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By Dyson NF

Nickel sulphide precipitated from waste liquors at the Yabulu plant of Queensland Nickel Pty Ltd was pressure leached under various conditions. Leaching at 130¦C and 700 kPa of air dissolved 95 per cent of the nickel as the sulphate in less than 2 h. Leaching at 130¦C and 350 kPa of oxygen dis- solved 95 per cent of the nickel in less than 1 h. Dissolution was faster with oxygen than with the equivalent pressure of air. Crystallization of hydrated nickel sul- phate from the resulting clarified leachate is readily achieved. Because the sulphide pre- cipitate also contains minor amounts of iron, copper and cobalt, the crystallization product contains these metals in excess of the amounts required for electrolytic-grade nickel sul- phate. This grade of product could only be produced if the contaminants were removed prior to crystallization. Alternatively, the "crude" nickel sulphate could find a market as a feed for the electrolytic production of Ni-Fe coatings.

Jan 1, 1984

By B. Yawney

A copper-nickel sulfide concentrate was leached in water at about 2000C under oxygen pressures of about 0.35 MPa. Oxidation of sulfide to sulfate was virtually complete in about 30 minutes, resulting in greater than 95% copper and 98% nickel extractions. Leaching temperature was shown to be the most important factor affecting metal extractions. Measured rates of oxygen consumption were used to develop batch kinetic data. Mini-plant continuous pressure leaching tests agreed with batch leach results. A proposed overall flowsheet is briefly examined.

Jan 1, 1976

By Pollard D. M

Chalcopyrite samples from two different localities were leached in oxygenated mixed chloride-sulphate lixivants at elevated temperatures and atmospheric pressure. The oxidation of chalcopyrite was found to follow predominantly linear kinetics. The slope of the major region was dependent on stirring rate, oxygen flowrate and chloride concentration while only slightly dependent on the surface area of the sample leached. This region was found to predominate only at low temperatures. The oxidised chalcopyrite releases cuprous and ferric ions into solutions. Chloride ions complex these dissolved ions to effectively move the equilibrium of the leaching reaction to the right. When the level of chloride in solution was below 6 g/l, the unstable cuprous ions were found to reprecipitate with sulphur as covellite. When no chloride was present and the lixivant was a solution of sulphuric acid then ferric sulphates precipitated. The overall leaching reaction occurring in the leaching system is: CuFeS2 + 5H+ + 1.25 02 = Cu 2+ + Fe 3+ + 2S¦ + 2.5H20

Jan 1, 1987

By Ma Lianren, Wang Duolun, Chenzhe Li, Hongyan Xie, Fenglan Luo, Huixin Jin

In this study, the oxidation of low-grade pyrolusite to potassium manganate in alkaline solutions under O2 pressure has been investigated. The effects of different conditions on the high-grade and low-grade pyrolusite leaching process were investigated based on thermodynamic calculation, as well as the reaction mechanisms and kinetics of the low-grade pyrolusite during the leaching process. The results showed that the manganese conversion rates of the two types of pyrolusite were almost the same, and reaching 99% for high-grade pyrolusite and 96% for low-grade pyrolusite under optimal conditions. The optimum condition for low-grade pyrolusite sample JM-2 was achieved as 0.5 MPa of the oxygen partial pressure, 55% of KOH, 14 of the initial alkali-manganese ratio, and ≤ 48 μm of the mineral granularity at 260 °C within 150 min of leaching time and 500 rpm. In alkaline leaching of low-grade pyrolusite, Mn(IV) was oxidized into Mn(VI). The particles changed from large particles to flakes and finally formed crystals. Finally, the shrinking core model was used to fully describe the leaching kinetics of the manganese. It was demonstrated that the leaching of manganese was controlled by the chemical surface reactions and the activation energy which equals 115.9121 kJ/mol.

Dec 3, 2022

By F. Nava-Alonso, A. Uribe-Salas, C. Rodriguez-Rodriguez

Ozone has been proposed to pretreat refractory ores before the cyanidation process for precious metals extraction. As pyrargyrite is one of the silver species most common in Mexican refractory ores, the ozonization of this silver sulfide was studied. The effect of pH and ozone concentration on silver dissolution was evaluated by means of a factorial experimental design. Two levels of sulfuric acid concentration and ozone in gas concentration were evaluated: 0.18 and 0.72 mol/L of acid and 0.054 and 0.077 gO3/L, respectively. The highest silver dissolution was obtained when using the higher acid and ozone concentration.

Jan 1, 2011

By Patrick G. Hatcher

Studies of sedimentary humic acids by nuclear magnetic resonance (NMR), stable isotopes, and elemental analysis show they are derived by oxidative degradation of complex plant macromolecules that are insoluble in aqueous or organic solvents. The mechanism by which humic acids originate is fundamental to our understanding of the role of organic matter in ore deposition, because these substances can complex and mobilize a number of metal ions. The organic matter associated with uranium ores of the San Juan Basin, New Mexico and Carlin-type disseminated gold deposits of Nevada has certain organic geochemical characteristics that suggest an origin from humic acids.

Jan 1, 2013

By Michelle Mouton, Johanna van Deventer, Jussi Vaarno

Mintek has been involved in numerous projects to remove Fe and Mn from dilute Co sulphate solutions by means of oxidative precipitation using air/SO2. Test work was done using a gas induction system, designed and supplied by Outotec. Various aspects, such as SO2 concentration, SO2 flowrate, impeller rotation speed and pH were investigated on a 2 m3 scale. Batch tests were performed using a residence time of 5 hours. Mintek has been involved in numerous projects to remove Fe and Mn from dilute Co sulphate solutions by means of oxidative precipitation using air/SO2. Test work was done using a gas induction system, designed and supplied by Outotec. Various aspects, such as SO2 concentration, SO2 flowrate, impeller rotation speed and pH were investigated on a 2 m3 scale. Batch tests were performed using a residence time of 5 hours. Impeller rotation speeds of 0-220 rpm were tested, and it seemed that speeds of between 80 and 220 rpm gave similar Fe and Mn removal rates. Co and Cu losses were generally below 1% and 5% respectively at pH 3.

Jan 1, 2007

By N. Mulaudzi

The use of SO2/air gas mixtures as an oxidant to precipitate Mn from Co(II) leach liquors was investigated. The effects of SO2/air ratio, pH and temperature on Mn precipitation were evaluated. It was found that the use of SO2/air gas mixtures resulted in significantly higher Mn precipitation kinetics compared to using air or pure O2 alone. The SO2/air ratio was varied from 0% to 6% SO2(v/v) in air and similar Mn removals were achieved at 0.75% to 3% SO2 at pH 3. The solution pH was varied from pH 2 to pH 4; Mn precipitation did not increase considerably from pH 2 to pH 3, but increased significantly at pH values higher than pH 3. Cobalt co-precipitation also increased as pH increased, with 1% Co co-precipitation at pH 3. An increase in temperature from 30°C to 60°C also increased Mn precipitation and 100% Mn precipitated at 50°C. Cobalt co-precipitation also increased significantly with an increase in temperature. An activation energy of 25 kJ/mol was calculated from the Arrhenius plot, which is an indication that the precipitation reactions were both chemically and diffusion controlled. XRD analysis showed that Mn precipitated in the form of Mn2O3 instead of MnO2 that was predicted from thermodynamic data. SEM and XRD analysis also revealed that the precipitate consisted mainly of gypsum or bassanite (99%), with the Mn containing phase (< 1%) distributed within the gypsum phase. The co-precipitated Co reported to the Mn phase. Keywords: manganese precipitation; SO2/O2 gas mixtures; cobalt solutions.

Jan 1, 2009

By E. G. Parker

"Sherritt&apos;s zinc pressure leaching process converts zinc sulphide concentrates directly to zinc sulphate solutions and elemental sulphur. Thus, one pressure process step replaces both the roasting and leaching operations of the conventional roast-leach route. In addition, high single-pass extractions eliminate the need for residue treatments to recover unleached zinc. Because pressure leaching produces elemental sulphur, rather than sulphur dioxide, acid plants and smoke stacks are not required, and air pollution control and work-place hygiene are greatly improved. .In 1977, Cominco Ltd. and Sherritt Gordon Mines Limited jointly operated a three-tonne-per-day pilot plant to demonstrate pressure oxidative leaching of Sullivan zinc concentrate and the subsequent separation of elemental sulphur. The process consisted of regrinding the concentrate, continuous leaching at 150°C at elevated oxygen pressures in a four compartment autoclave and the subsequent recovery of elemental sulphur, either in the molten liquid form from a decantation autoclave or as a flotation concentrate. Of the zinc contained in the concentrate, 97% was extracted in 90 minutes, and 96% of the sulphur was converted to the elemental form.Following the successful pilot campaign, Cominco began building the world&apos;s first commercial zinc pressure leaching plant. This plant, which was in operation by late 1980, will eventually treat about 25% of Cominco&apos;s planned zinc capacity of270,000 tonnes per year.This paper describes the general process principles, the results obtained from the pilot plant and the integration of the process into Cominco&apos;s operations at Trail. The application of pressure leaching to a ""grass-roots"" plant is also discussed, and compared with conventional roast-leaching."

Jan 1, 1981

By E. Maziar Sauber

In order to prepare a more desirable feedstock for a rare earth elements separation refinery, cerium, a penalty element in the refinery feedstock, should be removed from the mixed rare earth elements oxide or carbonate feedstock. In this study, cerium (III) to cerium (IV) oxidation by calcium hypochlorite and subsequent precipitation was used to remove cerium from a mixed rare earth elements chloride solution. A factorial design of experiments was used to determine the effect of process variables such as temperature, pH, and oxidizer addition on the oxidation of cerium (III) using synthetic solutions. Under certain test conditions, all of the cerium was successfully removed from the chloride solution, and some REE accompanied cerium and reported to the precipitate. This proposed technology can allow for low cost removal of cerium from mixed rare earth elements chlorides.

By J. J. Egan

ADVANCES in the production of quality steel have emphasized the need for greater knowledge of the amount and distribution of oxygen in the steel. Control of inclusion content and quality is largely dependent on such knowledge. While many analytical methods have been de-vised for the accomplishment of this end, few are without serious limita-tions in accuracy, convenience, or skill required in application. Usually at least two methods are necessary to determine total oxygen and constituent oxides. Because of the great importance of this problem and the specific interest in the application of such methods of analysis, the various procedures were carefully reviewed at the Union Carbide and Carbon Research Laboratories, with the view of developing a method free from the limitations mentioned above. Intensive experimentation finally led to an improved iodine extraction analysis described by Cunningham and Price. I After this had been thoroughly checked from the standpoint of the analytical chemist, it was rechecked from that of the metallurgist. This involved preparation of a number of small heats of varying composition with determination of total oxygen in the molten metal by the alumina method2 and an analysis of the solidified material without the aluminum addition by means of iodine extraction; the oxides of iron, manganese, silicon and aluminum also being determined by the iodine analysis. The report of this work constitutes the subject of this paper.

Jan 1, 1933

By J. W. Hickman

INTRODUCTION MOST of the electron diffraction studies of oxide films which form on metals and alloys have been carried out by oxidizing the specimens in an auxiliary furnace, cooling down to room temperature and then inserting the sample in the camera and taking a diffraction photograph. Prior to the investigations at the Westinghouse Research Laboratories, no systematic study of the oxidation of any metal or alloy had been made over a wide temperature range with photographs taken at elevated temperatures except the investigation of iron by Jackson and Quarrell.1 In order to interpret the electron diffraction patterns of the oxides which may form on alloys, it seemed advisable to make a comprehensive study of the oxidation of the purest metals available in the bulk form. Thus far studies have been completed on iron,2 cobalt,2 nickel,2 chromium ,2 Copper2, tungsten,3 molybdenum,3 beryllium ,4 uranium,4 thorium4 titanium5 and zirconium5 while investigations are in progress on tantalum and columbium, The next step in the study is concerned with the investigation of the oxides which form on binary alloys. Some of the alloys consist of a single, phase while others contain more than one phase. The identification of the oxides on the surface of a binary alloy may be more difficult than on the metals since oxides containing both metals as well as those of each metal separately may form. Furthermore, it is possible that solid solutions of the various oxides may occur. In these cases the electron diffraction method may not be able to identify the oxidation products unequivocally, Examples of solid solutions which may present difficulties are MoO2 and W02, Fe3O4 and FeO-Cr2O3 since the diffraction patterns are so similar. Since electron diffraction can determine only the structure of the oxide, the chemical composition must be inferred from the diffraction data based upon X ray diffraction investigations of specimens of known composition. It is possible in some cases to decide whether a given solid phase reaction can occur on the surface of an alloy by a study of available thermodynamic data. Table I lists the equations for the formation of most of the oxides from the elements together with values of log10 KR for the several temperatures. [OF°R = -RT In KR 0 and-~75T = logi°KR] [?F°R] and KR are the free energy and equilibrium constant of the reaction. Calculations may be made using the values given in Table I to determine whether a given solid phase reaction is possible thermodynamically. For example, a solid phase reaction should occur between aluminum and chromium&apos; oxide to form

Jan 1, 1948

By Robert Mehl

PART I. ORIENTATION RELATIONSHIPS IN OXIDE LAYERS Oriented overgrowths and intergrowths among both metallic and nonmetallic substances have been recognized and studied for well over a century. The work of Widmanstätten in 1808 on the geometrical struc-ture in meteorites, a structure known by his name, demonstrated that oriented intergrowths can occur in purely metallic systems. This fact led to much of the early microscopic study of alloys, contributing greatly to the advance of physical metallurgy. The problem has been attacked again in recent years in a comprehensive fashion, with the object of dis-covering what atomic movements may occur during phase changes in alloy systems. Much of this work has appeared in the A.I.M.E. TRANS-ACTIONS in a series of papers published by Mehl and coworkers beginning in 19311. Although many aspects of this general problem remain unsolved, it may be said that the orientation of a new phase forming by precipitation from solid solution or by transformation invariably bears, a unique relationship to the orientation of the phase from which it formed, and that similarity in atomic patterns on atomic planes in the two phases play an important part in determining the orientation relationship. Analogous orientation relationships exist in oriented intergrowths in nonmetallic systems-mineral or inorganic. In 1827 Haidinger2 dis-covered natural intergrowths of hematite and magnetite, and demon-strated that the rough form of the magnetite octahedrons was delineated by small crystals of hematite, of which the basal (00.1) planes lay parallel to the octahedral cleavage planes of the magnetite. The description of this orientation relationship was later completed by von Rath3, who showed that the edge (00-1):(10-1) in hematite lies normal to the [111]

Jan 1, 1937

By P. Somasundaran

Flotation of oxide minerals is controlled by a number of factors, such as surface potential and solubility of the mineral, concentration and type of various inorganics, properties of the collector, pH, ionic strength and temperature. The role these factors play depends on the mechanisms of adsorption of the collector inorganics or polymer additives. The major mechanisms include electrostatic interactions, chemical adsorption, chain-chain interaction between adsorbed collector species and modifications of the surface by inorganics. In real systems, flotation is, however, markedly affected by various other processes, including aging of the minerals, surface precipitation of the collector on the mineral and associative interactions between various collector species leading to highly surface active, for example, ionomolecular complexes. These effects are reviewed here with selected examples.

Jan 1, 1999

By George Stone

THE method of making oxide of zinc direct from the ore was invented and developed at the works of The New Jersey Zinc Co. at Newark in the middle of the last century. The process was invented by Burrows, who had not the ability, financial or technical, to work out the details necessary to make it of commercial value. This was done by Col. Wetherill, whose name is commonly attached to this process. The, grate bars used are also frequently called Wetherill grates, which is a misnomer because they were in common use for boiler firing at the time and he never claimed their invention. The invention of the process was due to the efforts of The New Jersey Zinc Co. to find a profitable means of working the ores from Franklin and Sterling Hill, N. J. These are a mixture of franklinite, willemite and zincite, containing about 20 per cent. of zinc. The first attempts were to make spelter, which were not successful, owing to the low grade of the ore and the fusibility of the residue. Failing in this, the next attempt was to make oxide in large muffles and reverberatory furnaces. This succeeded, although the cost of operation was high, the recovery low, and the quality of the product uncertain. In 1855, the new process was patented and has been in successful operation ever since. Essentially, the process is to spread a mixture of coal and ore on a body of burning coal on a perforated grate and blow an excess of air through the grate. The zinc is reduced in contact with the coal, volatilizes and burned by the excess of air in the upper part off the furnace and in the flues. It is then carried to the hag rooms by the excess air and products of combustion which are forced through the flues by fans. In its main features, the process is the same today as at the time of its invention, but the details have been so modified that it would hardly be recognized by its originators.

Jan 9, 1917

L. E. WEMPLE, St. Louis, Mo. (written discussion *).-Mr. Stone refers to cadmium as one of the worst impurities in ores used for the production of zinc oxide for pigment purposes, because it is very volatile and its dark brown oxide and bright yellow sulphide both have strong coloring powers so that small fractions of 1 percent. injure the whiteness of the oxide. Numerous tests have recently been made by the American Zinc, Lead and Smelting Co. to determine what effect the percentage of cadmium, as ordinarily present in zinc ores, has upon the color of oxide made from such ores by the usual grate-furnace process. It has been found that while the cadmium is readily volatile and may be detected in the oxide product by chemical analysis, the oxide product is not discolored, but is of a clear white color. Analysis of the 12 leading brands of zinc oxide, French process, lead-free, and leaded grades now on the market for pigment purposes, show them to contain from 0.02 to 0.35 per cent. cadmium, figured as metal. If these proportions of cadmium were present as oxide or sulphide, the percentages would run from approximately 0.022 to 0.40 per cent. in the first case and 0.025 to 0.45 per cent in the latter case. All these grades of oxide are widely used for pigment purposes and are of a clear white color, except the leaded grades, the whiteness of which may be diminished by the lead sulphate. Tests made with admixtures of as low as 0.02 per cent. of cadmium oxide or sulphide to zinc oxide of the greatest hiding power (lead-free

Jan 1, 1918

By C. K. C. K. Gupta

The rare earths in elemental form are required for a variety of scientific and technological purposes. They are not easily obtained in this form, due to the great chemical stability of the rare-earth compounds and the strong tendency of elemental metals to react with everything they come in to contact with, especially at high temperatures. Beginning in the 1950s, when sufficient quantities of separated rare earths became available, as the result of intense research and development, three processing routes were developed to accomplish the preparation of all 16 naturally occurring rare-earth elements. They are chemical reduction of the halide intermediates, the oxides and electrochemical reduction of chlorides and oxide-fluoride mixtures. Not all the processes are effective with all the rare earths. In spite of the celebrated similarity of trivalent rare earths, the physical properties of individual rare-earth elements are sufficiently different that a variety of techniques are required for their preparation. The development of reduction processes for the rare-earth metals are covered in this paper, with focus on the oxide reduction routes. The strong reliance of effective reduction processes on the fundamental science of reduction reactions is highlighted.

By L. M. Bianchi

"Oxide, nitride and other compound coatings often do not have adequate properties for newer applications when produced using very high deposition rates and simple evaporation techniques. Solar control, abrasion resistance, low reflectance and barrier effective engineered coatings require exacting properties. Such properties can be obtained by adapting the activated reactive evaporation (ARE) technology to Web production processes. Adaptions of the HAD and MAD processes will be described along with data on the high deposition rates obtained. These fast production capabilities were developed in order to make the processes economically competitive.IntroductionThe Physical Vapor Deposition technique (PVD) has been used to coat steel strip for over 20 years. (1) However, its use as a production process has been very limited because of the high cost of the PVD coating process and because, in some instances, the properties of the coating were not good enough to meet the customers requirements. Nevertheless, the PVD process has found wide application in the airplane engine and electronic component markets. These production processes have stimulated further development and advances in the technology.In 1971, Profession R. F. Bunshah developed the Activated Reactive Evaporation (ARE) process which was then used to produce hard coatings such as carbides, nitrides, oxides and other refractory compounds. (2) The process from a fundamental viewpoint -produces a coating on the substrate via the evaporation of metal in the presence of a low pressure (typically around 1 millitorr) of reactive gas, with a plasma created in the space between the metal source and the substrate.The plasma may be created by many means but its function is two-fold. First, it activates the reaction between the metal vapors and the reactive gas atoms/molecules resulting in the formation of a compound that deposits on the substrate. Second, because the plasma is in contact with the substrate, it results in a negative bias on the substrate and produces bombardment of the growing film with ions and energetic neutrals from the plasma. This bombardment causes many significant changes in the microstructure, properties and appearance of the coating.Recently another new technology Pulsed Magnetron Systems (PMS) has been introduced into PVD. This new technology has been pioneered in production scale equipment by Dr. S. Schiller (3) and associates. The use of a pulsed power supply on the magnetron prevents the problem of the anode being coated with a insulating layer which will then lead to micro and macro arcing producing defects in the coating."

Jan 1, 1998

By Raymond Ward

IN the past few years several papers have appeared dealing with different aspects of the oxidation of dilute alloys, especially with respect to the formation of internal oxides or subscales. Subscale has been defined1 as that layer or zone of oxide particles precipitated in a matrix of metallic metal in which the oxide particles are dispersed uniformly and occur by diffusion of the oxygen inward from the metal surface. Alloys composed of a solvent metal more noble than the alloying elements are subject to subscaling or internal oxidation. In these alloys the solute must be present in such quantities that if the alloy is exposed to an oxidizing atmosphere at elevated temperatures, the rate of diffusion of the oxygen into the metal will be greater than the rate of diffusion of the solute outward. There is a composition range of the iron-silicon system that falls into this classification. Knowledge of the nature and rates of oxidation of iron-silicon alloys is of great commercial importance, but very little information of this nature is available. Darken2 recently has made calculations to show the limits of concentration of silicon for which subscales are produced in iron-silicon alloys; however, the main thesis of his paper was to analyze and to explain the already existing data. The purpose of this paper is to present the effect of com position, temperature, time, and atmosphere on the type of scale-metal layer obtained and to give some qualitative indication of the effect of these variables on the rates of oxidation. Since this paper is a study of silicon steels that are available commercially, extremely low-silicon and high-silicon alloys are not included. EXPERIMENTAL PROCEDURE The alloys used in the experiment were taken from heats of silicon steel that ranged in analysis from 0.70 to 5.8 per cent silicon. This composition range takes in most of the commercial silicon steels. In Table I are listed the compositions of alloys used. Other than iron and silicon, the alloys normally contained approximately the following impurities: carbon, 0.03 per cent; manganese, 0.07; phosphorus, 0.008; sulphur, 0.02; copper, 0.07; tin, 0.01, and from nil to a trace of chromium, nickel and copper. All of the alloys used were melted in open-hearth furnaces, except where otherwise noted, and were hot-rolled to 0.100-in. plate. Samples approximately 1/2 in. square were then cut from these materials. So that the surface conditions of the samples used for oxidation would be standardized, each sample was ground through 000 emery paper immediately before oxidation. Two different techniques were employed in carrying out the oxidizing treatments. One consisted simply of heating the samples with free access to air. In this treatment the samples were set on edge on a refrac-

Jan 1, 1945

By William E. Ford, Edward Salisbury Dana

I. Oxides of Silicon. 11. Oxides of the Semi-Metals : Tellurium, Arsenic, Antimony, Bismuth ; also Molybdenum, Tungsten. III. Oxides of the Metals. The Fifth Class, that of the OXIDES, is subdivided into three sections, according to the positive element present. The oxides of the non-metal silicon are placed by themselves, but it will be noted that the compounds of the related element titanium are included with those of the metals proper. This last is made necessary by the fact that in one of its forms TiOz is isomorphous with MnOp and PbOz. A series of oxygen compounds which are properly to be viewed as salts, e.g., the species of the Spinel Group and a few others, are for convenience also included in this class.

Jan 1, 1922