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The oxidation of sulphide minerals in aqueous suspension is discussed from several viewpoints. Limitations of our present knowledge are pointed out, and several points where further information would be of special interest are mentioned.Firstly, some properties of minerals and their effect on oxidation are discussed. Properties of different species, such as crystal structure, lattice bonding, and "metallic" properties are mentioned, and then the effect of variation within a given species is discussed. The effect of physical factors, especially particle size, is also considered. Other variables discussed include the importance of solution composition, and its effect on the nature and rate of reaction, and the use of various oxidising agents. Some factors concerned with the whole system, such as temperature, pulp density and stirring rate are then considered.Finally, the nature of various oxidation products is discussed with reference to the kinetics of reaction and the nature of the rate limiting step. It is suggested that more attention should be paid to electrochemical explanations of the reaction mechanism.INTRODUCTIONKnowledge of the factors governing the rate of oxidation of sulphide minerals in aqueous suspension is a prerequisite for the effective control of many ore treatment operations. Rapid oxidation of sulphides is usually desired during the leaching of sulphide ores and concentrates, but in the cyanidation of gold ores, or in the leaching of uranium ores, any oxidation of sulphides may be regarded as an undesirable side reaction. Knowledge of many of the factors involved is also of interest in connection with the oxidation of sulphides in flotation circuits and in natural ore forming processes.Systems for which some reasonably quantitative data have been published are listed in Table 1. Qualitative...

Jan 1, 1961

By M. J. Sinnott, H. B. Probst

AN extensive survey of the factors which affect austenite grain growth has already been made.' These factors are temperature, time at temperature, rate of heating, initial grain size, hot-working, alloy content, ofheating,initialand rate of cooling from the liquidus-solidus temperature. In the present work, a vacuum-melted temperature.electrolytic iron was used and the variables studies were temperature, time at temperature, and prior ferrite grain size. Other factors were maintained constant. The iron used in this study was vacuum-melted electrolytic iron of nominal composition of impurities of 0.07 wt pct. It was supplied as a ½ in. round cold-drawn bar. This iron was tested in three conditions: as-received, annealed 6 hr at 1200°F, and annealed 6 hr at 1600°F. Samples were ? in. disks cut from the bar. The prior anneals were carried out in vacuum and the isothermal treatments were carried out in vacuum-sealed Vycor tubing. The thermal etch technique was employed to determine the austenite grain size. Prior to sealing the test specimens, one surface of the sample was polished metallographically. This surface, after heating, was examined to determine the austenite grain size, since the austenite boundaries are revealed by thermal etching. This is essentially the only technique available for measuring the austenite grain size of low carbon steels or pure irons without altering the composition. It has been shown to yield results that are in agreement with other methods used for determining austenite grain sizes.' The specimen size was quite large compared to the grain size measured, so inhibition of growth due to size effects is probably negligible. After vacuum sealing, each sample was placed into a furnace at temperature and at the completion of the run was quenched into a mercury bath. The growth temperatures used were 1700°, 1800°, 1900°, and 2000°F controlled to -~10"F. Growth times were varied from 10 to 240 hr. The long times were used in order to eliminate the nucleation and growth effects occurring during the initial transformation. Time was measured from the introduction of the capsule into the hot furnace to the time of quench. Grain-size measurements were made with the use of a grain-size eyepiece of a microscope. By determining the number of grains per square millimeter at X100 and taking the square root of the reciprocal of this number, the average linear dimension of the grains was determined. Figs. 1 and 2 are plots of these data as a function of time and temperature for the various conditions investigated. The variation of D, the linear dimension of the grains, was assumed to follow the equation3 D = A tn. The curves of Fig. 1 were obtained from the data by the use of the least-squares method of analysis. Fig. 1 is for the growth of the as-received stock and Fig. 2 is for growth after prior treatments. Differentiating the foregoing equation gives an expression for the rate of growth dD/dt = G = nAtn-1 = nD/t. Both D and G as functions of t are given in Table I. It should be noted that G is a function of time; the growth rate is rapid at early stages and decreases with increasing time. Since increasing temperature increases the growth rate, it has been common practice to use the empirical relationship G = Go e-Q/RT to relate temperature to growth rate. The growth rate customarily has been taken at constant values of D on the basis that the rate of growth is related to the boundary surface tension and this is measured by the curvature of the boundary. At constant D values, the growth rate is a function of time and temperature. The growth rate can be related however to temperature at constant time, and this has the advantage that under these conditions the growth rate is a function only of temperature. Obviously the Q values, activation energies, obtained for each assumption will not be the same and the question of which is the more correct is a moot one, since the assumed exponential relationship in either case has no particular theoretical significance. By plotting G, at constant grain size, vs 1/T, the activation energy over the temperature range of 1800" to 2000°F is found to vary from 30,000 cal per mol at the smaller grain sizes to 50,000 cal per mol at the larger grain sizes. The 1700°F data do not correlate with the data at higher temperatures. The activation energies for the 1200" and 1600°F prior annealed materials were calculated as 50,000 and 62,000 cal per mol, respectively, using the reciprocal time to a given grain size as a measure of the growth rate. Plotting G, at constant times, vs 1/T yields an activation energy of 12,300 cal per mol for the tem-

Jan 1, 1956

By M. Kaufman, D. Rosenthal

IT would be of great importance to our understanding of the phenomena of fracture in metals if a unique relationship could be established between stress and some easily measurable parameter of deformation up to the fracture. It is known that no such relationshir, has been found when the parameter was the mechanically measured strain,' the major part of which is plastic. The present investigation was initiated to determine, among other things, if the X-ray or lattice strain" might be a • For the definition of lattice strain see ref. 2. more suitable parameter. To this end, annealed stress free*' specimens of 61s aluminum alloy were ** Freedom of stress in this particular case means absence of those stresses which can be checked by the technique employed. tested at room temperature and liquid nitrogen temperature (—195OC), by first maintaining the same temperature from the beginning until the end of the test, and then with crossovers from one temperature to the other. Three major factors had to be taken into consideration in designing the specimens and testing equipment. The test setup must allow X-ray pictures to be taken while the specimen is under load (for as much as 2 hr at a given load). Provision must be made for maintaining the test specimen at the temperature of liquid nitrogen as well as at room temperature. In addition, the specimen must be able to rotate to allow the X,ray beam to take in as large a sample of grains as possible, to maintain centering, and to correct for effects of large grains. The final design of the specimen and equipment is shown in Figs. 1 and 2. The specimen and grips are hollow, enabling liquid nitrogen to be poured in through a funnel-container arrangement while the specimen is rotating. The diameter of the specimens at the 2 in. gage section is 5/16 in. with a 3/16 in. diameter hole through the center. A small pilot valve in the lower grip allows a very small stream of liquid nitrogen to escape, thus assuring circulation of the liquid at all times. A low temperature silicone grease-tissue paper packing is used to seal all joints. The specimen is held in the grips by a pin. Spherical socket joints at top and bottom are used to allow for proper alignment. The grips are connected to the thrust bearings by means of plastic couplings to decrease the heat flow. Rotation is accomplished by means of a motor which drives a plastic gear (integral with the lower coupling) through a semiuniversal joint to allow for deforma- tion of the specimen. The torque applied to the specimen is very small. The maximum stress caused by this torque at the highest loads reached was found to be less than 200 psi, The whole unit was mounted in a 10,000 Ib testing machine. An insulation cage was placed around the specimen to cut down air circulation, and consequent frosting of the specimen, and also to reduce radiation and convection heat losses. A narrow window, covered on both sides with a thin plastic materiai allows the X-ray beam to reach the specimen. Thermocouples placed just outside the pilot hole at the lower grip, in the bottom of the funnel container and near the top of the funnel container permitted checks of the

Jan 1, 1955

By W. A. Tiller, D. H. Lane

A simple zone melting technique for investigating the effect of ultrasonic irradiation upon ingot solidification is described. The effect of i) ultrasonic power level, ii) freezing velocity, iii) constant or variable frequency, iv) direction of irradiation, and v) transducer-cozlpling bar joint upon the grain size of type 316 stainless steel have been investigated. The results of this study support the postulate that the ultrasonic vibrations increase the nucleation probability in the layer of liquid adjacent to the freezing interface. In the first paper of this series,l the possible mechanisms whereby ingot structure may be altered by irradiating a solidifying melt with ultrasonic vibrations have been discussed. A new technique for efficiently introducing the ultrasonic energy into the solid-liquid interface region was presented and applied to ingot preparation by the consumable-electrode arc-melting technique. The experimental results support the postulate that the ultrasonic vibrations may refine the ingot structure by increasing the nucleation probability in the zone of liquid adjacent to the solid-liquid interface. The present paper describes the application of the same technique to a relatively simple laboratory-scale zone-melting apparatus. This apparatus is found to be well suited to the detailed study of ultrasonic technology in this area and allows one to determine, in particular, the minimum ultrasonic power level needed to produce a certain grain size in a particular material. The results of this study support the nucleation mechanism for grain refinement, but do not provide any deeper insight into the specific nucleation mechanism responsible for the effect. EXPERIMENT The apparatus used in these experiments is shown in Fig. 1 and illustrated schematically in Fig. 2. The material to be studied, type 316 stainless steel, was in the form of a 3/4-in. sq bar 30 in. long. This bar was placed in a square open-topped mold with open ends made from high-purity graphite coated with a flame-sprayed Al2O3, skin. Surrounding the crucible was a molybdenum susceptor with 3/8-in. diam holes spaced at 1-in. intervals along its length to serve as sight ports. A tapered transducer horn was brazed to one end of the specimen. The entire assemblage was enclosed in a quartz tube, the transducer itself projecting out one end and resting in a cooling tank. A vacuum seal between the coupling bar and the end plate enclosed one end. A similar plate and seal enclosed the other end. The system is gas tight and can be operated under vacuum or an inert atmosphere. For these experiments, flowing argon at 15 in. of Hg pressure was used. The heat source for melting the stainless steel specimen was a 2-in. long 3-kc induction coil placed around the quartz tube; this source heated the susceptor, inductively melting about a 3-in. zone of the sample by radiation. To move the molten zone at a specified rate, the induction coil was moved down the tube at this rate with the aid of a simple pulling device. Thus, the sample could be irradiated at varying ultrasonic frequencies and power levels and could be solidified at varying rates. The power input to the transducer was measured using a "John Fluke Model 120 VAW-Meter." 1 The power delivered to the interface region is probably only about 50 pct of that measured on the VAW-meter. In a typical run, when the ultrasonic power was turned on, the interface of the molten zone closest

Jan 1, 1961

By William Gleason

"While the American Exploration & Mining Association (AEMA) was preparing to close one chapter and begin another during its annual conference in Spokane, WA Dec. 3-7, word of a significant victory on an issue that has been important to the association for many years came from the halls of Washington, D.C.During a keynote address on Dec. 6, Joe Balash, assistant secretary of Land and Minerals Management for the U.S. Department of the Interior (DOI), told a sold-out lunch crowd that the DOI had released final drafts of proposed revisions to the Obama-era greater sage grouse conservation plans. The revisions suggest removing hundreds of thousands of acres of federally protected habitat in Utah, and easing restrictions on energy development and other activities, including mining, in Colorado, Idaho and Wyoming.The protections of the sage grouse were put in place by the Obama administration in 2015. The sage grouse, a prairie fowl, is considered by conservationists to be a key indicator species for the health of America’s sagebrush ecosystem. The previous plan to protect the ground-dwelling bird imposed restrictions to development in sage grouse habitat, but did not place the birds on the endangered species list — a move that many believed would have imposed far more rigid rules.AEMA, and its executive director Laura Skaer, led the way in the fight against the Obama-era greater sage grouse plan, arguing that the plan unnecessarily hurt economic development.“We were the first organization to point out that the greater sage grouse was being used to stop mining, oil and gas production and grazing on public lands in the interior mountain west,” said Skaer who is retiring from AEMA with a significant legal win on this front. “Early on, we cautioned that the proposed Land Use Plan Amendments would be worse than a listing (of the sage grouse) under the Endangered Species Act. Very few believed us until they saw the plans with all of the restrictions and the recommendation for a 4-million-ha (10-million-acre) withdrawal from mineral entry. We were the only organization that filed comments on all 88 Land Use Plan Amendments in 11 states covering more than 24.2 million ha (60 million acres).”"

Feb 1, 2019

By Donald T. Hawkins, Ralph Hultgren

The lorsion effusion method has been used to measure the vapor pressure of lead over pure lead and eight Pb-Sn alloys ranging from 9.1 to 87.9 at. pct Pb in the temperature range 950° to 1125°K. The resulting ?H°y 298 = 46,630 ± 200 cal per g-atow for pure lead is in excellent agreement with previous work. Deriued ?Gph values for the alloys were smoothed and correlated with previous heat of formation data to obtain entropies for the liquid alloys. values for the tin component were calculated by Gibbs-Duhem integmtion. Surfhce depletion of these liquid alloys was found to be absent, as shown by the fact that the measured pressure remained substantially constant with time in contrast with previous measurements on iron-rich solid Fe-Mn alloys. The activities and Gibbs (free) energies of the liquid Pb-Sn system are not well known although the heats of formation have been accurately determined by K1eppa.l Vapor pressure determinations of the activity of lead by Voronin and Evseev2 disagree with those of Predel.3 Elliott and chipman4 measured activities by the electromotive -force technique in the ternary Pb-Sn-Cd system. From the resulting values of the activity of cadmium, they were able to calculate the activities of lead and tin for the binary Pb-Sn system at the compositions xsn = 0.33 and 0.67. Atarashiya, Uta, Shimoji, and Niwa5 determined the activity of tin from Hz-H2O equilibrium measurements, but their results are subject to question due to uncertainty in the final state of their samples. To resolve these differences, measurements of the activity of lead were made using a torsion-effusion apparatus. Among other advantages, this apparatus rapidly detects errors caused by surface depletion, which tends to reduce the apparent vapor pressure of the more volatile component. If the measured torques remain nearly constant with time, only bulk depletion is occurring. This contrasts with the rapid decrease in torque found in solid Fe-Mn alloys at high temperatures and low manganese contents.6 EXPERIMENTAL 99.999+ pct Pb was obtained from the American Smelting and Refining Co. and 99.999 pct Sn from Vulcan Detinning Co. Eight Pb-Sn alloys were prepared by melting together weighed amounts of the pure metals in evacuated Pyrex tubes and quenching the melts in water. Loss of weight in preparation was less than 0.02 pct in all cases. The effusion cells were made from high-purity, nonporous graphite. Graphite was chosen because of its resistance to reaction with lead and tin and because it can be accurately machined with precision orifices. Two cells were used with overall dimensions as shown in Fig. 1. The orifices of cells 1 and 2 were, respectively, 1 and 1.5 mm in diam.

Jan 1, 1968

By Michael J. Virnig, Murdoch W. MacKenzie, Michael R. Davis

The objective of this paper is to present preliminary capital and operating cost estimates (±25%) comparing conventional carbon-in-solution (CIS) with resin-in­solution (RIS) using AuRIX® 100 for the recovery of gold and silver from typical heap leach solutions. Preliminary testwork was carried out with AuRIX® 100 using real and synthetic leach solutions to determine the technical viability of the resin for gold/silver recovery and to provide process design parameters for the preliminary RIS circuit. The scope of the resin testwork was sufficient to support the level of accuracy applied in the capital and operating cost estimates. No parallel testwork was carried out with activated carbon. Industry standard design data and operating data from existing CIS operations were used as a basis for the comparison. Both the capital and operating cost comparisons indicate a substantial savings for a RIS circuit using AuRIX® 100 (- 14 to 18% in terms of capital and 25 to 35% in terms of operating costs) over a conventional CIS circuit depending upon solution flows and grade.

Jan 1, 1999

Use controlled blasting techniques to reduce blast-produced overbreak damage to underground mine ribs and back for both safer working conditions and improvements in productivity. The Problem Blasting is used in metal and non-metal underground mine slopes, drifts and crosscuts to fracture rock to be excavated and further processed. Standard blasting also produces fractures in the rock beyond the desired excavation area. This is sometimes evident by rough surfaces, undercutting and other signs of excessive damage. This damage contributes to rockfalls in the mines, a major cause of injuries and fatalities, and equipment damage. A variety of controlled blasting techniques has been developed for civil engineering projects where long-term stability is essential. For several reasons, these methods arc not widely used in mining. For example, these methods incur additional costs and time; there is little need to maintain stable openings over long periods of lime; and there is the perception (hat corrective remedial techniques, such as rock bolting, are more practical. Basically the benefits of these methods are not demonstrably clear for application in underground mines.

Jan 1, 1991

By J. D. Zhu, T. Ohmichi, H. Yasuda, S. Kashiwai, I. Ohnaka

"Since the casting process affects the properties of castings, its computer simulation has been greatly developed in the last decades. This paper presents our recent works, especially on mold filling simulation, because most casting defects such as porosities and inclusions that greatly affect the properties originate during mold filling. The first topic is the mold filling simulation with consideration of cavity pressure change during mold filling, including direct observation of flow phenomena with X-ray and pressure measurement. The second .one is the mold filling simulation in the lost foam process, in which gasification of polystyrene pattern and gas outflow through the coating and mold have been considered. The simulation can predict not only the mold filling sequences but also periodical vibration of the gas layer between the melt and pattern. The third one is the comparison of simulation of Al melt flow in a metallic runner and direct observation through a transparent mold, showing that the entrapped gas or inclusions is expelled ahead through the melt and its simulation needs very fine meshes. These examples show that the comparison of simulation and observation is very important to develop the numerical simulation further.IntroductionThe mechanical properties of castings are greatly affected by casting defects such as porosities and inclusions, and solidification structure. Although recently the structure simulation has greatly progressed [1-4 ], the application in plants is very limited, because the structure is mostly determined by chemical compositions and cooling rate, enabling us to estimate it from the structure of past similar castings without simulation.On the other hand, the casting defects often vary with each casting or time. Among the defects, porosities and inclusions are main causes to deteriorate the properties and mostly originate during mold filling. Therefore, a lot of efforts to simulate the mold filling and estimate those defects have been made in the last decades [l,5,6]. These efforts have been mostly to develop numerical techniques to solve the Navier-Stokes equation. However, the flow phenomena in molds have not been well understood, because the direct observation of the flow phenomena in mold is not easy. This means the accuracy of the simulation is still not clear."

Jan 1, 2000

By Heinrich Möller

The electro-oxidation of 0.1 M ethylene glycol at gold, platinum and gold-platinum alloy electrodes in different heat treatment conditions has been studied in 0.5 M NaOH, at room temperature. Poisoning of all the electrodes occurs. However, the alloy electrodes poison at a faster rate than the pure gold and platinum electrodes. This indicates that the initially higher activity of these electrodes cannot be the result of decreased poisoning through a "third-body" effect.

Oct 1, 2003

By Kwang K. Koh, Nicholas C. Nahas, Richard C. Neavel

Sodium, a relatively abundant element in Illinois coal, is reported to cause fouling of utility boiler heat exchange surfaces. Distilled water extraction of 22 Illinois coal samples resulted in average removal of more than 50% of their included sodium. Chlorine was the dominant anion. Extraction rate conformed to Fick's law of diffusion. Extraction with hot water increased both the rate and maximum amount removed. A commercial-scale countercurrent staged process can be envisioned as technically feasible.

Jan 1, 1978

By Alfred E. Hunt

Professor EGGERTZ first published a method based upon the fact that, when steel is dissolved in dilute nitric acid, and heated until the separated flocculent carbonaceous matter goes into the solution, the liquid assomed a brown color proportionate in intensity to the amount of the combined carbon in the steel. This method has been so variously modified that at present but few chemists use exactly the same procedure. It is the object of this paper to present

Jan 1, 1884

By Fathi Habashi

New technology first introduced by Nippon Steel Corporation at Kitakyushu in Japan in 1976 now used at a number of plants in other countries, known as dry quenching of coke, uses nitrogen in a closed circuit to avoid environmental emissions. In addition, heat is recovered in the form of steam, from the red-hot coke. In steel plants oxygen is used extensively and therefore by-product nitrogen from air liquefaction can be effectively utilized in this way.

Jan 1, 2014

By J. E. Murphy

The high-purity thorium metal was prepared by the Bureau of Mines from electrolytically produced thorium alloys. The thorium-chromium and thorium-manganese alloys were separated into the component elements by vacuum distillation. Chromium and manganese impurities remaining in the thorium metal after distillation at 1,850° C were <0.005 weight-percent. Removal of volatile impurities such as aluminum, calcium, magnesium, and lead was also accomplished.

Jan 1, 1969

By José Murilo Mourão

A pelotização de minério de ferro hematítico demanda grande quantidade de calor para a produção de pelotas de boa qualidade. Avalia-se, neste trabalho, a quantidade teórica de calor, necessária para a queima de três tipos característicos de pelotas, e destacam-se pontos importantes do processamento de queima nos fornos de pelotização, no sentido de otimizar o consumo de calor..

Oct 30, 2017

By Zhonglin Ye, Yifeng Shi

"This paper has outlined forms of Au & Ag losses in copper smelting process and methods for increasing Au & Ag recovery, analyzed factors influencing Au & Ag recovery in copper converting process, presented Au & Ag behavior in copper electrorefining process, and reviewed effect of current density/electrolyte circulation rate during electrolysis and surface finish of cathode on Au & Ag losses. Measures and research direction for decreasing Au & Ag losses in electrolysis have also been introduced. Based on Au & Ag behavior in copper electrorefining process and previous studies by others, new approach for increasing Au & Ag recovery in copper smelter has been discussed. And brief comparison has made between continued multiplication method and equilibrium method application in the case of calculation of Au & Ag recovery in copper smelter.IntroductionAs gold and silver are the major by-products from copper smelting process, efficient Au & Ag recovery has become one of the key approaches for copper producers to increase economic efficiency. With similar physicochemical properties, Cu, Au and Ag belong to the first subgroup of elements in the same periodic table. Au and Ag will be enriched into Cu phase firstly when both matte-slag phase and copper-matte phase appear in copper smelting process. However, great changes have taken place in Au & Ag proportions into individual phase due to changes of physicochemical conditions in each smelting process. Metallurgists at home and abroad have carried out a great deal of pilot plant tests and laboratory tests in order to increase Au & Ag the former Soviet Union with regard to Au & Ag losses in copper smelting process in the 1970s and 1980s, and he proposed solutions to increase Au & Ag recovery in copper metallurgical plants. As more than 20 years passed, Jingchun Lu's paper, Discussion on Increasing Au & Ag Recovery in Copper Smelting System, remains as a literature of the most comprehensive study. Based on Jingchun Lu's literature, the authors of this paper discussed new approaches to increase Au & Ag recovery in copper metallurgical plants with combination of many researches done by other researchers for over 20 years."

Jan 1, 2013

By Felipe Darabas Rzatki

Polyether ether ketone (PEEK) is a high performance thermoplastic often selected for high temperature tribological applications under chemically aggressive environments. The present work evaluate the tribological behavior of a high performance PEEK composite under ambient and high temperature (30 and 80°C, respectively). The atmosphere was also varied (air or tetrafluorethane). An AMTI tribometer equipped with a hermetic chamber and a heating system was used to carry out sliding tests of PEEK cylinders on 304 stainless steel polished discs (Sq < 10 nm) with reciprocating movement and 175 N normal force. Surfaces roughness analyses were performed with a white light interferometer. As expected, there was a strong influence of temperature on the tribological behavior of the samples tested in ambient atmosphere (25% decrease in friction coefficient associated with a 100% increase in wear rate). On the other hand, samples tested in tetrafluorethane atmosphere showed no significant friction temperature dependence.

Jul 31, 2018

By A. Poitras

The Cummings Complex consists of three superposed sills, exhibiting a differentiation pattern: the lowest sill being the most basic and the highest sill, the most acid. Each sill is also characterized by an internal petrographic and geochemical variation which is evidence of differentiation due to fractional crystallization. The REE concentrations in the different units of the complex indicates that the three sills are comagmatic. The interpretation of these results permits the formulation of an emplacement model not previously proposed for this complex.

Jan 1, 1984

By L. Hacini

The start-up is the most critical phase of the cell life, as an uncontrolled start-up could lead to early infiltrations, instabilities, and in some cases to the cell death. Lots of efforts are put to increase the lifespan of cells, as it has a major impact on both the operating costs and the environmental footprint of the aluminum industry. Obviously, a true size test on a cell is a resources- and time-consuming approach that could be used only to validate mature concepts. Moreover, numerical modelling is a low-cost and versatile tool capable to test a wide range of potential ideas and concepts. In the present article, a thermal electrical mechanical slice model is presented. This model describes the preheating and bath periods of a P155 aluminum cell start-up, as used at the Grande Baie smelter. The impact of sodium diffusion and expansion is also included in the model. This model will be useful to study different problematical issues such as the global behaviour of lining materials, shell and cradle deformations during start-up and several start-up scenarios. Such a model will also be able to answer some interrogations regarding early infiltrations and their impact on the lifespan of the electrolysis cell.

Jan 1, 2011

By K. L. Komarek, P. F. J. Landler

Synthetic polycrystals of wustite were reduced ilz H2-H2O mixtures over limited roncentration ranges wiltun the wustite. field and the weight changes were continuously followed with a McBain quartz spiral balance. The reduction was. found to be controlled by a combined surface plus solid-state diffusion reaction. The solid-state diffusion had an activation energy of 38 kcal. Self--diflusioities of iron decreased with itzcreasing vacancy concentration. The activation energy of. the surface reaction runs different tor- different samples. The surface reaction-rate constan increased with increasirzg vacancy concentration. THE reduction of the oxides of iron has been studied for many years. Edstroem&apos; has summarized the early work and has provided much information on the reduction of magnetite and hematite by hydrogen and carbon monoxide. More recent summaries are those by smeltzer2 and Themelis and Gauvin.3 Most investigators have reported that the iron metal which forms the outer layer during gaseous reduction is rather porous. According to Kohl and Engel14 the formation of such a porous iron layer depends on the properties of the underlying wiistite layer, on the reaction of the gas with the wustite surface, and on the transport of matter through the wustite layer. McKewan, Quets, Wadsworth, and Lewis, and Knacke 10 have found that, if a porous iron layer is formed, a surface reaction between gas and wustite at the bottom of the pores controls the rate of reaction. Seth and ROSS 11 and Warner 12 have pointed out that the influence of the gaseous pore diffusion through the porous iron layer cannot be neglected. It has further been shown that the wiistite layer formed during reduction is dense and that transport of matter across the layer occurs only by solid-state diffusion of iron ions.13,14 The solid-state diffusion rates observed by Edstroem and Bitsianis 14 and the surface reaction rates observed by Quets eta1.&apos; show that an interaction of the two steps in controlling the reaction rate has to be considered. In this investigation the reduction of wustite was studied with respect to the interaction of the two steps, isolated from any other effects, by reducing wustite within the wustite field from higher to lower oxygen concentrations with H2-H2O gas mixtures. A similar study with CO-CO2 mixtures has been performed by Levin and wagner.15 Fused synthetic wustite polycrystals were reduced in steps of 0.4 wt pct from 24.4 to 23.2 wt pct 0 and over a temperature range from 700" to 1050°C. A few tests were also conducted with reduction steps from 24.4 to 23.6 wt pct 0 and 24.5 to 23.2 wtpct0. The Fe-O phase diagram is shown in Fig. 1 where the composition of the gas phase in equilibrium with the condensed phases is plotted as pct H2 vs the temperature. A careful study of the literature led to the conclusion that the fully drawn equicomposition curves (in wt pct O) in the wustite field used by Edstroem 1,16 and other authors needed some correction. Based on results by Darken and Gurry17 (shown as open circles) and on some of our own data, four corrected curves for 23.2, 23.6, 24.0, and 24.4 wt pct O were calculated (drawn as dashed lines in Fig. 1) which should replace the fully drawn equicomposition curves. MATERIALS AND APPARATUS Materials and Specimen Preparation. Wustite was prepared from iron sulfate (Fisher Scientific Co., New York) which had a purity of over 99.92 pct, with small amounts of manganese, copper, and zinc adding up to 0.03 pct. From the aqueous solution iron oxalate was precipitated and decomposed to magnetite according to Economos. 18 The magnetite powder was pressed into cylinders and sintered in vacuum at 900°C for several hours. The sintered compacts were placed in a platinum crucible of 2.5 cm diam which was fitted into a high-purity alumina crucible and then inserted into the center of the graphite heating element of an electric resistance furnace.lg The furnace was evacuated to below 1 p Hg and the magnetite sample was slowly heated. The evolution of gases during heating deter-

Jan 1, 1967