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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 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 R. J. Murphy, N. J. Grant, J. W. Dowding

A large number of blast furnace slag-metal tests were examined to determine if the manganese reduction could be used as a primary indicator of the degree of oxidation or reduction of the slag and of its desulphurizing power. Slag basicity and temperature were also evaluated. Two laboratory heats were made and sampled prior to reaching equilibrium to check blast furnace data. IN a recent investigation of the factors affecting desulphurization in the blast furnace, is was evident that manganese reduction appeared to parallel the course of desulphurization. Grant, Kalling, and Chipman1 pointed this out in a series of time studies utilizing closely controlled laboratory melts. Fig. 1 is a composite plot of sulphur removal and manganese reduction as a function of time under two slags of different basicity. Manganese reduction appears to approach equilibrium at approximately the same rate as does sulphur. It was also demonstrated that the addition of oxygen to the slag, as manganese oxide, caused a sharp reversal of sulphur from the slag to the metal.' It has been shown that "Excess CaO" was a primary factor in measuring the degree of desulphurization under ideal reducing conditions,1,2 the following reaction being representative of the process: CaO (slag) + S + C (solid) = CaS(slag) + CO (gas) It was also evident that a second reaction could drive the sulphur from the slag into the metal. A suggested reaction was' CaS (slag) + 0 = CaO (slag) + S Any change in the oxidizing power of the system would thus affect both the sulphur and the manganese without causing any change in the calculated basicity of the slag. "Excess CaO," "Excess Base," and other similar basicity values, under such oxidizing conditions, would therefore not be the best measure of desulphurizing power; instead, as was shown by and Chipman" he oxygen content of the slag at low oxygen levels would be the controlling factor. Unfortunately, the extent to which FeO is reduced in the blast furnace makes it difficult to utilize slag FeO as an accurate indicator of the degree of oxidation. By comparison, manganese reduction in the blast furnace proceeds more slowly and is generally only about 40 to 70 pct complete. manganese, which is present in significant amounts and is readily analyzed, offers an opportun-

Jan 1, 1954

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. H. Swislzer

TWO-LIQUID miscibility gaps have been found to exist in both the CaO-SiO, system above 1705 and the Cr,03 system above 2200"c. Glasser and 0sborn3 studied the extension of these miscibility gaps into the Ca0-Si0,-Crz03 ternary system and reported that the two-liquid region is not present at temperatures below the monotectic temperature of 1705°C in the CaO-SiO, system. The present authors, in connection with other work on surface-tension measurements and foam stabilities in the same ternary system,4 observed that the miscibility gap exists at temperatures as low as 1600°C. A brief experimental study was devoted to deter- mining tie-line positions in the two-phase region. The technique used was to obtain a separation of phases at 1600°C, then to quench-in the high-temperature phases and obtain a chemical analysis of each phase. It was necessary to take special precautions in obtaining a phase separation because of a tendency toward emulsification of the two liquids. The procedure followed is described in the schematic drawing in Fig. 1. A small platinum crucible containing several pinholes on its sides was placed inside a larger platinum crucible. An excess of Crz03 was placed in the outer crucible, together with a prefused binary CaO-Si02 mixture, and the Cr203 was allowed to diffuse through the pinholes and saturate the same binary CaO-SiOl mixture in the smaller crucible. After equilibration at 1600°C, the inner crucible contained only the lighter liquid (liquid A) saturated with Cr203. The outer crucible contained layers of both liquids. Experimental data were obtained by analyzing the entire contents of the inner crucible and only the bottom layer of the larger crucible (liquid B). The upper layer of the outer crucible was not suitable for chemical-analysis purposes because dispersions of the second phase sometimes were found in the samples. The technique is described in more detail in Ref. 4. The same method was used by Grieveson and urkdoan&apos; to study a miscibility gap in sulfate-ferrite melts, where the liquids were difficult to separate because of similarities in density. In addition to the phase-separation experiments, a few others were conducted to obtain information

Jan 1, 1964

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 H. M. Otte

Certain choices for the shear elements of the inhomogeneous distortion in the phenomenological theory of martensite formation are examined for their agreement with crystallographic and X-ray data of iron alloys. The assumption that the shear elements must represent slip or twinning systems characteristic of bcc metals is found to covey all observations, even when a small uniform dilatation is taken into consideration. In bct martensite, (011) becomes a possible twinning or faulting plane, in addition to {112), and qualitatively similar X-ray line broadening is to be expected from both. The basic concept inherent in the current theoriesl-4 of the formation of martensite is that the interface between the parent (austenitic) and product (martensitic) phase is an invariant strain plane (i.e., one that is undistorted and unrotated). Experimental evidence that the interface is of such a nature is available in certain transformations2&apos;5&apos;6 but for the transformation in iron alloys direct observation has not proved enlightening. Internal strains resulting from the formation of the small martensite platelets within the parent austenite matrix7 make it difficult to produce the desired evidence. Indirect evidence, however, such as the continuity of scratches in passing from untrans-formed to a transformed region, strongly indicates that the habit plane in iron alloys is an invariant strain interface. The scatter in habit planes in a given specimen8 would suggest that internal stresses have a slight but definite influence. On the other hand, composition changes which affect the lattice parameter can alter the habit plane appreciably, and by an amount greater than the scatter.&apos; The success of the theories depends on the choice made for the "inhomogeneous distortion" or "complementary shear&apos;&apos; in the analysis and also on the choice for the parameter 6 representing a small uniform dilatation. In the approach developed by Wechsler, Lieberman, and Read&apos;," it is implicitly assumed that 6 is unity. In the case of iron alloys, all observations cannot be explained without varying either the inhomogeneous distortion or 6 . Bowles and Mackenzie3 considered only the effect of varying d. They found it difficult to reconcile the wide scatter of habit planes with the theory and were forced to the conclusion that it may also be necessary to consider variations or different choices of the inhomogeneous distortion. Wechsler and Read" considered a limited number of possible choices for the inhomogeneous distortion, but no variation in 6, though this could easily have been introduced if so desired. It is the purpose of the

Jan 1, 1961