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By Richard Schellinger, Ronald H. Carlson, Robert D. Norris

INTRODUCTION A very important key to the success of an in-situ leach venture is proper choice of well field chemistry, in which type and concentration of oxidant plays a significant role. For proper design of well field and plant, an engineer must be able to estimate uranium production levels and their change with time. The rate controlling step in the uranium leach process is generally acknowledged to be the oxidation step (Goddard and Brosnahan, 1980; McKnight and Anthony, 1979; Mays, 1979). Uranium head grade is very dependent upon concentration of oxidant injected into the ore zone. If oxidant levels are too low, uranium production requirements will not be met; if levels ate too high, excess oxidant will be wasted in side reactions with gangue material and leach economics will suffer. To date, no reliable laboratory technique exists for generating data easily translatable to field conditions. Empirical correlations based upon lengthy field testing have been the major tools avail- able to the design engineer to date. During the past five years, FMC has developed lab- oratory techniques for studying uranium leach chemistry under conditions simulating as closely as possible the field situation. Both agitated batch and consolidated core leach procedures have been developed. Results of FMC agitated batch studies are described in detail in a companion paper (Carlson, et. al., 1980). This paper will focus on the technique developed for leaching consolidated undisturbed core under simulated down-hole conditions. Through use of a follow-up computer model (Winkley, 1980), generated data can be translated to expected field response, thus providing the design engineer with valuable information in a relatively short period of time. CHEMISTRY In addition to uranium (+4), other oxidant-consuming species present in uranium ore are iron sulfides and carbonaceous material. Iron sulfides are usually present in concentrations far exceeding those of the other two materials and, therefore, represent the major oxidant-consuming species present in uranium sandstone ore. Previous studies (Carlson, et. al., 1980) have shown that iron sulfides exist in both Texas and Wyoming ores as a mixture of pyrite and marcasite (FeSz); furthermore, uranium mineralization (existing as uraninite) was shown to exist as a fine granular material coating or imbedded in iron sulfide crystals and sand grains (i.e. quartz and feldspars). The leach chemistry of a uranium ore body can be described by the following equations using hydrogen peroxide (Hz021 as oxidant:

Jan 1, 1980

By Knox Van Dyke, Vincent Castranova, Lixin Wu, Mark J. Reasor, James M. Antonini

"One of the proposed mechanisms involved in the pathogenesis of silicosis is that inhaled silica dust activates a ""respiratory burst"" in pulmonary phagocytes, such as macrophages and neutrophils. This increase in oxidative metabolism results in enhanced generation of reactive oxygen species which if produced in excess, would overwhelm natural defense mechanisms and cause damage to the lung parenchyma. This damage would then result in scarring, fibrosis, and decreased gas exchange.Weiss and LoBuglio' have listed several oxygen species produced by phagocytes which may be involved in cellular injury. These oxidants include superoxide anion, hydrogen, peroxide, hydroxyl radical, and hypochlorous acid. Superoxide anion (0;) is generated from molecular oxygen by the plasma membrane bound enzyme NADPH oxidase according to the following reaction:Once generated, superoxide anion can form hydrogen peroxide:In the presence of myeloperoxidase and halide, hydrogen peroxide can form hypochlorous acid:Superoxide and hydrogen peroxide can also form highly reactive hydroxyl radicals. Hydroxyl radicals can be generated slowly by the Haber-Weiss reaction:In addition. hydroxyl radical production can be catalyzed via the Fenton reaction:Hydroxyl radicals can also be generated from the reaction of superoxide and hypochlorous acid as follows:Recent investigations suggest that, in addition to the reactive oxygen species discussed above, nitric oxide may be a potential mediator of silica-induced toxicity.2-4 Nitric oxide (NO') can be generated by the cytosolic enzyme nitric oxide synthase according to the following reaction:NO synthase exists in two forms. i.e.. a constitutive. Ca2+-calmodulin-dependent form and an inducible. Ca2+-calmodulin-independent form. In pulmonary phagocytes. the activity of the constitutive form of NO synthase is low. However. NO synthase can be induced in macrophages and neutrophils by a variety of stimulants such as lipopolysaccharide. interferon y. chemotactic peptide, platelet activating factor, or leukotriene B4.3.5Once generated. nitric oxide can combine with superoxide anion to form peroxynitrite as follows:Peroxynitrite is a potent oxidizing agent. In addition, peroxynitrite can form peroxynitrous acid. which in turn can produce hydroxyl radical and nitrogen dioxide (all of which exhibit strong oxidizing potential) by the following reactions:Oxygen metabolites have been shown to cause lung damage in vivo.6 Such damage includes edema. leakiness of the alveolar endothelial/epithelial barriers, and airway constriction.7 Superoxide and hydrogen peroxide have been associated with membrane damage and cell lysis.8 These oxidants have also been associated with alteration of cytoskeletal structures at cell-cell junctions and elevation of transepithelial conductance in cultured monolayers.9 Macrophages or neutrophils can be stimulated by bacteria or phorbol myristate acetate to produce sufficient oxidant levels to lyse lymphoma cells.10 This cell killing is inhibited by catalase but is unaffected by superoxide dismutase. hydroxyl radical scavengers. or azide. i.e., an inhibitor of peroxidase. This implicates hydrogen peroxide as the active oxidant. Similarly. Weiss et al.11 have reported that hydrogen peroxide is critical in the death of cultured endothelial cells due to neutrophil activation. In addition. hydroxyl radicals generated by monocytes have been associated with cell injury.12 Lastly. peroxynitrite has been shown to oxidize sulfhydryl groups and to inactivate proteinase inhibitor making the lung more susceptible to damage caused by phagocytotic enzymes.' Therefore. a strong case can be made that activated pulmonary macrophages and neutrophils are capable of causing oxidant injury. This chapter presents in vitro and in vivo data indicating that silica is associated with the production of reactive oxygen species from these pulmonary phagocytes."

Jan 1, 1998

By F. M. Doyle, K. Osseo-Asare, E. Peters

With the aid of molecular orbital theory, a discussion is presented of the relationship between the electronic structures of ions and molecules, and the elementary steps involved in homogeneous electron transfer reactions. An electronic theory of the reactivity of oxidants and the mechanism of action of oxidation catalysts is then presented, with emphasis on the oxidative decomposition of metal sulfides. For model oxidants, two molecular reagents: O2 and Cl2, and two ionic reagents: Fe3+ and CU2+ were selected; silver (1) was chosen as the model catalyst. The reactivities of these reagents are rationalized in terms of constraints on orbital overlap, the availability of unoccupied d orbitals, and the rearrangement of electronic configurations.

Jan 1, 1993

By T. L. Baum

External oxidation during in-line heat treatment of TRIP steels can cause problems for the subsequent coating process. This research aims to elucidate the kinetic rates of internal oxidation, external oxidation and decarburization and their interdependence under different gas atmospheres and temperatures. A rolled steel sample chemistry of 0.14 wt.% C, 1.8 wt% Mn, 0.6 wt.% Si and 1 wt.% Al is used as a case study. Thermogravimetric techniques are used to examine the net mass change in a sample during heat treatment and the results show an initial mass decrease and later an increase for particular partial pressures of H2O. SEM-EDS, optical microscopy and glancing-angle x-ray are used to quantify the microstructure. The cross-section of the samples have 4 distinct zones: (i) an external scale, rich in fayalite, (ii) an internally oxidized region with Al, Si and Mn oxides in an Fe matrix, (iii) a decarburized steel region, characterized by large ferrite grains and low carbon content, and (iv) a relatively unaffected steel core with a structure similar to the starting material.

Jan 1, 2006

By Geoffrey Gilbert

A study of specimens shows that the key to both oxidation and enrichment at Duck-town is the behavior of pyrrhotite, which is in part dissolved and in part replaced by marcasite. Enrichment takes place chiefly at the expense of marcasite. THE material that forms the basis of this paper was collected in the spring of 1922, during a ten-day visit to Ducktown by the writer in the company of Prof. L. C. Graton. The time available for the work was far too short to allow anything like a thorough study of the deposits, and structural and stratigraphic questions, though they have an important bearing on the origin of the primary ores, were necessarily left untouched. Attention was focussed on the zone of oxidation and enrichment; and by devoting most of our time to the upper levels, open pits, and old workings, and examining the deeper levels only thoroughly enough to obtain a fair idea of the nature of the primary sulfide ore, we were able to make a reasonably complete survey of the various orebodies. With this field work for a background, the writer later made a study, in the Harvard laboratories, of the specimens obtained during the visit. As some of the facts brought to light by this study appear to be new, it seems worth while to set forth the outstanding features and a proposed explanation of them. Much of the Ducktown material that is obviously of greatest significance, as regards oxidation and enrichment, is soft and crumbly. Notwithstanding the desirability of gaining from such material all possible information as to its mineral composition and textural relationships, but little has heretofore been learned regarding it; but, by suitable preparation of this material in connection with the present study, it has been possible to examine it under the microscope without any disturbance of its texture and about as satisfactorily as if it were hard, fresh ore. The information thus gained has contributed measurably to the results set forth in this paper.

Jan 3, 1924

By Paul L. Allsman

Butte mining district contains extensive manganese vein deposits forming a peripheral zone. Oxidation in the veins studied usually extends to a depth of about 75 ft. Secondary minerals formed by oxidation were found to be ramsdellite-always accompanied by intermixed pyrolusite-and cryptomelane. Enrichment of the gossan is accomplished by reduction of weight upon oxidation; theoretical enrichment is 32.2 pct. Additional enrichment is caused by leaching of soluble minerals, particularly calcium and magnesium carbonates. Butte mining district contains extensive manganese vein deposits in the outer zone, surrounding the copper and zinc deposits and corresponding to the well known silver zone. This article describes the mineralogy of the manganese veins, the oxidation and enrichment processes, and the use of this information in prospecting.

Nov 1, 1956

By J. J. Talja

An investigation of oxidation of various nickel concentrates was carried out using differential scanning calorimetry (DSC). The aim of this study was to determine the ignition temperature and investigate other oxidation behavior of various sulfide-based nickel concentrates. Variables in the experiments were mineralogy, particle size and partial pressure of oxygen with temperature increasing linearly at 25 K/min from 323 to 1023 K (50-750 °C). The igni¬tion temperature was determined to represent the starting point of rapid oxidation. The reac¬tion enthalpies of the concentrates were determined and the amount of heat generated up to various time were used to calculate the extent of reaction. Mineralogical changes at various stages of oxidation were also investigated. For this purpose a second set of DSC-experiments were carried out in which each experiment was interrupted at a desired temperature between 673-873 K. From these tests the weight loss of samples were determined and changes in the individual constituent of sulfide minerals were analyzed. For pentlandite-based Ni-concentrates the ignition temperature was 705-710 K (approximately 435 °C). Pyrite was the first sulfide to oxidize. Reactivity of the violarite-based concentrate was greater than those of the pentlandite-based concentrates. The stoi-chiometry of pentlandite changed before ignition because of preferential oxidation of iron. Rapid oxidation of the pentlandite mineral occurred at about 823 K (550 °C). By 900 K about 90 % of the iron in pentlandite was converted to hematite, and NiS containing some iron was formed.

Jan 1, 1994

By J. Pang, S. Chander

The mechanisms of chalcopyrite oxidation in alkaline solutions have been studied using cyclic voltammetry and impedance spectroscopy techniques. The cyclic voltammetry was used to elucidate oxidation/reduction reactions, whereas impedance spectroscopy was used for in-situ characterization of the interface. To analyze the impedance spectra, equivalent circuit models were constructed based on a layer- wise growth of reaction products. Parameters of the equivalent circuit were calculated by comparing the experimental spectrum with that expected on the basis of equivalent circuit. From the value of equivalent circuit parameters, properties of the surface layers were inferred. These properties change substantially with the change in oxygen and/or collector concentration in solution. From such changes the effect of oxygen and collector concentration on the contact angle and flotation behavior of chalcopyrite were interpreted.

Jan 1, 1991

By J. Pang

The mechanisms of chalcopyrite oxidation in alkaline solutions have been studied using cyclic voltammetry and AC impedance spectroscopy techniques. Analysis of the impedance spectra using equivalent circuit models has made it possible to suggest layerwise growth of surface films. From the value of equivalent circuit parameters, properties of the surface layers are inferred. These properties change substantially with the change in oxygen and/or collector concentration in solution and give rise to changes In contact angle and flotation response. In agreement with prior investigations, the present study shows that flotation recoveries alone cannot be used to determine the effect of collector on flotation of chalcopyrite. The rate of flotation is a more sensitive parameter to determine the role of collector on floatability of chalcopyrite.

Jan 1, 1989

At the Orieco mine quartz veins carrying sulphides were localized in parts of an extensive fault zone in the Mathinna Beds during late Middle Palaeozoic mineralization.These deposits were subsequently exposed, and oxidation of the sulphides by percolating groundwaters resulted in the formation of gossans at the surface, and replacement close to the permanent water table of the more soluble sulphides by copper sulphides (chalcocite, coveIlite). A restricted zone containing copper oxides (cuprite, tenorite), copper carbonates (malachite, azurite), iron arsenates (scorodite, pharmacosiderite) and possibly rare copper sulphates occurred above the water table.The renewed oxidation of these deposits following mine development has been facilitated by the ready circulation of air and water combined with the formation of large free surfaces ideal for evaporation of aqueous solutions. Under these new conditions of high initial sulphate concentration, low pH, and relatively high Eh, the previously formed mineral assemblage is unstable and numerous Cu (Fe,Zn)-sulphates and Fe (Cu,Pb)-arsenates are presently forming in fractures in the fault zone and on the adit and stope surfaces for some considerable distance from the Sulphide-rich ore shoots. The observed spatial sequence of the major sulphates with respect to the sulphide-rich zones (Le. chalcanthite-antleritebrochantite and langite) is consistent with decreasing sulphate concentration and increasing pH away from the oxidizing sulphides.

Jan 1, 1970

By H. J. H. Pieterse

Agitation requirements in oxidation autoclaves can vary widely depending on the mineralogy of the feed material and the specific process selected. Before selecting an agitation system it is important that the client specify the desired throughput, mineralogy, chemistry, kinetics, compartments, overall retention time, and the desired oxygen utilization. In selecting the agitation system, the factors mentioned above as well as oxygen solubility, oxygen mass transfer coefficients, and specific power are evaluated. Much research effort has been directed toward open tank systems for fermentation and oxidation processes. However, for high pressure autoclave oxidation processes little information is available. In this review the author's experience in the autoclave industry and some of the available literature are utilized to compare the installed power per unit volume with some of the methods proposed for open tank oxidation. Equations that appear to give results close to that experienced in the industry have been identified. Further work is required in this area to develop a higher degree of confidence in the ability to predict the power required for any given case.

Jan 1, 2004

By R. G. Reddy

The oxidation kinetics of A13Ti intermetallics have been studied at the temperature range of 850°C to 100O0C in pure dry oxygen. The oxygen diffusion rates were investigated using TGA method. Parabolic rate constants were calculated. The oxidation scales were analyzed using SEM, EDS and X-ray diffraction. A continuous A120, scales with a little TiO2(rutile) were formed on the intermetallic surface. The A13Ti intermetallic exhibited excellent oxidation resistance among the Ti-Al base intermetallics.

Jan 1, 1997

By S. C. Sharma, M. Krishna, N. Sanmukha

"The oxidation behavior of an aluminium composite with 0, 2, 4, and 6% by weight of hematite at 200 to 500 °C has been investigated. Within the experimental temperature ranges a parabolic weight gain was observed. The, weight gain as a function of oxidation time becomes linear after an initial period on oxidation formation, an oxide scale was found whose morphology depends on temperature, cooling rate and sub-scale formation at the interface between the matrix and reinforcement. The presence of hematite particulate reinforcement has very little effect on the oxidation behavior. The interface oxidization rate was found to be higher than that of other regions. The, oxidation products were either metallic oxides or ceramic oxides. The exposure time of specimens to oxidation was 1000 minutes at various temperatures. In the present work key principles of alloy oxidation were discussed. Also the paper emphasizes various reactions taking ' place and the activation energies involved in the oxidation reactions.IntroductionMetal matrix composites (MMCs) reinforced with ceramic particulate, whiskers, or fibers have received increasing attention due to their potentially high fracture toughness and strength 1-5. Particle reinforced Aluminium MMCs find potential application in several thermal environment, especially in the automobile engine parts, space applications, such as drive shafts, cylinders, pistons, and brake rotors6.With the exception of gold, no metal or alloy is stable at room temperature, they tend to form their respective oxides. Most of the metals in the solid or liquid state are morphologically unstable when exposed to air at higher temperatures. An investigation relating to the temperature profiles of the piston area in a diesel engine has shown that the temperature can reach as high as 500¬800 K in certain regions of the piston. As the piston and cylinder areas are exposed to high temperature environment, the MMCs should have sufficient stability on both mechanical and chemical strength (oxidation). Oxidation occurs at grain boundaries in alloys and at the interface of the particulate and matrix in MMCs, which usually enhances intergranular fracture, resulting in premature failure and severe brittleness 8-10. Therefore for high-temperature applications, it is essential to have a thorough understanding of the oxidation behavior of aluminium MMCs."

Jan 1, 2000

By Chikabumi Yamauchi, Mitsuru Tanahashi, Jutaro Miura, Takaharu Iwadachi, Toshiharu Fujisawa

"Tue oxidation behavior of molten Cu-Be alloys was investigated by exposing· the molten Cu-Be alloys to various Ar-O2 atmospheres to control the oxygen partial pressure, PO2 = 10 ~105 Pa at 1423 K. The following results were obtained:• The oxygen · partial pressure in gas phase affects the morphology of the oxide formed on the surface of the alloy and · the oxidation rate of beryllium.• At lower oxygen partial pressure, a molten Cu-Be alloy is covered with a homogeneous and compact internal layer of BeO. Thus, the beryllium oxidation rate can be minimized.• By adding a small amount of calcium or zirconium into the molten Cu-0.5 mass% Be alloy, a protective BeO layer is formed even at higher oxygen partial pressure. Thus, the beryllium oxidation rate can be reduced.IntroductionCopper-beryllium (Cu-Be) alloys are well recognized for their unique properties, such as high electrical conductivity, high strength, high fatigue strength, excellent properties at elevated temperatures, good formability and good corrosion resistance. .This extraordinary collection of properties are the reasons why Cu-Be alloys are expected to be ""Key-materials"", which are necessary to further advance science and technology and to be applied in.various fields such as electronic devices, machine parts, repeater housings of undersea optical fiber communication cables, etc.However, a large amount of beryllium is oxidized to BeO in melting stage of the current Cu-Be alloy production process, because beryllium is a highly reactive element. This is one of the ·main factors that negatively affect the production yield and th_e product quality."

Jan 1, 2000

By Xuerong Wen

The oxidation behavior of TiAl3 intermetallics was investigated as a hnction of time at 1273K in pure dry oxygen. The oxidation experiments were carried out using TGA method. The oxidation scales were analyzed using SEM, EDS and X-ray diffraction methods. The structures of oxides formed at the different oxidation times were analyzed. The mechanism of oxidation of TiAl3 intermetallics was discussed.

Jan 1, 1998

By Cong Wang, Kexin Jiao, Yongan Zhao, Haibin Zuo, Jianliang Zhang

The carbon composite brick is a new refractory used in blast furnace hearth and bottom. It caused wide attention due to its high thermal conductivity and low erosion by molten iron. In this paper, chemical constituents, SEM-EDS and X-ray diffraction were carried out in order to understand reaction mechanisms. A series of experiments of oxidation resistance characteristics were made. The oxidation mechanisms of carbon composite bricks in the presence of air were analyzed. According to the analysis on many experimental results, the oxidation process of carbon composite bricks under different temperatures were controlled by different mechanisms. In the condition of high temperature, SiO2 as oxidation product hindered the diffusion of O2, and reduced the oxidation loss of graphite in the internal.

Jan 1, 2015

By R. C. Reed, A. Akhtar

Oxidation of the third generation cast single crystal, nickel-base superalloy CMSX-10 is examined using isothermal tests at 900°C and 1000°C for times ranging from 20 hours to 100 hours. X-ray diffraction, scanning electron microscopy and energy dispersive secondary X-ray analysis were used to characterize the microstructure. It was found that the external scale formed at 1000°C is made up of (Ni,Co)O and the spinel NiCo2O4. The (? + ? ') microstructure of the superalloy transforms into the intermetallic (3 phase prior to the onset of internal oxidation. Internal oxidation results in the formation of (Ni,Co)Ta2O6 and (Ni,Co)WO4. No evidence was found for the formation of alumina (Al203), and the spinels NiCr2O4 and NiAl2O4 in this third generation superalloy. Results of the laboratory investigation are compared with those of an aero-engine turbine blade removed from service and examined earlier.

Jan 1, 2004

By O. Jay Myers

THE war effort has furnished the necessary impetus for better magnesium foundry practice. Four or five years ago, there were but a few formulas in general use for cores and mixtures for magnesium castings. Certain sands, binders, and inhibitors were specified and the proportions of these materials in each mixture were maintained between very narrow limits. As more and more war industries entered the field, much research was carried out and methods and practices were improved. Magnesium founding is still in a state of flux; therefore it is not uncommon to find one foundry spraying inhibitors on its cores, and another foundry using sand mixtures with incorporated protective agents. The basic core or dry-sand mold mixture for magnesium in use today is compounded with sand, core oil or resin binder, cereal, and moisture. Core oil or resin binder are added for baked strength while the cereal binder and moisture are for green strength. The normal mixtures (based on the weight of the sand) contain from 0.5 to 1.5 per cent of both cereal binder and core oil, and the moisture content varies between 1.5 and 5 per cent. The ratio of core oil to cereal binder varies from 60:40 to 40:60, while the correct amount of moisture depends upon the method of coremaking. PROTECTIVE AGENTS In all magnesium practice, protective agents are used in conjunction with the core and molding sands to prevent oxidation of the metal. The use of these inhibitors is not novel, but publications covering this field are not entirely adequate. Beck1 says Magnesium alloys decompose water to form magnesium oxide, hydrogen being liberated in the process (Mg + H20 -+ H21 + MgO). This reaction results in the blackening of the skin and the appearance of areas of porosity on the casting surface, the cavities of which are filled with a grey oxide powder (these are termed `burns'). Although sand cores for magnesium castings are thoroughly dried during the baking cycle, burning will take place on the castings unless the metal is protected properly. This type of burning is more difficult to define than the "water-magnesium" reaction cited by Beck. A possible explanation may lie in the following equation: 2Mg + 02 -s 2MgO Here, the source of the oxygen is not water, but the air in the mold cavity, together with the chemically combined oxygen in the core-binding media. Generally, two methods are used to prevent this reaction from taking place.

Jan 1, 1945

By Seshadri Seetharaman, Nurni N. Viswanathan, Haijuan Wang

"In order to make the stainless steel making process efficient and environment friendly, it is essential to minimize the loss of chromium to the slag phase. With a view to investigate the advantages of using CO2 to attain moderate oxygen partial pressures in the oxidant gas during the decarburizations of stainless steel, the present experiments were carried out to understand the oxidation kinetics of Fe-Cr alloys and Fe-V alloy with gas mixtures containing CO2. In the present work, the oxidation behavior of Fe-Cr and Fe-V was examined by thermogravimetric analysis (TGA). Various mixtures of O2 and CO2 were used as the oxidant gas and the oxidation rate was followed by the weight changes as a function of time.The experiments demonstrated that the oxidation rate is independent of temperature at present experimental situation, but has strongly related to the Cr-content of the alloy as well as the oxygen partial pressure in the oxidant gas mixture. The wetting of alumina by the iron drop and the change of the drop shape during the course of the oxidation were investigated by X-ray radiography."

Jan 1, 2010

By B. M. Fisher

A process for making electrolytic copper of high quality from copper flotation concentrates is described. The concentrates are first slurried and then subjected to a high-temperature, high-pressure, oxidation-leaching operation under controlled conditions. The resulting slurry from the oxidation-leaching operation is cooled or flashed to atmospheric pressure and then subjected to a solids-liquid separation. The separated liquor, containing the recovered copper values, is cooled and then fed to an electrolytic deposition operation where metallic copper cathodes of high purity are produced. The spent electrolyte is then subjected to a sulfide treatment to precipitate the residual amounts of copper not deposited in the electrolytic cells. The precipitated copper sulfide is recovered and recycled in the form of a slurry to the initial stages of the process.

Jan 1, 1976