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By Claude H. P. Lupis, John F. Elliott

WAGNERL described the thermodynamic behavior of a metallic solution consisting of the solute components 2, 3,... at very dilute concentrations in the solvent, 1, in terms of the excess partial molar free energy, or alternatively the logarithm of the activity coefficient. In the Taylor expansion of FiE, by neglecting the second- and higher-order differential terms, he obtained the excess partial molar free energy as a linear function of the composition:

Jan 1, 1965

By J. M. Snook, F. C. Langenberg

FOR a better understanding of the melting and refining processes, the oxygen content of the steel bath should be determined. The oxygen content influences many process and product variables such as the efficiency of alloy recoveries, the ingot structure (through reaction with carbon in the steel), certain reaction rates, cleanliness (formation of indigenous oxide inclusions), and mechanical properties. Many methods of sampling liquid steel for oxygen have been devised. These methods can be divided into two main groups: 1) taking samples directly in the furnace or ladle;'-'0 2) removing the metal from the furnace or ladle in a sampling spoon and pouring it into a mold, or drawing the metal from the spoon into a sample holder.11-l4 The advantages and disadvantages of the two general sampling methods are presented in Table I. The bomb-sampling technique described by Huff, Bailey, and Richards8 has been used by the Crucible Steel Co. in certain research projects where oxygen contents were needed. It was recognized that a localized boiling condition could result when the mold is introduced into the steel bath, although the work of Gilbert and Bailey9 seems to indicate that the carbon boil occurring in the bomb-sampler cavity has a negligible effect on the oxygen content. In order to confirm the reported negligible effect of a carbon boil, additional work was done with adaptations of the conventional bomb sampler. The methods used are shown in Fig. 1 and are as follows: 1) Type A: aluminum wire (0.125-in. diam) coil in cavity; steel cap over mouth 2) Type B: aluminum cup in cavity; aluminum cap over mouth, 3) Type C: aluminum cup in cavity; steel cap over mouth, 4) Type D: fine aluminum wire (0.013-in. diam) in cavity; steel cap over mouth. The amount of aluminum wire in the Type A and D samples varied from 0.8 to 1.2 pct of the sample weight. The aluminum cups averaged 2.0 pct of the sample weight; the latter were used to ensure that the steel contacting the walls of the bomb cavity was fully killed. Samples were taken from plain carbon heats made in open-hearth furnaces. This grade of steel before silicon additions is essentially an Fe-C alloy and the effects of other alloying elements on the oxygen activity can be neglected. The results of sampling with the bomb samplers is shown in Fig. 2 where the percent oxygen is plotted against the percent carbon on log-log paper. Spoon sample results on the same grade of steel where the sample was killed in the spoon are shown in Fig. 3. The oxygen contents were determined by the vacuum fusion method. A comparison of Figs. 2 and 3 shows that the oxygen concentrations obtained with the spoon-sampling method (metal killed in the spoon after slag removed

Jan 1, 1960

By J. B. Wagstaff

The raceway in front of the tuyere of the blast furnace has been studied quantitatively and a correlation obtained for the penetrastudiedtion of the blast. Some evidence is presented for the height and width of the raceway which suggests that all the raceways of a ffurnace overlap. The size of the coke in this zone has been measfurnaceoverlap.ured photographically during normal operation and results are given for the various areas. IN an earlier paper,' it was shown that a raceway exists opposite each tuyere of a blast furnace. This raceway is formed by the jet effect of the air emerging from the tuyere and consists essentially of a turbulence in which coke particles are recir-culated at high speed. Its presence was deduced originally from observations on movies taken with a high-speed camera through the tuyeres of various furnaces and was confirmed by experiments made on a model. In the model described,' this raceway was shown as operating in a vertical plane only, although there was a suggestion in the motion-picture film exhibited at that time that the raceway was three dimensional, unless artificially restricted. There was also some doubt then about the factors influencing its size. This paper describes the next steps in the investigation. Since the size of the raceway is obviously of importance in the operation of the furnace, it seemed worth while to study the subject more carefully. It is probably in this region that about half the coke in the furnace is consumed, so that the movement of the stock column may well be controlled by raceway behavior. Furthermore, there is some evidence to suggest that the coke is packed densely in the center of the furnace to form the "dead man" and more loosely above the raceway. It is therefore probable that the bulk of the gases passing up the stack flow from the top surface of this raceway. Clearly then, a knowledge of this critical zone is of interest to the blast furnace operator, and the first half of this report is devoted to a quantitative discussion of the subject. A further topic of interest among operators is the degree of breakdown of coke in the furnace, with which is inseparably linked the importance of a strong coke. Indeed, the whole question of the optimum size and type of coke may be as dependent on the condition of the coke in the bottom of the blast furnace as at the top. Attempts have been made from time to time to obtain samples of coke from the tuyeres and other furnace openings but they all suffer from the fact that the coke is filled to a varying degree with metal and slag and is probably broken up by the very act of taking the sample. It has proved difficult to make any reliable studies of coke size by these methods. However, it did seem possible to use the highspeed movies mentioned earlier1 to estimate the size of the coke. These movies provide an accurate record of individual coke particles so that, in theory at least, it should be possible to measure the size of the particles one by one and to obtain, for the first time, information on the coke being blown around the raceway under actual operating conditions while the furnace is performing normally. Such a study has been made and is discussed in the second half of this paper. The results obtained enabled the blast furnace data to be correlated with the model results given in the first half. Raceway Size In order to make a quantitative study of the size of the raceway it was necessary to devise some apparatus of laboratory scale, which could be handled quickly and easily. This focused attention on models, which in turn means that the laws of similarity governing this particular process must be ascertained. Method of Procedure: Since the work was to be carried out on a smaller scale than the blast furnace, the linear dimensions of the model became unimportant provided that the scale was known; it is only important to insure that the container does not affect the raceway being observed. The studies therefore were carried out in a glass-sided box, 11 in. high x 7 in. wide x 3 in. deep, using air jets ranging

Jan 1, 1954

By S. Y. Ezz

The quality and extent of fluidization of fine iron ore beds with gases were investigated. Factors affecting the rate of reduction with H, and the sintering of the partially reduced material were studied. Trials to retard sintering by covering the particles' surface with nonsintering materials were successful. THE gaseous reduction of iron ores is a gas-solid reaction. Hence the fluidization technique seems ideally suited to it. However, a serious drawback

Jan 1, 1961

By W. W. Mullins

The development, by the mechanism of volume diffusion, of a grain boundary groove on an interface separating a solid phase and a saturated fluid phase is calculated under the following assumptions: 1) isotropy of the interfacial free energy 's, 2) applicability of the Gibbs-Thompson formula relating curvature and chemical potential, 3) a nearly planar groove surface. The groove profile is found to have a .fixed shape and linear dimensions that are proportional to (time)1/3. The constant of proportionality is evaluated and involves ?s in such a way that the latter my be evaluated from grooving kinetics. A grain boundary that intersects an interphase interface will tend to produce a groove along the line of intersection (Fig. 1). The ultimate motivation for the formation of the groove is the reduction in interfacial free energ that occurs as the grain boundary contracts. Smith has discussed the way in which the free energy of the interfaces determines their dihedral angles at the groove root and has given a detailed analysis of the effect of the dihedral angles upon the nature the microstructures developed in polyphase alloys. Herring2 has extended the considerations to the case in which the free energy of an interface depends on its orientation and has thus added torque terms to the condition for interface equilibrium. Although the grain boundary and the interphase interface may quickly achieve the proper equilibrium angles where they intersect, as determined by the balance of equivalent tensions and torques,"2 the groove will generally continue to grow (though with decreasing speed). Thermodynamically, this continued growth reflects the fact that the lowest free energy cannot be achieved until the entire grain boundary has been eliminated; mechanistically, the growth occurs in response to inhomogeneities of chemical potential that are caused by the constraint of fixed dihedral angles at the groove root. The latter point is illustrated in Fig. 1, which shows that atoms* near the groove are on the convex side of a cylindrically curved surface and therefore have a higher chemical potential than atoms on the flat interface beyond. Thus atoms tend to leave the curved groove shoulders and force the groove to deepen. When both phases are solid additional chemical potential gradient may arise from whatever strain fields are necessary to insure continuity of material across the interface. In the discussion that follows, this complication due to strain will not occur since we always assume one phase to be a fluid and the other a solid. The transport processes that may operate to permit growth of the groove are surface (interface)* diffusion, volume diffusion in the phase on either side of the interface, and evaporation-condensation when one phase is gaseous. (Also a melting-freezing process is responsible for groove enlargement on a solid-melt interface as discussed in Sec. VI). The theory of grain boundary grooving has been discussed in detail for the processes of surface diffusion and of one type of evaporation-condensation.3'4 The theoretical predictions for the mechanism of surface diffusion have been confirmed in an experimental study of grooving kinetics in copper.5 In this paper, the theory of groove development by volume diffusion will be presented. Volume diffusion can occur either by atomic migration in the solid S or by diffusion of S atoms in the fluid phase, or solvent, adjacent to the groove surface. As discussed in Sec. V, volume diffusion in the solid should be less important than surface diffusion in forming a groove. Apart from verifying this statement then, the main interest of the present analysis centers on diffusion in an external solvent. The solvent may be either a liquid (e.g., water, or-

Jan 1, 1961

By C. Richards Honeycutt, Frederick C. Langenberg, Guenter Pestel

Solidification in a moving electromagnetic field was successful in altering the as-cast grain structure of steel ingots. The equipment is described and exerimental results are presented for several different alloys. Conditions for optimum grain refinement are described and an empirical design constant presented. The effect of the grain refinement on hot workability is briefly discussed. T HE grain structure of a steel ingot teemed into a metal mold can be defined by macroscopic examination in semiquantitative terms. For example, the relative volume of obviously differing structures can be estimated with the classic definitions of chill, columnar, and equiaxed zones. Experimental evidence has proven that the grain structure of an ingot is affected by changes in such factors as teeming temperature, rate of teeming, degree of turbulence, size of ingot, mold characteristics (including preheat temperature, design and coating), and composition of the metal (especially as it affects the range of solidification). Significant advances have been made in fundamental solidification studies; but the principles which have been developed are difficult to apply tothe complex and changing phenomena that occur simultaneously during ingot solidification. In particular, many attempts have been made to refine the as-cast structure of ingots, with special emphasis on the columnar grains. The formation of large columnar grains is generally considered harmful to the further fabrication of an ingot. It may also result in undesired ani-sotropic properties. However, columnar grains are not undesirable in all grades, or product applications, and caution must be exercised to determine in which grades and applications columnar grains are not desired in the ingot. Although the literature on the refinement of as-cast ingot grain structures is too vast in general to review here, it is noteworthy that such methods are additions of artificial nuclei, mold vibration, mechanical stirring or ultrasonic agitation of the molten metal, and controlled cooling and reheating during solidification have been tried with varying degrees of success. However, it is doubtful that any method of refining the as-cast ingot grain structure has been completely successful on a commercial basis. The purpose of

Jan 1, 1962

By C. Richard Honeycutt, Frederick C. Langenberg, Guenter Pestel

Otto Schaaber (Institut für Harterei-Technik, Bremen-Schönebeck, Germany)— Langenberg, Pestel, and Honeycutt gave an interesting example of the grain refining effect nonstationary magnetic fields may execute on a solidifying metal. Probably some additional comments, based on more than a decade of experience with this method of influencing crystallization, may be useful. They refer to an attempt to explain the mechanism of grain refinement by such fields, and to recent European developments which have not been mentioned in the paper. I. During studies of the temperature distribution in a metal body near the phase boundary solid/liquid, an anomaly was observed under certain special conditions: a) direction of heat transfer as horizontal as possible, b) steady state (equilibrium, i.e,, solidification resp. melting rate exactly zero). In the liquid phase, immediately adjacent to the phase boundary, the temperature was found to be constant over an appreciable distance in spite of a high value of heat transfer (40.000 to 70.000 keal/ m2h).3 Convection, which might explain this phenomenon, could not be observed. Therefore another explanation had to be sought. The assumption that a metallic melt, especially at temperatures near the point of solidification, contains some sort of atomic arrangement with a higher degree of order than the surrounding liquid, now is generally accepted. Considering the differences in energy between such an arrangement and its environs, a transport of heat even in absence of any temperature gradient is conceivable by continued formation and redissolution of regions with a higher degree of order, i.e., with lower energy level.3 At this stage, it was not necessary to postulate any special condition as to the form or size of these regions or the distance between arrangements to be newly formed and those to be redissolved. However, a simple consideration shows that an energy transfer from one region to another will only be possible without loss of energy, if the distance between will be equal to the lattice parameters, and if, secondly, crystallographic axis or planes will be parallel.4 By the way, this assumption might give a reasonable explanation of the well known orientation effect of the heat flow during solidification. Any measures to prevent columnar crystallization should act upon this ordering mechanism: a) the regions with a lower energy (higher order) should not be allowed to arrange themselves parallel to the direction of heat flow, and their growth should be disturbed; b) all conditions leading to an appreciable heat flow of uniform direction should be avoided or removed. Condition a) may be satisfied by a physical force preferably under 90 deg to the main axis of the columnar crystals (i.e., parallel to the solidification front) acting on the ordered regions; condition b) by equalizing any differences in

Jan 1, 1962

By G. I. Madden, L. H. Van Vlack

WhEN basic refractories which contain peri-clase, MgO, are used in steel furnaces, they are altered by iron oxide to form magnesiowiistite, (Mg,Fe)O, and an iron-rich magnesioferrite, (Mg,Fe)Fe2O4. Silica, which is usually present, produces a silicate liquid that surrounds the solid phases. The individual crystalline grains of the above two solid phases grow at elevated temperatures. Previous papersL" showed that, if either periclase or magnesiowiistite is present as the only solid phase, its grain size increases in proportion to temperature and in proportion to the square root of time; the growth rate is reduced slightly if the amount of silicate liquid is increased. Similar results have been observed for iron-rich magnesioferrite.3 To determine the effect of the presence of two solid phases on the rate of grain growth, micro-structural studies have been made on samples containing both magnesiowustite and magnesioferrite. The experimental procedure was the same as that followed in the previous studies of this type.'12 Briefly, this included determination of compositions from the available phase relationships4 that would produce the two phases of interest at the firing temperature and using reagent-grade raw materials to prepare mixtures of these compositions. The mixtures were pressed into pellet-size samples and then fired at the desired time and temperature. The samples were water-quenched to preserve the microstructure present at the firing temperature. Standard reflected-light metallographic techniques were used for sample examination and sample analysis. Grain sizes were determined by measuring the mean diameter of a number of randomly selected grains in a two-dimensional microsection. A large cross section of the sample was covered to prevent biased data resulting from such effects as localized differences in the radius of curvature of the crystal grains. Examination indicates that grain growth is restricted when more than one solid phase is present. This is illustrated in Fig. 1 for: (a) magnesiowustite plus a silicate liquid; (b) magnesioferrite plus a silicate liquid; and (c) magnesiowiistite and magnesioferrite plus a silicate liquid. Fig. 2 plots the

Jan 1, 1964

By F. C. Schora, H. P. Meissner

COUNTERCURRENT staged processes involving chemical reactions between solid and gas streams are becoming more common. Such operations are generally carried out in a series of fluidized beds with each bed acting as a stage. Fig. 1 is a schematic illustration of a series of stages located in a single column, with a solid stream moving down through this column from stage to stage counter to a rising gas stream. The reduction of iron oxides with hydrogen and carbon monoxide is one of the reactions which can be advantageously carried out in such a countercurrent system. Calculation of the performance of a countercur-

Jan 1, 1961

By F. C. Schora, H. P. Meissner

Both a graphical and an analytical technique are presented for calculating stream compositions and temperatures in adiabatic staged systems in which solids travel countercurrently to a gas stream. Such a system might be a tower containing several plates, on each of which the descending solid is fluidized by the rising gas stream. Examples are presented in which chemical reactions occur, including the oxidation of SO, by a solid catalyst and the gaseous reduction of iron oxides. COUNTERCURRENT staged processes involving reactions between solid and gas streams are becoming more common. These operations are generally carried out in a series of beds of fluidized solids, with each bed or "plate" acting as a stage. Fig. 1 is a schematic diagram of such a series of stages located in a column, down through which a solids stream moves from stage to stage counter to a rising gas stream. Typical reactions carried out in such systems are the dehydration of aluminum trihydrate, the calcining of limestone, and the gaseous reduction of iron oxides. Calculation of the performance of these counter-current systems rapidly becomes more complex with increases in the number of stages and in the number of chemical reactions occurring. Calcula-tional procedures for isothermal operations of such systems have been described.4 Actual tower operations, however, are generally adiabatic, and in consequence far from isothermal. The object here is to present both graphical and analytical techniques applicable to such adiabatic towers operating continuously and in steady state. In this introductory discussion, the graphical techniques presented are of the McCabe-Thiele type, rather than of the Pon-chon type. In all the examples presented, it will be assumed that both thermal and chemical equilibrium are attained in each bed. The assumption that the gas and solid streams leaving each bed are at the same temperature as the bed is in accordance with the familiar behavior of actual fluidized solid systems. Chemical equilibrium, on the other hand, is not necessarily attained in any given stage between these two streams, even with deep beds, since reaction rates may be slow. In the last section of this paper, discussion is presented of methods suitable for use when chemical equilibrium is not attained. The adiabatic tower in Fig. 1 has "n" stages numbered from 1 to n, starting with the bottom stage as number 1. In analyzing this tower's performance, it is important to express gas flow rates in terms of a key component or element which remains completely within the gas stream throughout the tower. Similarly, solid flow is best expressed in terms of a key compound or element which remains within the solid phase throughout the tower. Thus, in burning limestone with a hot flue gas, the gas flow might be expressed as G, the pound mols of nitrogen flowing through the tower per unit time, while solid flow might be expressed as S, the pound atoms of calcium in all forms in the solid stream per unit of time. Defined in this way, both G and S are constant throughout the tower. The enthalpy of the gas and solid streams are now best expressed in terms of these key components. That is, the gas stream enthalpy H is expressed as Btu in the total gas per mol of the key component in the gas. Similarly, the solids stream enthalpy h is expressed as Btu in the total solid stream per pound mol (or pound atom) of the key component in this stream.

Jan 1, 1962

By J. Chipman, N. J. Grant, J. H. Walsh, T. B. King

WITH the development of adequate sampling and analysis techniques, much information has been obtained concerning the behavior of hydrogen in the steel bath during the course of steelmak-ing operations. From studies of this type it has become clear that the slag has an important role to play in determining the hydrogen content found in commercial products. A knowledge of the behavior of hydrogen in slags is necessary to round out our knowledge of hydrogen in steelmaking practice; with this information we are better able to assess practical methods of control. In this paper a method developed for analyzing slags for hydrogen content, studies of the solubility of hydrogen in synthetic slags, and studies of the variation of hydrogen content in slag and steel in industrial heats will be described. Previous Work—While very little has been done in the past to determine the hydrogen content of metallurgical slags, measurements have been made on such slag-like materials as geologic magmas and glasses. Goranson as made extensive studies of the solubility of water in natural and synthetic granites. Many workers have investigated the solubility of gases in synthetic and commercial glasses, but the recent work of Russell" is the most extensive. Russell found that the solubility of water in glass was proportional to the square root of the water vapor pressure in water vapor-oxygen mixtures. It was found that the solubility could either increase or decrease with temperature depending on the glass composition. Wentrup, Fucke, and Rief,' and Piper, Hagedorn, and Backes' have extracted hydrogen by holding a slag at 1300" and 800°C respectively in vacuum. Wentrup et al. reported hydrogen and water vapor as evolved together while Piper et al. passed the evolved gases from the hot extraction treatment over hot ferromanganese to reduce the evolved water vapor to hydrogen and, therefore, reported the analyses in terms of total dissolved hydrogen. Yavoiskii has reported hydrogen and nitrogen analyses on steelmaking slags. Dobrokhotov, Povol-skii, and Khan have studied the hydrogen content of basic open hearth steel under slags of varying viscosity. These authors reported that the hydrogen content of the steel bath increased as the fluidity of the slag was increased by the addition of bauxite. They recommended that a viscous slag be used and the steel tapped without deoxidation in the furnace to ensure a low final hydrogen content. Analysis of Slags for Hydrogen Development of Apparatus—The vacuum fusion analysis equipment described by Shields, Chipman, and Grant" was modified for the analysis of slags." This method depends upon the reduction of water in the slag to hydrogen, which is readily determined by the method used for hydrogen in steel. Preliminary experiments were made with a eu-tectic ferrosilicon melt as the reducing agent. Other experiments included the use of graphite and molybdenum crucibles. The ferrosilicon alloy bath was found to produce a thick coating on the furnace tube which could adsorb hydrogen. Graphite produced CO by the reduction of FeO, MnO, and SiO2 in such quantities that analysis for hydrogen was virtually impossible. Molybdenum, while giving a low blank value, could reduce the slag sufficiently to produce a volatile oxide which again was found to adsorb hydrogen. The arrangement finally adopted is shown in Fig. 1. The molybdenum sheet served as the induction-heated susceptor, and was separated from the escaping gases by alumina guide tubes. An outer jacket of alumina protected the quartz furnace tube, and alumina and quartz stools completed the assembly. The falling sample is shown wrapped in aluminum foil, 0.002 in. thickness, which acted as the reducing agent' This foil was careful'~ washed in acetone and an d and then dried in hot air before wrapping the weighed slag sample for charging into the apparatus. Investigation of the hydrogen content of the aluminum foil itself showed that a small quantity of hydrogen was released in vacuum, but had no relation to the weight of the aluminum charged. This quantity of hydrogen was

Jan 1, 1957

By Franklin J. Hill, Theodore D. Tiemann

Sized fractions of Wisconsin Gogebic taconite were reduced with hydrogen over the temperature range from 600° to 1000°C. In general, the degree and rate of reduction increase with temperature. Particle size has no observable effect except in the smaller fractions at 900°C and above, where reduction is impeded, possibly due to the siliceous nature of the ore. Gaseous diffusion appears to be significant as a rate controlling factor at certain stages. THE depletion of high grade iron ore reserves in the United States has established the need to utilize all available iron ore deposits, both in long range planning and from the viewpoint of national emergency. This has led to extensive research and development in this field. The beneficiation of Wisconsin Gogebic taconite ore has been previously studied by investigators at the University of Wiscconsin, 1 the United States Bureau of Mines,, Battelle Memorial Institute, 3 and others. Methods investigated have included concentration by flotation processes, magnetic and gravity separation, magnetic roasting and various combinations of them. The foregoing studies have been concerned with the production of an enriched ore suitable for blast furnace use. If the ore could first be reduced to metallic iron and then beneficiated, the product could be used directly in the open hearth or electric steel-making furnace. The by-passing of the blast furnace should enhance the economic feasibility of the beneficiating process. The work reported here,4 was undertaken to establish data on the hydrogen reduction of Wisconsin taconite that would eventually lead to the development of an economic direct reduction process for this and perhaps other low grade siliceous ores. The volume of work on direct reduction can be judged by the fact that 240 direct reduction processes were patented in the United States alone up to 1951, 5 and numerous additional processes have since been developed. Some of the factors contributing to direct reduction development are: 1) The increasing capital cost of the blast furnace and its accessory equipment. 2) The decreasing availability of high grade domestic ore. 3) The high cost of steel scrap for use in the open hearth and electric furnaces. In general, direct reduction processes can be divided into two types; those using a solid reductant (coal, peat, lignite) usually carried out in a kiln, and those using a gaseous reductant (H2, CO) in a shaft furnace or a fluidized bed retort. As there is no low cost coal readily available in northern Wisconsin but natural gas could be quite easily obtained, it is believed a gaseous reductant process would offer the greater feasibility for use on Wisconsin taconite. It is hoped that this preliminary work will beof interest to other investigators in this increasingly important field. TACONITE ORE The ore used in the investigation was obtained originally from the U. S. Bureau of Mines, and consisted of a representative composite made up from trench samples of the Norrie, Pabst, Plymouth, Pence, and Yale members of the Wisconsin Gogebic range iron formation. Chemically, the ore contains approximately 52 pct SiO, and 30 pct Fe. X-ray diffraction and other studies indicate the principal minerals to be quartz (SiO2), hematite (Fe2O3), and goethite (Fe2O3. H2O). Minor amounts of iron containing silicates, siderite (FecO3), and magnetite (FeO-Fe2O3) are present. The iron minerals and quartz are so finely disseminated that the ore requires grinding to less than 200 mesh (74 µ) for essential liberation.l,2 The iron content of each of the several size fractions studied is shown in Table I. EXPERIMENTAL METHOD The method used throughout the investigation was based on that developed by the U. S. Bureau of Mines in Minneaopolis6,7 in which the course of reduction is followed by the loss in weight of the ore sample. More specifically, a 100-g sample of the size frac-

Jan 1, 1962

By D. J. Carney, E. C. Rudolphy

Large macroscopic nonmetallic inclusions were related to altered fireclay refractories by chemical and microscopic means. Pouring refractories are discussed as a source of these large inclusions. Nozzles and wells are major contributors. Use of alkali and titania contents as tracers is described. Recommendations are offered to minimize the sources of inclusions from pouring refractories. IN any attempt to improve the cleanliness of plain carbon and alloy steels, consideration must be given not only to the proper deoxidation practice to minimize inclusions, but also to sources of inclusions from pouring refractories. In some cases, the inclusions resulting from deoxidation may be minor in amount, yet a relatively dirty steel may be produced as a result of improper care in the pouring practices for the steel. The number of studies of inclusions resulting from pouring refractories has increased recently and some excellent reports on this subject have already been published.'4 Some of these reports were reviewed briefly in a companion paper by M. P. Fedock.5 Mr. Fedock's contribution is a fine addition to the studies necessary to improve steel cleanliness for the ultimate benefit of all steel producers and consumers. In the interest of constantly improving cleanliness, the authors have been actively engaged for the past two years in experimentation to determine more closely the sources of inclusions in steel. One phase of this work was associated with efforts to define more closely the sources of macroscopic inclusions which have been experienced on occasional heats. The term "macroscopic inclusions" is defined in general as those inclusions which are visible to the naked eye or at low magnifications of the order of less than X25. These inclusions sometimes can be seen in the macro-etch tests of billets and slabs. This report summarizes a few of the field experiments and laboratory studies conducted at the South Works of the United States Steel Corp., which were made regarding nozzles, wells, and ingot scums, as well as inclusions occurring in steel products. The data in the present study, together with the data of Mr. Fedock concerning ladle erosion, should be of value in regard to future studies of inclusions arising from pouring refractories. The knowledge gained as a result of data collected thus far at South Works has been helpful in improving the cleanliness of the products and in pointing the way toward further improvements. Similarity of Large Inclusions to Refractories and Altered Refractories In the routine inspection of billet etch tests, occasional inclusions visible to the naked eye have been observed. These large inclusions most frequently occur near the top of the ingot and near the billet surface. When such material was encountered, careful examinations were made in an attempt to determine the origin of these inclusions. In a relatively few cases, examination revealed that the material was unaltered fireclay refractory of a type similar to that used for hot-top material, with only the surface of the inclusions having an altered appearance under the microscope. However, the great majority of these inclusions were completely altered-refractory material. The term "altered refractory" is defined

Jan 1, 1955

By John Chipman

DESPITE the rapidity of chemical reactions at steelmaking temperatures, deoxidation reactions cannot be expected to reach equilibrium immediately after addition of a deoxidizing agent. A considerable period of time may be required merely to obtain complete mixing of the deoxidizing element throughout the volume of steel to which it is added. Evidence in the literature indicates that in some cases the time is long compared with that allowed for completion of the experiment or for teeming of the heat. The great turbulence observed during the filling of the ladle is no guarantee of complete dispersion on a fine scale throughout the heat. During the process there are initially certain volume elements which are high in deoxidizer and others which retain substantially their original oxygen content. Mixing consists of the subdivision and ultimate destruction of these liquid segregates through the process of shear and elimination of concentration gradients by diffusion. The shear process does not continue indefinitely and a quiescent state may be reached in the ladle before all volume elements of divergent deoxidizer and oxygen content are completely eliminated. In furnace deoxidation the time required for complete mixing may be very long unless continuous stirring is employed.' In Fig. 1, let the circle represent one small volume element of aluminum-rich metal surrounded by oxygen-rich steel in which no stirring movement remains. Further mixing requires inward diffusion of oxygen and outward diffusion of aluminum, resulting in precipitation of A12O3 in the diffusion zone. It is important to note that such a precipitate may itself interfere with the diffusion process. Moreover, if the precipitate forms as a film with even minimal mechanical strength, it may interfere not only with diffusion but with shear as well, thus stabilizing compositional differences in volume elements of greater than microscopic size. A film surrounding such a volume element would have little or no ability to rise or to sink unless it enclosed a liquid whose density differed from that of the ambient. Consider now the effect on the overall composition of the melt. Fig. 2 represents the A1-O equilibrium at the temperature of the bath. High-aluminum elements of composition X may exist alongside high-oxygen elements of composition Y in such proportions that the average composition 2 has a much higher A1-O product than that corresponding to equilibrium. The A1-O product supposedly corresponding to equilibrium at 1600 °C was found by Wentrup and Hieber2 to be 10-10, by Hilty and crafts3 to be 2 X 10-9 and by Gokcen and chipman4 to be 2 x 10-14. Only the last named investigators approached equilibrium by means

Jan 1, 1962

By Orvar Nyquist, Klaus W. K. Lange, John Chipman

Liquid Fe-C-Si alloys containing 0 to 12 pet Si and up to 4 pet C were equilibrated with carburizing gases at 1550°C. Two to 5 alloys simultaneously were held in close proximity for 5 to 7 hr to establish uniform carbon activity in the group. Analysis of the data gives the activity coefficient of carbon as a function of the mole fractions of carbon and silicon, Fig. 7. Values of the interaction coefficients at infinite dilution are

Jan 1, 1962

By J. A. Pusateri, M. A. Orehoski, N. R. Arant

Plant studies on commercial-size ingots and laboratory experiments with induction furnace heats have demonstrated that the major source of ingot cracks is associated with two conditions arising during top-pouring practice: 1—solidification during pouring, and 2—turbulence created by the impact of the stream. Methods of controlling the two factors were effective in eliminating or significantly reducing ingot cracks. BECAUSE the process of removing surface defects from hot-rolled product is so costly, the steel industry is striving constantly to develop methods of preventing, or at least decreasing, the occurrence of surface defects. Investigations have revealed steel-making and processing variables related to major surface defects, and controlling these variables has led to improvements in surface quality. However, the fundamental causes of major surface defects, such as ingot cracks, have not been determined; consequently such defects persist. At the Research and Development Laboratory of the United States Steel Corp. in Pittsburgh, a seam research program was initiated to determine the fundamental causes of certain major defects. As a part of the program, ingot cracks in killed, finegrained C1020 steel were selected for study. A cost survey indicated that, of the steels produced in sizable tonnages, carbon steels in the range of 0.18 to 0.23 pct C content require the most conditioning. Since this is particularly true of C1020, any im-provement of surface quality that might be effected from the study would be beneficial. Also, since the frequency of ingot cracks is exceedingly high for this grade, the steel would provide an excellent opportunity for a thorough study of the ingot-crack-ing problem. Why steels in this carbon range tend to exhibit more ingot cracks than do other steels was not considered in the investigation; the mechanism of ingot-crack formation was of paramount importance. Also, only the top-pouring practice was considered in the investigation, because this pouring procedure is used more extensively than others. In this study, ingot cracks are defined. as deep surface defects that sometimes are observed in an ingot prior to rolling but usually are observed during the initial stages of rolling on the primary mills. These defects may occur at any angle to the rolling direction but are most prominent in the transverse or nearly transverse direction. The appearance of ingot cracks on the rolled product varies with respect to their angle of formation and with the extent of rolling after their first occurrence. Ingot cracks are also termed "deep seams," "arrowheads," "irregular cracks," and "transverse cracks." Fig. 1 shows ingot cracks in a rolled bloom. This report summarizes: l—the exploratory investigation of commercial-size ingots; 2—the labor-atory investigations related to determining the source of ingot cracks and developing corrective methods; and 3—the plant evaluations of laboratory methods of decreasing ingot cracks. Exploration of lngot Cracks in Commercial Ingots Materials and Experimental Work: At the Du-quesne Works of the United States Steel Corp., five heats of killed, fine-grained C1020 steel were selected for the exploratory phase of the seam-research program. The heats were made by open-hearth practices that are considered most conducive to good surface quality. They were top-poured into 22x25 in. big-end-up hot-topped molds. One as-cast ingot and four other ingots rolled to the following cross-sectional sizes were set aside from each heat: 16x20 in.; 9 1/2x10 in.; 5x5 in.; and 2x2 in. The processing of the heats, from the time of charging in the open hearth furnaces to the end of the rolling operation on the primary mill, was observed carefully and recorded. The cast ingot and the four rolled ingots from each heat were examined for surface defects. The cast ingots were split longitudinally near the vertical center plane to expose the ingot structure beneath badly cracked regions. Also, a series of transverse sections was cut at about 1 in. intervals in a badly cracked area of one ingot. All sections were ground, polished, examined by sulphur printing and deep etching, and photographed. The rolled ingots

Jan 1, 1955

By D. J. Rose, W. M. Armstrong, A. C. D. Chaklader

The wetiability of single crystals of MgO by specimens of vacuum-cast iron was studied using the sessile drop technique in vacuo at 1550ºC. Formation of FeO at the liquid-vapor interface caused the contact angle (6) to decrease from 117 to 65 deg during the first minute. After cooling, all specimens possessed a peculiar annular interfacial deposit of Fe,O,. Within the annulus the interface showed no sign of chemical attack. Chemical reaction occurred where the iron was alloyed with Ti, V, Cr, Nb(Cb), Ta, cmd Zr. Vnriation of 6 with alloy concentration was studied. Although vanadium md chromium improved the wettability of MgO by iron, the effect of Zr, Ti, Nb, and Ta was indeterminable because the 8 derived from sessile drop considerations was that of the metal against a restrictive peripheral volume of liquid oxide wetting the substrate. INTEREST in the nature of metal-ceramic interactions has been stimulated by progressive development of metal-ceramic combinations. One of the more valuable methods used for bond investigation is the sessile drop technique. Recent attempts to improve wettability through solute additions to the drop have revealed that the solute may a) react with the oxide creating new compounds at the solid-liquid interface, b) adsorb at the interface in a monolayer formation, or c) distribute throughout the drop uniformly causing no wettability variation. This work, part m in a series1,2 of investigations of interface reactions between metals and ceramics, embraces a study of the Fe-MgO system. MgO possesses a large negative free energy of formation (-173 kcal per g mole 0, at 1550ºC) compared to FeO at this temperature (-73 kcal per g mole 02). Hence the electronegativity difference between the drop and substrate allows selection from an extensive group of metal solutes with intermediate electronegativity differences that would, in the absence of chemical reactions, be expected to adsorb pre- ferentially at the solid-liquid interface. However, the high oxygen pressure of MgO in vacuo creates an oxidation environment which influences the solute behavior. Recent studies of the Fe-MgO systemJ74 have been restricted by chemical reactions that obscured observations. In view of the current interest in liquid-phase sintering of metal-ceramic combinations under partial oxidizing conditions,5 a more comprehensive study of the Fe-MgO system seemed beneficial. EXPERIMENTAL PROCEDURE 1) Specimen Preparation. Optical-grade MgO single crystals and Ferrovac vacuum-cast iron were used in all experiments. A spectrographic analysis of the iron indicated 0.008 C, 0.05 V, 0.005 Mo, 0.01 Ti, 0.002 S, 0.01 Cr, 0.001 Mg, 0.01 Si, 0.003 A1 (wt pct). The MgO crystals were cleaved along (100) planes into plates approximately 20 by 20 by 1 mm. Following annealing in vactto at 1100°C for 3 hr, surface irregularities were removed by a chemical etch in phosphoric acid at 100°C. The iron rod was machined into small cylinders approximately 0.250 in. in diam and length and these were carefully cleaned in organic and acidic solutions to remove surface impurities. All specimens were weighed to the nearest 0.1 mg. 2) Apparatus. The apparatus described in detail by previous authors1,2 was modified for this work. A Polaroid Land Camera was incorporated into the optical system so that drop measurements at ten-second intervals after melting were possible with ultra-high-speed self-develop ing film. 3) Procedure. The iron cylinders were placed upright on the MgO plates and positioned in the molybdenum susceptor. After furnace assembly the system was pumped down to a vacuum of 1 µ and flushed with H2 at 800°C. The system was again evacuated to 5 x 10-5 mm of mercury and the temperature raised to 1550°C within 2 min. The molten drops were photographed at appropriate time intervals. TWO min after melting the iron vapor pressure caused gas discharge, or corona, within the tube. The specimens were then slowly cooled to room temperature, sectioned and examined metallographi-cally. X-ray identification of interfacial reaction products was attempted by the powder diffraction technique. Alloying elements (Ti, V, Cr, Zr, Ta, Nb) were added to the iron in various concentrations up

Jan 1, 1963

By A. R. Orban, R. B. Engdahl, J. D. Hummell

The initial phase of a research program on smoke abatement from Bessemer converters is described. In work sponsored by the American Iron and Steel Institute, a 300-lb experimental Bessemer converter was assembled to simulate blowing conditions in a commercial vessel. Measurements of smoke and dust were also made in the field on a 30-ton commercial vessel. During normal blows the dust loading from the laboratory converter averaged 0.51 lb per 1000 lb of exhaust gas. This was similar to the exhaust-gas loading of a commercial vessel. The addition of hydrogen to the blast gas of the laboratory converter caused a decided decrease in smoke density. Smoke was also reduced markedly when methane or ammonia was added instead of hydrogen. The research is continuing on a bench-scale investigation of the mechanism of smoke formation in the converter process. DURING the past 2 years, on behalf of the American Iron and Steel Institute, Battelle has been conducting a research program on the control of emissions from pneumatic steelmaking processes. The objective of the research program is to discover a practical method for reducing to an unobjectionable level the emission of smoke and dust from Bessemer converters. PRELIMINARY INVESTIGATION Although conceivably some new collecting technique may be devised which would be economically practicable for cleaning Bessemer gases, no such system based on presently known principles seems feasible because of the extremely large volume of high-temperature gases involved. Hence, the research is being directed toward prevention of smoke formation at the source. A thorough review was first made of former work to determine the present status of the cleaning of converter gases. No published work was found on work done in the United States on collecting smoke or on preventing its formation in the bottom-blown, acid-Bessemer converter. In Europe, however, a number of investigations have been made on the basic-Bessemer converter. Kosmider, Neuhaus, and Kratzenstein1 conducted tests on a 20-ton converter to obtain characteristic data for dust removal and the utilization of waste heat. They concluded that because of the submicron size of the dust, special equipment would be necessary to clean the exhaust gases. Dehne2 conducted a large number of smoke-abatement experiments at Duisburg-Huckingen in a 36-ton Thomas converter discharging into a stack. A number of wet-scrubbing and dry collectors were tried unsuccessfully. A waste-heat boiler and electrostatic collector with necessary gas precleaners was felt to be the best solution for this particular plant. Meldau and Laufhutte3 determined that the particle size was all below 1 µ in the waste gas of a bottom-blown converter. Sel'kin and zadalya4 describe the use of oxygen-water mixtures injected into a molten bath in refining open-hearth steel. They claim that with use of oxygen-water mixtures the amount of dust formed was reduced between 33.3 and 20 pct of its previous level, and emission of brown smoke almost ceased. Pepperhoff and passov5 attempted unsuccessfully to find some correlation between the optical absorption of the smoke, the flame emission, and the composition of the metal in a Thomas converter in order to determine automatically the metallurgical state in the melt. In a recent U. S. Patent (NO. 2,831,762)' issued to two Austrian inventors, Kemmetmuller and Rinesch, the inventors claim a process for treating the exhaust gases from a converter. By their method the inventors claim that the exhaust gases from the converter are cooled immediately after leaving the converter to a degree that oxidation of the metal vapors and metal particles to form Fe2O3 is inhibited in the presence of surplus oxygen. Gledhill, Carnall, and sargent7 report on cleaning the gases from oxygen lancing of pig iron in the ladle. They claim the Pease-Anthony Venturi scrubber removed 99.5 + pct of the smoke, thereby reducing the concentration to 0.1 to 0.2 grain per cu ft, which resulted in a colorless stack gas after the evaporation of water. Fischer and wahlster8 developed a small basic converter and compared the metallurgical behavior of the blow with that of a large converter. Later work by Kosmider, Neuhaus, and Hardt9 on the use of steam for reduction of smoke from an oxygen-enriched converter confirmed that the cooling effect of steam is detrimental to production. From review of all of the published information on the subject, it was concluded that a practical solution to the smoke-elimination problem had not been found. Accordingly, it was deemed desirable to investigate the feasibility of preventing the initial formation of smoke in the converter.

Jan 1, 1961

By M. T. Simnad, G. Derge, I. George

Measurements of current efficiency on iron-silicate slags in iron crucibles showed that conduction is about 10 pct ionic in slags with less than 10 pct silica and about 90 pct ionic in slags with more than 34 pct silica, increasing linearly in the intermediate range. The balance of the conduction is electronic in character. Silicate ions are discharged at the anode with the evolution of gaseous oxygen. Transport experiments show that the ionic current is carried almost entirely by ferrous ions, which may be assigned a transport number of one. THERE has been increased evidence in recent years that the constitution of liquid-oxide systems (slags) is ionic.1-3 The principal studies designed to establish the structure of liquid slags have been by electrochemical methods', " and conductivity measurements1,6,7 which also have indicated the presence of semiconduction in several silicate systems1,4-0 and in pure iron oxide.' It is well known that many slag-forming metallic oxides have an ionic lattice type in the solid state, and their properties are determined to a large extent by the lattice defects and ion sizes. As Richardson8 as pointed out, the detailed models of liquid slags cannot be found on thermodynamic data only but "must rest on a proper foundation of compatible structural and thermodynamic knowledge, combined by statistical mechanics." A careful thermodynamic study of the iron-silicate slags has been carried out by Schuhmann with Ensio9 and with Michal.10 They obtained experimental data relating equilibrium CO2: CO ratios to slag composition and made thermodynamic calculations of the activities of FeO and SiO, and of the partial molal heats of solution of FeO and SiO2 in the slags. It was found that the activity-composition relationships deviate considerably from those to be expected from an ideal binary solution of FeO and SiO2. However, the partial molal heat of solution of FeO into the slags was estimated to be zero. Their experimental results were correlated with the constitution diagram for FeO-SiO2 of Bowen and Schairer,11 with the results of Darken and Gurry" on the Fe-O system, and with the work of Darken"' on the Fe-Si-O system. All these studies were found to be consistent with one another. The variation of the mechanism of conduction with composition in the liquid iron-oxide-silica system in the range from pure iron oxide to silica saturation (42 pct SiO2) in iron crucibles was reported in a preliminary note." The current efficiency, or conformance to Faraday's law, showed some ionic conductance at all compositions, the proportion increasing with the concentration of silica. The current-efficiency experiments since have been extended. Furthermore, transport-number measurements have been completed in silica-saturated iron silicates to determine the nature of the conducting ions. Experimental Current Efficiency in Liquid Iron Oxide and Iron Silicates using Iron Anodes: This study was carried out by passing direct current through slags in the range from pure iron oxide to iron oxide saturated with silica (42 pct silica), using pure iron rods as anodes and the iron container as the cathode. A copper coulometer was included in the circuit to indicate the quantity of current passed during electrolysis. Assuming that the cation involved is Fe-+, the theoretical quantity of iron lost from the anode according to Faraday's law may be calculated and when compared with the actual loss observed, gives an indication of the extent to which Faraday's law has been obeyed. It also gives an indication of the presence and extent of ionic conduction in the melt. Preparation of the Slags: About 100 g of chemically pure Fe,O, powder is placed in an iron pot which is heated by induction until the contents liquefy. In this way, FeO is produced according to the reaction Fe2O3 + Fe = 3 FeO. More Fe2O3 or SiO, powder is added and, when a sufficient quantity of molten slag is obtained, the induction unit is turned off, the pot withdrawn, and the molten slag poured on to an iron plate. Homogenization and Electrolysis of the Slag: Apparatus—After considerable development, the setup illustrated in Fig. 1 proved to be quite satisfactory. A is an Armco iron cylinder, 1 in. ID and 1/8 in. wall, consisting of three sections placed one on top of the other. The bottom section is a pot about 5 in. long with a small hole drilled in its bottom to allow withdrawal of gases during evacuation of the apparatus. The middle section is 6 in. long and consists of a pot which serves as the slag container, while the top section is a hollow-cylinder continuation of the slag-container pot. The height of this latter section is about 5 in., giving an overall length of approximately 16 in. The iron cylinder is constructed in this way for ease of fabrication, the individual sections becoming welded together after the

Jan 1, 1955

By Keith R. Bock, Norman Parlee, Albert M. Barloga

Coils of pure iron and iron-carbon alloy wire (0.05 to 0.80 pct C) and sufficient sulfur to saturate the solid phase were equilibrated in evacuated or argon filled tubes. After rapid cooling, and removal of the outside nonmetallic layer, the wires were analyzed for carbon and sulfur and the data used to construct an Fe-S binary and isotherms of the Fe-C-S ternary in the range 1149° to 1427°C. THE solid solubility of sulfur in steel is of interest in connection with such phenomena as hot shortness, burning, and so forth. "Burning," the more or less permanent damage that some steels suffer when heated for forging or rolling, has been shown to be related closely to the behavior of sulfur and less closely to carbon and oxygen.' Attempts to interpret burning phenomena in steels fail because of lack of data on the Fe-C-S and the more complex systems in this family. Rosenqvist and Dunicz 2 and Turkdogan, Ignatowicz, and pearson3 have largely elucidated the Fe-S diagram in the region of interest but no information on the Fe-C-S diagram in this region appears to be available in the literature. This paper deals with the elucidation of the Fe-C-S diagram in these interesting ranges. The method employed is different from those used by previous workers2'3 on the Fe-S system. EXPERIMENTAL METHOD Pure iron wires (Ferrovac E) or iron carbon alloy wires of 1 mm in diam were cleaned with acid and acetone, coiled, and placed in silica tubes (7 mm OD and 5 mm ID) previously closed at one end. Enough sulfur was added to assure saturation of the solid iron phase. The filled tubes were either simply evacuated and sealed, or filled with argon at a reduced pressure and sealed. The argon was required at the higher temperatures to prevent collapse of the tubes. The filled and sealed tubes were placed in the middle uniform temperature zone of a Globar tube furnace and equilibrated at temperatures ranging from 2100°F (1149°C) to 2720°F (1493°C). After equilibration the tubes were removed from the furnace and quenched in air or water, the form of quenching being found to have no effect on the results. The tubes were broken open and the coils were placed in a 1 : 1 HC1 solution to remove the sulfide-rich layer. The coils were then cut into small pieces and analyzed for sulfur and carbon. In the early stages of the investigation different equilibration times ranging up to 17 hr were tried and the cores of the wires were analyzed to test for saturation. One hour appeared to be sufficient to reach maximum sulfur content at 1454°C and 2 hr sufficient at 1149°C. The practice adopted was to use at least 3 hr at the higher temperatures and at least 5 hr at the lower temperatures. The iron-carbon alloy wires used were made by carburizing pure iron wire with carbon monoxide gas in a one inch diameter ceramic tube at about 1204°C. Differing carbon contents were obtained by allowing fairly large coils to react with the gas for varying lengths of time at a flow rate of 800 cc per min. The reacting times ranged from 15 min to 4 hr depending upon the amount of carbon desired. The furnaces used were controlled by means of Leeds and Northrup Speedomax Type H instruments with D.A.T. Control attachment. Thermocouples were calibrated against the melting points of gold and copper. The temperatures recorded appear to be accurate within i2.7OC. Starting with run No. 85 and continuing with the

Jan 1, 1962