and depressed the solubilization of iron in the system. A systematic oxidation leach study carried out in (1) ammonium chloride and (2) sodium chloride systems showed that the former system required little or no HC1 addition while the latter required 2 mol of HC1 per mol of dissolved copper (plus zinc). The copper was recovered from the cuprous or cupric chloride leach solutions by cementation with iron. Extractions of 99% copper and zinc, 97% silver, and negligible iron were obtained. Sulphur was oxidized to the elemental or sulphate form; the relative proportions of the total sulphur were 60 and 30% for system (1) and 80 and 10% for system (2). A flowsheet for a conceptual process with minimal reagent requirements was proposed.

Jan 1, 1976

By P. G. Comba

Many gold producing states are requiring rinsing of spent heaps to render the leached ore compatible with the environment and are placing restrictions on effluent pa, cyanide, and metals concentrations. Parameters which may affect efficient rinsing of heaps have been investigated by the U.S. Bureau of Mines in laboratory column studies. Rinse profiles for cyanide, metals, and pH as a function of the volume of water passed through the spent ore are presented. Fresh water rinsing of spent ore in columns showed that rinsing of cyanide was not affected by the rinse solution application rate. Interrupted rinsing with a rest period between applications reduced the volume of water required to meet effluent cyanide concentrations. chemical oxidation of the effluent with recycle of the rinse solutions reduced effluent cyanide concentrations and the volume of waste solution generated. Water rinsing was not successful in reducing the alkalinity of the cement agglomerated ore. A dilute acid solution had to be applied after cyanide removal to reduce effluent pa levels to specified limits.

Jan 1, 1992

By Hideki Minoura

"Two novel electrochemical techniques for the preparation of highly crystallized CdS film have been presented. One is cathodization of a conductive substrate in an acidic chemical bath containing cadmium salt and thioacetamide, where electroreduction of proton at small current densities induces a growth of highly crystallized CdS thin films, whose growth is not disturbed by the reactions in the solution phase. The other technique is electoreduction of aqueous Cd2+— SCN complex. An advantage of this technique lies in no formation of solid particles in the bulk, of the bath.IntroductionIn recent years much attention has been paid to materials preparation by solution processing because of its advantages in lowering the cost as well as the stress to the environment, as compared to the conventional gas phase techniques which unavoidably require high temperature and/or vacuum. We have been trying to explore novel techniques for preparing functionalized compound semiconductors by aqueous solution process. Semiconductors which we have been mainly focusing on are CdS and ZnO, which are important semiconductors finding applications in various devices. In the present paper, some of the techniques that we have recently established for the preparation of highly crystallized CdS will be presented.Methods of the CdS film processing in solution phase (wet process), which have been reported so far can be divided into two major groups; one is chemical bath deposition (CBD) in alkaline solution containing Cd2+ and thiourea 1)4) and the other is electrodeposition (ED) in acidic solution containing Cd2+ and thiosulfate ions - 5)-8) or organic solutions containing dissolved sulfur 9)-11)."

Jan 1, 2000