Search Documents

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 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

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 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

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

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

Jan 1, 1951

By A. W. McReynolds

E. OROWAN*—I observed the phenomenon of jerky yielding many years ago with zinc25 and cadmium single crystals. A significant point was that the jerks occurred not only when the stress was raised but also (sometimes, after a pause of many minutes during which no trace of creep was observable) at constant stress. The phenomenon may be closely linked with the inertia of the testing machine and of the specimen, although the inertia alone cannot account for it. If, during the test, the resistance of the material to plastic deformation suddenly diminishes while the applied force remains constant, a sudden deformation follows until the yield stress has risen, by strain hardening, to the level of the applied stress (= the value of the previous "upper yield point."). When this is reached, the rate of deformation has attained a maximum value because, up to this moment, the applied force was higher than the plastic resistance of the specimen, and the difference was used for accelerating the moving parts of machine and specimen. The kinetic energy accumulated is now transformed into plastic work by further deformation; that is. the deformation overshoots the point at which the plastic resistance equals the applied static force. When the kinetic energy has been used up, therefore, we are left with a specimen the yield stress of which is higher than the applied stress, and no further deformation can occur (apart from a little creep) until either the applied stress has been raised to the new yield stress level, or the yield stress has fallen by thermal recovery to the level of the applied stress. While this occurs, a new upper yield point can develop, for example, by precipitation.26

Jan 1, 1950

By Donald A. Corrigan, John Chipman

It is shown that the heat of solution of nitrogen in liquid-iron alloys is Proportional to the interaction coefficient. This proportionality forms the basis for a method of predicting nilrogen solubility at any temperature when the interaction coefficient is knoun at 1600°C ov when the solubility is known at some one temperature. A method for predicting the solubility of nitrogen in liquid steels, including alloy steels, was proposed some years ago by Langenberg.&apos; Since the data available at that time were restricted to temperatures of about 1600°C, his predictions were similarly restricted. More recently, Nelssonz devised an approximate method for estimating nitrogen solubilities at higher temperatures. It is the purpose of the present paper to present a method by which the solubility of nitrogen at any temperature within the steelmaking range may be predicted from the known interaction coefficients at 1600°C. Nitrogen in iron and in all of the alloys to be considered here is known to obey Sieverts&apos; Law; hence the activity of nitrogen in an alloy of fixed composition is proportional to its concentration, here expressed in weight percent. The activity of nitrogen is defined as equal to its weight percent in the binary Fe-N solution at any temperature. Its activity coefficient in any alloy is the comparison being made at equal values of T and PN2. In all alloys the activity coefficient changes with composition, log fN being a linear function of the percent of alloying element at low concentrations. In the following calculations the alloy compositions are restricted to those in which this linear relation is exhibited. For most systems this is a fairly wide range, for example up to 5 pct V and to 10 pct Cr or Ni. For this composition range. complex alloy is the same as that in the Fe-N-j ternary solution. Langenberg&apos;s method of prediction was based on Eq. [3], the values of log fN for various additions being taken from a graph. Instead of using the simple addition indicated in Eq. [3], he used a more complex method suggested for Fe-S-j alloys by Morris and Buehl.3 For the composition ranges in which Eq. [2] is valid the two methods are equivalent. Nelson extended the prediction to other temperatures on the assumption that logfN is inversely proportional to absolute temperature. It may be shown that inverse proportionality would result if the partial molal entropy of nitrogen were unaffected by addition of the alloy element, an assumption which Nelson designated as a "regular" solution. It has been shown recently by the authors4 that this assumption is not a good approximation. The heat of solution of nitrogen (N2) in an alloy may be obtained if the solubility is known as a function of temperature. Measurements of this nature have been reported recently by Beer5 for Fe-Mn alloys, by Nelsson2 for Fe-C, by El Tayeb and parlee6 for Fe-V, and by Pehlke and Elliott7 for many alloys embracing a wide range of compositions. In connection with the work of the last named authors it is noted that their Fig. 22 gives the heat effect per half mole rather than per mole of N2. In using their data we have shifted some of their values slightly by using the best straight line in preference to their curve. Their data, supplemented by others from the literature, are summarized in Table I. In Fig. 1 the heat of solution of nitrogen is shown as a function of composition for the several alloy systems. The difference between the heat effect in the alloy. AH; and that in pure

Jan 1, 1965

By R. C. Buehl, M. B. Royer

A three ton per day blast furnace using blast temperatures up to 2200°F was operated to recover manganese from open-hearth slag and manganiferous iron ore. The spiegel product containing 12 to 24 pct Mn was blown in a basic converter to high manganese oxide slag as described in the paper which follows this one. HE steel industry, which uses over 900,000 short tons of contained manganese yearly, depends on the maintenance of supplies of manganese from foreign sources such as India, Gold Coast, and Union of South Africa. Domestic ores furnish less than 10 pct of the yearly requirements of metallurgical ores and, unfortunately, the United States has no large, or even moderate, grade deposits that could supply a major portion of the requirements for many years. It may be necessary to obtain manganese from low grade materials, even though the cost is appreciably higher than when imported ores are used. An American Iron and Steel Institute questionnaire prepared in 1949 revealed the startling fact that open-hearth slags contained about as much manganese as is imported annually. The quantity of slag produced each year by integrated steel plants (not including cold-melt shops) and the manganese contained in the slag follows: Flush slag, 4,500,000 net tons a year containing 408,000 net tons Mn; tap slag, 7,230,000 net tons a year containing 364,000 net tons Mn; for a total of 772,000 net tons Mn. Some of this slag is returned to blast furnaces but about 75 pct would be available for the recovery of manganese. In several decades, when many of the present sources of high manganese ores have been depleted, open-hearth slag and manganiferous iron ore may become the major source of the manganese required for steel production. In 1948, manganese-ore imports from the U.S.S.R. were 427,000 net tons or 34 pct of the foreign ore. Imports from this source were only 81,000 tons in 1949. It became evident that adequate stockpiles of manganese could not be accumulated for many years. The Bureau of Mines initiated an extensive research program on methods for increasing domestic production of manganese and entered into a cooperative agreement with the American Iron and Steel Institute for recovering manganese from open-hearth slags whereby the Institute provided additional research funds and trained operating personnel. Description of Process and Equipment Numerous pyrometallurgical and hydrometallur-gical processes and combinations of the two can be applied to the recovery of manganese from open-hearth slag and manganiferous iron ore. The process being developed at the Pittsburgh Station of the Bureau of Mines consists of: 1—Reduction of open-hearth slag in a blast furnace to recover the iron and manganese as spiegel-eisen with 12 to 24 pct Mn. 2—Selective oxidation of the manganese from the blast-furnace metal in a basic-lined converter to produce a high manganese slag with up to 60 pct Mn content, which is a synthetic ore for the production of ferromanganese. This process has the advantage over other processes in that the equipment which would be used, such as blast furnaces and converters, has been highly

Jan 1, 1953

By S. Ramachandran, N. J. Grant, T. B. King

MANY investigations of the rate of the sulfur transfer reaction between carbon-saturated iron and blast furnace type slags have been made." It is evident that the reaction is complex, the rate being affected by the presence of elements dissolved in the metal that are readily oxidized and therefore capable of existing in the slag phase. Thus Goldman, Derge, and Philbrook- have shown that carbon, silicon, manganese, and aluminum, in order of increasing effectiveness, accelerate sulfur transfer from iron containing these elements to blast furnace type slags. Quantitative information is still, however, not available on the relation between what have been termed side reactions, such as silicon transfer and CO evolution, and the sulfur transfer reaction itself. In other words, the stoichiometry of the reaction has not been investigated. In the present investigation, the transfer of all reacting elements and the evolution of CO have been measured simultaneously in order to establish the mechanism of the reaction which occurs in practice. Information of this nature cannot be deduced from equilibrium studies. It should be pointed out that in kinetic studies of this type quantitative conclusions are applicable only to the system studied. This restriction should be borne in mind when attempts are made to compare results from different investigations. Apparatus The apparatus used enables slag and metal samples to be taken at frequent intervals and also provides a continuous record of the amount of gas evolved. A sketch of the apparatus is given in Fig. 1. It may be considered in three sections: 1) furnace section, 2) blank volume section, and 3) pressure measuring section. The furnace section is shown in detail in Fig. 2. It consists of two graphite crucibles, C and D, super-

Jan 1, 1957

By W. O. Philbrook, L. D. Kirkbride

IN the normal operation of the iron blast furnace, reduction of the iron oxides is accomplished almost entirely above the tuyeres.&apos; Blast furnace slags usually contain less than 0.5 pct FeO, although higher values may occur with abnormal operation. There is reason to conjecture, however, that incompletely reduced ore may sometimes reach the hearth and enter the slag as a result of heavy slips or, perhaps, even from cores of excessively large lumps of a charge material of poor reducibility. The possibility of reoxidation of iron droplets falling in front of the tuyeres has been considered by several writers. It would be of interest, to know how rapidly iron oxides reaching the slag for any of these reasons could be reduced by reaction with coke or with the high carbon liquid iron in the hearth. In comparison with the hundreds of papers that have appeared on various aspects of the reduction of solid iron oxides by gases and in the presence of several forms of carbon, little work has been published on the reductioin of liquid oxides or slags. Dancey measured rates of reaction of the pure liquid oxides, both FeO and Fe,O,, with molten iron containing about 4.3 pct C. The oxide was dropped into the cup formed in the upper surface of the iron by rotating the crucible and melt. Under these conditions, reduction of either FeO or Fe,O., was completed in less than 10 sec. The present study was concerned with the reduction of FeO from blast furnace-type slags containing less than 5 pct FeO and melted over carbon-saturated iron in stationary graphite crucibles. The results were considerably different from those found by Dancey, as will be discussed later. Although this work is of interest in relation to hearth reactions in the blast furnace, interpretations must be made with caution because the experimental conditions do not duplicate those within a furnace and may not even lead to the same reaction mechanism. The authors were motivated in undertaking this work by an additional interest—the part played by FeO reduction in the mechanism of de-sulphurization of iron by slags under similar experimental conditions. Derge, Philbrook, and Goldman eveloped detailed experimental evidence to support a three-step mechanism for desulphurization like that originally proposed by Holbrook and Joseph&apos; (These reactions are written in molecular form for convenience, but this is not intended to imply the existence of molecules of FeS in the bulk metal phase nor to deny the likelihood of ionic reactions in the slag.) Earlier work by Chang and Goldman" had shown that the overall reaction follows first-order kinetics with respect to sulphur and that the rate of reaction is proportional to the slag-metal interface area, which observations have been confirmed by subsequent work. Later studiese,&apos; have established the influence of al.loying elements on the first and last steps of the reaction. This paper reports a study of step 3 alone, uncomplicated by the simultaneous process of sulphur transfer. Apparatus and Procedure The experiments were made in a conventional high frequency induction furnace powered by a 35 kva Hg spark gap converter. The graphite crucibles used for most of the runs were 14 cm (5.5 in.) deep and 4.8 cm (1.9 in.) ID with 0.75 cm (0.3 in.) wall. An insulating cover with a small opening for withdrawing samples was used to minimize heat loss and infiltration of air into the furnace. The crucible was charged with 300 g of carbon-saturated iron and either 65 or 100 g of prefused slag analyzing 38.0 pct SiO,, 15.4 pct A10 and 47.1 pct CaO. To obtain the cleanest possible interface at the start of the reaction, the metal and slag were brought to temperature together to prevent the rejection of kish graphite that would have been caused by the chilling effect of a large addition of cold slag to carbon-saturated iron. After temperature control had been established, the desired amount of iron oxide was added in the form of a prefused slag of composition 73.6 pct FeO, 7.7 pct AWX and 19.0 pct SiOl. This slag addition was observed to be molten in somewhat less than 1 min, and a very vigorous reaction proceeded for 1 to 2 min after its introduction. Zero time was taken as 2 min after the ferrous silicate slag addition. Slag samples weighing about 0.5 g each were taken periodically by a copper chill sampler." The weight of the initial slag was large relative to the weight of samples removed, so that the slag weight never varied by more than 5 pct during any run. Temperature was measured by a calibrated W/Mo thermocouple immersed in the metal, with a graphite tip cemented over the fused silica protection tube to prevent attack by slag and metal. After some difficulties with uncertain temperatures during the first two runs, the practice adopted to position the thermocouple for reproducible results was to lower the protection tube to touch the bottom of the crucible and then raise it 0.5 cm. The apparent temperature gradient between the bottom of the crucible and the top of the slag was found to be 15°C (27°F). but much of this spread was probably the result of inadequate immersion of the protection tube to off-set conduction losses along the graphite tip when the thermocouple was inserted only into the slag. The temperature of the bath was controlled within 25°C (9°F) during a run.

Jan 1, 1957

By R. D. Burlingame, T. L. Joseph, Gust Bitsianes

DESPITE almost fifty years of commercial practice, the sintering of iron ore has received little fundamental study. Much of the theoretical work1-&apos;has dealt with the constitution of sinter produced under widely varying conditions. While these studies have broadened our knowledge of the changes that occur in the sintering zone and in the freshly formed sinter during the early stages of cooling, they provide little insight into the changes that precede the formation of sinter. These preliminary changes merit study as a part of the overall process. Hessle. working with beds of Swedish magnetite concentrates, was one of the first investigators to study the sintering process in its entirety. On the basis of temperatures observed at various levels of the bed during sintering, he postulated a number of distinct reaction zones to account for the chemical changes leading to the formation of sinter. A more direct method of attack is that of arresting the sintering zone after it has progressed part way through the bed. A study of a vertical cross section through such a quenched bed provides direct information on the changes taking place at various levels. This method was used by McBriar et al.&apos; to show that several well-defined zones of chemical change existed within beds that were typical of British sintering practice. The same general method of attack was developed independently in the present investigation to study partially sintered beds typical of American practice. Experimental Sintering Equipment The sintering operation was carried out on an experimental scale with the equipment shown in Fig. 1. The refractory-walled sintering chamber A was 11 in. deep and averaged 9 in. in diameter. Air was introduced through a tapered flow section B, which contained the orifice C for accurate metering of the incoming air. This section was located directly above the square ignition housing D, which in turn rested upon the sintering chamber A. The bed was ignited with burner E. The required suction for the operation was furnished by a fan F, which had an air capacity of 500 cfm (stp). Hot exhaust gases from the sintering chamber were cleaned in the dustcatcher G before entering the exhaust fan. In the study of partially sintered beds, it was essential to find some technique for removing the entire charge from the sintering pot without disarranging the unsintered bottom portion. This problem was finally solved by sintering the charge in a removable basket, which snugly fitted the sintering chamber. This basket was constructed of two thicknesses of window screen and was lined with a 3/16-in. layer of asbestos paper. The bottom of the basket consisted of two thicknesses of wire screen, which were fastened to the basket wall. For high fuel mixtures, additional insulation was provided by a somewhat thicker layer of asbestos cement. Preparation of Partially Sintered Mixtures The moist feed was carefully placed in the sintering basket, to prevent segregation of the particles, which varied widely in size and composition. A thermocouple was placed in the center of the basket with the hot junction halfway down, and the mixture was evenly distributed around it. During ignition and throughout the sintering of the upper half of the bed, the hot junction temperature increased very little. When the sintering zone reached the halfway point, as indicated by the sudden increase in the hot junction temperature, the charge was quenched. During quenching the suction was turned off and the orifice was tightly stoppered to prevent further influx of air. At the same time, nitrogen was admitted to the sintering chamber through the orifice tap. As soon as the nitrogen had displaced the air and products of combustion, the charge was removed from the sintering pot for immediate dissection. It is impossible to preserve the exact zone structure of the bed at the instant that combustion is arrested unless the downward transmission of heat is also immediately stopped. Fortunately, heat transfer is very slow in beds containing a stationary fluid, especially if the particle size is small. It follows that the minimum quantity of nitrogen should be used to displace the air and that static conditions be established as soon as possible. A very steep temperature gradient across the combustion zone for some time after the quench was evidence of in-

Jan 1, 1957

By Arnulf Muan, Hobart M. Kraner

Ferromanganese alloys react with aluminu-silica brick in blast furnace hearths and cause the formation of new phases with low refractoriness and consequent failure of the refractory lining. The nature of these reactions is explained on the basis of petrographic observations, thermodynamic data, and Phase equilibrium considerations. Animproued hearth design resulted from these findings. The production of ferromanganese in blast furnaces presents many problems which are not encountered in the production of iron in the same furnaces. One of the most serious of these problems is the rapid failure of refractories caused by their reaction with the ferromanganese metal. The present paper describes such a "hearth attack", its symptoms, causes, and cure. Following an introductory discussion of operating practice in ferromanganese blast furnaces, results are presented of a petrographic examination of samples from a furnace which had to be shut down because of refractory failure. The causes of this failure are then analyzed on the basis of petrographic observations combined with thermodynamic and phase equilibrium data available in the literature. The latter type of data were subsequently used as a guide in recommending improvements in hearth designs which have since proven themselves successful in practical operations. I) FERROMANGANESE BLAST FURNACE PRACTICE It is considered good practice to blow in a furnace on iron and operate it in this way for a period of time preliminary to producing ferrornanganese. During this time, iron generally penetrates the bottom refractories six or more feet below the original working surface of the hearth. Not only does this metal pervade the joints to these depths, but the pores of the refractories are usually also filled by molten iron. The high throughput of the iron furnace provides ample heat to maintain a high temperature in the hearth refractories. This, together with a high ferrostatic pressure, causes porous clay brick of the hearth to shrink. During subsequent use of such a furnace in ferromanganese production, the iron in the pores of hearth brick if; replaced to some extent by ferromanganese. The replacement is usually not complete. This is probably due to the lower metal throughput and lower prevailing temperatures resulting from this in the brick of the hearth bottom. When the ferrornanganese furnace is banked—or when the temperature in the furnace falls due to a furnace delay—-manganese oxidizes even though the atmosphere is largely CO. Considerable expansion accompanies this oxidation of manganese from metal to oxide. The hearth refractories are then subjected to the disintegrating forces of the volume expansion. These forces may in extreme cases be large enough to lift the furnace off its mantle supports as was described in a previous paper.&apos; When cooling takes place slowly, however, and the temperature remains at a fairly high level, the refractories undergo fluxing action by the MnO. This latter reaction and the reduction of SiO2 of the clay brick is the general subject of the present paper. The observations to be described herein were made on a ferromanganese furnace located at the Johnstown plant of Bethlehem Steel Co. The furnace was lined entirely with clay refractories and had operated on iron for 266 days and on ferromanganese for 96 days prior to being taken off because of a hearth wall failure. II) PETROGRAPHIC EXAMINATION AND CHEMICAL ANALYSIS The photograph reproduced in Fig. 1 shws a cross section of the upper part of an 18 by 9 by 4-1/2 in. bottom block removed from the blast furnace. This brick came from a depth of approximately 6 ft below the original working face of the bottom. It will be noted that the 4-1/2 in. dimension is almost the same as when the brick entered the furnace. Three characteristically different zones marked I, II, and III on the print of Fig. 1 are apparent. Results of chemical analyses of the original brick and samples from each of these zones are listed in Table I. Petrographically the various zones were characterized as follows: The central zone marked I was essentially un-reacted brick. The microstructure consisted of fine needles of mullite, and the pores in this entire area were filled with iron. This is characteristic of

Jan 1, 1962

By N. A. Warner

Dense cylindrical specimens of artificial hematite were reduced in hydrogen over a range 0-f total pressures between 0.1 and 1.0 atm and temperatures between 650" and 950°C. Hydrogen reduction at a total pressure of 1.0 atm in the presence of a chemically inert diluent and reduction in hydrogen/water mixtures were also studied Znter.face movement during reduction was followed using metallographic techniques. Substantiu1 partial-pressure gradients are shown to exist in both the gas film and the reduced iron layer. The results are consistent with a mixed-control mechanism involving an interaction of gaseous-difusion effects with a first-order reversible chemical reaction at the iron/wüstite interface. Over the hydrogen-pressure range of 0.1 to 1.0 atm, the rate is not directly proportional to the hydrogen pressure in the bulk gas stream. Nitrogen dilution of the reducing gas masks the true effect of hydrogen partial pressure by influencing the effective molecular dif-fusivity and gives an apparent first-order relationship. The transport of hydrogen and water vapor across the iron layer is consistent with molecular gaseous diffusion rather than a Knudsen diffusion mechanism. ALTHOUGH the literature on the reduction of iron oxides is very extensive, it is only comparatively recently that a definite quantitative model for the reduction of hematite has been proposed. This development has been largely due to the work of McKewan. An extensive literature review of previous work has recently been compiled by Themelis and Gauvin. Exclusive control by gaseous diffusion in the reduction of hematite has been recently advocated by Kawasaki and coworkers.&apos; Although the results of the latter workers are of considerable practical significance, the extreme porosity (approximately 30 pct) of their specimens precludes their application to a kinetic evaluation of the reduction of dense polycrystalline hematite. The salient features of the kinetic model used by McKewan for the gaseous reduction of dense hematite at temperatures in excess of 560°C (when FeO is stable) are: 1) The reduction is a topochemical reaction taking place through &apos;the series FeO/FesO4/FeO/ Fe; 2) The gas-solid type of reaction takes place only at the FeO/Fe interface and the internal reduction: FeO proceeds by solid state diffusion; 3) The iron layer formed is quite porous and offers negligible impedance to gaseous diffusion; 4) The rate-controlling step in the reduction is a chemical process occurring at the Fe/FeO interface. In view of the relatively fast reaction rates involved when hematite is reduced in a stream of hydrogen, it seemed possible that the simplifying assumptions of negligible diffusional resistance in both the bulk gas phase and the reduced iron layer could introduce serious errors in the interpretation of experimental reduction data. The present work was initiated to elucidate the effect of gaseous diffusion on the reduction rate and to determine its possible influence in the formulation of the reaction mechanism at the metal/oxide interface. EXPERIMENTAL Procedure and Apparatus. Dense cylindrical compacts of artificial hematite were prepared by sintering pressed compacts of reagent-grade ferric oxide, containing 99.6 pct FezO, in air at 1200°C for 80 hr. The resulting compacts had a final porosity of less than 2 pct and a height and diameter of approximately 1 cm. Variations in sintering atmosphere from air to pure oxygen, in sintering time from 20 to 80 hr, and temperature from 1150" to 1250°C had no effect on the subsequent reduction behavior. The reduction of the samples took place in a vertical tube furnace in which was placed a 1-in. transparent silica tube. The 24-in. heated length

Jan 1, 1964

By D. C. Hilty

It has long been known that in melting high-chromium steels, some of the carbon might be oxidized out of the melt without excessive simultaneous oxidation of chromium, and that higher temperatures favor retention of chromium. The advent of oxygen injection as a tool for rapid decarburization of a steel bath permits significantly higher bath temperatures, and it was quickly recognized that the use of oxygen injection facilitated the oxidation of carbon to low levels in the presence of relatively high residual chromium contents. Up to the present time, however, specific data pertaining to the chro-mium-carbon-temperature relations in chromium steel refining have not been available. Individual steelmakers have evolved practices more or less empirically, but there has been very little real basis for predicting how effective any given practice can be in permitting maximum oxidation of carbon with minimum loss of chromium. The current investigation, therefore, was undertaken in an effort to establish the fundamental carbon-chromium relationship in molten iron under oxidizing conditions. As reported below, the equilibrium constant and the influence of temperature on that constant have been derived for the iron-chromium-carbon-oxygen reaction in the range of chromium steel compositions with what appears to be a fair degree of precision. The practical application of the result will be obvious. Experimental Procedure The laboratory investigation was carried out on chromium steel heats melted in a magnesia crucible in a 100-lb capacity induction furnace at the Union Carbide and Carbon Re- search Laboratories. The charges for the heats consisted of Armco iron, low-carbon chromium metal, and high-carbon chromium metal, the relative proportions of which were calculated so that the various heats would contain from approximately 0.06 pct carbon and 8 pct chromium to 0.40 pct carbon and 30 pct chromium at melt-down. When the charges were melted, the bath temperatures were raised to the desired level, and the heats were then decarburized by successive injections of oxygen at the slag-metal interface through a ½-in. diam silica tube at a pressure of 30 psi. The duration of the oxygen injections was from 30 sec to 2 min. at intervals of approximately 5 to 30 min. It did not appear that length or frequency of the injection periods had any significant effect on the results; cansequently, no effort was made to hold them constant and they were controlled only as was expedient to the general working of the heats. Between successive injections, the heats were sampled by means of a copper suction-tube sampler that yields a sound, rapidly-solidified sample representative of the composition of the molten metal at the temperature of sampling. This sampling device is a modification of the one described by Taylor and Chipman.1 An attempt was made to vary bath temperatures between samples, but it quickly became evident that, unless the variations were small or unless the new temperature was maintained for a minimum of 15 min. during which an injection of oxygen was made in order to accelerate the reactions, a very wide departure from equilibrium resulted. For most of the runs, therefore, temperature was maintained relatively constant at approximately 1750 or 1820°C. A few reliable observations at other temperatures, however, were obtained. Temperature Measurement The high temperatures involved in this investigation were measured by the radiation method, utilizing a Ray-O-Tube focused on the closed end of a refractory tube immersed in the metal bath. The immersion tubes employed were high-purity alumina tubes specially prepared by the Tona-wanda Laboratory of The Linde Air Products Co. These tubes were quite sturdy under reasonable mechanical stress at high temperature. They were unusually resistant to thermal shock, and chemical attack on them by the melts was slow. With care, it was found possible to keep these tubes continuously immersed in a heat for as long as 5 hr at temperatures up to 1850°C, before failure by fluxing occurred. The Ray-O-Tube—alumina tube assemblage was similar to those supplied commercially for lower temperature applications. In operation, the alumina tube was slowly immersed in the molten metal to a depth of approximately 5 in., and the device was then clamped solidly to a supporting jig where it remained for the duration of the run. A photograph of the equipment, in operation with Ray-O-Tube in place and oxygen injection in progress, is shown in Fig 1. When in position in a heat, the instrument was calibrated by means of an immersion thermocouple and an optical pyrometer. For calibration through the range of temperatures from 1500 to 1650°C, a platinum -platinum + 10 pct rhodium thermocouple in a silica tube was immersed alongside the alumina tube. Output of the Ray-O-Tube in millivolts and the

Jan 1, 1950

By C. E. Sims, F. W. Boulger, H. A. Saller

Most of the data on equilibrium constant and the deoxidations potentialities of those elements, considered to be stronger deoxidizers for steel than is silicon, have been calculated from thermodynamic data. The reason for this is, primarily, the obvious difficulty of obtaining direct experimental evidence of equivalent accuracy. This is an excellent use of the principles of thermodynamics and has given valuable data not otherwise available. Such results, of course, can be no more accurate than the physical constants used in the calculations, and one can never be sure that the basic data are either complete or accurate. In fact, as in the case with silicon,1 there are not only discrepancies among the calculated theoretical values of the equilibrium constant for deoxidation of steel but also between the theoretical and experimental values. It is highly desirable, therefore, to obtain experimental values for checks on calculated results whenever possible. If they disagree, both cannot be right, but if there is good agreement, their value is enhanced. The present work was done in an effort to obtain experimental evidence in regard to some of the common alloying additions but more particularly the so-called "strong" deoxidizers for steel. The method used was to determine the minimum concentration of the deoxidizer that would effect a certain definite degree of deoxidation in steel. The criterion of deoxidation was the change from the large globular Type I sulphide to the eutectic Type II as described by Sims and Dahle.2 This change is sharp and definite, and inasmuch as it can be produced with equal facility by aluminum, zirconium, and titanium, it is considered a manifestation of a certain degree of deoxidation and not an alloying effect. Ostensibly such a procedure could give only a comparison of deoxidizing powers and no absolute values. Nevertheless, repeated observations have shown that, when increasing increments of aluminum are added to a steel, the residual aluminum content begins to increase simultaneously with the appearance of Type II inclusions. Thus it seems warranted to postulate that the Type II inclusions appear coincident with the virtual elimination of FeO as an active constituent of the steel. Experimental Procedure The data obtained were primarily from the microexamination of polished and unetched specimens and from chemical analysis. Experimental heats weighing 200 to 250 lb were made in a basic-lined high-frequency induction furnace. The base composition was nominally that of a medium-carbon casting steel to which the appropriate additions were made. Specimens were poured into sand-cast ingots 3 in. in diam as shown in Fig 1. Sand-cast ingots were used to prevent chilling and to allow sufficient time in freezing for normal inclusions to form of a size large enough to be studied readily. In the first few heats, the tapered wall ingot was used, but in the majority, the extra large riser was used to prevent piping in heavily deoxidized steels. Specimens for microexamination were taken from the location shown in Fig 1, and drillings for chemical analysis were taken from a similar location. The procedure was to melt the base composition and deoxidize with the usual manganese and silicon additions and then to pour an ingot. The furnace was then tilted back, and the first increment of strong deoxidizer or special alloy was added and allowed to disseminate through the melt, with enough power on to hold the temperature constant, for 45 sec. Then a second ingot was poured. After this, another increment was added, and after the same holding time another ingot was poured. In this way from 9 to 12 ingots were poured from each heat, each successive ingot having progressively larger total additions of alloy. Eighteen heats were made altogether, and the range of alloys used and additions made are outlined in Table 1. The three principal types of sulphide inclusions found are illustrated in Fig 2. The globular Type I sulphides are characteristic of silicon-killed steels, the eutectic Type II are characteristic of steels deoxidized with a small amount of aluminum, while the larger, angular Type III are usually found in steels with a residual aluminum content above about 0.02 pct. In all specimens studied, the transition from Type I to II either did not occur at all or was very abrupt and clear cut. There never was any doubt as to just which increment produced the change, although the individual additions were small, in the order of 0.01 pct. The change from Type II to Type III was considerably less sharp, and, in some cases, both types were found together. Inasmuch as the formation of Type III sulphides is apparently not a deoxidation phenomenon, they will not be discussed here.

Jan 1, 1950

By A. Simkovich, R. W. Lindsay

The possibility of using sodium sulfide slags to remove copper from ferrous alloys has been investigated by Jordan1 and by Langenberg.2, 3 In these studies, such slags were determined to be capable of removing copper and sulfur from the melt. The present work represents additional effort to clarify the effects of temperature on copper removal. The experiments were performed in a 17-lb induction furnace. Graphite crucibles contained the melts and kept the baths saturated with carbon. Temperatures were measured with a calibrated optical pyrometer and were controlled by manipulation of power input to the furnace. Estimated accuracy of temperatures in this investigation is ± 10°C (18°F) for measurements prior to slag additions, and + 20°C (36°F) after slag formation. The procedure consisted of melting 800 g of electrolytic iron. During this step, powdered graphite covered the exposed iron surface. After a predetermined temperature was reached, copper shot was added. A sample of the molten alloy for chemical analysis was then aspirated into a silica sheath. Next, a slag-forming mixture of sodium sulfite and graphite was added instantaneously to the melt. The sodium sulfite amounted to one-tenth the charge weight of iron; sufficient graphite was added to combine with oxygen in the sodium sulfite, assuming formation of carbon monoxide and reduction of the sulfite to sulfide. Subsequent to the slag addition, the molten alloy was sampled periodically, with the exception of heat A in which no intervening samples were taken between the slag addition and the end of the run. The iron was poured into a graphite mold, and the ingots sectioned and drilled for samples. Results of selected heats are presented in Table I. Analyses of samples drawn from the iron prior to slag addition are listed under zero time. Two samples from heat D were reported with copper contents greater than the initial concentration in the bath. Owing to the gradual but complete disappearance of slag during this heat, it is believed copper momentarily became more concentrated in the upper portion of the bath while reverting from the slag. This is the region from which samples were drawn. It should be noted that analysis of the ingot was equal to the copper content at the time of slag addition. The terminal temperatures of heats D and E, and the initial sulfur content of heat A are also to be noted. Because of the large temperature drop which occurred when slag was formed in heat D, power input to the furnace was increased in heat E after the slag addition, causing a higher terminal temperature. In heat A, the initial sulfur concentration was relatively high as compared to heats B through E owing to contamination by some slag remaining in the crucible from a previous heat. It is evident from Table I that copper was removed at the onset of slag formation. Roughly 30 pct of the copper was taken into the slag, with the exception of heat D, which had approximately 50 pct removed. For a comparatively short time of slag-metal contact, it appears that no gain is to be made in copper removal through use of high or low temperatures. If the slag initially formed remains in contact with the iron for an extended period, temperature has a marked effect upon copper removal, as can be seen by studying results for the two extremes in temperature. At about 1425°C, the copper level remained relatively constant after the initial removal by the slag. However, in the region of 1670°C, a definite reversion of copper occurred. Reversion was incomplete in heat D, and complete in heat E. The final temperatures of heats D and E differed by about 75°C. This temperature difference is thought to be the reason for only partial copper reversion in heat D. It is believed the effects of temperature noted above are related to the evolution of a white fume, which appeared in every run except heat A. (In the case of heat A, the fume was practically indiscernible.) After each slag addition, a yellow flame formed for about 5 sec. When the flame subsided, a white fume appeared. Upon contact with surrounding cooler surfaces, this fume deposited as a white solid. In the experiments made at 1425°C, evolution of fume continued unchanged to the end of the runs. However, heats D and E exhibited a different behavior. A very noticeable decrease in fume evolution from heat D was observed. Furthermore, this heat had much less slag remaining than did runs A through C when the experiments were terminated. No slag remained at the end of heat E; evolution of fume from this heat ceased prior to pouring. Spec-trographic analysis of the white deposit indicated sodium to be the major metallic element, with the maximum concentration of iron and copper as 0.1 and 0.01 pct, respectively. It is supposed the white fume observed in these experiments is principally sodium oxide (Na2O), formed by oxidation of sodium in the slag and subsequent sublimation. (Sodium oxide is a white to gray substance in the solid state; at 1275oC, it sublimes.4) According to this mechanism, elevated temperatures would accelerate removal of sodium from the slag, sulfur pickup by the

Jan 1, 1961

By S. Gilbert, G. R. Bailey

A further evaluation of the bomb-sampling method for determining the oxygen content of liquid steel is presented. The results of this study and their close agreement with the results of an earlier evaluation confirm the conclusion that the bomb-sampling method is valid for obtaining representative samples for the determination of the oxygen content of a liquid steel bath. WHAT constitutes the most desirable procedure for obtaining a sample suitable for determining the oxygen content of a liquid steel bath has been a controversial subject for several years. In 1952 Huff, Bailey, and Richards&apos; described a modification of the bomb-sampling technique originated by McCutcheon and Rautio.&apos; In both the modified and original techniques, a small cast-iron or steel mold containing aluminum wire and appropriately covered is inserted into the furnace, coated with slag, and then plunged into the metal bath. Upon entering the metal, the cover melts and a sample of the steel bath enters the mold. The data presented by Huff, Bailey, and Richards&apos; indicated that reproducible samples could be obtained by their method. Furthermore, the oxygen analyses from samples obtained by their method agreed better with those from controlled laboratory experiments than did analyses from samples obtained by methods previously suggested for sampling large liquid-metal baths. Most techniques, other than bomb-sampling, require that a sample of liquid steel be removed from the furnace in a well slagged spoon and poured into an iron mold containing aluminum or into a massive copper mold for rapid chilling. Pouring in this manner requires that the sample pass through the air. The controversy, then, is somewhat as follows: Proponents of the spoon-sampling method and similar dip-and-pour methods feel that the introduction of a cold steel mold into a molten steel bath may result in a localized boiling condition that may deplete the steel of oxygen to a significant degree in the area where the bomb is introduced. Conceivably this boil could cause results that are, on the average, too low and nonrepresentative of the bath composition. On the other hand, samples that are spooned and then poured through the air may also be nonrepresentative because of oxidation by the atmosphere. The restrictions imposed in sampling with a spoon are much more stringent than those imposed when sampling with the bomb-type mold within the furnace. The spoon sample must be taken in a well slagged spoon, a requirement that depends on the condition of the slag in the furnace. Also, the samples must be poured as quickly as possible, without shaking the spoon and without allowing slag to enter the mold. The necessity of fulfill-

Jan 1, 1955

By G. F. Huff, G. R. Bailey, J. H. Richards

An improved bomb-sampling technique for obtaining samples for oxygen analysis from liquid steel is described. Analyses of samples taken from open-hearth furnaces by the improved method show sufficient agreement with laboratory data to indicate the accuracy of the method is better than that of other existing sampling methods. THE bomb-sampling method of determining the oxygen content of a liquid-steel bath was studied by obtaining and analyzing more than 200 samples from normal open-hearth heats. Of these samples, about 60 were obtained with a bomb of conventional design;&apos; the remainder were taken with a somewhat modified bomb designed to give greater protection against slag contamination. In the new device, the contacting faces of the cast-iron mold halves are machined so that they fit closely; the opening at the top of the bomb is covered with a thin steel cap; and the top of the bomb is further covered with a wood block held in place by heavy steel wire. After the bomb has passed through the slag layer and has entered the steel bath, the wire melts and the wood block floats to the surface. Thereafter, the steel melts through the thin cap and flows into the bomb cavity where it is deoxidized with aluminum wire. An assembled bomb, ready for sampling, is shown in Fig. 1. To standardize sampling procedure, the samples were usually taken through the center door and at the bottom of the furnace; that is, the bomb was on the bottom when the metal cap melted. After each addition to the furnace, at least 20 min elapsed before a sample was taken. The oxygen contents of all the samples were determined by using the vacuum-fusion method, two or more specimens from each sample being analyzed. The specimens were cubes of metal cut from a region in the interior of the bomb sample, as shown in Fig. 2. Drillings for carbon analysis were obtained immediately above the oxygen-analysis region. Reproducibility of Results In determining the reproducibility of the results obtained with the modified bomb, the following four factors were studied: 1—variation in the oxygen concentration of duplicate specimens taken from a single sample; 2—variation in the oxygen concentration of duplicate samples taken in quick succession: 3—effect of the amount of aluminum wire

Jan 1, 1953