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By J. S. Kennedy, G. L. Simard, A. A. Lefrew, C. M. Judson, R. B. Booth

DITHIOPHOSPHATE collectors are commonly used in the flotation of sulphide minerals. Studies of the interaction of a typical dithiophosphate collector with galena surfaces have been previously reported from these laboratories.'* These fundamental studies were carried out by employing phosphorus labeled radioactive dithiophosphate. Radioactivity determinations then could be used to measure readily and accurately the small concentrations of dithiophosphate that are present under conditions of flotation processes. Measurements were made on ground mineral, determining the amount sorbed indirectly from the concentrations in solution; and studies were also made with single crystals, determining the amount sorbed directly by counting the crystal surface. The rates, isotherms and reversibility characteristics of dithiophosphate sorption, the competition between phosphate and dithiophosphate for the mineral surface, and the exchange of sorbed dithiophosphate with dissolved dithiophosphate were studied. These studies have now been extended by sorption measurements in flotations with a Fagergren machine. For this work, the selective flotation of galena and sphalerite from quartz was chosen, using ammonium di-(sec-butyl) dithiophosphate as the collector, sodium cyanide as depressant for sphalerite, and copper sulphate as an activator for sphalerite. While the selective flotation of galena and sphalerite using a single dithiophosphate collector is not typical of flotation practice (two different collectors are generally used), it was found that a reasonably good separation could be obtained by using zinc sulphate with the sodium cyanide in the galena flotation and by cleaning the sphalerite concentrate or by carrying out the sphalerite flotation in an alkaline medium. Data of practical importance on the distribution of collector between the concentrates, tailings, and solutions were obtained, particularly with regard to the effect of copper sulphate and sodium cyanide. In addition to the selective flotation of galena and sphalerite from quartz, single flotations of galena-quartz and sphalerite-quartz mixtures were carried out, along with blank flotations on quartz alone. The present paper describes the results of these experiments. As in previous papers, the term sorption is used to designate uptake of collector by the mineral, without implication as to the nature of the processes involved. Experimental Materials: The mineral system was a ground synthetic mixture of galena, sphalerite, and quartz. The galena was from Galena, Kans., and contained 75 pct lead (theoretical 85.6 pct Pb for PbS); the sphalerite, from Ottowa County, Okla., contained 63 pct zinc (theoretical 67.2 pct Zn for ZnS); and the quartz from Klondike, Mo., analyzed as 99.97 pct SiO,. Sulphur labeled radioactive di-(sec-butyl) dithiophosphate was prepared from SS supplied by the Oak Ridge National Laboratory on allocation from the U. S. Atomic Energy Commission. The synthesis consisted of precipitating barium sulphate, reducing the barium sulphate to barium sulphide, acidifying to form hydrogen sulphide, and oxidizing the hydrogen sulphide with iodine to elemental sulphur.

Jan 1, 1953

By J. S. Kennedy, A. A. Lefrew, C. M. Judson, R. B. Booth, G. L. Simard

DITHIOPHOSPHATE collectors are commonly used in the flotation of sulphide minerals. Studies of the interaction of a typical dithiophosphate collector with galena surfaces have been previously reported from these laboratories.'* These fundamental studies were carried out by employing phosphorus labeled radioactive dithiophosphate. Radioactivity determinations then could be used to measure readily and accurately the small concentrations of dithiophosphate that are present under conditions of flotation processes. Measurements were made on ground mineral, determining the amount sorbed indirectly from the concentrations in solution; and studies were also made with single crystals, determining the amount sorbed directly by counting the crystal surface. The rates, isotherms and reversibility characteristics of dithiophosphate sorption, the competition between phosphate and dithiophosphate for the mineral surface, and the exchange of sorbed dithiophosphate with dissolved dithiophosphate were studied. These studies have now been extended by sorption measurements in flotations with a Fagergren machine. For this work, the selective flotation of galena and sphalerite from quartz was chosen, using ammonium di-(sec-butyl) dithiophosphate as the collector, sodium cyanide as depressant for sphalerite, and copper sulphate as an activator for sphalerite. While the selective flotation of galena and sphalerite using a single dithiophosphate collector is not typical of flotation practice (two different collectors are generally used), it was found that a reasonably good separation could be obtained by using zinc sulphate with the sodium cyanide in the galena flotation and by cleaning the sphalerite concentrate or by carrying out the sphalerite flotation in an alkaline medium. Data of practical importance on the distribution of collector between the concentrates, tailings, and solutions were obtained, particularly with regard to the effect of copper sulphate and sodium cyanide. In addition to the selective flotation of galena and sphalerite from quartz, single flotations of galena-quartz and sphalerite-quartz mixtures were carried out, along with blank flotations on quartz alone. The present paper describes the results of these experiments. As in previous papers, the term sorption is used to designate uptake of collector by the mineral, without implication as to the nature of the processes involved. Experimental Materials: The mineral system was a ground synthetic mixture of galena, sphalerite, and quartz. The galena was from Galena, Kans., and contained 75 pct lead (theoretical 85.6 pct Pb for PbS); the sphalerite, from Ottowa County, Okla., contained 63 pct zinc (theoretical 67.2 pct Zn for ZnS); and the quartz from Klondike, Mo., analyzed as 99.97 pct SiO,. Sulphur labeled radioactive di-(sec-butyl) dithiophosphate was prepared from SS supplied by the Oak Ridge National Laboratory on allocation from the U. S. Atomic Energy Commission. The synthesis consisted of precipitating barium sulphate, reducing the barium sulphate to barium sulphide, acidifying to form hydrogen sulphide, and oxidizing the hydrogen sulphide with iodine to elemental sulphur.

Jan 1, 1953

By L. J. Dijkstra

During the past several years an extensive study has been made of the internal friction of iron containing carbon or nitrogen in solid solution.1,2,3,4,5 It has been found that a sharp peak is observed in a plot of the internal friction vs. temperature of measurement. With a frequency of about one cycle per second, this peak occurs at 20°C for N and 36°C for C. The physical origin of this anomalous internal friction was traced by Snoekl to the local tetragonal symmetry of the interstitial positions in body centered cubic (bcc) iron. A change in stress induces a change in the equilibrium distribution of the interstitial atoms among the three types of interstitial positions, the three types corresponding to the three directions along which the tetragonal axis may lie. It is the continual striving of the interstitial atoms to maintain an equilibrium distribution that gives rise to a phase lag between strain and stress during oscillation, and hence, to internal friction. A similar type of internal friction has been observed in the bcc lattice of tantalum containing in interstitial solid solution C, N or 06. The theory of this anomalous internal friction leads to the prediction that its magnitude is strictly proportional to the concentration of either the carbon or the nitrogen in solid solution, provided the concentrations are small. This prediction has been verified3 for the range of solubilities ohtainable in alpha iron. This proportionality provides us with a new tool for the study of nitrogen and carbon in alpha iron. It thus enables one directly to follow the precipitation of either of these solute atoms from solid solution and also directly to measure their solubility as a function of temperature. A preliminary study of precipitation using this method has already been presented by the author.3 The purpose of this paper is to present more extensive observations upon the precipitation of N and C in alpha iron, as well as to present observations upon the solubility of N and C in alpha iron which, at least in the lower tempera- ture range, are believed more accurate than those previously obtained by other methods. The interpretation of the observations upon precipitation involves the use of the appropriate equilibrium diagrams. For ease of future reference in this paper the equilibriunl diagrams for the Fe-N and Fe-C systems are accordingly reproduced as Fig 1 and 2, respective]y. Experimental Procedure The specimens were made of West-inghouse Puron iron and consisted of wires 0.025 in. in diam and about 1 ft long. By a wet hydrogen treatment the specimens were purified of C and N. In

Jan 1, 1950

By A. Choudhury

Deep open-pit mines are becoming increasingly common in the highly mineralized arctic and sub-arctic regions. Air inversion is a frequent occurrence in these regions, and is exacerbated by complex geometry of the open pit and the surrounding natural topography of an open-pit mine. The resulting inversion cap is known to contribute to the degradation of air quality in the open pit, resulting in loss of production. This paper discusses the development and validation of a three-dimensional model that simulate the flow of air and the transport of gaseous contaminants in an arctic open-pit mine and the analyzes effect of the geometry of the mine and the slope angle of the pit on the contaminants profiles in the mine.

Feb 27, 2013

EdgaR S. Cook, Pottstown, Pa.:—Many friends and acquaintances seem to be under the impression that the Warwick Iron & Steel Co. received a' license from Mr. Gayley, free of cost, as an inducement to adopt the process. This impression is not correct, since the license was paid for, and I think it was the first payment that Mr. Gayley received for the use of his process. As president of the Warwick Iron & Steel Co., I am responsible for its earnings, and with only the experience at the Isabella furnaces as a guide, the directors of the company considered that there was a great risk in expending the large sum of money required for the plant. They, however, acted favorably upon my recommendation, and to this extent I am responsible for the installation at the Warwick furnaces. I made the best agreement possible with Mr. Gayley, and naturally our company received certain advantages. It will be contrary to all experience if subsequent plants do not show some improvements and economies in construction. It is to our indirect benefit that all subsequent licenses granted by Mr. Gayley should be charged at a much higher rate than we paid; and I trust that he will see to it that all such licenses granted, especially to companies making merchant iron, shall be at a maximum figure. The Warwick Iron & Steel Go. is not interested in any way in exploiting the merits of the Gayley dry-blast process; on the contrary, looking at the subject from a narrow and selfish standpoint, it is to the advantage of our company that no merchant blast-furnace competing with our iron-product should be equipped with a dry-blast plant. There is a clause in the contract with Mr. Gayley, whereby our company agrees to furnish him with all the data derived from the operation of the dry-blast plant, and that he or his

Jan 1, 1909

By D. T. Randall

The burning of coal without smoke is a problem that concerns the Government directly because of the advantages of smokeless combustion both in public buildings and on naval vessels. In addition, smoke abatement is a factor in conserving the fuel resources of the United States. Hence, as part of its general investigation of the best methods of utilizing the coals of this country, the Bureau of Mines, which is in charge of the fuel-testing work formerly carried on by the United States Geological Survey, has made extended tests to determine the conditions necessary for the smokeless combustion of bituminous coal in boiler furnaces. Bulletin 39,¢ a preliminary report, treats the smoke problem from a theoretical point of view, detailing the steps that are being taken by municipalities, manufacturers, and citizens to abate smoke, also showing the possibility of a clean city. The present bulletin not only shows that bituminous coals high in volatile matter can be burned without smoke, but also that large plants carrying loads that fluctuate widely, where boilers over banked fires must be put into service quickly and fires forced to the capacity of their units, can be operated without producing smoke that is objectionable. Proper equipment, efficient labor, and intelligent supervision are the necessary factors.

Jan 1, 1918

By Jarvis ST

Colliery spoil is the major constituent of colliery spoil 'rockpaste' which has been used to infill abandoned limestone mines in the West Midlands of England since the early-1980s. The other constituents of rockpasle are pulverised fuel ash, lime and water. A key property of the rockpaste is its ability to flow within the mine workings over considerable distances before setting. This paper describes the work carried out to identify suitable sites as sources of colliery spoil for making rockpaste and goes onto consider the flow properties of the material and the monitoring methods used on-site. A full-scale trial comprising mulling a 6600 nt' section of an abandoned mine was conducted prior to the mulling of the Littleton Street Mine which had a volume of about 500 000 m'. As well as describing the methods used for monitoring the movement of rockpaste material, a description is also given of a dip-meter developed specifically for the purpose of measuring the level of paste in the mine. This paper shows how a colliery spoil based paste has been successfully rued for infilling abandoned mine workings. The monitoring systems developed for use in the two case studies presented in this paper are now being used extensively for infilling other abandoned mine workings. To-date over I I mines with a total volume exceeding two million cubic metres have been backfilled.

Jan 1, 1998

By M. H. Merriss

In the last few years, there have been developed at the plant of the Nichols Copper Co., Laurel Hill, 'Borough of Queens, New York City, improvements in electrolytic copper refining by the series system that have materially increased the flexibility and economy of that system. The purpose of this paper is to discuss, as of interest to refiners and to those who have copper to refine, as well as to the engineering profession in general, the changes' that have taken place resulting in wider application and increased efficiency of the series system. Copper is electrolytically refined in two ways, which are spoken of as the "multiple system" and the "series system." In both systems, the electrolytic tanks are in series electrically. In the multiple system the electrodes in a single tank are in multiple or in parallel, thus: There are two important adaptations of the series process, one represented by the series electrolytic tank room at the Baltimore Copper, Smelting & Rolling Co., Baltimore, Md., and the other by that of the Nichols Copper Co.'s plant. At Baltimore, the anode is rolled to perfect

Jan 1, 1926

By Tomas Astorga

APEC, the Asia Pacific Economic Cooperation is the forum of 18 economies, having a combined GDP of approximately 56% of the total world income, and over 45% of global trade. Its mining sector produces a large portion of the main minerals and metals in the world. In 1997, APEC economies produced 67% of world copper output, 55% of gold, and over 45% of other base metals. Mining in APEC captures more than 60% of the total mining investment in the world. Against this background, the Expert Group on Minerals and Energy Exploration and Development, in short GEMEED, was created in 1996, under the auspices of the APEC Energy Working Group. The sustainable development of mining activities is a main concern in APEC and GEMEED. Several programs related to the subject are actively being pursued by the Expert Group. Among them, it should be noticed the creation of an Environmental Cooperation Sub Group coordinated by Japan, whose main aim is to encourage proposals related to the environmental soundness of mining projects in the region. Also, it should be noted the existence of a Database Steering Committee whose focus is the development of an information network related to mining opportunities in the region GEMEED is a gathering of experts from all the APEC economies. As such, it represents a privileged forum to discuss policy issues related to mining. On this regard, the paper focuses on concrete actions taken by GEMEED to enhance the sustainability of the copper activity in the region.

Jan 1, 1999

By Erwin S. Sperry

The oxidation of metals melted in contact with air takes place with dissimilar results. Tin, lead or zinc are examples of a class, the oxides of which float on the surface of the melted metal. First a film is produced, which covers the surface; then, if agitation from any cause exposes new metal to the action of the air, additional oxidation takes place, and the film is increased in volume. This change goes on until a considerable quantity of oxide (or " dross," as it is technically called) is formed; depending, of course, upon the duration of the exposure of the metal to the atmosphere. When such metals are poured, the dross may be skimmed off; and clean metal will be left underneath. The removal of such oxides is, therefore, merely a mechanical process. In the case of copper, however, the result is quite different. The sub-oxide of copper (Cu2O) is readily soluble in molten copper; and therefore, instead of the formation of a film of oxide, to be finally removed as dross, the surface of the metal remains bright and clear, because the oxide has been dissolved as soon as it was produced. It is customary in the process of copper-refining to leave a small quantity of oxide in the metal, in order to oxidize any traces of bismuth, arsenic or antimony which have not been entirely removed. As a result, these metals exist in the commercial product as oxides, and not as metals, which would form an

Jan 1, 1901

By Bradley Stoughton, Henry M. Howe

This paper presents an experimental verification of some of the predictions made by one of us1 concerning the influence of certain conditions of casting upon the size and position of the pipe, and the position of the segregate, in steel ingots. The predictions which we have been able to verify are the following: A. That the pipe is shortened and the segregate raised: 1. By slow casting; 2. By casting with the large end up instead of down; 3. By retarding the cooling of the top, e.g., by means of a sinking-head. B. That the pipe is shortened by slow cooling. C. That the pipe and segregate lie in the last-freezing part. Our procedure was to cast ingots of wax (commercially pure stearic acid) containing a little bright green copper oleate (usually 1.5 per cent.) under varying conditions; to saw each ingot open along a longitudinal plane passing through its axis; and to examine the longitudinal section thus laid bare. In order to make the segregate or enriched part more distinct in color from the impoverished part, a very little red cerasine was added. An experiment which will be described later showed that the cerasine itself does not segregate markedly, if at all. Hence we may assume that the strong contrasts between the green and red shown in so many of our ingots are due, not to segregation of cerasine, but to that of the green oleate, in the wax which in itself is uniformly reddened with cerasine.

Jan 1, 1908

By I. Yochev, A. A. Metelev, A. I. Stepanenko, A. P. Purgin, M. G. Viduetsky, A. M. Panshin, I. F. Garifulin

"Pneumatic flotation cells of the KFM series are intended for the concentration of various ores and technogenic materials. The key operating principle of the flotation cells of the KFM series is the preparation of pulp for flotation in blowers, offering the advantage of an accelerated flotation process. This report summarizes the results of the implementation and operation of the KFM cells at Russian and foreign projects in 2015-2017. Their implementation and operation experience confirms the high efficiency of the KFM cells, especially in the head of lead and zinc, copper and zinc, copper flotation processes:head KFM-600 flotation cell recovers from lead-zinc ore (Rudmetal AD modular concentrator) up to 52% of lead in a single stage (without cleaner flotation) in a salable lead head concentrate (grade of up to 76% lead, 2.3% zinc). The flotation cell proved to be much more efficient than originally expected in the process description in the design phase,flotation of the copper-zinc ore from Novo-Shemur deposit (PJSC Svyatogor concentrator) in two KFM- 1400M cells recovers up to 65% of copper and 70% of zinc in a high-grade bulk copper-zinc concentrate containing 12-13% of copper and 25-28% of zinc. The installation of the two cells with a combined capacity of 26 m3 allowed to decommission 4 chambers of FPM-16 pneumomechanical flotation cells with a combined capacity of 64 m3 with a simultaneous increase in the overall ore concentration performancea single KFM-1400M cell (13 m3) recovers from the copper ore from Volkov deposit (PJSC Svyatogor concentrator) 53% of copper into a high-grade copper head concentrate (33.0% of copper). For comparison, the pneumomechanical cell FPM-16 (capacity 16 m3) has almost half as low copper recovery (29.6%) into the head concentrate at a lower grade (30.5% copper)."

Jan 1, 2018

By Shadia J. Ikhmayies

The SnO2/CdS/CdTe thin film solar cells were fabricated on glass substrates by using the spray pyrolysis (SP) technique for the deposition of the SnO2 and CdS layers and vacuum evaporation for the CdTe layer. The transmittance curves were used to investigate the interdiffusion in the two interfacial regions SnO2/CdS and CdS/CdTe by taking the first derivative of the absorbance as a function of wavelength. The appearance of new bandgaps around the bandgaps of SnO2:F, CdS:In and CdTe layers is a strong evidence on the interdiffusion in the two interfacial regions and/or the formation of quantum dots.

Jan 1, 2010

By M A. Gontalves, A F. D C Varajpo

The Rio Capim kaolin district, located in the north-east of Parß State, Brazil, constitutes one of the worldÆs largest high-whiteness kaolin reserves for the paper coating industry. It contains, at the base of the main ore, a soft kaolin that gradually changes at the top into a ferruginous duricrust followed by a flint kaolin. The flint kaolin is completely discarded during the exploitation of the soft kaolin. With the view of a more complete beneficiation, aiming at a sustainable development of the minerals industry, the use of this residual flint kaolin has been considered for the manufacturing of zeolites. Zeolites were synthesised from the flint kaolin through a reaction between metakaolinite with soda at 80¦C, for durations of 24 to 144 hours. The transformation into metakaolinite was carried out at 800¦C and was not affected by the titanium oxides. For a synthesis time of only 24 hours, a zeolite 4A very close to its theoretical definition was obtained, whereas for synthesis times longer than 96 hours, a slight formation of hydro-sodalite was also observed. The synthesised zeolites were tested as cationic adsorbents on 0.5 molar solutions of Cu, Pb, Cd and Zn. The adsorption was measured for contact durations of one and three days. It was noted that the exchange kinetics were slow and that the retention was significantly greater after three days than after one day. The retention was greater than 50 per cent of the theoretical exchange capacity for Pb, Cd and Zn, which was different to Cu, where the retention exceeded its theoretical exchange capacity.

Jan 1, 2008

By Pieter Steeneklm, Mazi’ Rejaee

"EXECUTIVE SUMMARYThe automotive industry's search for increased fuel efficiency through component weight reduction has driven the growth in consumption of magnesium metal in the form of die cast alloys. This trend, which began in North America and should soon accelerate in Europe, will require enhanced recycling services since each tonne of metal used for die cast parts production produces about 500 kg of scrap.Currently, the European die cast market is plagued by very high tolling prices for scrap recycling due to lack of competition and high transport costs due to the distances between the scrap generator and the recycling facility. This situation clearly increases the cost of magnesium die cast components and reduces magnesium's competitiveness with other materials. The challenge for the magnesium industry in the short term is to provide cost ·effective recycling solutions for the die cast industry. In addition effective recycling, in the medium to long term, is needed for the anticipated large volumes of secondary or used scrap that will become available as the die cast components reach the end of their life cycle. This paper will present The Antheus Integrated Magnesium Project as a Novel approach addressing some of the key recycling related issues facing the magnesium industry, in particular the die casters. The paper outlines the many advantages of an integrated magnesium metal park, in an overall goal of increasing magnesium metal's competitiveness."

Jan 1, 2000

By T G. Vizcarra, T J. Napier-Munn, A T. Karbowiak, M G. Hart

Squeezing extra performance from existing equipment (‘sweating the assets’) is key to continuous improvement initiatives, particularly during times of cost cutting where the option of spending additional capital to facilitate circuit upgrades can be severely constrained. A common challenge, however, is identifying the best combination of settings for different process variables, as their effects can be camouflaged by interactions with other process variables and, of course, noise in historical data.This paper describes a recent investigation at Boyne Smelters Limited to identify strategies to coarsen the product of its dry, fixed-speed, open-circuit AG mill, without the need for installing pre-screens prior to the mill. The product is used as insulation material for the reduction of alumina to aluminium, and an excessively fine product was inhibiting the ability of the cover material to dissipate heat from the underlying anodes. The approach was to undertake a series of experiments, designed according to statistical criteria, to elucidate the effect of key process variables (feed blend and power draw) upon the product sizing. The results provided clarity about what strategies would encourage the production of a more desirable mill product (with some surprises). The study is a good example of how properly designed experiments can identify hidden potential in processing circuits, thereby mitigating the need for capital-intensive upgrades.CITATION:Vizcarra, T G, Hart, M G, Karbowiak, A T and Napier-Munn, T J, 2018. Getting the most from existing processes: using cleverly designed experiments to optimise the line 3 AG mill at Boyne Smelters Limited, in Proceedings 14th AusIMM Mill Operators' Conference 2018, pp 207–216 (The Australasian Institute of Mining and Metallurgy: Melbourne).

Aug 29, 2018

By Binxu Zeng, Mark Jolly, Xiaojun Dai

"The traditional investment casting foundries use batch melting and chunky running systems to produce casting components. This method leaves the energy saving issue as subsidiary one. In our research project, one of the partners, the AEROMET international PLC provides the thin wall aluminium component ""filter housing"" for test. The AERO MET uses traditional casting route to produce the filter housing, which only gives 5% --10% yield. In this paper, numerical simulation method is used to analyse filling and solidification of the casting running system. The CRIMSON running system of the filter housing is designed by using casting simulation software, MAGMAS and Flow3D. By working with AEROMET, various configurations of the casting running systems were tested and analysed. Using them ultiple life cycle approach, the energy content of new process is compared with traditional one. It indicates that the CRIMSON process only uses 36% of energy consumed by the traditional route.IntroductionThe investrnent casting is a metal for ming process using expendable patterns, which is a standard casting technique and is widely used to produce quality parts. Its accuracy, versatility and integrity tie itself to important and precious engineering components in Aerospace industry. However, traditional investrnent casting process usually uses chunky runner system and gravity filling method. It not only reduces the casting yield of the product but also causes the pouring defect during the casting. As author's previous research showed that gravity filling method pouring basin and down sprue are two main resources of entraimnent defects generation. No matter how good the running system is, entraimnent defects such as double oxide films (DOF) and bubbles will I get into the casting to cause problem."

Jan 1, 2013

By R. E. Cech, T. D. Tiemann

It has been shown that hydrogen may be made to serve as a rapid and eflicient reducing agent for Cu, Ni, Co, and Fe sulfides if a scavenging agent for hydrogen sulfide is intimately mixed with the sulfide particles being reduced. Accelerated reduction kinetics are demonstrated for nickel sulfide. Copper, nickel, and cobalt sulfides, when treated at certain temperatures in a combined reducing agent-scavenging agent system, are converted to voluminous masses of fibrous metal product. Studies have been carried out to determine the conditions which lead, on the one hand, to irregular poly crystalline fibers and, on the other, to long single crystal filaments a few microns in diameter. A mechanism is proposed to account for the formation of single crystal filuments. The sulfide minerals of Cu, Ni, Co, and Fe are an important source of these metals yet there has been comparatively little scientific effort devoted towards understanding reduction mechanisms of these minerals. This may be, in part, due to the fact that the most convenient reducing agents for carrying out such studies, viz., hydrogen and carbon, do not react appreciably with sulfides. We have found that the reaction of hydrogen with metal sulfides can be markedly accelerated by placing a scavenging agent for hydrogen sulfide in close proximity to the metal sulfide. A brief series of experiments demonstrating relative reduction rates is reported in this paper to illustrate the effect. With the reduction process thus accelerated we have observed an unusual type of reduction behavior on some of the sulfides investigated. Under certain conditions the metallic product of the reduction reaction takes the form of filaments growing outward from the sulfide particles. The present paper deals largely with efforts to classify the various types of growth forms observed. This study has shown that filamentary growths from sulfides take a much greater variety of forms than has heretofore been reported by Ercker,1 Hardy,2 and Nabarro and Jackson3 in their reviews of metallic growths from copper and silver sulfides. THERMODYNAMIC CONSIDERATIONS The thermodynamics for hydrogen reduction of metal sulfides is quite unfavorable. For the sulfides considered here equilibrium constants typically range from 10-3 to 10-5. These low equilibrium constants impose severe kinetic limitations on reduction since hydrogen sulfide must be transported out of the system at concentrations of only a few hundred ppm. Unless extremely high gas flow rates are employed the atmosphere surrounding any sulfide particle will always be essentially in equilibrium with the sulfide. If, however, one places an efficient scavenging agent for hydrogen sulfide in close proximity to the metal sulfide particles the concentration of H2S near the metal sulfide will be held to a very low value. This would permit the reduction reaction to proceed with little or no inhibition from a buildup of reaction product gas. It is well known that calcium oxide is capable of removing hydrogen sulfide from a hydrogen gas stream of low dew point.4 If a sufficient quantity of calcium oxide is mixed with the metal sulfide particles the reaction: CaO+H2S=CaS+ H2O [l] will substitute moisture in place of hydrogen sulfide in the gas stream and this will not affect, in a direct manner, the reaction: MeS +H2=Me + H2S [2] A convenient method of considering the thermodynamics of the combined reducing agent-scavenging agent system is to consider the atmosphere when the partial pressure of hydrogen sulfide is the same over both the metal sulfide and the scavenging agent, i.e., pH2S (1) =pH2S (2). As a consequence: pH2O (1) pH2(2) =K1K2 The chemical driving force for reduction will depend inversely upon the moisture content of the gas and will be 0 when, in the system, pH2O = pH2.K1K2. Table I lists values of the equilibrium constants for reduction and H2S scavenging reactions for a number of sulfides at several temperatures. Data are taken from Rosenqvist4,5 and Kelly.6 The equilibrium constant products calculated from this data show that the limiting level of gaseous reaction product has been increased by a factor of 10' to l04 as a result of substituting a reducing agent-scavenging agent system for a simple reducing agent system. One possible side effect which must be considered is the possibility that the moisture evolved in the scavenging reaction might cause the atmosphere in the system to be sufficiently oxidizing to favor the formation of oxide rather than metal. This possibility was examined by comparing the equilibrium constant products listed in Table I with equilibrium constants for hydrogen reduction of the respective metal oxides. It was found that for copper, nickel, and cobalt the combined reduction-scavenging reactions could not develop a sufficiently high oxidizing potential in the

Jan 1, 1970

By Jianzhong Li, Yunkai Wang

Lead substrate anodes are widely used in the electroplating and electrolytic field. However, with the change of internal stress, the oxide films are gradually generated on the surface of lead anode. Their structure and stress properties were studied during the oxidation by means of Raman spectra, XRD, SEM. The result showed that the diffraction peaks of lead were mainly found at the initial oxidation stage. With increasing oxidation time, Pb diffraction peaks were weakened and the diffraction peaks of PbO/PbO2 strengthened remarkably. When the oxidation time was above 10 min, monoclinic PbCrO4 was also generated in the oxide film with CrO4 2 ions solution as electrolyte. Raman spectra revealed that Raman peaks of PbO/PbO2 were gained. In addition, Raman peaks of PbCrO4 at 830–840 cm−1 were found using the CrO4 2 ions as electrolyte. Based on the relationship of the internal stress of oxide film and Raman peaks shift, PbO/PbO2 induced obvious stress generation in CrO4 2 ion electrolyte. The nucleation style of oxidation film was 3D progressive nucleation at first. After the peak current, it turned to be 3D instantaneous nucleation. In the oxidation process, the internal stress of PbO/PbO2.

Mar 1, 2017

By G. L. Tufford, R. L. Bleifuss

Low-grade manganiferous iron ores of Minnesota's Cuyuna Range, in general, do not respond to conventional mineral dressing techniques because of their fine-grained texture. Reducing these ores to magnetite with subsequent magnetic separation and flotation have not given satisfactory results because, in many instances, concentrate grade and manganese recovery are low. Metallization of iron and concurrent reduction of higher manganese oxides to MnO, as in the R-N process, followed by recovery of iron by magnetic separation and manganese by leaching, seems to be a technically feasible process. High-temperature x-ray diffraction studies show that solid-state reactions between iron and manganese, with the formation of intermediate iron-manganese oxides, occur during reduction and affect recovery of both iron and manganese from the final product. Solid state reactions also occur between FeO, MnO, and SiO, at temperatures as low as 900°C. The kinetics of these reactions are such that they become an important factor in the treatment of ores by the R-N process. These investigations suggest a temperature and gas composition cycle that would maximize both iron and manganese recovery. During the past ten years, iron ore shipments from the Cuyuna Range of Minnesota have decreased sharp1y. Because of adverse grade, structure, and cost, many Cuyuna ores are no longer competitive with high-grade foreign ores and domestic pellets. The low-grade manganiferous iron ores from the Cuyuna Range, in general, do not respond to conventional mineral dressing techniques because of their fine-grained texture. Reducing these ores to magnetite for subsequent magnetic separation and flotation has not given satisfactory results because concentrate grade and manganese recovery are often low. However, a technically feasible process appears to be metallization of the iron and concurrent reduction of manganese oxides to MnO with recovery of metallic iron by magnetic separation and extraction of manganese from the tailings by leaching. In 1962 the R-N Corp., with a grant from the Area Redevelopment Administration, conducted an amenability study of the metallization of manganiferous iron ore from the Cuyuna Range. The results of this preliminary investigation were sufficient to interest the Economic Development Administration in sponsoring further studies of the process with emphasis on secondary recovery of manganese from the nonmagnetic tailings. Inasmuch as the metallization process has considerable influence on the final form of the manganese - its texture and distribution between the magnetic concentrate and nonmagnetic tailings-the investigation included a study of metallization of the ore as well. Therefore, the investigation conducted at the Mines Experiment Station covered three interrelated phases: (1) laboratory R-N roasting studies and magnetic separation tests, (2) laboratory chemical extraction experiments of the nonmagnetic tailings, and (3) a mineralogical study of the crude ores and their various roast products. High-temperature x-ray diffraction investigation of the Fe-Mn-Si0,-0, system is the main topic of this paper and an extension of the mineralogical work. GENERAL GEOLOGY The Cuyuna Range is known for its complicated geologic structure, complex orebodies, and generally indifferent response to attempts at conventional beneficiation. Several geologists have made intensive studies of the Cuyuna Range, including Leithl (1907), ~darns' (1910), Zapffe3 (1925), Grout and Wolff4 (1955), and schmidt5 (1963), whose study was the most comprehensive of all. The Range is covered with glacial deposits - till, out-wash, and lake sediments -up to 250 ft thick. Bedrock stratigraphic units of the Cuyuna Range consist of three tightly folded Precambrian sedimentary formations. The lower unit is the Mahnomen formation, composed of 2000 or more feet of argillite, slate, siltstone, and quartzite. The middle unit is the Trommald formation, which varies from 45 to 500 ft in thickness and comprises the major iron-bearing formation. The upper unit is the Rabbit Lake formation, consisting of over 2000 it of argillite, slate, and interbedded lenses of lean iron formation. In the central part of the Cuyuna Range, the units have been folded into a series of

Jan 1, 1969