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By John F. Elliott, John R. Rawling

The rate of reduction of silica to silicon by carbon at 1550° to 1700°C in iron blast-furnace type slag-metal systems has been investigated. In the tower portion of the temperature range oxygen transport in the metal boundary layer at the slag-tal interface is probably rate limiting. A second step, which apparently involves a chemical process in the slag at the slag-metal interface, appears to be rate limiting when the oxygen-transport limitation is avoided. Above 1650°C rate control of the reduction by carbon probably is mixed between the two steps. INVESTIGATIONS1.2 into the equilibrium distribution of silicon between graphite-saturated slags and metals typical of iron blast-furnace practice show that, under the experimental conditions specified, the reduction of silica to silicon is relatively slow compared with the rates of other slag-metal reactions under similar conditions. For this reason, the reduction of silica in blast-furnace slag-metal systems was considered to be an interesting subject for further study. Investigations of the kinetics of the reaction3-5 suggest that several possible steps may be rate controlling, and that the rate-controlling step depends not only on the physical state of the systems but also on the configuration of the apparatus. The main objects of the investigation reported here were to sug- gest plausible reaction paths for the reduction of silica under the experimental conditions chosen and to determine the step or steps which control the rate of reduction of silica. EXPERIMENTAL Two types of experiments involving the reduction of silica from the slag were carried out. In the first, the only reducing agent present was carbon (graphite), for which the over-all reaction is (SiO2) +2C(gr) —Si + 2Co(g) [l] The second type was a graphite-saturated ferro-silicon-iron concentration cell. In it silica in the slag could be reduced either by carbon according to Eq. [I], or by a reaction of electrochemical nature in which silicon was oxidized at the ferrosilicon-slag interface and silica was reduced at the slag-iron interface without the formation of CO. The two types of experiment are described below. Reduction of Silica with Carbon as the Only Available Reducing Agent. The reduction of silica was accomplished by allowing a liquid lime-alumina-silica slag and graphite-saturated iron to react in an induction-heated graphite crucible. The crucible was 2.25 in. diameter and 5 in. deep; it was fitted with a graphite stirrer which penetrated through the slag and into the metal, Fig. 1. The slag and metal charges weighed 350 g each. Pure carbon monoxide at a pressure of 1 atm was maintained above the melt by passing the purified gas through the crucible at a rate of 0.5 liter per min. The gas did not stir either the slag or metal. Temperature measurements were made by sighting an optical pyrometer down the hollow stirrer rod into a 1/4-in. hole drilled in the stirrer blade. The crucible temperature was maintained within *15"C of the required value by manual control of the power supply to the

Jan 1, 1965

By W. O. Philbrook, A. E. El-Mehairy

The reduction by hydrogen of individual particles of dense hematite implanted in beds of inert spheres is controlled by single-particle kinetics. No evidence of reagent starvation was found down to low flow rates established by pressure gradients as low as 0.01 in. H2O per- in. of depth in beds of spheres as small as 3/16 in. diam. The optimum size for most rapid reduction of beds of homogeneous ores results from the effect on reducing potential of the gas of competing factors of supply and consumption. A recent publication1 presented the results of a study of the rate of reduction of iron ore in a fixed bed by hydrogen introduced at constant pressure differential. Under these conditions the reagent flow rate varied directly with the bed permeability, which was a function of particle size and shape and bed voidage, and inversely with the temperature-dependent viscosity of the gas. The present note adds data from supplementary experiments designed to reveal whether or not any partial reagent starvation arising from a flow-dependent transport resistance in the gas phase might have been operative. Kinetic studies were made of the reduction of individual spheres of iron oxide inserted into beds of inert spheres, so that the reagent flow rate and aerodynamic conditions were again determined by bed characteristics and temperature. The experimental techniques and apparatus were similar to those previously described.' The synthetic iron ore spheres were wet-rolled by hand from powdered, reagent-grade* Fe2O3 and subsequently dried and then fired in air at 1250°C. The indurated pellets has almost no porosity as indicated by their specific gravity of 5.10. The beds were made of dense alumina spheres, closely sized to the same dimension as the iron oxide spheres, in the following diameters: 3/16, 1/4, 5/16, and 3/8 in. Each bed was hand-packed of particles of a single size to a controlled voidage of 0.32 and depth of 3 in. within a capsule having an internal diameter at least 10 times the particle diameter. A few weighed iron oxide spheres were individually planted in the central plane of the bed of inert spheres at points away from the wall. Reduction was carried out at atmospheric pressure by purified hydrogen at 670°, 800°, and 985°c. The reagent was supplied at precisely controlled pressure differentials of 0.01, 0.02, and 0.03 in. of water per in. of bed depth. This gave a range of flow rates similar to that used in the study of beds of ore and comparable with blast-furnace practice in terms of mols of reducing gas per hr per sq ft of cross-section. Viscous flow prevailed in all beds under the experimental conditions of this study. The reduced particles were checked for loss in weight and then sectioned for metallographic examination. Occasional particles were found to have contained minute internal cracks that interfered with the concentricity of the reduction interfaces, and data for such particles were rejected. An experimental rate constant for the reduction of the imbedded Fe2O3 spheres was calculated on the assumption that the rate was proportional to the metal-oxide interface area by an equation that has been found by McKewan2 to describe the reduction of single spheres

Jan 1, 1962

By H. W. Hockin, D. r. Brandt, R. H. Walsh, P. L. Dietz, P. R. Girardot

New Jersey, Florida, and Canadian ilmenites were reduced with hydrogen or coke under various experimental conditions and the phase changes occurring in the ilmenite upon reduction have been studied by microscopic examination of polished sections and by X-ray diffraction. The products formed were dependent upon the type of ilmenite, temperature, time and reducing agent. Of the reducing agents, hydrogen was the more effective at lower temperatures. 1 HE possible utilization of ilmenite as a source of both iron and titanium has resulted in the development of a number of methods for the separation of the iron and titanium content. Slagging processes as currently used in Canada are typical of such methods. Somewhat less attention has been given industrially to the reduction of the iron content at less than the slagging temperature. Although references maybe found to such work, in general only one type of ilmenite, either natural or synthetic, has been studied by each author. We have attempted to draw some relationship between the results of experimental reduction and the type of deposit from which the ilmenite was derived, as evidenced by phases occurring in the ores and in the reduction products. Ilmenite ores having from 27 to 61 pct titanium dioxide were included in this study and in each case reduction was carried out at such temperatures that only limited coalescence of the particulate iron product occurred within the ilmenite grains. The history of the individual ilmenite samples and the temperature of reduction were found to determine the occurrence of various phases and the mode of distribution of the iron. REVIEW OF EARLIER WORK ON REDUCTION One of the earliest references to the reduction of ilmenite at less than the slagging temperature was made in 1917.' The metallic iron produced was_____ leached out by the action of dilute sulfuric or hydrochloric acid, to leave a product high in titanium dioxide. Subsequent to this, numerous patents2-'? and other references13"21 have appeared concerning reduction of ilmenite by carbon, hydrogen, carbon monoxide, methane, coal gas, water gas, or the like in the absence of fluxing agents. Mineragraphic examinations were not reported, and in the main, the only examinations made were chemical analyses. However, in two cases3,13, titanium suboxides were reported in the products and in one case2' rutile was reported, in addition to metallic iron. Both were identified by X-ray diffraction. While reductions in the absence of fluxing agents were generally followed by either a wet or dry chemical process for removal of the metallic iron, a Canadian source17 reported removal of the metallic iron by magnetic separation. By the addition of fluxing agents during reduction, the metallic iron has been coalesced into "pearls." Each reference to such a process23-28 has shown that the coalesced iron could be removed by magnetic or gravity means after the product was crushed. In the absence of fluxes, the coalescence did not generally occur. The major part of the present study has been limited to reductions without fluxing agents in order to determine the primary reactions of naturally occurring ilmenites. Titaniferous iron ores have also been studied,29-33 17, l9 their reduction having been used as the basis of a commercial process for beneficiation of such ores in Norway29 and more recently considered in the United States34,35. The ease of reduction of titaniferous iron ores relative to that of hematite or magnetite has been referred to,33 with the conclusion that the more

Jan 1, 1961

By D. J. Carney, J. Chipman, N. J. Grant

An absolute calibration has been achieved for sampling and analyzing liquid steel for hydrogen based on Sieverts' values of hydrogen solubility in iron. Further checks were made in nickel, iron-nickel, and 18-8 stainless melts. The sampling method was successfully applied to a large number of commercial steel melts in various types of furnaces. The concurrent problem of sample storage was also solved. THE problem of sampling of liquid steel for hydrogen is more difficult than the problem of analysis. Hydrogen has a greater mobility than any other element; it is the only element that will diffuse out of steel at room temperature. In accordance with the known relation between temperature and diffusivity, the diffusion of hydrogen is extremely rapid at the temperature of liquid steel. Consequently, in the past, attempts to quench molten steel to retain the dissolved hydrogen have not been as successful as similar attempts with nitrogen or oxygen. The retention of hydrogen is especially difficult since it will continue to escape at room temperature even if the molten metal has been rapidly quenched. The hydrogen sampling methods may be classified broadly as (1) the rapid quenching techniques which attempt to preserve super saturation and (2) those methods which attempt to collect the gases evolved as the metal freezes and cools to room temperature. With all methods of sampling but especially with the rapid quenching methods, there is also a concurrent problem of storing the sample until analysis is undertaken. The two problems are interrelated and must be considered together when discussing liquid steel sampling techniques. The major obstacle in liquid steel sampling has been that there was no way of evaluating properly the various sampling and storage techniques which have been developed. It has not been possible to compare the accuracy of the various methods. For evaluation of sampling methods some known standard is required; this may be found in the published work on the equilibrium solubility of hydrogen in liquid iron which has been determined in three separate investigations.1,2,3 The data are shown in table I. Sieverts' original method of obtaining gas solubilities involved measurement of the volume of gas required to saturate the liquid metal contained in an evacuated bulb of known volume. This procedure, improved by introduction of high frequency induction heating, has yielded reproducible results which appear to be entirely dependable. Using Sieverts' method, it has been proved for iron and other metals and alloys that the hydrogen solubility is proportional to the square root of the pressure of the hydrogen gas above the liquid, so that one may work with various partial pressures of hydrogen to put different amounts of hydrogen in solution. From Sieverts' law it is possible to know accurately what amount of hydrogen is dissolved in the liquid metal at the time of sampling. The accuracy of a sampling method may be gauged by reference to this known solubility. It was the purpose of this investigation to develop a method for sampling liquid steel and for storing the sample so that the analytical result would represent the actual hydrogen content of the metal bath. For this purpose an induction furnace was

Jan 1, 1951

By D. J. Carney, J. Chipman, N. J. Grant

G. Derge—With the development of this last weapon, there is not much of a chance for hydrogen. It is certainly a very interesting paper, and it gives us more confidence in sampling liquid steel for hydrogen than we have ever had before. This satisfactory work gives considerable confidence to all of the chilled methods of sampling which should be more or less successful depending upon the degree of chilling obtained. J. T. MacKenzie—How do you handle a nonmagnetic specimen in that device? D. J. Carney (authors' reply)—I left that out in going over the analytical procedure. For the 18-8 steel, what was done was to get some iron wire which was degassed. One turn of wire was made around the sample; it was inserted into the analytical apparatus, and that was enough to allow the magnet to pull the sample and drop it in the furnace. Other methods could be devised for this apparatus to do the same thing. This was just a quick method. C. E. Sims—This method of sampling and analysis is very ingenious, and the results obtained attest to a satisfactory degree of accuracy. It was noted in the paper that the samples are satisfactory only when there is a complete absence of pipe. This should be empha- sized, particularly in view of the fact that they are cut off under water. Some reservations are held in regard to the adequacy of the method of sample storage prior to analysis. Cooling on dry ice undoubtedly slows down the rate of diffusion to a marked degree, and it obviously suffices when the analysis is made within a few hours. All of the samples, except some of high-nickel steels, were analyzed within 12 hr. It is still unknown how long this method would be safe. In the work at Battelle Institute, it was impracticable always to start analysis within 12 hr for various reasons. Some samples did not reach the laboratory for several days, and some were held as long as a month before analysis. During this period, they were held over mercury, and the gas evolved at room temperature was collected and analyzed. It should be mentioned that both the mercury and the container must be kept very clean.

Jan 1, 1951

By R. A., D. L. Sponseller, Flinn

Using specially del'eloped titanium nitride crucibles and a pressurized syslem, it has been possible to determine the solzibilitv of liquid calcium in liquid iron and iron-base alloys. At 2925°F the solubility is 0.032 wt pet Ca in pure iron. The solubility is increased by aluminum, carbon, nickel, and silicon additions, and lowered by additions of gold. An inflection in the calcium-solubility curve occurs as carbon is added to iron. At approximately 0.87 Wt pet Ca the CaC, phase replaces liquid calcium, and the calcium concentration de- creases as more carbon is added to the iron. The maximum solubility, 0.36 wt pet Ca, was obtained in iron containing 10.5 wt pet Si. The data have important implications regarding the use of calcium in process metallurgy, as well as providing an interesting test of theories of metallic solutions. Reasonably good agreement is found with theories of Alcock and Richardson and of Wagner, and criteria are suggested which permit these theories to be applied more readily to systems of this type. AT the present time relatively little is known about the factors influencing solubility in liquid metals. Information of this type is important for such matters as the control of impurity levels in liquid metals, the use of magnesium in ductile-iron production, and the use of liquid-metal alloys as fuels and coolants in nuclear power plants. One important example of restricted solubility concerns the extent to which liquid calcium will dissolve in liquid iron. This is a matter of considerable interest in view of the strong potential of calcium for removing certain impurities in steel,. as well as the ability of calcium to desulfurize, inoculate, and produce spheroidal graphite in cast irons.' Since ferrous materials normally contain other elements in addition to iron, the interactions of third elements with the Fe-Ca system are of interest. In view of the foregoing, this investigation was conducted to determine the solubility of liquid calcium in liquid iron and the effects of various third elements upon the solubility. For reasons of theoretical and engineering importance, the elements investigated were aluminum, carbon, gold, nickel, and silicon. Numerous attempts were made in the early part of the present century to determine the solubility of calcium in both liquid iron and steel, employing a variety of open-melt and closed bomb-type systems.2-4 From the results of these tests Wever concluded that calcium is insoluble in liquid and solid iron.5 These investigations were unsatisfactory in that they failed to insure the presence of a liquid layer

Jan 1, 1964

By T. Busch, R. A. Dodd

The solubility of hydrogen in pure iron and pure nickel, and of nitrogen in pure iron, has been determined and agrees well with earlier data. Nitrogen is insoluble in pure nickel and cobalt. The solubility of nitrogen in Fe-Ni alloys also confirms earlier- work. The solubility of hydrogen in Fe-Ni alloys increases non-linearly with increase in nickel content, but the solubility of hydrogen in Ni-Co and Fe-Co alloys reaches a minimum at 75 and 50 at. pet, respectively. The solubility of nitrogen in Fe-Co alloys decreases approximately linearly with increase in. cobalt content. Nitrogen is insoluble in Ni-Co alloys. Determined interaction parameters are in good agreement with predictions of Gokcen and Ohlani. THE solubility of hydrogen and nitrogen in liquid iron and iron alloys has been studied by various investigators.'-l' The method of solubility measuremerit due to Sievertsl is usually preferred when the vapor pressures of the liquid components are sufficiently small, but other techniques such as sampling the equilibrated melt and then analyzing by vacuum fusion have been used quite often. Previously reported data on the solubility of hydrogen and nitrogen in ostensibly pure liquid iron are summarized in Table I; certain of the quoted results were obtained by interpolation of the published data. Agreement between the various investigators is only fair, indicative of the experimental difficulties involved in obtaining gas solubility data. The only report found on the solubility of hydrogen in pure nickel is that of Sieverts.2 The solubility of nitrogen in iron-nickel alloys has received some attention, 10, 11 the results indicating that the solubility decreases with increase in nickel content, becoming zero for pure nickel. There is no published information on the solubility of these gases in either pure cobalt or alloys containing cobalt EXPERIMENTAL PROCEDURE Sieverts' method of solubility measurement was used throughout the investigation. The construction of the melting chamber is somewhat different from A. Optical pyrometer F. Alundum cover B. Vycor chamber G. Alumina crucible C. Furnace coils H. Alundum sand D. Glass water jacket I . Alundum thimble E. Chamber support J . Detachable vycor base sealed with de Khotinsky cement

Jan 1, 1961

By N. A. D. Parlee, N. M. El Tayeb

Fe-V alloys with small percentages of vanadium show no deviations from Sieverts' Law up to P~, = 1 atm in the 1600º to 1750ºC region. At somewhat under 8 pct V and up to at least 20pct V, at 1604" and 1661 °C, nitrogen absorption follows Sieverts' Law at low Pn2 values, but deviates from this law beyond critical values of pn2, due to formation of a nitrzde phase of approximately VN composition. The behavior below these solubility limits can be described at all temperatures by the equations: RAO and parlee1 suggested that the nitrogen absorption curve for liquid iron alloys takes the general form shown in Fig. 1 when an alloy nitride precipitate is formed. They showed that the precipitation of 6 titanium nitride from liquid Fe-Ti alloys follows this general scheme and dealt with the general theory involved. Recently, Evans and Pehlke2 reported their research on the precipitation of aluminum nitride from liquid Fe-A1 alloys. Fountain and Chipman's recent paper3 on the precipitation of boron nitride from solid solution contains a fine example of the analogous behavior which they have been studying in the solid state. Researches on the absorption of nitrogen by liquid Fe-V alloys have been described by various authors.1,4-7 Most of this work has been confined to fairly low vanadium concentrations and rather high temperatures because of difficulties variously described as, formation of surface scums, bridging, and so forth. This behavior and the rough thermo- dynamic calculations made by chipman,8 over eleven years ago, indicated that excessively high vanadium concentrations should not be required for vanadium nitride precipitation. It seemed desirable to look for and study this precipitation in order to fill out the thermodynamically interesting nitrogen absorption data on these alloys. EXPERIMENTAL METHOD The general method used was essentially the same as employed by Rao and parlee,1 in which a Sieverts type of apparatus was used and the precipitation of the nitride detected by the "break-point" in the Sieverts' Law line, and by the visual observation of the formation of the new phase on the surface of the melt. There were, however, a few differences in apparatus and technique as described below. The oil manometer used by Rao and parlee' to measure low partial pressures of nitrogen was not employed. The present authors sought to avoid as much as possible the exposure of the liquid alloy to low total pressures of gas during the 6 to 10 hr long runs because of the heavy iron evaporation-loss errors involved. This was achieved, partly by keeping evacuation times to a minimum with fast pumping but largely by the use of two burettes, one for argon and one for nitrogen, and using them to equilibrate the alloy with mixtures of argon and nitrogen rather than nitrogen alone. Each run involved a careful sequence of operations. After melting, de-

Jan 1, 1963

By J. C. Humbert, J. F. Elliott

The solubility of nitrogen in liquid pure Fe, Cr, and Ni, in liquid Fe-Ni, Fe-Cr, and Ni-Cr alloys and Fe-Cr-Ni alloys, has been measured by the Sieverts' type apparatus between 1500° and 1800°C. Tabulations and graphs of the solubility data and activity coefficients are shown. Heats of solution are reported. Interaction coefficients of the several elements in Fe. Cr, and Ni ave also reported. THE solubility of a gas in a liquid metal is usually measured by either the quenching technique or the so-called Sieverts' method. In the quenching method, 1-3 the melt is equilibrated at the desired temperature and pressure with the gas phase having a known fugacity of the gas being studied. The melt is sampled and the sample is quenched and analyzed chemically for its gas content. In Sieverts' method the melt is contained in a closed chamber. The apparent volume of this chamber, i.e. the "hot volume," is usually determined by introducing a known quantity of an inert gas having very closely the same physical characteristics as does the experimental gas. Alternatively, the experimental gas is used with an inert specimen having the same general physical characteristics as does the experimental melt. Subsequently, the experimental melt is equilibrated with the experimental gas by introducing a known quantity of the gas into the calibrated chamber. The solubility of the gas is obtained from P-V-T relationships. The quenching method suffers from' the limitation that some gas may be gained (as in the case of Cr-Fe alloys) or lost (as in the case of Fe-Ni alloys) during solidification and cooling of the sample. With Sieverts' method sampling and analysis are unnecessary. However, errors can result from the difficulty of determining accurately the "hot volume,"

Jan 1, 1961

By D. C. Hilty, W. Crafts

The solubility of oxygen in iron containing aluminum has been determined at 1550°, 1600°, and 1650°C and found to be much higher than predicted from theoretical considerations, possibly due to equilibria with an iron-aluminum spinel phase rather than pure AI,O.. The presence of manganese greatly increased the deoxidizing power of aluminum. DEOXIDATION and inclusion formation in steel have proved to be elusive phenomena that are difficult to control in spite of much effort to understand and evaluate the reactions. Study of the problem indicated that more accurate data on the solubility of oxygen in iron containing deoxidizers were essential to further progress, and an empirical determination of oxygen solubilities has been initiated at the Union Carbide and Carbon Research Laboratories, Inc. The investigation has included the effects of aluminum, silicon, manganese, and combinations of these elements at 1550°, 1600°, and 1650°C. The equipment and experimental procedure as well as the results of a study of the effects of aluminum are described below. In general, it was found that the solubility of oxygen in iron containing aluminum is much higher than predicted, possibly because of the formation of complex nonmetallic phases, and that manganese greatly increases the deoxidizing power of aluminum. The generally accepted deoxidation curves for 1600°C are summarized in fig. 1, from "Basic Open Hearth Steelmaking"'. These curves are assumed to represent the solubility of oxygen in the presence of deoxidizers and should indicate the limits of mis-cibility gaps in the phase diagrams of the systems that control the formation and character of non-metallic inclusions as described by Benedicks and Lofquist'. They were derived mainly by application of the methods of thermodynamics to the available experimental observations, and by calculations based on the thermal constants of the pure substances when experimental data were lacking. Among the more notable researches contributing to the development of knowledge of oxygen solubilities are those of Korber and Oelsen8, 4, C. H. Herty, Jr. and associates5,6, Krings and Schackmann7, Went-rup and Hieber8 Schenck and Briiggeman9, Vacher and Hamilton'" and Chipman and co-authors 1,11,12,13 Practically, the deoxidation curves are of limited value in predicting oxygen content and rationalizing deoxidation practices. The reasons for this inadequacy appear to be error from inaccurate data, oversimplifying assumptions, interacting effects of combined deoxidizers, and possibly unknown extra-equilibrium and side reactions. Although inclusion formation is a very complex reaction it must be re-

Jan 1, 1951

By D. C. Hilty, W. Crafts

J. Chipman—It has been my privilege to discuss this work with the authors on several occasions and to observe at first hand the experimental methods employed. I wish, therefore, to emphasize certain points which they have mentioned only briefly with regard to the experimental techniques. The rotating induction furnace as here employed interposes liquid metal between slag and refractory thus preventing the two nonmetallic parts of the system from reaching equilibrium with one another. It is therefore impossible for the metallic phase to be completely in equilibrium with both the slag and the crucible. The metal also acts as a partially permeable membrane allowing certain components, including oxygen, to diffuse from slag to crucible. This transfer results in building up on the face of the crucible a layer of material whose composition is in part dependent on that of the bath. Reactions between the layer and the solid refractory are slow, as evidenced by the rather good life of the crucible. Hence it seems probable that the layer is more nearly in equilibrium with the metal than with the underlying crucible material and that, once it is established under a bath of a given composition, its further reactions with that bath are slow. Additions to slag or bath may be followed by changes in the layer; and time must be allowed for virtual completion of such changes, before it can be assumed that slag and metal are in equilibrium. We may judge from the results reported that, in general, this was the case and that the data represent at least quite close approximations to slag-metal equilibrium. Data on deoxidation and on oxygen solubility are no better than the analytical methods employed. The vacuum fusion method as used by the authors seems entirely adequate for the samples analyzed. I have had frequent occasion to compare results with their laboratory, always with very satisfactory agreement. The determination of aluminum at very low concentrations is perhaps an even more difficult procedure. Here also the colorimetric method used has been worked out with great care and is undoubtedly the most dependable method available. The discrepancy between observed and calculated deoxidation or solubility lines is not to be explained as the result of experimental errors, either in the sampling or analysis of the metal. Nor is it to be blamed upon inaccuracies in the several kinds of indirect data upon which the calculated results were based. It is true that both the observed and the calculated lines admit of some uncertainty as to their exact locations, but the uncertainties are small compared to the wide gap which separates the two lines. The authors have pointed out the real cause of the discrepancy. In all of their experiments the solid phase was not Al2O3 but a mixed oxide containing iron and aluminum. This suggests an extension of the calculated values to include equilibrium with the spinel FeO . A12O3. The free energies of FeO and A12O3 are known, that of the spinel is not. However, it cannot differ greatly from that of its component oxides for even in the more stable spinel, chromite, the free energy of formation from the oxides is less than 10,000 cal. For purposes of calculation we shall call this free energy X and solve for values of X lying between zero and 10,000 cal. The other data required are taken from the forthcoming revision of "Basic Open Hearth Steelmaking" and are given in the following equations in which underlined symbols indicate elements dissolved in liquid steel and the standard concentrations are 1 pct. ?F° at 1600°C, cal ?LA = 2 Al + 3 O; + 107,200 FeO = Fe + 0; + 5,460 FeO + A12O3 = Fe + 2A1 + 4 0; + 112,660 — X The corresponding equilibrium concentrations are shown in fig. 21. The line marked A12O3 corresponds to the first equation, those marked FeO . AL2O3 correspond to the last, with X = 0, 5000 and 10,000 cal, respectively. The two upper lines represent the data of Hilty and Crafts and of Wentrup and Hieber. The points are the observations of Hilty and Crafts in the presence of 0.50 pct Mn.

Jan 1, 1951

By Maxwell Gensamer

Jan 1, 1960

By E. T. Turkdogan

In this theoretical paper, a transport-reaction mechanism is suggested for the enhancement of the rate of vaporization of metals, or other materials, brought about by the process of convection and condensation. Based on theoretical reasoning it is predicted that, when there is a temperature gradient surrounding the heated object, a slight increase in the rate of vaporization brought about by natural convection is enhanced further as a result of condensation of the vapor close to the surface of the object. In order to derive the effective vapor-concentration profile, consideration is given to the super saturation of the vapor necessary for the homogeneous nucleation of the condensed phase from the vapor. For the formulation of the rate equation based on this mechanism, adequate information should be available on the transport properties of gases and vapors at elevated temperatures and the method of calculating nucleation pressures of the vapor. The methods of deriving such data are discussed in the paper and a rate equation is calculated for the vaporization of iron in helium for various temperature gradients in the boundary layer. Considerations are also given to the effect of oxygen on rates of vaporization of metals under isother ma1 and nonisotherma1 conditions. THE study of the methods of enhancement or retardation of basically transport-controlled vaporization reactions is of theoretical interest with possible practical implications. There are several ways of bringing about such effects. For example, Turk-dogan, Grieveson, and Darken1 demonstrated that the rates of vaporization of metals under isothermal conditions were increased by several orders of magnitude, up to the maximum rate attainable in vacuo, by introducing some reacting gas into the inert atmosphere surrounding the metal. Such an effect is brought about by the interaction of the counter-diffusing reacting gas and metal vapor in close proximity of the metal-gas interface. Another case which is often experienced in practice is that of vaporization affected by natural convection. Although several theoretical and experimental studies of this problem have already been made, no detailed consideration has been given to the possible effects of condensation of the vapor in the boundary layer on vaporization rates, which constitutes the subject matter of this paper. BASIC CONCEPT OF ENHANCED DIFFUSION-LIMITED VAPORIZATION When a heated object, for example a metal sphere, is submerged in a fluid medium, heat is transferred from the surface of the object to its surroundings by four simultaneously occurring transfer processes: i) free-molecular conduction at the gas-solid interface over the distance equal to the mean free path of the gas, ii) conduction and convection through the fluid-dynamic boundary layer, iii) latent heat of mass transferred, and it!) radiation. The free-molecular conduction becomes pronounced only when the total pressure in the system is very low, e.g., below 1 mm Hg. Therefore, this term may be neglected for ordinary pressures. At low mass-transfer rates, due to vaporization of the object, the contribution of process iii) to the heat transfer can also be neglected. Finally, since the temperature profile is not affected by radiation, the latter need not be considered. The natural convection is brought about by gravitational body forces arising from a decrease in the

Jan 1, 1964

By K. C. Mills, E. T. Turkdogan

The results on the rates of vaporization of Fe-Ni alloys, levitated by an electromagnetic field in a stagnant atmosphere of helium, are shown to be in close agreement with those predicted theoretically. AS shown in Part I of this series of papers, the rates of vaporization of metals enhanced by convection currents are increased further by the process of condensation of metal vapor when there is a steep temperature gradient in the boundary layer. At the time this theoretical work was completed one of the authors (K. C. Mills) had already carried out some experimental work on the rates of vaporization of molten Fe-Ni alloys. The experimental work was done under conditions which make it possible to compare the experimental rate data with those predicted on theoretical grounds. EXPERIMENTAL The object of the experiments was to evaluate the activities in a number of binary metal systems. The details of the experimental technique are given in another paper by Mills, Kinoshita, and Grieveson,2 and, for the present purpose, a brief mention of the relevant features of the experimental method will be adequate. Using an induction coil, the metal weighing about 1 to 1.5 g was levitated by the electromagnetic field in a stagnant atmosphere of pure helium. The helium was freed from oxygen and water vapor in the usual manner, and its pressure in the vaporization chamber was maintained at 1 atm through a bleeder device. The vaporization chamber consisted of a pyrex tube, 2.8 cm diam, with a side arm connected to the helium bleeder. The bottom of the tube, shaped conical, was surrounded by the induction coil, and the top was sealed with an optical flat for the purpose of measuring the melt temperature with a two-color optical pyrometer. By suitable adjustment of the high-frequency power input, the metal was brought to the desired temperature in about 30 sec of levitation. After a specified vaporization time, e.g., 3 to 4 min, the alloy was quenched by switching off the power. The amount of metal vaporized was determined from the difference between the initial and final weights of the sample. During the vaporization time, temperature fluctuations of about ±10°C were observed. COMPARISON OF EXPERIMENTAL DATA WITH THEORETICAL VALUES The experimental results are given in Table I. As already mentioned, the attainment of the vaporization temperature took about 30 sec from the moment of levitation. Therefore, the times recorded in Table I are 30 sec less than the total time; this is considered to be a reasonable estimate of actual vaporization times.

Jan 1, 1964

By Philip D. Anderson, Ralph Hultgren

Heat contents of extremely pure iron were measured over the range 300"to 1433"K, using a diphenyl ether calorimeter. Results from three samples containing widely differing impurities agreed with one another and with Previously reported results at higher temperatures (1184 ° to 1809°K) by Olette and Ferrier. From these data a table of heat contents of iron has been Prepared which is believed to be more accurate than those previously available. CP values have been derived which are consistent with these heat contents, with the best experimental Cp data, and with the thermodynamic conditions of equilibrium between bcc and fcc iron. The opinion is expressed that low-temperature extrapolations of presently known Cp values for y-Fe are not reliable. It would seem that the thermodynamic properties of iron, which is by far our most important metal, should have been well established long ago. This is not the case, however. As discussed by Olette and Ferrier,' there is objection to every earlier heat content measurement. While the best true Cp determinations agree well at temperatures below the Curie point, there is wide divergence at higher temperatures. Several investigators have examined available data and attempted to calculate thermodynamic functions for iron that are consistent with the two equilibrium temperatures of bcc and fcc iron. The two primary efforts were those of Austin' in 1930 and Darken and smith3 in 1948. The recommended values differ considerably; integration of Austin's Cp values leads to a heat content at 1100°K which is 300 cal per g-atom higher than the value recommended by Darken and Smith. The compilation of Fisher4 in 1949 was based on the selection of Austin. In 1956, Weiss and Tauer obtained yet another set of values by resolving Cp values into components due to dilation, lattice vibration, electronic excitation, and magnetism. The magnitude of contribution by each component and its dependence on temperature was estimated by semiempirical means. Their values are not self-consistent in that they do not form smooth curves when plotted vs temperature; moreover, their calculations cannot easily be repeated since they do not give the values of some of the parameters used. Clearly, experimental values for iron were in a most unsatisfactory state. The presently described measurements of the heat content of iron were therefore undertaken, covering temperatures as high as 1433°K. While the work was in progress, the high-temperature (1193" to 1789"K) heat content measurements of Olette and Ferrier' were published; in the region of temperature overlap the present results agree with Olette and Ferrier well within experimental accuracy. It is believed that the present results, combined with those of Olette and Ferrier, provide for the first time a reliable set of heat contents of iron from room temperature to the melting point. From these data, guided by available Cp measurements, it proved possible to derive Cp, entropy, and free energy function values for @-iron from room temperature to the melting point, and for y- iron in the temperature region of its stability. Exhaustive study led to the conclusion that extrapolations of y-iron functions to room temperature were not reliable enough to be useful; hence these have been omitted from the tables. EXPERIMENTAL Materials. Three samples of extremely high purity iron from different sources, containing widely different impurities, were measured. The first of these, designated "Chipman", was kindly supplied by Dr. K. K. Kelley of the U. S. Bureau of Mines from a lot which was made many years ago by Dr. John Chipman of the Massachusetts Institute of Technology. The second, designated6'Teddington", was supplied by the National Physical Laboratory, Teddington, England, from a lot zone-refined by them. The third sample, designated "Irsid", was supplied by the Institute de Recherches de la

Jan 1, 1962

By D. J. Carney, J. Chipman, N. J. Grant

SINCE the beginning of this century it has been known that hydrogen contributes to the porosity of steel and that it is harmful to its mechanical properties. The evidence for this has been largely qualitative. Steel to which hydrogen was purposely added. in sufficient .amounts was shown to be either porous or brittle or both, whereas similar steel of low hydrogen content was shown to be free of porosity and to possess normal physical properties. There have been a considerable number of qualitative experiments of this type. Also, early in this century, a few attempts were made to measure the amount of hydrogen normally dissolved in commercial steels. This was usually done by placing the sample under an inverted liquid column such as mercury and collecting the evolved gas. These attempts, while not successful in measuring actual amounts of dissolved hydrogen gas, were able to prove that this gas will diffuse out of steel at room temperature, and that the amount of hydrogen dissolved is normally very small. On the basis of such qualitative evidence, hydrogen has been and still is blamed for a great number of the troubles encountered in the steel industry. In recent years, partial solutions for many steel-working problems have been obtained. These have led to increased interest in accurate quantitative work on hydrogen in steel, with the expectation that the results might possibly answer a few of the remaining unsolved problems. Commercially, two of the obvious questions which are in need of an answer are: (1) what are the most important sources of hydrogen, and (2) what quantity of hydrogen can be tolerated in various steels? There are many other unanswered questions. To begin to find the answers it seemed logical to start at the beginning of steel production with the liquid metal. Further, it seemed almost imperative to solve first the problems of analysis and sampling of the metal for hydrogen. Once these problems have been solved, it would be possible to answer more of the important commercial problems mentioned above. As a consequence, it was decided to design an analytical apparatus and, upon satisfactory completion of this, to develop an accurate method of sampling liquid metal for hydrogen.

Jan 1, 1951

By D. J. Carney, J. Chipman, N. J. Grant

G. A. Moore—The tin-fusion method has been a very favorable possibility for many years. The authors apparently have settled the question that delayed the method for a long time by showing that no hydrogen is absorbed in the tin. This, of course, is very important. I want to make a few remarks concerning the absolute accuracy of analysis, which must be the final basis for deciding among the various methods. From the figures in the paper, there seems to be some remaining slight discrepancy on the actual amount of hydrogen present in various samples which may be presumed essentially identical. (This is of the order of the precision of individual analyses but appears in averaged results.) From the analyst's viewpoint, the tally of hydrogen content can be regarded as occurring in three portions. First is a large portion which comes off easily and automatically during sample storage and later on heating in the apparatus. This is fairly easily analyzed. Second is an item which may be either positive or negative in the tally sheet. In warm or hot evolution, this is a portion which, in practice, can never be re-

Jan 1, 1951

By W. O. Philbrook. K M Goldman, M. M. Helzel

RADIOACTIVE calcium has been used to learn whether calcium can be detected in iron saturated with carbon after it has been melted under CaO- A12O3- SiO2 slags similar to those used in the iron blast furnace. It was hoped that the radioactive tracer technique might make possible a general study of steelmaking reactions in which calcium or calcium oxide are involved. No calcium could be found in the metal under conditions which were favorable for the reduction of calcium, and it has been concluded that the calcium content of the iron was less than 6 x 10 - pct. Some of the problems encountered have been instructive with regard to pitfalls and limitations of tracer methods. Calcium oxide occurs in almost all iron- and steelmaking slags, and it is essential to the success of all commercial basic steelmaking processes. Calcium alloys are sometimes used in the deoxidation of steel and for the innoculation of gray iron. The element calcium is therefore almost as ubiquitous in the steel industry as are carbon and oxygen, but calcium has been thought to be completely immiscible with iron in both the liquid and the solid states.' It does not seem entirely unreasonable to Suppose, however, that some low concentration of calcium might exist in liquid iron under a basic slag with other conditions being favorable, just as silicon and other elements can be introduced into iron by reduction of their oxides from slags under appropriate circumstances. The radioactive tracer technique offered a more sensitive method than chemical analysis of testing this supposition. The reasons for interest in this investigation were strong enough to justify a recognized risk of failure. On the theoretical side, information on the distribution of calcium between liquid iron and a slag and the rate at which the equilibrium distribution is approached would contribute strongly to the general theory of slag-metal interface reactions. Furthermore, any evidence on the presence of calcium in liquid iron might provide a vital clue to the mechanism of the desulphurization of iron by slags. All of the reactions which have been proposed to explain desulphurization postulate that the sulphur ultimately becomes fixed in the slag as calcium sulphide, but the mechanism by which sulphur

Jan 1, 1951

By T. L. Joseph, G. Bitsianes

THE layered structure of partially reduced iron ore was described in a previous paper.' Reduction by hydrogen was found to take place at well-defined interfaces between layers of the solid phases. In the present investigation, a detailed study was made of the wiistite phase that had formed during the partial reduction of a cylindrical compact of chemically pure hematite. An unusually wide band of wiistite permitted a rather detailed study of this phase. The specimen was made from Baker's C.P. hematite in the form of a cylinder 1.5 cm in diameter and 1.8 cm long. A dense ore structure with about 6 pct porosity was attained by heating the specimen in air at 1100°C for 3 hr. To confine reduction to the top surface, a ceramic coating was applied to the bottom and sides of the cylindrical compact. The specimen was then partially reduced in hydrogen at 850°C and subjected to a coordinated sequence of macro-, micro-, and X-ray examinations. A section of the partially reduced cylinder is shown in the macrograph, Fig. 1. Four layers consisting of metallic iron, wustite, magnetite, and unreduced hematite are clearly shown. The effort to force reduction to proceed downward in topochemi-cal fashion was only partly successful, as some reduction occurred along one side and bottom of the cylinder. A rather wide layer of dark wustite phase had formed, however, and permitted sampling for X-ray studies as indicated. To supplement previous work and to study the wustite layer in more detail, ten separate layers were removed for X-ray examination. Broad and diffuse patterns were obtained with the as-filed powders, especially with those of iron and wiistite, and the condition indicated a cold-working and variable composition effect within the respective layers. This condition was corrected by annealing the entire series of powders at an appropriate temperature. For the annealing treatment, the ten powder samples were wrapped in silver foil, sealed under vacuum in small quartz tubes, and heated at 750°C for 16 hr. The specimens were then drastically quenched in cold water to preserve the annealed condition. These annealed specimens were X-rayed in turn and the compiled patterns are shown in Fig. 2. The standard patterns for iron and its oxides have been interjected at appropriate positions for purposes of comparison and phase identification. All of the patterns obtained were clearcut and concise so that positive identifications could be made for all of the phases. The outermost layers A, B, and C were composed almost entirely of iron with a small amount of wiistite being detectable at the X-ray limit of phase detection. Layer D from the iron-wustite interface showed both of these phases. The next four layers E, F, G, and H were all in the dark phase band which had been tentatively identified as wustite by the macroexamination, Fig. 1. The diffraction data with their single-phase patterns of wiistite for these layers checked the visual evidence. Continuing the X-ray analyses after layer H, the macrograph (Fig. 1) shows that layer I came largely from the magnetite zone but included some fringes of the wiistite-magnetite interface. The diffraction pattern for the sample confirmed this observation. Layer J came from the unreduced core of the specimen and its diffraction pattern indicated a preponderance of hematite phase. The reduction behavior of synthetic compacts has thus been found to be similar to natural dense iron ore. The previous results were supplemented with measurements of the diffraction films and calculations of the respective unit parameters. These X-ray data are summarized in Table I and offer some interesting correlations as to the compositions of the various phases undergoing reduction. The iron layers that were analyzed gave lattice parameters close to that of pure iron at 2.8664A. Evidently this iron was present in layers A through D as a pure phase with little or no oxygen dissolved in its lattice. With the wiistite layers an entirely different situation prevailed in that there was a definite and

Jan 1, 1955

By W. O. Philbrook, H. E. Burner, F. S. Manning

The equation of continuity for the hydrogen reduction of hematite in a fixed bed of closely-sized particles is solved assuming a flat velocity profile, negligible temperature gradients, md negligible axial diffusion. A kinetic expression from the literature is used which assumes the reduction process is controlled at the oxide-metal interface. The integral fractional conversion is computed, and the importance of particle diameter, flow mte, temperature, bulk axial diffusion, and inter- and intra-particle mass trarnsfer is predicted. Comparison with experimental data suggests one or more additional undefined variable(s) is significant. Equipment modifications are suggested for fidture experimentcll work. WITH the increasing desire to "design" the ore feed of a blast furnace, it has become necessary to define more quantitatively the process variables and to evaluate the extent of their control upon the reduction process. The bulk of the work reported in the literature has centered about the reduction of single particles; however, the blast furnace process more closely resembles reduction of a fixed bed than that of single particles. To simplify this analysis, the isothermal reduction by hydrogen of a natural hematite in a fixed bed of closely-sized particles is examined. With appropriate modifications in the kinetic and flow rate expressions, the approach employed should be extensible to mixtures of carbon monoxide, hydrogen, and inert nitrogen, and to adi-abatic conditions, thus approaching the blast furnace process more closely. The fixed bed variables which are investigated in this study are particle diameter, flow rate, temperature, and bulk axial diffusion, as well as inter-and intra-particle mass transfer. Of particular interest is the effect of particle size upon fractional conversion for a bed operating under constant pressure drop. The constant pressure drop concept bears a close resemblance to the blast furnace process, where regions of larger particles may provide a greater permeability to divert most of the reducing gas flow from the regions of smaller ore particles. Under such conditions one would expect qualitatively that, for sufficiently small particle sizes where the flow rate is small and the total surface area is large, the reduction rate would be limited by the gas flow rate. Initially the gas entering the bed reacts very rapidly and the composition approaches the equilibrium conversion value a short distance from the reactor inlet. This concentration "wave-front" then moves up the bed as the flow of reducing gas is continued, leaving in its wake an ever increasing layer of reduced particles. Providing that the reducing gas leaves the bed at equilibrium concentrations, conversion is expected to increase with an increase in flow rate, and hence with an increase in particle diemater. Conversely, for sufficiently large particles the flow rate will be high but the surface area available for reaction will limit the reduction rate. Since the total surface area decreases with an increase in particle size, conversion, in this case, is expected to decrease as the particle diameter is increased. It is clear then that between these two extremes an optimum particle diameter must exist. THEORETICAL DEVELOPMENT Above the temperature where wiistite is stable (about 560°C) the reduction of hematite proceeds through the series Fe2O3/Fe3O4/FeO/Fe. On the basis of microstructural studies and earlier work, Edström1 has postulated a mechanism for the reduction of an ideal hematite lattice: 1) Iron phase formation at the boundary between wiistite, iron, and gas (for sufficiently porous iron). 2) Diffusion of iron across a wustite layer. 3) Phase boundary reaction of Fe3O4 to FeO. 4) Diffusion across a dense magnetite layer. 5) Phase-boundary reaction of Fe2O3 to Fe3O4. According to the mechanism postulated, gaseous reaction product has to be removed only at the boundaries between wüstite and iron or gas, the only possible exception being enveloped Fe3O4 specks. On this basis McKewan2,3 has proposed that one may consider the hematite reduction process as a simple two-phase system of oxide/metal. If, for FeO and Fe3O4 layers of negligible thickness, the hypothesis is made that the rate of formation of a

Jan 1, 1963