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By E. T. Turkdogan, M. L. Pearce

The rates of sulfurization and desulfurization of calcium aluminate, silicate, and ferrite melts by CO + CO2 + SO2 mixtures at 1550°C are reported. It is shown that for melts 10 to 15 mm deep transport of sulfide ions within the melt controls the rate of sulfur transfer. The rate data from shallow melts, i.e., 1 to 4 mm deep, have been analyzed on the basis of a diffusion or a reaction controlled process and indications are that the both processes may play a part in controlling the rate of sulfur reaction. The rates of desulfurization of silicate XVEACTION equilibria between metals, metal oxides, and gases have received considerable attention in recent years. However, the understanding of and aluminate melts increase with increasing PCO2/PCO ratio in the gas stream, the effect being most marked for aluminate melts. The sulfide equilibrium data obtained from the present work are shown to be in accord with the results of previous studies. It is shown that carbon dioxide has a measurable solubility in silicate, aluminate, and ferrite melts. Consideration is given to the partial equilibria which control the directions and the rates of reactions occurring simultaneously in complex heterogeneous systems. the kinetics of heterogeneous reactions, particularly those occurring at elevated temperatures has not been improved appreciably. Almost all the metallurgical reactions occur in heterogeneous systems involving two or more phases. Although in many authoritative text books and original Papers the basic principles concerning the kinetics of heterogeneous reactions are clearly underlined, they are seldom used to the best advantage in kinetic studies, particularly those involving the metallurgical reac-

Jan 1, 1963

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 Walter Crafts, D. C. Hilty

The liquidus diagram for the iron field of the Fe-S-O system has been derived experimentally. The solubility of oxygen in molten Fe-S alloys has been measured at several temperatures and found first to decrease slightly and then increase rapidly with increasing sulphur content. IT is well-known that the types, distribution, and amount of inclusions in any given steel are closely allied with the oxygen and sulphur contents of the metal, so that the term "deoxidation" as conventionally applied in steelmaking refers not only to the control of oxygen and oxide inclusions but to collateral modification of sulphide inclusions as well. Inclusions commonly occur in steel as mixtures of oxides and sulphides, sometimes closely associated and sometimes apparently completely divorced. Their effects on the properties of the metal may vary widely depending on their types and distribution as well as on their quantity. The mechanism by which inclusions form, however, and the means for controlling it are exceedingly complex and not well understood. Nevertheless, as described by Benedicts and Lofquist' and by Wentrup' all oxide and sulphide inclusions, excluding mechanically entrained matter, must result from specific modifications of the basic equilibria of the Fe-S-O system. In an investigation of the mechanism of deoxidation and inclusion formation being carried out at the Union Carbide and Carbon Research Laboratories, it became evident that quantitative data for the fundamental Fe-S-O system were essential to a better understanding of the problem. Consequently, the liquidus surface of the portion of the Fe-S-O diagram of interest in steelmaking has been determined, and the solubility of oxygen in liquid iron containing sulphur has been measured. Fe-S-O Diagram The portion of the Fe-S-O diagram of specific interest in steelmaking is the Fe-FeS-FeO corner. Of the contiguous binary diagrams for this partial system, only those for Fe-FeO and Fe-FeS are known with reasonable certainty.3 Several attempts to derive the FeO-FeS diagram have been made, chief among them being the work of Giani as reported by Oberhoffer,4 and, more recently, that of Vogel and Fulling." Although both Giani and Vogel and Fulling published diagrams for the FeO-FeS system, their observations indicated that the oxide component approximated Fe3O4 rather than FeO, so that there is doubt whether the system is truly binary. Benedicts and Lofquist and also Wentrup published qualitative sketches of the ternary diagram based on the assumption that it was of the type described by Marsh for a ternary system in which two of the contiguous binary systems are simple eutectic systems and the third exhibits a solubility gap in the liquid. Apparently, however, the only previous effort to establish the diagram experimentally was that of Vogel and Fülling whose results are reproduced in Fig. 1. Although defining approximately the limits of the miscibility gap and the location of the ternary eutectic, point E in Fig. I, Vogel and Fülling's diagram must be considered only semiquantitative. It was derived from a limited number of observations mainly along two quasi-binary sections, and the directions of the tie-lines and the location of the critical point, K in Fig. 1, were estimated by computation. Experimental Procedure The experimental technique employed for the present investigation involved melting mixtures of ferrous sulphide and ferric oxide in contact with iron. Since it was considered that in this part of the system the vapor pressures of sulphur and SO, are so low that they would not affect the results significantly, the melting was carried out in a current of argon to sweep out products of any initial re-

Jan 1, 1953

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 F. L. Robertson, C. H. Bacon, J. W. Till

A description is given of the development of a process for making low sulphur steel on furnaces fired with 2 1/2 pet sulphur oil. Slag and metal are analyzed at melt. Slag weight is estimated. A simple method for calculating necessary lime additions for making 0.025 and 0.035 pct sulphur steel is given. DURING the last 15 years John Summers & Sons have been confronted increasingly by the problem of producing a low sulphur steel from high sulphur materials. The principles adopted, the processes used, the data collected on a furnace specially set aside to study this problem, and speculation on future developments are dealt with in this paper. This study is limited to two melting shops which make sheet steel only, of the following analysis: C, 0.06 pct; Mn, 0.33; S, 0.04, 0.035, 0.03, and 0.025; and P, 0.02 and 0.015. All the processes described have reference to the manufacturing of this steel and are not necessarily applicable, without modification, to other steels. The raw materials used are given in Table I. Development of Process About 1934, Schenck's work on phosphorus was applied to frame quantitative rules for the removal of phosphorus, with great success. We could however, neither in our own work nor in the voluminous literature, find any assistance to frame quantitative furnace rules to remove sulphur. Perhaps, we should have persevered with Schenck's outstanding chapter on sulphur in The Physical Chemistry of Steelmaking, but we missed the importance of one (Ss) sentence on p. 478. "Evidently this ratio -------- is [S] the important quantity to be considered from the point of view of chemical reaction; it is clear that the sulphur content of the steel alone, as frequently given in the literature cannot suffice for judging the success of the reaction unless special details are given regarding the sulphur charge and the amount of slag."' We were not however very successful in getting values for Schenck's "n" that agreed with (S) arrived at by our direct analysis. [S] In addition to Schenck's work much attention was given to V value. The formula selected for V was: (SCaO) — 1.57 (2 P2O5) (S SiO2) After plotting many charges a curve was obtained, based upon the relationship between the percentage sulphur in the finished steel and V value, Fig. 1. For a long time this was used as standard with about a 60 to 70 pct success on producer-gas fired furnaces, if all uprising scrap was used and no bought scrap used. An inspection of this curve shows clearly that it is not a quantitative manufacturing process, and that it was not sure enough to go to the trouble and expense of doing stage analysis for P,O,,

Jan 1, 1952

By D. C. Hilty, W. Crafts

A qualitative pseudoternary solidification diagram for the Fe-S-O system modified by manganese is proposed and supported by experimental derivation of an isothermal section at 1475°C and substantially 1 pct Mn in the solid-metal phase. The solubility of oxygen in liquid iron containing 1 pct Mn and sulphur contents up to 0.9 pct has been measured at 1600°C and found to increase as the sulphur content exceeds 0.15 pct. AS has been pointed out previously,' all oxide and sulphide inclusions in steel, excluding mechanically entrained matter, result from modifications of the basic Fe-S-O system. Therefore, one method of attack on the problem of the mechanism of deoxida-tion and inclusion formation is to examine the influence of deoxidizers on the Fe-S-O liquidus diagram. This approach has been adopted in work on the subject being carried out at the Metals Research Laboratories of the Electro Metallurgical Co. and has resulted in the postulation of types of solidification diagrams for the Fe-S-O system modified with common deoxidizers. This method has been of considerable assistance in interpretation of the factors affecting the formation of inclusions.' For the most part, however, these diagrams have been highly speculative. They were constructed primarily by inference from the pertinent binary and ternary systems and from the appearance of inclusions produced by specific deoxidizers. Moreover, since the systems contain four or more components, simplifying assumptions and qualifications were necessary in order to permit their representation as modifications of the Fe-S-O diagram. Consequently, experimental confirmation of the type of construction employed for these diagrams is desirable, and the present paper is concerned with such evidence. The addition of manganese to the Fe-S-O system was selected for initial investigation. Manganese is an important component of practically all steel and is, therefore, of fundamental interest. Because of its great affinity for sulphur, manganese has a more profound effect on the sulphide side of the Fe-S-O diagram than any of the other common deoxidizing eletments. In addition, more quantitative information pertaining to the contiguous binary and ternary systems involving iron, manganese, sulphur, and oxygen is available than for the other deoxidizers. Fe(Mn)-S-O Solidification Diagram Many of the side diagrams of interest in connection with this system are known. The Fe-Mn binary has been well established by several investigators;% the Fe-O system has been clarified by Darken and Gurry;' and FeO-MnO diagrams have been published by Herty,5 Andrew, Maddocks, and Howat,6 and by Hay, Howat, and White.7 The Mn-O diagram does not appear to have been derived experimentally, but the portion of 'it that is of interest can be visualized easily from a consideration of the melting points of Mn and MnO and the fact that a broad miscibility gap must exist between them. The ternary Fe-Mn-O diagram has been discussed by Benedicks and Löfquist,8 Wentrup,9 and by Körber and Oelsen.10 Experimental study of the Fe-Mn-O system has been carried out by Körber and Oelsen and to a lesser degree by Chipman, Gero, and Winkler,11 Hilty and Crafts," and others. On the basis of published information, then, an outline of the Fe-Mn-O liquidus diagram can be constructed as illustrated by Fig. 1. In this, as in all succeeding diagrams, transformations such as the ?-? reaction in iron have been ignored for purposes of simplification. The arrows denote falling temperature. The distinguishing feature of this diagram is the broad region of liquid immiscibility extending

Jan 1, 1955

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 H. Kosmider, P. Coheur

New processes of blowing with an oxygen-enriched air or gas mixtures of oxygen and steam allow the steelmaker to produce, in a basic converter, a rimmed steel low in nitrogen (0.0020 pct), phosphorous (0.020 pct), and sulphur (0.020 pct). The physical properties (ductility) of the new steels are excellent. Furthermore, from the point of view of economy, these new methods of blowing offer outstanding possibilities. THE natural occurrence of geological deposits of iron ore and local economic circumstances led European blast furnace men to work large quantities of lean iron ore with a phosphorus content as high as 0.5 pct. The iron obtained from these ores generally contains 1.5 to 2.1 pct phosphorus, 3.6 to 3.9 pct carbon, 0.3 to 0.6 pct silicon, 0.04 to 0.08 pct sulphur, and 0.3 to 1.2 pct manganese. To produce steel from this pig iron, the steelmaker has at his disposal several processes. One of the simplest and most economical is the pneumatic process developed by S. G. Thomas in 1879. This process of steelmaking, called the Thomas process, consists of blowing through the bottom of a basic bessemer converter and is used widely in Western Europe, as shown in Table I. Due to the development of tonnage oxygen plants, this process has become more important because the use of oxygen offers new possibilities of steel manufacture. Not only may the quality of the steel be improved, but liquid pig iron also may be used, the composition of which does not meet the heat requirements of the blow with atmospheric air. It is not intended to present here a detailed scientific discussion of the basic bessemer process but rather to discuss briefly its industrial possibilities in the case of rimmed steel and when blowing with atmospheric air, oxygen-enriched air, or gas mixtures of oxygen and steam. This paper is based on the current practice at Klockner-Hüttenwerk Haspe&apos;s steel division, and at six Belgian and Luxemburg steel works. The latter are members of the Liege section of the C.N.R.M. (National Institute for Metallurgical Research) and are: ARBED, John Cocker-ill, Esperance-Longdoz, HADIR, Miniere et Metal-lurgique de Rodange, and Ougree-Marihaye, most of which are working with tonnage oxygen plants.&apos; In order to avoid any misunderstanding, it should be noted that most of the techniques to be men- tioned, or similar ones, are used currently at many steel plants in Western Europe. Background The basic converters used in Europe have a capacity of 17 to 65 tons of steel, and are similar in shape to the one in Fig. 1. The lining is brick or rammed dolomite and has a life of 250 to 500 blows. The bottom is rammed dolomite and has a life of 40 to 80 blows. As far as we know, the type of blast used does not appear to have any influence on the life of the lining. Bottom life, on the contrary, depends very much upon the composition of the blast. It is only when

Jan 1, 1955

By J. T. Norton, J. G. McMullin

The ternary system of gold-silver-copper is characterized by a solid solubility gap and a two phase region in which copper-poor and silver-poor phases coexist. At about 30 pct gold, the two phases become mutually soluble at temperatures below the melting temperature. As the gold content is increased, the solubility temperature of the alloys decreases until at about 80 pct gold, the two phases are soluble down to the lowest temperature at which the alloys will recrystallize. Although the general form of the two phase region is known, its boundaries do not seem to have been investigated extensively. In an X ray diffraction study, Masing and Kloiberl have outlined the boundaries of this two phase field at 400 and 750°C. Using only microscopic techniques, Pickus and Pickus2 determined a vertical section of the ternary diagram showing the 14 kt alloys (58.3 pct gold). These two reports are riot in complete agreement. It has been shown3 that some of the ternary alloys are susceptible to age hardening and that the hardening is caused by the separation of a homogeneous alloy into two phases at the aging temperature. While the gold-copper binary system is an outstanding example of super lattice formation, Hultgren4 has shown that a few per cent of silver added to gold-copper destroys the tendency for ordering. Because of the age hardening possibilities of these alloys, it seemed advisable to investigate the boundaries of the two phase field more in detail using an X ray diffraction method, so as to permit a better understanding of the aging phenomena and enable predictions as to the behavior of other alloys to be made. This is especially true for the 18 kt alloys (75.0 pct Au) at the lower temperatures since they are known to exhibit age hardening. Twelve ternary alloys were prepared having the compositions shown in Table 1 and graphically in Fig 1. The gold used was fine gold bars supplied by Handy and Harmon. The silver was a bar of high purity silver from the U. S. Bureau of Standards. The copper was a bar of vacuum-treated, high conductivity copper from the National Research Corporation. The pure metals in the form of powder were weighed out in proper proportions and melted in graphite in a high frequency induction vacuum furnace. They were heated to 1100°C and slowly cooled. The ingots were then removed from the crucible, inverted, returned to the crucible and remelted. This remelting procedure was intended to reduce segregation in the ingots. After remelting, the ingots were checked for weight loss. The weight loss in each ten gram ingot was held to less than 25 mg. The remelted ingots were cold rolled and then given a homogenizing heat treatment of 16 hr at 760°C to remove any remaining segregation. Powder specimens were prepared by cutting the ingots with a fine file, one half the required amount of powder being taken from each end of the ingots. When the X ray diffraction pattern showed any difference in lattice constant between the ends of the ingot, the ingot was remelted and given an additional homogenization treatment. All powder samples were sealed in evacuated pyrex tubes for heat treatment. Ordinary pyrex proved satisfactory for temperatures up to 650°C but above that temperature it was necessary to use a special high temperature pyrex glass. Annealing at temperatures below 500°C was done in a salt bath whereas for temperatures of 500°C and above an electric muffle furnace was used. In both furnaces the temperature control was ± 5°C. In all annealing treatments samples of cold worked powder were placed in a furnace which was already at temperature. In this manner the specimens recrystallized directly to the equilibrium structure for that temperature. Time at temperature was selected so as to allow complete recrystallization, but very little grain growth. Specimens were quenched from the annealing temperatures by breaking the pyrex tubes in cold water. X ray diffraction photograms were made of all the heat treated powders using copper radiation and a Phragmen

Jan 1, 1950

By d&apos, John C. Entremont

Pure iron was inductively melted in small refractory crucibles and optical pyrometer and immersion thermocouple readings were simultmzeously taken. The resulting emissivities of the liquid iron surface obtained were found to be greatly affected by both the gaseous atmosphere and geometrical changes in the physical setup. Quantitative values for these effects are indicated. FOR many applications in both the laboratory and plant, optical pyrometry is still the best means of measuring temperatures in the incandescent range. A prerequisite in evaluating the correct temperature is a good value of the emissivity of the surface. To obtain the emissivity from the tabulated values of the literature can be very confusing and often far from correct. There are many reasons for these difficulties, and it is not within the scope of this paper either to enumerate or to discuss them all. Its purpose is to show quantitatively how several factors affect the apparent emissivities obtained from experimental measurements on liquid iron surfaces. The black body is the reference state for the quantitative values of emissivities and is defined1 as a body which absorbs all radiation incident on it, reflecting none; such a surface emits more radiation per unit area per unit time than any surface which reflects any radiation, and is given a value of unit emissivity. All bodies having reflective power thus have emissivities less than unity and are considered nonblack or grey bodies. The ratio of the radiant energy emitted by the flat, nonblack surface to that of a perfectly black surface of equal area and temperature is the emissivity of the surface. The above definitions are applied to flat, polished, opaque surfaces, very seldom encountered in actual measurements, and for this reason many authors have suggested that the word "emittance" be used for real bodies rather than emissivity. The emittance has reference to the material and its configuration rather than to its properties in the idealized state. Recent observations of molten iron in a small refractory crucible indicate that not only the configuration of its surface but the geometrical arrangement of its surrounding and the nature of the surrounding atmosphere have a pronounced effect on the emittance. Neglect of changes in such conditions may lead to errors as large as 40°C at 1600°C. Thus it is suggested that the term "apparent emissivity" be used and that it be recognized that its value pertains to a particular experimental arrangement only. As a result of not recognizing these differences in emissivities, which are obtainable from changes in the physical setup of an observation, many investigators have incorrectly quoted their values as those of the emissivities of particular materials rather than as an apparent emissivity for their particular arrangements. As a consequence, values of the emissivity of liquid iron ranging from 0.3 up to 0.55 are found in the literature. In an effort to establish an accurate optical temperature scale for liquid iron solutions in which de-oxidation studies were to be carried out, it was observed that the temperature relationship, obtained by simultaneously taking immersion thermocouple

Jan 1, 1963

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 F. W. Luerssen, J. F. Elliott

F LUSHING the early slag from a stationary open Fhearth having a high percentage of hot metal in its charge is necessary in order to remove silica from the system. The flush slag is strongly oxidizing and is somewhat acidic. It has, however, considerable capacity to extract phosphorus from the bath and it also removes considerable manganese. It seems probable that factors which control the distribution of phosphorus and manganese between slag and metal in the refining period also should be dominant in the flush and postflush periods. Several studies, as summarized elsewhere,1,2 support the viewpoint that conditions closely approaching equilibrium for these elements are rather readily established during the refining period. Over the years these studies have repeatedly demonstrated that 1—high slag v01ume, 2—low bath and slag temperature, 3—basic slag, and 4—strongly oxidizing slag favor rapid elimination of phosphorus from the bath to the slag. They also show that the following conditions favor retention of manganese in the bath: 1—low slag volume, 2—high bath and slag temperature, 3— basic slag, and 4—minimum oxidizing power of slag. When it is considered that the flush slag often carries as high as 75 pct of the manganese charged and only 25 to 60 pct of the phosphorus charged, it is evident that in removing silica much manganese is sacrificed but phosphorus removal is far from conplete. Because of overriding circumstances, this is accepted in most operations and actually it is considered to be inevitable. This may account for the fact that little attention has been paid to conditions affecting the elimination of phosphorus and manganese in the flush slag. A recent study of the behavior of various charge oxides has developed considerable information on the flush and postflush periods. Because the data are felt to be of general interest, they have been brought together and Presented in this paper. The object is to show the various factors in the flush and postflush periods which influence elimination of phosphorus and manganese. Physical Conditions During and After Flushing Physical conditions existing during the flush vary from plant to plant, from shop to shop, from furnace to furnace, and even from heat to heat. They are strongly influenced by the physical and chemical character of the charge oxide which is ordinarily necessary to provide sufficient oxidizing power early in the heat. Invariably the period is characterized by a vigorous reaction between the principal re-actants: the hot metal being added and the charge oxide. During the flush, it is probable that the slag acts to some extent as an oxidizer; but, because of the critical influence of the behavior of the charge oxid&apos;e on flushing action, it seems apparent that the oxide itself is the dominant oxidizer. Fig. 1 shows the course of two heats which were selected as being typical of the group studied. Heat A was charged with 55 pet hot metal, based on the total metallics charged, and heat B had 57 pct hot metal. As indicated in Table I and Fig. 1, the melt-down slag, which is not usually voluminous and which is principally FeO, expands greatly in volume and will show rather high levels of SiO2, MnO, and P2O5 very soon after the beginning of the hot metal addition. Simultaneously, large volumes of CO are liberated which cause violent mixing of slag and metal. It is of interest to note that the time required to bring carbon down to a low level is very much longer than that required for the removal of silicon, manganese, or phosphorus. At the end of flush, carbon in the bath is still approximately 2 pct. When strongly reducing hot metal is brought into contact with strongly oxidizing conditions within the furnace! it is probable that the rate of mass transfer to the slag (and atmosphere) of silicon, manganese, phosphorus, and carbon initially depends principally on the rates at which the two participating phases are brought into contact That is, it depends on the nature of the various reactions. Later in the flush period, when the scrap is virtually all dissolved and the action of the bath has settled down to a steady and somewhat gentle boil, it is likely that other factors, such as the transfer of oxygen across the slag-metal interface, become dominant. The temperature of the slag-metal system is far from uniform. Heat is being driven by the flame down through the slag. Bubbling and surging of the metal also frequently brings portions of the bath in contact with the flame. At areas of contact between the ore and liquid metal, or slag and liquid metal, the oxidizing reactions generate much heat. On the other hand, scrap is being melted which tends to absorb large quantities of heat. Because the liquid bath is high in carbon, the steel scrap is brought into solution rapidly. This can proceed at a rather low temperature; and until much of the scrap has been taken into solution, the bath temperature would not be expected to increase appreciably. Consideration of these factors leads to the conclusion that during the flush period the slag should be rather hot and the bath relatively cold. Both observation and temperature measurements bear this out. Experimental Data The extended program of charge oxide evaluation permitted study of the widely varying conditions existing during the flushing period. Slag and metal analyses and bath temperatures reported herein (Tables I and 11) were obtained toward the latter portion of the work. Four different types of charge oxide, sinter, two types of hydraulic cement-bonded soft ores, and a pyrobonded agglomerate were used in the study. Although the heats reported were from only one 205 ton furnace, they show variations in flush slag analyses all the way from 25 pct FeO, which is typical with the use of a hard natural charge ore, to 45 pct FeO which resulted when a very poorly agglomerated fine ore was used. The physical behavior of the flushes showed a correspondingly wide variation from well controlled reactions to violent surges following periods of inac-

Jan 1, 1956