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By Kiyoshi Azuma, Hiroshi Kametani

Dissolution of a ferric oxide in acid solution is divided into two different types In the accelerated type dissolution proceeds in three stages 1) an inittal reaction during which the dissolved amount of oxide is nearly proportional to the cube root of time ; 2) an accelerated reaction: and 3) a final stage during which dissolution approaches completion. This course of dissolution gives an S-shaped curve in the above sequence OH a log weight percent of dissolved oxide against log time graph. In the parabolic type dissolution proceeds in four stages: first and second stages similar to those of the accelerated type; 3) parabolic-rate dissolution during which the dissolved amount of oxide is nearly proportional to the square root of time: and 4) a final stage. The effect of the kind of acid, the temperature of solution, and the concentration of acid was investigated. The results are discussed and a rate equation is proposed. AN attempt has been made to obtain some information on dissolution of a ferric oxide in various acid solutions. In view of hydrometallurgical processes the dissolution of ferric oxide is of less importance than that of zinc oxide or copper oxide in general. One of a few processes which intend to dissolve ferric oxide is an elimination of iron impurity from acid-insoluble materials. However, most leaching processes of oxide ores and cinders are accompanied with more or less dissolution of iron. According to Pryor and Evans1 the rate of dissolution of a ferric oxide in various acids decreased in the order of hydrofluoric acid > hydrochloric acid > sulfuric acid > perchloric acid. This order was in accord with the order of decrease of the complexing affinity of the anion for ferric ion,

Jan 1, 1964

By F. H. Deily, Jean M. Quets, Milton E. Wadsworth, John R. 222-000-000-012 Lewis, D. S. Rowley, R. J. Howe

Samples of synthetic magnetite were reduced in hydrogen-water vapor atmospheres in the temperature range 450o to 900oC. The reaction was always surface controlled, indicating the final products of reaction are nonfirotective. Three separate cases have been identified from the kinetic results: Case I, reduction of magnetite to iron below 570°C; Case II, reduction of magnetite to iron above 570°C; and Case 111, reduction of magnetite to wustite above 570 oC. In Cases I and 111 the kinetics have been explained by the formation of oxygen anion vacancies in the magnetite surface followed by associated diffusional processes. In Case 11 the observed kinetics have been related to the concentration of iron cation vacancies in the wustite layer formed, followed by associated steady-state diffusional processes. The concentration of cation vacancies in the wustite is maintained constant by the magnetite-wustite equilibrium. THE reduction of the oxides of iron has been a subject of study and interest for many years. However, few attempts have been made to interpret the results in terms of the mechanism of reduction of an iron oxide by either hydrogen or carbon monoxide. Stalhane and Malmberg' using CO, H2, and CO-Hz mixtures, developed the rate expression: where m = mass of oxide reduced, t = time, k = a constant, s = surface area, P = partial pressure of of CO or H,, and P, = partial pressure of the reducing gas at equilibrium. The rate of reaction per unit area was proportional to the difference between the partial pressure of the reducing gas and its pressure at equilibrium. Hansen, Bitsianes, and Joseph2 studied the reduction of pellets of hematite to magnetite with mixtures of CO-CO,. They concluded that below 450°C the reaction proceeded according to a model in which CO reacts with the hematite surface producing an oxygen ion vacancy. The rate controlling step was then assumed to be oxygen ion diffusion through vacancies resulting in the formation of magnetite. They derived an expression giving the rate of reduction proportional to the cO/CO, ratio. Recently McKewan3 published results for the reduction of magnetite spheres in atmospheres below 570°C. He explained his results by an equation of the form where K, is the equilibrium constant for wustite-iron equilibrium attributed to the formation of wustite as an intermediate in the reduction of magnetite. According to McKewan, Kp is an equilibrium constant for H, -HO adsorption in which oxygen is deposited on the surface from the H,Oand subsequently acts as a poison for reduction by hydrogen. Sample Preparation and Experiments. In this work the authors used the same apparatus and experimental procedure employed in the hydrogen reduction of magnetite. Sintered disk samples weighing approximately 1.5 g and measuring 1.2 cm in diameter and 0.25 cm in thickness were prepared by a method described previously.4 Partial pressures of hydrogen and water vapor were controlled by bubbling hydrogen through a series of flasks containing distilled and deionized water maintained at constant temperature in an oil bath. The total flow rate of the reacting gases—hydrogen and water vapor—was approximately 0.5 liter per min. The entire external system was maintained at a temperature above the oil bath to prevent condensation of water vapor. This was accomplished by wrapping electrical resistance elements over all surfaces. The glass column containing the weighing system-a McBain balance suspended from a gold chain-was enclosed in an aluminum tube heated by nichrome resistance wire enclosed in an insulating material. The temperature of the glass column was held constant by means of a series of thermocouples connected in parallel to a Leeds and Northrup temperature controller. This was necessary since variations in temperature resulted in expansion and contraction of the glass column and could be readily observed with the cathetometer. The spring extensions were measured through a window with a gaertner cathe-

Jan 1, 1962

By R. D. Pehlke, P. D. Goodell, R. W. Dunlap

The rate of dissolution of steel bars in molten pig iron has been measured experimentally in the temperature range 2300° to 2650° F. The rate of solution is shown to be a .function of bath composition, temperature, and stirring. A kinetic model based on carbon diffusion in the liquid phase has been derived to fit the experimental results. THE rate of scrap melting has long been an important variable in steelmaking operations. With the advent of the oxygen steelmaking process and the accompanying shorter heat times, the rate of scrap melting has now become one of the rate-limiting factors in steel production. As observed in commercial practice, the solution rate is influenced by the compositions of liquid and solid, the temperature, agitation, and time. However, no definitive work has been done on the Fe-C system, and there is very little information in the literature regarding the relative effects of these variables in steelmaking systems. A number of questions have been raised in regard to scrap utilization in basic oxygen steelmaking operations. Consideration has been given to the optimum size and shape of scrap, and to the use of preheated scrap as a means for decreasing the pig-iron requirement in oxygen blowing. The determination of an optimum scrap practice for a specific installation depends to a large extent upon the economics of the scrap market and also upon the behavior of scrap in the vessel. The present research was undertaken as a preliminary study in evaluating the behavior of steel in a pig-iron bath under various conditions of temperature, composition, and agitation, as might be encountered in oxygen converter operations or in any steelmaking operation where scrap behavior is an important process variable. Related studies have been carried out on non-ferrous systems. The solution rate of solid aluminum in a molten A1-Si alloy has been studied.' Furthermore, the increasing use of liquid metals has created considerable interest in studies related to dissolution of a solid in a liquid, or mass transfer taking place between a solid interface and a liquid metallic phase.2-10 In an effort to clarify the relative importance of factors influencing the dissolution of scrap in Fe-C alloys, this paper presents the results of a study of the rate of dissolution of a low-carbon steel cylinder in a molten Fe-C bath at various bath compositions, temperatures, and conditions of agitation. An attempt has been made to determine the mechanism of solution, and a model has been derived to fit the experimental results. The rate of heat transfer between the molten pig-iron bath and the solid-steel cylinder has also been studied. EXPERIMENTAL PROCEDURE A molten bath of pig iron (nominal composition 4.2 pct C, 0.5 pct Mn, 0.8 pct Si)* was held in a 200- *In view of the fact that the composition of the pig-iron bath was slowly changing with time because of steel dissolution and reaction with the surrounding atmosphere, intermittent samples of the liquid bath were taken throughout each experiment, Table 1. lb induction melting unit. The internal diameter of the furnace was 8-1/2 in. and the bath depth approximately 14 in. Cold-finished 1020 steel cylinders of 1/2-, 3/4-, 1-, 1-1/2-, and 2-in. diameters were cut into 1 -ft lengths for use as test specimens. One end of each bar was machined to fit a hand-driven, mechanical stirring device which rested on top of the furnace. This fixture permitted 7 to 8 in. of the bar to be immersed in the melt. The steel cylinders were cleaned to free the surface of grease and oxide. The rods, at ambient temperature, were immersed into the molten pig-iron bath. The melt temperatures studied in this investigation were 2300°, 2500°, and 2650°F. Different agitation conditions were achieved by operating with a) the power to the furnace, giving induction stirring; b) induction stirring plus mechanical stirring, using hand rotation with a chain and sprocket assembly at approximately 200 rpm; c) mechanical stirring alone with the power off; and d) the power off and no mechanical stirring resulting in minimum agitation, i.e., only that caused by natural convection currents in the bath. The samples were immersed in the melt for prescribed times ranging from 30 sec up to 6 min. Immersion times were measured with a stopwatch and temperature control of the melt was achieved by power adjustment following temperature measurement with an optical pyrometer. The measurements with the calibrated pyrometer were checked out to within less than 10°F with simultaneous thermocouple measurements. Following immersion, the bars were water-quenched and the diameters were measured with a micrometer at several positions on the reduced area, and by volumetric displacement. The dissolution rates calculated from the

Jan 1, 1965

By Renato G. Bautista, Theodore D. Tiemann

A kinetic study of the hydrogen reduction of taconite from the Wisconsin Gogebic range was made over the temperature range from 500° to 1000°C on eleven size fractions from 4 to 150 mesh. Two stages of reduction were observed, a rapid initial reaction followed by a slower reaction presumably taking place at an internal receding FexO-Fe interface. Calculated mean activation energies for the two reactions were 7800 and 14,600 cal per mole respectively. In recent years there has been an increased interest in the direct reduction of iron oxide ores to metallic iron by means of gaseous reducing agents such as hydrogen and carbon monoxide.1,2 These investigations have been motivated by the desire to develop a process that will by-pass the blast furnace in the production of steel. The majority of these processes have been developed to produce metallic iron by direct reduction from high-grade iron oxide ores.3"5 Very little work has been done on the low-grade siliceous iron oxide ores.6"8 The work reported here is directed principally towards the fundamental aspect of the reduction reactions of siliceous iron oxide ores, since the practical aspects of the gaseous reductant process were discussed previously. The ore used in the investigation was obtained originally from the United States Bureau of Mines10 trench sample of the Yale member of the Wisconsin Gogebic range iron formation. The Yale taconite has an average analysis of 28.2 pct Fe and approximately 50 pct SiO2. Chemically, these nonmagnetic taconites contain on the average about 53 pct silica and 30 pct Fe. An average analysis calculated fron the USBM10 figures for a composite of the five members (Norrie, Plymouth, Pence, Pabst, and ale) of the iron formation is given in Table I. Mineralogically, based on previous X-ray diffraction and other studies, the principal minerals are hematite (Fe2O3), geothite (Fe2O3.H2O), and quartz (SiO2). Minor amounts of iron containing silicates, siderite (FeCO3) and magnetite (FeO. Fe2O3) are present.10,11 The iron minerals and the quartz are finely disseminated requiring extremely fine grinding for liberation. For the experimental work, the ore sample was screened into a number of size fractions, the analyses and densities of which are given in Table II. EXPERIMENTAL PROCEDURE The reduction experiments were carried out in a 24 in. by 2 in. ID nichrome-wound vertical-tube furnace mounted on a stand. A 1 1/2 in. OD zirconium-oxide combustion tube was used inside the furnace to contain the atmosphere. To the top of this combustion tube was joined a pyrex ground-glass joint to which was attached a glass bulb with a small (1.0 mm) opening at the center, and with two outlets controlled with a stopcock on each side. A pyrex-glass joint with connections to three stopcock joints for introducing hydrogen, nitrogen, and mixtures of hydrogen and nitrogen gas was joined to the tapered bottom of the combustion tube. The sized ore fractions were contained in a 1 in. diameter by 1 1/2 in. 150-mesh nickel screen basket. The basket was suspended in the furnace from a balance by means of a supporting nickel wire which hung freely inside the combustion tube. The furnace temperature was controlled by a Leeds and Northrup Speedomax Type G controller, connected to a chromel-alumel thermocouple placed

Jan 1, 1962

By G. R. St. Pierre, A. J. Wilhelem

In connection with the reduction of hematite or magnetite to metallic iron, it appeared desirable to study the rate of reduction of each oxide to the next lower oxide under conditions which excluded all other condensed phases. For this purpose, pellets of Fe,O,, Fe,O,, and oFeOo were prepared. A gas train for the preparation of Ar-Hz-H20 mixtures was employed to establish a continuous flow of a controlled atmosphere over a pellet suspended on a balance. In this manner the following individual reduction steps could be studied: For example, pellets of hematite were reduced solely to magnetite by adjusting the gas atmosphere such that it was oxidizing to wustite. In other words, the reaction was complete when the hematite pellet had been totally converted to magnetite. The pellets were prepared from Baker Chemical ferric oxide. The ferric oxide powder was moistened and handrolled. Air sintering at 950°C produced Fe,0, pellets with a density of 3.65 g per cm3. The pellets ranged in size from 0.6 to 1.2 cm diam. The magnetite and

Jan 1, 1962

By E. S. Machlin

The kinetics of vacuum distillation, vacuum-melt surface reactions, crucible-melt surface reactions and boiling are analytically investigated. No disagreement with experiment is obtained upon applying a rigid flow model to describe the behavior of the melt in the vicinity of reaction surfaces. The theory focuses attention upon measureable parameters rather than upon the adjustable parameter, stagnant layer thickness, associated with other theories. The rigid flow theory is thus capable of quantitative evaluation and experiments to achieve this evaluation are suggested. KINETICS, rather than thermodynamics, often determine the degree of refinement achieved in vacuum melting. There is little understanding, however, of the kinetic principles involved in vacuum refining. This paper represents an attempt to achieve this understanding. There are two reactions which need to be con- sidered. The first is the refining reaction. The second shall be called the polluting reaction. It is the reaction associated with the introduction of components of the crucible into the melt. The mechanisms of both reactions are unknown. Many models can be constructed to describe either the refining or polluting reactions. For example, consider the refining reaction C + Q = CO(g). One model that can be imagined is that the carbon and oxygen combine in the melt to form CO which then diffuses to a melt-

Jan 1, 1961

By K. C. Mills, E. T. Turkdogan

A number of investigators1 6 have noted the presence of a liquid miscibility gap in the Fe-Sn binary system. However, the first attempt to measure the

Jan 1, 1964

By H. F. Beeghly

UNTIL recently the only criteria by which steels were judged were their cost and their mechanical, chemical, and physical properties. The user was concerned with such properties as corrosion resistance, tensile strength, response to thermal treatment, hardness, ductility, and, to a growing extent in recent years, with behavior at high temperature. As plans were made to build power reactors, a new set of properties became important—the nuclear characteristics, which had to be considered by the designer and engineer in building his plant. The nuclear engineer developed methods for the rare and new metals and produced them in high purity, often at great expense. The pure metals then provided the raw materials for tailor-made alloys. For more common structural metals, such as steel, the nuclear industry depended on commercially available materials. Generally, the quantities required were small and specifications were rigid. It is not surprising, therefore, that difficulty was frequently encountered in procuring structural mate-

Jan 1, 1957

By G. W. Healy, W. Craft, D. C. Hilty

By means of a theoretical extension of the Cr-C temperature relation in molten chromium steels to low chromium contents and by a correlation of the ratios of chromium to iron in the slag and metal, a method has been developed for estimating the amount of metallic oxidation during the oxidizing period of a chromium steel heat. Application of this method has indicated that due to temperature limitations metallic oxidation may be excessive for very low carbon steels charged with more than a small amount of chromium. IN the melting and refining of chromium steels the oxidation of carbon to a low level is accompanied by the oxidation of chromium and iron in considerable amounts. For the subsequent recovery of chromium and associated iron from the slag, the amounts of metal oxidized must be known for efficient reduction and control of composition. Further, in order to arrive at an accurate understanding of the process, so that chromium-bearing scrap can be used effectively, information is required on the relation between composition of the charge and weight of metal oxidized to reach the desired carbon content. Crafts and Rassbach1 recently developed an empirical relation between chromium, iron, and manganese oxidized per ton of steel charged, and final carbon content and temperature. This relation did not show any dependence on amount of chromium charged. However, it was felt that such a dependence might be present, so a further analysis of the data was undertaken. Cr-C Relation at Low Chromium Levels Crafts and Rassbach's results were based on temperatures estimated from the Cr-C relation previously established experimentally by Hilty,2 and on a single temperature observation (immersion thermocouple) on a heat made at low temperature from a charge of carbon steel scrap containing only a small amount of residual chromium. The temperatures estimated from the Cr-C relation were for heats charged with chromium-bearing scrap and which contained substantial amounts of chromium (2 to 10 pct) at the end of the oxidizing period. No data, other than that from the low temperature heat just mentioned, were available for the low and intermediate chromium ranges. In order to extend the range in which temperature may be estimated, the Cr-C relation requires further consideration. The Cr-C relation, expressed as suggests that carbon is zero at zero chromium in the bath. This is obviously absurd, because as chromium approaches zero the carbon content must approach the limit established by the Fe-C-O equilibrium. It is evident, therefore, that the Cr-C relation as defined by Eq. 1 is not valid below some minimum chromium content that may vary with temperature. On the other hand, it is probable that any such limiting chromium content is less than 4 pct at 3200°F, since the experimental data from which the Cr-C relation was derived included several observations at that level with no deviation. In any event, it is apparent that further evaluation of the results presented by Crafts and Rassbach is dependent upon a means for estimating the Cr-C temperature relation in the low chromium region. From the observations of Chen and Chipman9 and thermodynamic data given in Basic Open Hearth Steelmaking,4 the following relation can be calculated for melts containing small amounts of chromium and carbon assuming a carbon monoxide pressure of 1 atm: % Cr -21,250 K' = (%C)2; logK1 == —t— +13.88 [2] Moreover, by plotting Eq. 2 for any given temperature on cartesian coordinates, it can be extrapolated graphically to the limiting carbon content at zero chromium for the specified temperature without serious complications. By means of Eq. 2 and its extrapolation, the Cr-C temperature relations originally established experi-

Jan 1, 1954

By Ford R. Bryan, Edward F. Runge

BECAUSE of the need for ductile heat resistant alloys of non-strategic composition, there has been metallurgical development of Fe-A1 alloys possessing improved ductility and hot strength, together with high oxidation resistance. Iron and alu- minum form solid solutions up to approximately 35 pct Al. Alloys in the 8 to 12 pct A1 range are characterized by excellent oxidation resistance, high electrical resistivity' and, when appropriately alloyed, have creep rupture strength equivalent to that of the austenitic stainless steels.' At higher aluminum levels, the magnetic properties are of considerable interest. Nachman and Buehler" have recently reported on the desirable magnetic characteristics of the 16 pct alloy.

Jan 1, 1957

By Lawrence H. Van Vlack, Otta K. Riegger

Periclase-type oxides were examined microscopically after being exposed to siliceous liquids. The rate of grain growth was found to be inversely proportional to the grain diameter. Grain growth proceeds more rapidly at higher temperatures, but is retarded by increasing liquid contents. aMag-nesiowiistites with higher MgO contents grow less rapidly than those with higher FeO contents. The growth rate is reduced by the presence of a second solid phase. The silica-containing liquid penetrates as a film between the individual magnesiowus tite grains. This is independent of time, temperature, amount of liquid, or the MgO/ Fe0 ratio. When present, olivine and spinel-type phases can provide a solid-to-solid &apos;&apos;bridge" between magnesioustite grains. THIS paper presents the results of a study of the microstructures of periclase type oxides in the presence of a silicate liquid. The purpose was to learn more about the effect of service factors such as 1) time, 2) temperature, and 3) liquid content upon A) grain growth, and B) liquid location among the solid grains. This study was prompted by the fact that periclase refractories are known to have very little solid-to-solid contact when the phases which are present are limited to periclase and liquid. Such a micro-structure gains industrial significance because it permits fracture during service when stresses are applied at high temperatures. The details of ceramic microstructures have not received extensive attention. This is in contrast to the extensive attention given to a) the phase relationships pertaining to refractory compositions, and b) the details of the microstructures of comparable metallic materials. A brief review will be made of the pertinent phase relationships and microstructural considerations in general, as well as of refractory compositions. a) Phase Relationships. This investigation was limited to those compositions in which (Mg, Fe)O was the solid phase. MgO and FeO form a complete series of solid solutions. Pure MgO has the name of periclase. The related FeO structure is called wustite. Both have the NaC1-type structure: however, wustite possesses a cation deficiency so that the true composition is Fe<10 even in the presence of metallic iron. The phase relationships involving solid (Mg, Fe)O and a silicate liquid are shown in Fig. 1. In this case. the liquid is saturated with (Mg, Fe)o. There-fore its SiOz content is below that encountered in orthosilicate liquids. As a consequence the liquid phase specie:; are primarily the following ions: and 0-&apos; plus occasional Fe+ ions. Two features are of importance: a) the liquid contains relatively small species and b) the liquid contains large quantities of the same species as the solid. viz., Fig. 2 shows the system, FeO-SiOz, which will be used in some of the discussions that follow. This diagram is the right side, vertical section of Fig. 1. Here, as pre\iously, the composition at the FeO end of the diagram is nonstoichiometric, varying from Feo.950 when the liquid oxide is in contact with the solid iron, to about Fe 0, when the solid oxide is in equilibrium with an atmosphere of equal proportions of CO and C02 at the solidus temperature. The Fe/O ratio will be maintained in wustite in the presence of SiO,. However, the FeM/Fe++ ratio in the liquid will be lower because of the effect OIF the SiO, on the activity of the FeO. With the addition of MgO to wustite, the over-all composition (IvZg, Fe)@, has a value of x lying between 0.9 and 1.0 when the COz/CO ratio is 1.0&apos;. b) Microstructures. In general, published attention to refractory microstructures has been directed toward the phase analyses that accompany compositional variations. This is illustrated by Harvey6 in his work on silica brick and by wells7 in his work on periclase brick. In each case, a series of altered zones is encountered which provides a sequence of phase associations. If due consideration is given to reaction kinetics, such an examination reveals phases that are compatible with equilibrium studies. Admittedly, however, it is often necessary to determine more complicated polycomponent systems to account for all the phases present.8 Relatively little attention has been given to microstructural geometry in ceramic materials. Certainly less attention has been given to this aspect of ceramic microstructures than to the size, shape, and distribution of the constituent phases in metals. Burke has pointed out that the grain size of oxides follows the same growth rules as for metals, viz.,

Jan 1, 1962

By E. T. Turkdogan, P. Grieveson

STAFF: Editor, Gerhard Derge Acting Editor, Paul G. Shewmon Carnegie lnstitute of Technology Sc hen ley Park Pittsburgh 13, Pa. Editorial Assistant, M. A. Redmerski Production Editor, Otto T. Johnson THE METALLURGICAL SOCIETY: Karl L. Fetters, President; J.S. Smart, Jr., Past-President; R. C. Cole, Vice President; R. L. Hennebach, Treasurer; R. W. Shearman, Secretary. PUBLICATIONS COMMITTEE OF THE METALLURGICAL SOCIETY: W. 0. Phil-brook, Chairman; H. L. Bishop, R. C. Cole, J. N. Hobstetter, W. A. Krivsky, E. R. Morgan, F. C. Langenberg, R. E. Lund, Paul Queneau, L. L. Seigle, R. L. Smith, and T. &apos;4. Wainwright. Review and selection of manuscripts is under the supervision of the following Publications Committes: Extractive Metallurgy Division: R. E. Lund, Chatrmon; M. E. Wodsworth, Vice Chairman; D. H. Baker, Jr., G. M. Bell, R. E. Groce, W. A. Krivsky, R. A. Lewls, Charles O&apos;Neill, A. W. Schlechten, R. E. Shinkoskey, and W. W. Stephens. Iron and Steel Division: T. V. Wainright, Choirman; H. L. Bishop, R. E. Boni, T. E. Dancy, C. W. Murphy, Johonnes M. Uys, J. B. Wagstaff, and R. G. Ward. lnstitute of Metols Division: J. N. Hobstetter, Chairman; P. A. Beck, J. J. Becker, G. F. Bolling, J. O. Brittain, J. 8. Clark, R. S. Davis, A. E. Dwight, R. W. Fountain, L. R. Girifalco, J. C. Gurland, H. S. Kclish, E. L. Harmon, J. J. Heger, A. A. Hendrickson, L. Himmel, J. P. Hirth, H. H. Johnson, Jr., R. R. Nosh, T. N. Rhodin, R. H. Richman, H. C. Rogers, W. Rostoker, C. Sherby, C. W. Spencer, L. Slifkin, J. K. Stanley, R. Steinitz, H. C. Stumpf, and R. Swolin. Published bimonthly by the American Institute of Mining, Metallurgical, and Petroleum Engineers, Inc., 345 East 47th Street, New York 17. N. Y. Telephone PLaza 2-6800. Subscription $30 per year for non-AIME members in United States and North, South, and Central America; $32, foreign; $7.50 for AlME members. Single copies, $6.00, single copies foreign, $6.50. The AlME is not responsible for any statement made or opinion expressed in its publications ... Copyright 1962 by the American lnstitute of Mining, Metollurgical. and Petroleum Engineers. Inc. . . . Registered cable address, AlME New York . . . Indexed in Engineering Index, lndustriol Arts Index, and Chemical Abstracts . . . Second class postage paid at New York, N. Y., and Ann Arbor, Mich. Volume 224, Number 6.

Jan 1, 1962

By J. E. Ostberg, G. Phragmen, A. Hultgren, S. Wohlfahrt

Detailed study was made of a number of rimming ingots, both low and high carbon, and especially upon effects of superimposed air pressure. Requirement to suppress core bubbles is between 10 and 15 atm; at 6.5 atm freezing was in semikilled manner and at 3 atm, steel was of rising type. Probable mechanism of freezing under various conditions is discussed. AN earlier paper&apos; reported an investigation made by a committee for studying rimming steel ingots appointed by Jernkontorets in Stockholm. The present paper is the outcome of some further work done by the same committee. Since the characteristics of ordinary rimming steel are connected closely .with the amount of gas liberated during freezing and since this amount of gas is governed by the pressure, it was considered of interest to ascertain in what manner and to what extent definite pressures applied to the top of the liquid steel in the mold would affect the solidification process and the consequent structure of a rimming steel of ordinary composition. The experiments were made at the Domnarfvets Steel Works. The steel was made according to normal practice in a 4-ton Rennerfelt electric furnace. Ferromanganese was added in the furnace; no aluminum was added, with one exception. Analyses of the four heats are given in Table I. The top-poured ingots measured about 12 in. sq x 48 in. and weighed about 1300 lb. One or two ingots of each heat were allowed to solidify under pressure, using a special device for admitting compressed air to the upper closed part of the mold, as shown in Fig. 1. A heavy plate sealed with asbestos was bolted to the top of the mold. The plate had a tapered aperture for pouring. Immediately after pouring the hole was closed by a wedged plug, and compressed air was admitted through a hole in the plug. Because of some delay in applying the plug, full pressure was not reached immediately. The pressure was adjusted to the desired value as indicated by a manometer. In order that the interior of the ingot might have the benefit of the pressure, the freezing of the top crust was delayed by a refractory lining applied to the top part of the mold, Fig. 1. Ingots were also cast from each heat without applied pressure, and with and without refractory lining at the top. Axial sections of ingots were cut either of the whole ingot or of some part of it of special interest; sections were polished and usually etched.&apos; To facilitate description of structures the following terms may be used for different types of ingots solidified under gas evolution: 1. Box-hat or boot-leg ingot: Abundant gas evolution during casting and during rimming; no rim holes. 2. Normal rimming ingot: Lively gas evolution during rimming; usually rim holes in lowest part of

Jan 1, 1952

By Donald J. Knight

HEAT Treatment at 1500&apos; F of a mild steel containing 0.1 pct C, in an atmosphere which is oxidizing to both carbon and iron, results in the progressive oxidation of the metal surface with little or no change in the carbon content of the underlying metal. Further heat treatment of the scaled metal in either a neutral atmosphere or in a vacuum may or may not result in the decarburization of the metal depending upon the physical nature of the scale. It is apparent that if a continuous layer of oxide is present on the steel surface, the reaction OScale + Cmetal Cogas cannot progress since the SO formed gas would be unable to leave the oxide/metal interface. Thus, in order for the reaction to progress, the oxide must be cracked or porous. Vacuum heat treatment at 1500" F of samples with a thick continuous oxide scale showed no decarburization of the steel. However, when cracks were introduced mechanically into the scale prior to the vacuum heat treatment notable decarburization of the metal resulted and a structure as shown by Fig. 1 obtained, i.e., reduction of the crack walls to ferrite. With reference to the diagram of Fig. 2, it would appear that a mechanism of the following type takes place. Carbon atoms arriving at an oxide/metal/void interface, such as &apos;A&apos;, Fig. 2(a), can combine with oxygen atoms from the scale and leave the reaction site as Cogas thereby reducing the oxide to metal. On a greatly magnified scale, Fig. 2(b),this will appear as a ferrite projection along the crack wall. Carbon atoms entering this projection can react with oxygen atoms at point &apos;C&apos;, which is a new interface, and so on leading to a progressive growth of the ferrite along the crack wall and to the surface, Figs. 2 (c) and 1. It would appear that the only means by which thickening of the ferrite film can take place is by a diffusion of oxygen through the ferrite film to react with carbon at the newly formed ferrite/ void interface. Since the diffusion rate of carbon is reportedly much greater than that of oxygen, and since there is a low probability factor of oxygen and carbon atoms arriving simultaneously at the same site on the ferritehoid interface, there will be a tendency for more rapid lengthening than thickening of the ferrite layer, as is observed.

Jan 1, 1962

By N. A. Gokcen, M. N. Dastur

In metallurgical process industries a knowledge of true melting and casting temperatures is very essential for increasing the operating efficiency as well as improving the quality of the finished product. Optical pyrometers are widely used for the purpose because of their cheapness and ease of operation. It is an unfortunate fact, however, that this mode of measuring temperature entails a source of severe error inasmuch as with all non-black bodies, the temperature observed is always below the true temperature owing to deficient emissive power. Hence, the need for emissivity correction arises. In 1913 Bidwell1 obtained emissivity values of 0.36-0.48 for a temperature range of 1520-1800°C. He measured the true temperature of molten iron by sighting into a carbon cavity immersed in the iron under an atmosphere of hydrogen. In 1914 Burgess2 determined the emissivity of a smooth surface of liquid iron free from oxide to be 0.37 under an atmosphere of hydrogen. He claimed to have attained an accuracy of within 5°C at 1500°C with an optical pyrometer using monochromatic light. He reported that no difference appeared to exist between the emissivities of pure iron and of steels containing considerable percentages of carbon, nickel or manganese; nor was there any appreciable variation of emissivity with temperature from 1530 to 1571°C. Wensel and Roeser3 found an elnissivity value of 0.4 for temperatures above 1375°C for cast iron. The average emissivity value for carbon steels reported by Leiber,4 odd,5 Hase6 and Umino7 range from 0.4 to 0.45. Knowles and Sarjant8 made an extensive study of emissivity of molten iron and steel over a wide range of workshop and laboratory conditions. Observations of true temperature were made with immersion thermocouples, and correlated with apparent temperatures indicated by optical pyrorneter readings taken on the pouring stream as it passed over the lip of the crucible. The emissivity of Armco iron was shown to be of the order of 0.4, rising slightly with increasing temperature. But for plain carbon steels containing up to 1.0 pct carbon the emissivity was shown to fall slightly with increasing temperatures. The results of their investigation are in agreement with those of Guthmann.9 Naeser,10 Spencer," Todd5 and Hase6 in regard to the relation between emissivity and temperature for plain carbon steels. However, Goller12 has found a rise of emissivity with increasing temperature for the same steels. Results of several investigations are given in Fig 1. Measurement of True and Apparent Temperatures The necessity for an accurate optical temperature scale for liquid iron in studies of gas-metal equilibria led to this investigation. Experimental measurements were carried out in the induction furnace used by Dastur and Chipman13 in their studies of the reaction of hydrogen with oxygen in liquid iron. The furnace as modified for this work is shown in Fig 2. The atmosphere of the furnace was a mixture of purified argon with hydrogen containing a small controlled amount of water vapor. Gases were preheated by means of a platinum-10 pct rhodium resistance coil. The stream of hydrogen sweeping across the surface of niolten iron vir-

Jan 1, 1950

By H. M. Kraner, R. C. Devries, K. H. Gee, E. F. Osborn

On the basis of liquidus measurements in the system COO-Mg0-Al2O3-Sio, and previously published data, diagrams have been constructed at 5 pct Al2O3, intervals from 5 to 35 pct Al2O3,. Liquidus temperatures and primary phase fields are shown. The optimum composition of a blast furnace slag for a given alumina content is indicated. At the optimum point, ordinary slags will be entirely liquid and will have maximum desulphurization potential and minimum viscosity. The relation of optimum composition of slags to the "plateau region" of the liquidus surface, and the application of these data on synthetic quaternary slags to actual slag compositions are discussed. Index of refraction of glasses is given as well as composition, temperature, and phase data for each mixture. THE usual blast furnace slag, as a first approximation, can be considered a mixture of the four oxides, CaO, MgO, Also,, and SiO,. Systematic, extensive data for the quaternary system, CaO-MgO-A1,0,-SiO, is therefore required for the understanding of the properties of such a slag as a function of composition and temperature. With sufficient data, it should be possible to fix unequivocably the relative amounts of lime, magnesia, and silica required for a given alumina content to result in a slag composition having optimum properties. Other constituents, such as FeO, MnO, Ti02, and S, have an effect on the properties of a slag, but as long as they are present in small and approximately constant amounts they produce only a second-order effect superimposed upon the major changes in properties of slags determined by the relative amounts of the four major components. Viscosity and desulphurization data have been reported for mixtures approaching blast furnace slags in composition, but systematic liquidus data have not been obtained. Inasmuch as a slag must be all liquid in order to be most effective as well as practicable, clearly the temperature above which a mixture is all liquid (liquidus temperature) is a type of data needed. Such data have been obtained through the study of 446 compositions and are pre- sented in this paper along with a discussion of their bearing on the optimum composition of blast furnace slags. For an orderly presentation of the data, the quaternary system is viewed as a tetrahedron with one component at each apex. Fig. 1 shows a tetrahedron representing the system Ca0-Mg0-A1,0,-Si0,. The base is the ternary system Ca0-Mg0-SiO,, A1,0, is the top apex, and the front face, the system CaO-

Jan 1, 1955

By H. Larson, J. Chipman

The ferrous and ferric oxide concentrations of slags, expressed as j = Fe+++/(Fe+++ + Fe++), have been established through gas-slag equilibrium at 1550°C in a range of oxygen pressure of 10-I to 10-9 equilibriumatm. The value of j is increased by basic additions (BaO, CaO, MgO, MnO) and decreased by acidic oxides (SiO2 and TiO2). Oxygen pressure is shown graphically as a function of composition for slags which are analogous to those at the slag-gas interface of the open hearth furnace. THE progress which has been made in recent years in understanding the chemistry of metallurgical slags has been based largely on studies of slag-metal and slag-gas equilibria. There is a considerable body of knowledge which is applicable to reactions occurring at the slag-metal interface in open hearth steelmaking. There is little information concerning reactions of the slag with the furnace atmosphere and hence little basis for an understanding of the transfer of oxygen, sulphur, or hydrogen between gas and slag. The oxygen pressure of the open hearth atmosphere is normally of the order of 10-1 to 10-3 atm which differs by several orders of magnitude from that of about 10" atm at the slag-metal interface. The chemical properties of the slag, for example, the ratio of ferric to ferrous iron and the ability of the slag to hold sulphur in solution, are greatly affected by changes in oxygen pressure. This investigation was undertaken to enlarge our knowledge of the effect of oxygen Pressure on steel-making slags. Using air or controlled mixtures of CO a CO2 a range of oxygen Pressures from 10.&apos; to 10.&apos; was covered. Review of the Literature There are only a few references in the literature which pertain directly to this investigation. The most important is that of Darken and Gurry1,2 on the system iron-oxygen. This work included the determination of the phase diagram of the system and also a study of the field of homogeneous melts and their oxygen pressures. Their apparatus and procedure were very similar to that used in this study. Iron oxide was melted in a platinum crucible under an atmosphere of CO2:CO, CO2:H2, H2O, CO2, air or O2 depending upon the partial pressure of oxygen desired. After equilibrium was reached, the sample was quenched and analyzed for ferrous and ferric oxide. By appropriate calculations these authors were able to determine the oxygen and iron activities in the various slags, heats of formation of the oxides of iron, and heats of solution of iron and oxygen in the liquid slags. In a subsequent paper&apos; the same authors made a less thorough investigation of the effects of additions of lime and manganese oxide on the composition of iron oxide melts. Only a few experiments were made and those in a narrower range of temperature and oxygen pressure. Darken&apos; has investigated the fusion temperature of iron oxide in contact with silica under various atmospheres. He found that the temperature changes from 1120° to 1447°C as the gas composition changes from CO2/CO equal to 20.8 to pure oxygen. A comprehensive paper by White" predates the work of Darken and Gurry. The decomposition of ferric oxide into oxygen and lower oxides of iron was studied from 1000° to 1650°C and under oxygen pressures from 2 to 76 cm of mercury. The effect of

Jan 1, 1954

By W. M. Wojcik, R. F. Kowal

Oxygen and sulfur distributions in commercial, 5-ton ingots of killed, medium carbon steel are described. Oxygen distribution is found to vary with deoxidation practice. Irregular distribution of oxygen within ingots makes necessary special precautions in sampling of rolled products for analysis of oxygen. Oxygen distribution is discussed in terms of recently published solidification concepts which had been successfully applied to simpler cases of segregation. These concepts have been found inadequate to explain observed oxygen distributions. Convective movements of the liquid metal, as determined by tracer elements, are shown to be capable of accounting for the observed distributions of oxygen. IN an effort to explore the origin of surface and subsurface imperfections in pierced steel products, a study of oxygen and sulfur segregation was made on ingots cast in open-top and hot-top molds. The results of our previous investigations1"3 have indicated the importance of the location and amount of oxide inclusions in an ingot. Inclusions close to the surface of the ingot have been found to contribute greatly to the formation of imperfections in the surface of finished products. This study of the effects of deoxidation and casting practice on segregation and the resulting oxygen distribution in ingots was initiated to determine the parameters controlling the location of inclusions in an ingot. Segregation of solute elements during solidification of low-melting binary alloys has been studied in the past.1, 5 Formation and growth of inclusions in iron melts have been studied under specific conditions."- In spite of these and other recent studies,10-12 segregation during solidification of commercial, killed steel ingots is not well understood. Consideration of solidification rates, of segregation during solidification of the chill, dendritic, and central zones, and of material balances for the segregated elements has indicated that a simplified theoretical solidification model is not adequate. However, the observed high oxygen contents in localized volumes of the dendritic zone can be rationalized if additional effects of convection currents in the ingots, precipitation, and rapid growth of new phases are considered. EXPERIMENTAL PROCEDURE Steelmaking and Processing. A group of nine killed. medium carbon steel heats having compositions listed in Table I have been studied. The deoxidation and mold practices used were varied to give a wide range of steel oxygen contents. The amounts of aluminum added to the ladle and the ingot casting practices (hot top and open top) were the main variables. The steel was made by a duplex practice in 160-ton tilting basic open-hearth furnaces. All nine heats were top-cast into 24 by 24 in. big end down, fluted molds, to a height between 60 and 76 in., using both open tops and exothermic hot tops. The deoxidation practice and the tapping and teeming details for each heat and ingot studied are given in Tables II and III, respectively. Hot-top practice is indicated by the letter H following the heat designation. Furnace and ladle temperatures were measured by standard disposable-tip, Pt/10 pet PtRh thermocouples. Teeming-stream temperatures were obtained as described by Samways et al.,13 by immersing a Pt/10 pet PtRh thermocouple, covered by a silica sheath, into the teeming stream under the nozzle. The output of this thermocouple was recorded with Leeds & Northrup Speedomax potentiometer. Calibration of the latter thermocouples was based on the freezing point of a pure iron/oxygen alloy (2795°F). The accumulated errors of measurements were within ±10°F. The thermocouple measurements were supplemented in this investigation by continuous recording of a ratioing, two-color pyrometer (Shawmeter), protected from smoke by a blast of clean air within the sighting tube, and calibrated to read with better than ±10°F accuracy. Following teeming of three heats, P, R, and T, tracer elements were added to the steel in the molds to obtain a record of the progress of solidification. As soon as the teeming stream was shut off, a 0.010-in.-thick steel can containing a mixture of crushed standard ferro-titanium and ferro-vanadium (0.05 pet of each alloy element) was plunged into the middle of the steel pool to a depth of 6 in. In about 30 sec no indication of the can or its contents remained. The surface of the open-top ingots solidified in 20 to 30 sec. A study of liquid metal movement and the precipitation of oxides was facilitated materially by use of the tracer technique as titanium has a low distribution coefficient between solid and liquid steel while vanadium has a high distribution coefficient.

Jan 1, 1965

By B. M. Larsen, T. E. Brower, J. W. Bain

A mass of circumstantial evidence is presented to indicate that the main source of alloy losses in open-hearth tapping is oxidation by air, with the steel apparently reacting with an amount of oxygen equivalent to about 30 times its own volume of air. The effect is erratic from heat to heat, depending largely on turbulence and distance of free fall of the stream of liquid metal. THIS paper reports another phase in a general study of oxidation in the open-hearth, various aspects of which have already been discussed in previous papers.1,2,3 It is based on experiments conducted on commercial, basic open-hearth furnaces at various times when opportunity offered, beginning about 1938, in an attempt to determine the mechanism and measure the amount of air oxidation during the flow of the tapping stream through the air into a ladle. This effect is closely connected, not only with alloy losses and control of chemical analysis, but possibly with various questions regarding inclusion content and steel quality and with a true picture of the deoxidation of steel in general. Thus it is believed that discussion of a large part of the results to date may be of assistance to others who are studying problems related to deoxidation or to steel cleanliness and quality. The literature reveals that strangely little attention has been devoted specifically to the effect of pouring steel through open air. Bardenheuer and Henke4 in 1939, in a paper devoted largely to overall losses of manganese in the basic open-hearth, reported that for a number of heats tapped into a tilted ladle held just beneath the runner so that the maximum distance of drop of the stream through the air was held to less than about 30 in., there was in most cases almost no loss of manganese from furnace to ladle. Hultgren,5 in 1945, showed that in high-carbon basic electric steel deoxidized in the furnace and containing no large inclusions as it left the furnace, large silicate inclusions, often rich in manganese oxide, were present in samples dipped from the pool in the ladle; also that the rise in content of large inclusions (above 0.01 mm dim) was greater when the metal stream was made to spray or flow in a turbulent manner. Our interest in this phase of oxidation in the open-hearth was first aroused by a study of alloy efficiencies on ladle additions. The frequency curves of manganese efficiency (net recovery of metal added in ladle) given in fig. 1 are of interest in this connection. Lowest, and also most variable (47 to 95 pct), recovery was in low-carbon heats having no coal additions to the ladle, progressing upward to a maximum average and least variable (82 to 97 pct) recovery in high-carbon heats killed with aluminum and silicon. Both coal additions and higher carbon contents in the tap stream, as well as additions of silicon and aluminum, help to lower the amount of manganese loss. But the most interesting point is the amount of manganese oxidized in many heats tapped at 0.50 to 1.06 pct carbon. It has been shown in a previous paper3 that the amount of oxygen in the tap stream in such heats is very small, usually below 0.01 pct, too small to oxidize any appreciable amount of manganese. Also, the fact that manganese should be oxidized at all in a metal solution containing such more stable oxide-forming elements as aluminum and silicon is an indication of some rather intense oxidizing effect such as could be caused by reaction with the air during ladle filling. Oxygen Balances from Tap Stream to Teeming Stream: Data in the form of alloy efficiencies, such as those shown in fig. 1, are not a proper measure of such a general oxidation effect. Having available

Jan 1, 1951

By W. D. Forgeng, R. L. Folkman, D. C. Hilty

The solubility of oxygen in molten Fe-Cr alloys has been determined at 1550° , 1600°, and 1650°C for alloys containing up to alloyshasbeenabout 50 pct Cr and found to decrease as chromium increases to 6 pet and then to increase gradually. Phase relations in the Fe-Cr-0 system at steelmaking temperatures have been evaluated and two previously unreported oxides have been identified. OPERATIONS in the melting and refining of chromium steels are dependent to a major degree on the reactions of chromium and iron with oxygen and are primarily directed toward controlling and modifying these reactions to secure maximum advantage in the utilization of chromium. Although fairly effective practices have been developed empirically, understanding of the specific reactions is limited. Moreover, the ability of molten steel to dissolve oxygen that subsequently precipitates as oxide inclusions during solidification is well known, so that clarification of the effect of chromium on the nature and mechanism of formation of these inclusions is desirable. Study of the problem indicated that increased knowledge of the fundamental Fe-Cr-0 system is essential to further technical and economic improvement. Consequently, an investigation of the influence of chromium on the solubility of oxygen in molten iron and of phases and phase relations in the Fe-Cr-0 system was undertaken at the Metals Research Laboratories of the Electro Metallurgical Co. as part of a general program on the effective utilization of chromium in chromium steel production. Experimental Procedure All of the experimental runs made during this investigation were carried out in the rotating crucible induction furnace which has been described in detail in a previous publication.&apos; In review, the principle underlying this furnace is that rotational forces in the crucible cause the molten metal to assume a concave shape in such a manner that the slag is contained in the molten metal cup, thereby minimizing slag/crucible contact and subsequent reaction. Practically all of the heats were melted in commercial-quality magnesia crucibles of the type usually furnished for laboratory induction furnaces. All of the runs were made under an argon atmosphere after the furnace chamber had been degassed. Bath temperatures were controlled by Pt—Pt-10 pct Rh thermocouples. The basic furnace charge consisted of a premelted 12 to 15 lb electrolytic iron slug which had been cast to a shape convenient for fitting into the rotating furnace crucible. A typical analysis of the electrolytic iron slugs is given in Table I. For certain runs, it was desirable to melt down charges containing high initial chromium contents. In these cases the chromium was added to the electrolytic iron during the premelting operations. Chromium was added to the rotating furnace bath in the form of electrolytic chromium of the analysis given in Table 11. In all of the constant temperature runs, the standard procedure was to melt down the electrolytic iron or alloy slug under vacuum, admit argon to slightly greater than atmospheric pressure, and adjust rotational speed to develop a well formed "cup" on the bath surface. The melt was then saturated with oxygen by an addition of ferric oxide and the temperature of the bath adjusted to within +5°C of the desired level. At this point the heat was permitted to come to equilibrium prior to sampling or further addition. This time interval was varied from 15 min to 2 hr but generally was about 20 min. After sampling, the desired chromium addition was made and the bath again equilibrated prior to subsequent sampling. This cycle of addition and sampling continued for the duration of the run which lasted from 4 to 8 hr. At the end of this period, power was shut off and the bath allowed to solidify in the furnace. Quenched metal samples were taken from the equilibrated melts by means of the "Taylor sampler" which has been described by Taylor and Chipman.&apos; Before being submitted to chemical analysis, all samples were carefully examined for surface slag occlusions and cold shuts. Later in the study, each sample was radiographed and examined metal-lographically in cross-section to determine the presence of internal defects. On the basis of these examinations, sound and apparently clean specimens were selected from the Taylor samples for chemical analysis.

Jan 1, 1956