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By C. E. Birchenall, G. Derge

IN studying the kinetics of slag-metal reactions, it has become increasingly apparent that a complete knowledge of all aspects of interface phenomena will be required to clarify these processes adequately. A part of the data required for all oxidizing slags used in the refining of impure iron to steel is the rate of exchange of iron between the slag and metal phases. The simplest equilibrium of this type is that between liquid iron and iron silicate slag when both phases are equilibrated with the silica crucible containing them. In this study, the exchange of iron between the two liquid phases has been measured by using radioactive Fe as tracer. The observed high exchange rate indicates the ease with which such interfaces may be crossed in refining processes. The experiments required for this study involved relatively minor and normal modifications of well established techniques. Melting was accomplished by induction heating in heavy walled, fused silica, rotating crucibles." Rotation was used to minimize dilution of the slag by crucible erosion. The melting stock was ingot iron. Slags were prefused in iron crucibles using chemically pure grade oxide reagents. The special conditions applying to the active iron additions will be described for individual experiments. Suitable precautions were observed with regard to protection against radiation hazards.' Identification of Activity This particular study was initiated several years ago, but held in abeyance because the radioactive iron available at that time contained a foreign activity which concentrated in the slag so as to mask the iron activity and render the results unin-terpretable. With the benefit of experiences from other studies, radioiron of suitable purity can now be prepared. As received from the Isotope Div. of A.E.C., the unit appears to contain Fe + Fe50 and a high activity cobalt. The cobalt and iron are separated by repeated ether extractions, and the purified iron stored for sufficient time for the Fe'7 44 day half-life) to decay to negligible activity, leaving only Fe as the active isotope. This was confirmed by the absorption curves for slag and metal samples from heat No. 1. In Fig. 1 the experimentally measured points for the absorption curves of slag and metal are fitted by the calculated slope of 5.8 mg per sq cm in aluminum, which corresponds to the Mn K doublet emission resulting from the capture of an orbital electron of Fe" by the nucleus. This shows that the radioactive species are the same in both slag and metal and identifies it as Fe55 Description of Individual Heats For the first heat, the radioactive iron was contained in the prefused slag. The active Fe55 had been precipitated with carrier and was added as Fe2O3 during fusion in the iron crucible. The charge of 500 grams of ingot iron was melted, the protective iron sleeve added, rotation started, and a prefused, inactive slag was added to allow the system to approach equilibrium. After about 5 min at temperature, the wash slag was skimmed and the active slag added. Initial slag and metal samples were taken as soon as the slag was molten. Additional samples were taken at indicated intervals thereafter. Slag samples were dipped with a small iron spoon and metal samples were sucked into 1/4 in. ID silica tubes. The slag and metal samples were pulverized and mounted for radioactive counting. The slag samples were analyzed chemically for FeO. Temperature was read after the last slag sample by immersion of a Pt-Pt-Rh thermocouple protected by a fused silica sheath. Since no significant variation of rate with temperature was observed

Jan 1, 1954

By F. L. Toy, C. E. Sims

PNEUMATIC processes for converting molten pig iron to steel were the major producers of steel during the latter half of the 19th Century and until shortly after the turn of the century, when these processes began losing ground to their rival—the basic open hearth process. The first pneumatic process for converting molten pig iron to steel was introduced almost simultaneously by Sir Henry Bessemer in England and by William Kelley in the United States during the decade 1850-1860, but it was Bessemer who pushed it to a successful commercial operation. The process itself is so basically simple that it has not lent itself to many extensive or revolutionary improvements since its inception. During the first 30 yr, numerous' designs of vessel and many modifications of practice were tried before the industry standardized on something resembling current practice. The evolution in construction has resulted in proportions and arrangements based more on mechanical expedience than on metallurgical requirements. Many of the early converters were stationary and had to be tapped similarly to the cupola or open hearth furnace. Such types were used for many years in Sweden and Germany, but the rotating or tilting types were favored in England and the United States. There was evident trouble with bottom tuyeres, becAuse about half of the early designs were constructed for side blowing with tuyeres submerged below the metal-bath surface. Even portable tuyeres, introduced from above, were tried. The principal advance, which made bottom blowing practical, was the invention, in 1863, by Henry Bessemer, and subsequent improvement by A. L. Holley, of a detachable bottom so that the tuyere section could be renewed. In the meantime, it was the demonstration, by Robert Mushet, of the value of manganese in overcoming hot-shortness in converter steel, that made the process metallurgically feasible. At first, only the acid practice was used, and Swedish pig iron, because of its low sulphur and phosphorus, was in great demand. The development of a suitable basic lining, by Sidney G. Thomas and Percy G. Gilchrist in 1876-1879, made the process applicable to the high-phosphorus ores of Europe. From the beginning of the use of the Thomas-Gilchrist process, trouble was experienced in obtaining sufficiently high temperatures in the blown metal, particularly in small heats. It is necessary, of course, to have the low-carbon blown metal at a considerably higher temperature for handling from vessel to ladle to molds than is needed for the molten pig iron. All of the increase in temperature in a pneumatic process must be obtained from the heat of combustion of the elements contained in the pig iron plus that from silicon when ferrosilicon is added. In bottom blowing practice, carbon is almost completely burned, but inasmuch as it cannot be oxidized to a higher state of oxidation than to CO when in contact with liquid iron, only a minor portion of the heat-producing capacity is utilized. Under such conditions, it is not considered to be an efficient source of heat. In the acid practice, therefore, silicon and manganese are the large heat producers, are quickly oxidized, and are efficient fuels. Too much manganese, however, thins the slag greatly and tends to promote excessive slopping or throwing of slag and metal from the converter during the blow. Most operators, therefore, like to keep the manganese content of the iron below 0.60 pct, and thus the main source of heat is the silicon, which must be at least 1 pct and sometimes 2 to 3 pct for small blows such as for castings. Ferrosilicon is sometimes added during the blow to obtain an adequate temperature level. In the basic (Thomas) practice, even more heat is required, because cold lime is added to flux the phosphorus after it is oxidized, and the basic slag must be maintained at a proper temperature. Silicon

Jan 1, 1951

By F. L. Toy, C. E. Sims

I. A. Sirel—I would like to ask Mr. Sims what would the preferred hot metal analysis be as far as manganese and silicon are concerned if you used specially made iron for this process instead of basic iron. C. E. Sims (authors' reply)—A preferred composition would contain somewhat less silicon than the basic pig iron used in these experiments. High silicon requires a large lime addition. Lime must be added in sufficient quantity to neutralize the silica formed and to leave an excess for dephosphorization. Manganese presents almost no problem in operation. It is almost completely oxidized and, in burning, develops considerable heat. The evidence indicates, however, that, in continuous commercial operation, there will be an excess of heat produced, and the bath will need to be cooled in some manner as by the addition of scrap or by utilizing the energy for the direct reduction of ore. There do not seem to be any serious limitations on composition of pig iron. One heat was made with an iron containing 2.27 pct silicon and the phosphorus finished at 0.007 pct. In another, the iron contained 0.45 pct phosphorus which was lowered to 0.019 pct. This indicates considerable leeway in composition. D. R. Loughrey—We are all very much interested in the recent discovery of very large deposits of iron ore both in Labrador and in Venezuela. I would like to ask Mr. Sims if the iron ore at either or both of these places is such that it would lend itself to the manufacture of iron suitable for use in the turbohearth. C. E. Sims-—According to my information, those ores are not essentially different from ores now used in this country for making basic pig. They should, therefore, be adaptable to this process. D. I. Brown—You have spoken about the leeway, or spread in analysis of the various irons you can use in the vessel. I would like to have you tell us, if you can, about the different kinds of steels which can be made in such a vessel. The turbohearth process, or it might more aptly be called pneumatic openhearth, is a little different from that used in most Bessemer shops and in the one in which I worked. If we had a blow in the air over 10 min, the boss was in the pulpit in a hurry

Jan 1, 1951

By W. A. Griffith

Fractional replication of factorial design, a general method for planning experimentation and for analysis of data obtained, is described as applied to a flotation investigation. This method leads to determination of optimum process conditions with minimum experimental effort. Its advantages over simple factorial design are demonstrated. A METHOD for planning experimentation and for analyzing the data secured will be demonstrated. This method, termed fractional replication of factorial design, employs a relatively small number of individual experiments to determine which of a large number of process variables are controlling, to determine which combination of levels of these variables is most likely to produce optimum results, and also to predict what results will be obtained with a particular combination of conditions not already tested. Although the general method is not new, having been developed by Finney in 1945,' the extent to which it can improve the effectiveness of applied research generally has not been recognized by metallurgists. The fractional replication procedure is particularly useful in flotation experimentation and an example from such an investigation will be used in the paper. However, it has equal value in any investigation in which similar experimental difficulties are encountered. In developing a flotation process for a particular mineral separation, the investigator is inevitably confronted with the following difficulties: 1—There are a large number of potentially important process variables. 2—Results of individual experiments are not highly reproducible, due in part to the difficulty in precisely controlling all the variables. 3—Considerable effort is expended in conducting individual experiments. 4—There are practical limits on the number of individual experiments which can be made. In situations of just such a type, modern statistical methods of planning experimentation and analyzing data have their greatest value. Applications of one such technique, called factorial design, to problems of this type have been described by Dorenfeld and others.'-' The simple factorial design is an efficient procedure when the investigator hopes to provide a comprehensive understanding of the effects and interrelationships of a small number of variables over a limited range. In applied research, this is seldom the main objective. Rather, the investigator usually wishes to determine which of the many potentially important variables are in fact controlling, which levels of the controlling variables will provide opti- mum metallurgical results, and what these results will be at optimum conditions. Interest in detailed trends is limited to the controlling variables and to levels in the region of optimum conditions. Simple factorial design has serious deficiencies for such objectives and is not the most efficient method of experimental design. Deficiencies of Factorial Design In a simple factorial design, an experiment must be made at every possible combination of each level of every variable, once these have been chosen and the levels of each to be included have been decided upon. As the number of variables or levels of each increases, the experimental program quickly reaches prohibitive size. For example, an investigation of only four variables, each at four levels, requires 256 individual experiments. Often upon completion of such an extensive program, it is found that one or more of the variables has metallurgically unimportant effects or that a poor estimate has been made as to the appropriate range of levels to be investigated. The result is that only a small proportion of the data obtained falls in the range of real metallurgical interest. Indeed, it frequently can be anticipated that certain combinations of levels of variables will not produce results of interest, but they still must be included so that the essential balance, or orthogonality, of the design will be retained. It may be true that factorial design will provide the greatest amount of information from a given number of experiments, but it does not necessarily follow that it will lead to the desired information with a minimum number of experiments. Much of the information provided may be of little value. Advantages of Fractional Replication The disadvantages of simple factorial design are overcome to a great extent by a modification known as fractional replication. This is a technique for sampling systematically the potential data of a full factorial experiment, that is, the data which would have been obtained if the complete factorially designed program had been completed. Only a fraction of the total array of experiments is made, but the experiments are chosen in such a way that the important advantages of factorial design and the accompanying analysis of variance are retained. The data obtained from the first group of experiments are used to determine which of several variables are controlling and which levels of these variables are most likely to produce the desired result. Unimportant variables and levels of variables then may be

Jan 1, 1956

By Takashi Katsura, Avnulf Muan

Equilibrium relations in the system FeO-Fe2O3 Cr2O3 have been determined at 1300°C at oxygen pressures ranging from that of air (0.21 atm) to 1.5 x 10-11 atm. The following oxide phases have stable equilibrium existence under these conditions : a sesquioxide solid solution with corundum-type structure (approximate composition Fe2O3-Cr2O3); a ternary solid solution with spinel-type structure (approximate composition FeO Fe2O3-FeO Cr2O3) and a ternary wüstite solid solution with periclase-type structure and compositions approaching FeO. The metal phase occurring in equilibrium with oxide phase(s) at the lowest oxygen pressures used in the present investigation is almost pure iron. The extent of solid-solution areas and the location of oxygen isobars have been determined. ThE system Fe-Cr-O has attracted a great deal of interest among metallurgists as well as ceramists and geochemists. Metallurgists have studied the system because of its importance in deoxidation equilibria, ceramists because of its importance in basic brick technology, and geochemists because of its importance for an understanding of natural chromite deposits. Chen and chipman1 investigated the Cr-O equilibrium in liquid iron at 1595°C in atmospheres of known oxygen pressures (controlled H2O/H2 ratios). The main purpose of their work was to determine the stability range of the iron-chromite phase. Hilty et al.2 studied oxide phases in equilibrium with liquid Fe-Cr alloys at 1550°, 1600°, and 1650°C. They reported the existence of two previously unknown oxide phases, one a distorted spinel with composition intermediate between FeO Cr203 and Cr3O4, the other Cr3O4 with tetragonal structure. They also sketched diagrams showing the inferred liqui-dus surface and the inferred 1600°C isothermal section for the system Fe-Cr-O. Koch et al3 studied oxide inclusions in Fe-Cr alloys and also observed the distorted spinel phase reported by Hilty et al. Richards and white4 as well as Woodhouse and White5 investigated spinel-sesquioxide equilibria in the system Fe-Cr-O in air in the temperature range of 1420" to 1650°C, and Muan and Somiya6 delineated approximate phase relations in the system in air from 1400" to 2050°C. The present study was carried out at a constant temperature of 1300° C and at oxygen pressures ranging from 0.21 atm (air) to 1.5 x 10-11 atm. The chosen temperature is high enough to permit equilibrium to be attained within a reasonable period of time within most composition areas of the system, and still low enough to permit use of experimental methods which give highly accurate and reliable results. These methods are described in detail in the following. I) EXPERIMENTAL METHODS 1) General Procedures. Two different experimental methods were used in the present investigation: quenching and thermogravimetry. In the quenching method, oxide samples were heated at chosen temperature and chosen oxygen pressure until equilibrium was attained among gas and condensed phases. The samples were then quenched rapidly to room temperature and the phases present determined by X-ray and microscopic examination. Total compositions were determined by chemical analysis after quenching. In the thermogravimetric method, pellets of oxide mixtures were suspended by a thin platinum wire from one beam of an analytical balance, and the weight changes were recorded as a function of oxygen pressure at constant temperature. The data thus obtained were used to locate oxygen isobars. The courses of the latter curves reflect changes in phase assemblages and serve to supplement the observations made by the quenching technique. 2) Materials. Analytical-grade Fe2O3 and Cr2O3 were used as starting materials. Each oxide was first heated separately in air at 1000°C for several hours. Mixtures of desired ratios of the two oxides were then prepared. Each mixture was finely ground and mixed, and heated at 1250" to 1300°C in air for 2 hr, ground and mixed again and heated at the same temperature for 5 to 24 hr, depending on the Cr2O3 content of the mixture. A homogeneous sesquioxide solid solution between the two end members resulted from this treatment. A Part of some of the sesquioxide samples thus prepared was heated for 2 to 3 hr at 1300°C and oxygen pressures of 10-7 or 1.5 x 10-11 atm. Reduced samples (either iron chromite

Jan 1, 1964

By G. M. Ikeda, J. G. Sibakin

An investigation was carried out to determine the variables affecting the coiling temperature of strip in the 56-in. hot strip mill. After statistical treatment, equations have been derived to determine the temperature drop between mill and coiler for both full spray (top and bottom) and top spray only practices. The individual influences of each variable in the temperature drop were derived for both practices. Limitations of the present practices were shown and adjustments in cooling for increased rolling speeds were suggested. A method of estimating the required number of sprays, their spacing, pressure, etc., to achieve a desired temperature drop is developed. MAXIMUM finishing temperature of a hot strip mill is mainly determined by the rolling speed, gage, and the temperature of the bar entering the mill. This finishing temperature may be limited by the maximum admissible coiling temperature in cases when either the cooling facilities on the runout table are not adequate or, more generally, when the cooling capacity of the runout table and the production capacity of the continuous mill are out of balance. Some time ago, the balance between these two factors was not considered detrimental to production. Recently, a new drafting schedule was introduced which increased the production rate, the entry temperature, and hence the finishing temperature. Thus, the restriction of the maximum specified coiling temperature became an important factor for many of the thicker gages. An investigation of the factors determining the coiling temperature may be, therefore, of considerable importance. A brief description of the available equipment will be a useful illustration of the techniques and methods used for this investigation. The 56 in. continuous hot strip mill is composed of six 4-high stands each containing two 221/2-in. diam work rolls and two 45-in. diam back-up rolls. Either of the last two stands can be used as the finishing stand. Which stand is used is dependent on the total percentage of reduction to be taken over the whole train, i.e., on the entry thickness and the final gage. The characteristics of these last two stands are given in Table I. Table I. Operational Characteristics of Nos. 5 and 6 Stands No. .5 NO. 6 Maximum voltage GOO 600 Power, hp 30(10 W00 I normal, kilonmp 4.35 3.73 Rpm of motor and rolls ISO 15 0 ITS to 300 Spettl ot strip, fpm 333 6 to 376T.2 103) to 2062 The speed of the finishing stand varies with the amount of reduction, strip width, and the exit gage. Finishing speeds in general use for varying gages are shown in Table 11. These speeds may change with an increase or decrease in the entry temperature of the strip. Even though the maximum speed of No. 6 stand is shown as 2062 fpm, this has so far never been attained,

Jan 1, 1957

By F. B. Foley

IT is with an unusual degree of personal satisfaction that I find myself in a position to pay tribute to the memory of Henry Marion Howe. One could not have spent any length of time in the presence of Dr. Howe without profiting intellectually. I do not hesitate to say that my years of association with him were the most stimulating of all my years of metallurgical study. He always impressed one with his own eager search for knowledge. Never dependent on the written word alone he sought information from anyone whose opinion he valued. His ability to piece together bits of apparently conflicting data from various sources so as to build up a logical hypothesis was unique. A small slight man with the intellect of genius he would have gone to the top in any endeavor he undertook and it was fortunate for metallurgy that its study attracted him as it did. Howe was a modest man. I like to recall an incident which left a lasting impression with me. The lab- oratory in his home, "Green Peace," was in the basement and access was by way of stairs leading down from his secretary's room. In using these stairs my attention was attracted many times to an ordinary cardboard shoe box which reposed on the shelf above the landing. It was crudely labeled on its side in black ink "Vanity Box." My curiosity was aroused to the point that I finally asked his secretary what it was. With some amusement she took the box from its shelf on the stairway, opened it and showed me its contents—numerous letters, from the foremost men of science of every civilized country throughout the world, commending his "Metallography of Steel and Cast Iron." I recall that in reply to one who thought there was not enough of Howe's own researches in his book he wrote, "Primarily I am a writer, secondarily an investigator." Howe wrote to make his readers think. No one ever strove harder than he to be right but above all, whether his viewpoint proved ultimately to be right or wrong, he was always content if by his stand, he provoked a reader to take the next step along the path to greater knowledge. I doubt that he was ever afraid to be wrong for he was always secure in the thought that his effort was guided by a sincere search for the truth. One continually searching for truth is entitled to occasional excursions up the wrong alley. A glance backward to the metallurgical confusion of some thirty to forty years ago, or need one go back so far, provides convincing proof of what a host of companions one may have in a common acceptance of ideas which the future will prove to be wholly untenable. Well over a hundred years have passed since investigators have interested themselves in the effect of increasing the temperature of iron and steel on their mechanical properties. We are told by Charles Walrandl in "Industrial Annals" for June 11, 1822, that bend tests, conducted in a Russian steel works of Prince Demidoff, on steel bars "highly heated" and bent during cooling became brittle when bent at an iris blue color. He concluded, "That when steel is heated to a temperature between 473°F and 662°F the mettle was more brittle between these limits than at a much lower or at a much higher temperature." It was a curious bit of information recognized as true to this day and still not explained satisfactorily. In 1878 Charles Houston in Annales de Mines associated this brittleness with an increase in tensile strength at 572°F. When this relatively low temperature is exceeded it is recognized that steel becomes weaker as temperature is increased up to the melting point, where no strength of practical importance remains. It is easy to believe, in fact it goes without saying, that this weakening as the temperature of a metal is increased is the result of the motion of the atoms making up the metal, a motion which itself is evidence of the temperature increase. However, if we are considering iron or steel we find that this decrease in strength is not a steady one, for, besides the increase in strength just referred to, one comes to a temperature, the critical temperature, where results of tests indicate the metal to be extremely weak and then as temperature increases to become sensibly stronger again. This apparent anomaly was made the subject of the first Howe Memorial Lecture, delivered by Albert Sauveur in 1924. It may be of interest to review these findings of Sauveur. He used two methods of investigation. One involved the twisting of bars. The bars were heated in an

Jan 1, 1951

By F. R. Cattoir, R. W. Kimball, C. T. Anderson, V. V. Donaldson

THIS paper is the second of a series on the effect of various elements on hot-working characteristics of Fe-C alloys to be issued by this laboratory. The investigations being conducted at the Ferroalloy Research Branch of the U.S. Bureau of Mines, Redding, Calif., involve fundamental research on the effects of various alloying materials and impurities on the physical properties of high purity Fe-C alloys. This paper deals with the determination of the limit of forgeability of steels containing varying amounts of manganese and sulphur. A paper discussing the hot-working characteristics and the physical properties of the forgeable alloys is being prepared. One of the principal impurities in all steels is sulphur.. The phenomenon, hot-shortness, commonly attributed to sulphur, has long been a source of expense and inconvenience to both the maker and user of steels. In steelmaking practice, this effect of sulphur has been overcome by the addition of manganese which, apparently, acts as a desulphurizer. Manganese is also used as a deoxidizer and alloying material. The critical and strategic position of man- ganese gives added importance to research which may contribute to its conservation and more effective utilization. It is not the purpose or intention in the present paper to give any explanation of the mechanism of either hot-shortness or its prevention but rather to report the results of forging high purity Fe-C alloys of the range of compositions near the limit of hot-forgeability. Temperatures for each phase of reduction were duplicated within 20" to 30°F for all tests. The starting material was sponge iron, which, after melting and purification, gave a high purity iron containing about 0.001 pct each of silicon and phosphorus. Scrap iron was not considered suitable because of its high percentage of contaminants and wide variation in analyses. The sponge iron was melted and refined for melting stock in a three-phase, direct-arc, size ST, Moore Rapid Lectromelt furnace with a 500 kva rating as described in the preceding paper. Additives were carefully selected to avoid addition of contaminants. The sulphur was added as resublimed flowers of sulphur or purified roll sulphur of analytical grade. The manganese used was dehydrogenated high purity electrolytic material produced by the Bureau of Mines plant at Boulder City, Nev. High purity aluminum in the form of wire was used for deoxidation. The limestone was obtained locally and had the following analysis: CaO, 53.7 pct; MgO, 0.8; ignition loss, 42.4; R2O3, 0.2; SiO2,3.0; and P2O5, 0.014.

Jan 1, 1955

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