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By N. A. Gokcen, J. Chipman

Aluminum and oxygen dissolved in liquid iron were brought into equilibrium with pure alumina crucibles and atmospheres of known H2O and H2 contents to study the reactions: 1—Al2O3(s) = 2 Al + 3 0; 2—Al2o3(s) + 3H2(g) = 2Al+ 3H2o(g); and 3—H2(9) +O = H2O(g). Aluminum strongly reduces the activity coefficient of oxygen and similarly oxygen reduces that of aluminum. Values of the product [% All" • [% O]3 are much smaller than those found in previous experimental studies and are of the order of magnitude of the calculated values. ALUMINUM is the strongest deoxidizer commonly A used in steelmaking, but the extent to which it removes dissolved oxygen has been debatable. The relationship between aluminum and oxygen has not been determined reliably not only on account of the usual experimental difficulties at high temperatures but also because of uncertainties in the analyses of very small concentrations of oxygen and aluminum. The earliest experimental attempt of Herty and coworkers' was followed by a more systematic study of Wentrup and Hieber.' These authors added aluminum to liquid iron of high oxygen content in an induction furnace and considered that 10 min was sufficient to remove the deoxidation products from the melt. Parts of the melts thus obtained were poured into a copper mold and analyzed for total aluminum and oxygen (soluble plus insoluble forms), assuming that the insoluble parts were in solution at the temperatures from which samples were taken. It is conceivable that the furnace atmosphere in their experiments, consisting of mainly air at 20 mm Hg pressure, was a serious source of continuous oxidation and therefore that their oxygen concentrations were correspondingly high. Scattering of their data was explained to be well within the maximum inaccuracy of 10°C in the temperature measurements and errors of ±0.002 pct each in the oxygen and total aluminum analyses. Maximum and minimum deoxidation values, i.e., values of the product [% All' . [% O] differed by factors of 10 to 15; mean values of 9x10-11 and 7.5x10-9 ere reported at 1600" and 1700°C, respectively. Hilty and Craftsv determined the solubility of oxygen in liquid iron containing aluminum, using a rotating induction furnace. Pure alumina crucibles used in their experiments contained the liquid iron which in turn acted as a container for slags of varying compositions consisting mainly of Al2O3, Fe2O3, and FeO. The furnace was continuously flushed with argon, and additions of aluminum and Fe2O3 were made in the course of each experimental heat. The inner surfaces of their alumina crucibles were covered with a substance other than pure Al2O3, containing both iron oxide and alumina. Although frequent slag additions can change the composition of slag in the liquid iron cup formed by rotation, the inner surface of the crucible must depend upon the transfer of oxygen or aluminum through the liquid iron for any adjustment in composition. It is not clear that their metal was in equilibrium with the crucible wall, but it is clear that it was not in equilibrium with Al2O3. Their deoxidation product, [% A].]" • [% O]3, varied by a factor of more than 50; the average values of 2.8x10- and 1.0x10-7 were selected for temperatures of 1600" and 1700°C, respectively. Aside from the experimental determinations, attempts have been made to calculate the deoxidation constant for aluminum indirectly from thermody-namic data. Schenck4 combined the thermodynamic data for Al2O3 and dissolved oxygen in liquid iron by assuming an ideal solution. His calculated values are 2.0x10-15 and 3.2x10-13 at 1600" and 1700°C, respectively. Later, Chipman5 attempted to correct for the deviation from ideality and derived an expression which led to deoxidation values of 2.0x10-14 and 1.1x10-12 at 1600" and 1700°C, respectively. The errors in these treatments originate mainly from inaccuracies of thermal data and uncertainties regarding the activity coefficients of dissolved oxygen and aluminum. The purpose of this investigation was to study the equilibria represented in the following reactions in the presence of pure alumina: Al2O3(s) = 2Al + 3O K = aAl2.ao3 [1] Al2O3(s) + 3H2(g) = 2Al + 3H2O(g) H2O K2 = aAl2(H2O/H2 ) [2] H2(g) +O = H2O(g) K3 = 1/ao (H2) [3] The experimental method consisted of melting pure electrolytic iron, usually with an initial charge of aluminum, in pure dense alumina crucibles under a controlled atmosphere of H,O and H2 and holding

Jan 1, 1954

By W. O. Philbrook

An engineering analysis indicates that the coke rate in present blast-furnace practice is set not by chemical or thermal needs but to give adequate charge permeability for economical driving rates. An equation showing interrelations among pressure drop, gas flow, and charge characteristics has been derived. Flooding conditions and the location of the fusion zone are discussed. Maximum ore size is probably limited by chemical re-ducibility rather than by heat transfer. THE intention of this paper is to show that the ].imitations on the production rate and coke requirement of the iron blast furnace are not primarily chemical or thermal in nature but are related to characteristics of the burden and operation that govern gas flow, heat transfer, and stock movement. A semiquantitative analysis will be developed in terms of standard engineering principles to give a useful picture of the relative importance of physical and mechanical factors in contrast with the chemical features of the process that are more commonly emphasized. Most of the details of calculation have been omitted in the interest of brevity and to avoid submerging the rnain points in a sea of arithmetic. Numerical values have been arrived at by objective methods from reported operating data or by reasonable estimates of material properties where exact data are lacking and then tested to see how well they fit practice, rather than by working backward to find what assumptions are needed to give the desired answers. The analysis is oversimplified in many ways because exact engineering relations have not yet been studied for bed distributions as complex as are known to exist in the blast-furnace stock column. One objective of this paper is to show that the blast furnace, in spite of its complexity, can be at- tacked by engineering methods in the hope that this viewpoint will stimulate the kind of research needed for a more exact treatment. The basic ideas and many of the conclusions presented are qualitatively well known. A careful literature survey to credit the source of all observations not original to the author would indeed be voluminous, and such has not been attempted. T. L. Joseph's Howe Memorial Lecture' gives an excellent background of what is known about the internal workings of a blast furnace. Other important reference works or sources of specific information will be noted. It is hoped that the present paper will contribute something new, in method of attack and interpretation, that will aid in a clearer understanding of how to operate the blast furnace to best advantage. Factors Limiting Production and Coke Rates The rate of combustion of coke in a blast furnace, as in any fuel bed, is exactly proportional to the rate at which air is supplied. It is axiomatic, then, that the production rate of a furnace is limited by the rate at which it will take wind, i.e., burn coke, and the amount of coke that must be burned at the tuyeres to make a ton of iron of suitable composition. These two possible limiting factors will be considered briefly in the order mentioned. One common restriction on wind rate is flue-dust production. Since the volume of top gas is nearly proportional to the blast volume (by a factor of about 1.35 on a dry basis), an increased wind rate causes a correspondingly increased linear velocity of top gas in the throat of the furnace. The higher

Jan 1, 1955

By E. C. Nelson

An equation is derived for calculating approximately the solubility of nitrogen in an alloy steel over a temperature range from 1200" to 1900°C using data on the effects of alloys on the activity coefficient of nitrogen in iron at 1600°C. Calculated values are compared with experimental data. STUDIES involving the solubility of nitrogen in complex iron alloys have been aided by a system devised by Lanenberg for calculating the solubility of nitrogen in ternary and higher alloys of iron at 1600C using available data on the activity coefficient of nitrogen in binary alloys. Calculated nitrogen solubilities agree well with experimental determinations on complex alloys,' and the calculation procedure is useful when experimental data on specific alloys are not required. A method for extending calculations of nitrogen solubilities in alloy steels to temperatures other than 1600°C would be useful because of the paucity of experimental data in this area. Assumptions which must be made to permit this calculation introduce an element of approximation; however, the calculation is useful in cases where a large number of alloys and temperatures are under consideration, and the precision of experimental measurements is not required. The activity coefficient can be freed from the isothermal restriction of Langenberg's calculation if it is assumed that the solution is "regular". This is a reasonably good assumption for solutions of nitrogen in iron alloys, because usually they are dilute and the heat of solution is relatively small. The presence of large amounts of certain alloying elements would make this assumption less tenable.3 One of the properties of a regular solution is: when "f" is the activity coefficient of a solute and "T" is the temperature in OK. If the activity coefficients at temperatures T and T2 are denoted by subscripts 1 and 2 respectively: The activity coefficient of nitrogen in a complex alloy then can be calculated at any temperature from the sum of the effects of the other solutes on the activity coefficient of nitrogen at 1600°C. It will be convenient to incorporate this expression into an equation which will give directly the logarithm of the solubility of nitrogen at any temperature in the presence of alloys. Two constants, the solubility of nitrogen in pure iron at 1600 "C and the partial molar heat of solution of nitrogen in iron are required. The heat of solution value of 1400 cal at 1600 °C quoted by Kubaschewski and vans will be used. The accuracy of the calculation will suffer if the heat of solution should change materially with temperature. In the absence of experimental data on the temperature dependence of this quantity, it will be expedient to restrict the application of the calcula-

Jan 1, 1963

By G. W. Healy, W. D. Forgeng, N. R. Griffing

The liquidus surface of the C-Cr-Fe system to 1900°C has been mapped from carbon solubility and freezing point measurements, metallographic observations, and published data. In the graphite field, the surface drops precipitously to meet a slope descending from the Cr3C2-C join through the mixed carbide fields to a meandering eutectic valley; this flows from the Cr-C to the Fe-C edge. On the low-cavbon side of the valley, the surface rises to the chromium corner. 1 HE purpose of this inquiry was to gain a more complete knowledge of the C-Cr-Fe liquidus surface. This required an extensive study of carbon and chromium-rich alloys which, in the past, have received the least attention. Sanbongi el al.1 measured the solubility of carbon in liquid alloys containing up to 25 wt pct Cr at temperatures of 1460" and 1545°C and found that it increased with chromium content and temperature. Lucas and wentrup2 also made solubility experiments in graphite crucibles, but at higher chromium contents in the range of 38 to 80 pct and at temperatures of 1550" to 1700°C; however, their experiments were relatively few, and the effect of temperature was not consistent. The present investigation included compsitions ranging from 0 to 94 pct Cr and 1.4 to 11.7 pct C at temperatures up to 1800°C. Saturation experiments in graphite crucibles, thermal analyses during freezing, and metallographic and X-ray diffraction studies were employed to obtain desired information which, together with published data from other investigations about the binary edges and the ternary system at lower carbon levels, made possible the construction of a comprehensive C-Cr-Fe liquidus surface. C-CR-FE LIQUIDUS SURFACE The derived ternary liquidus surface is shown in Fig. 1 where the solid curves are liquidus isotherms. The dashed curves and the binary edges are the liquidus field boundaries of the primary crystals, the arrows along these boundaries indicating their direction with decreasing temperature. Each intersection of three internal boundaries is the composition of liquid involved in four-phase isothermal equilibrium with the three primary crystals whose liquidus fields touch there. It may be observed that a total of six four-phase equilibria occur at melt temperatures. The general topography of the liquidus surface consists of a eutectic valley sloping down from the Cr-C edge at 3.2 pct C to the Fe-C edge at 4.25 pct C. The liquidus surface rises in two directions from the valley, one hillside terminating at the Cr-Fe edge while the opposing hillside rises toward the carbon corner out beyond the top edge of Fig. 1. Both hillsides are interrupted by intersections of surfaces or joints representing the liquid colmpositions of various three-phase equilibria. Seven primary crystals occur, namely a(bcc), ?(fcc), graphite, (Fe, Cr)3C capable of dissolving as much as 15 pct Cr, and three different chromium carbides in which iron is partially soluble by substitution for chromium. The composition ranges of the primary l~hases at melt temperatures are shown

Jan 1, 1962

By G. W. Healy

Activities of oxides in the ternary FeO-MnO-SiO system are calculated from data on the binaries, using the Gibbs -Schuhmann method. These activity data are used, together with thermodynamic relations, to calculate the contents of oxygen, silicon, and manganese in liquid iron, and the composition of the corresponding oxide phases in equilibrium with it. Excellent agreement was found between calculated and experimental metal compositions, indicating that thermodynamic methods, such as those presented, can supply useful data on slag-metal equilibria, and are therefore capable of wider application. When molten steel containing oxygen is treated with a deoxidizer, the product of the reaction is composed of the oxides of the deoxidizing elements together with more or less iron oxide. This assemblage of oxides is presumably very close to equilibrium with the melt since it is formed directly from elements dissolved in it. Therefore, it is likely that metal analyses corresponding to a given oxide phase composition are calculable with considerable precision where sufficient information is available on activities in both phases. The present study was made to test this hypothesis in the case of deoxidation by silicon and manganese. Here experimental data on the relationship among oxygen, silicon, and manganese in the metal phase are available, as are activity data for the MnO-SiO2, FeO-SiO2, and FeO-MnO binary systems. A further objective was to demonstrate in a specific example how gaps in the data may be filled by judicious interpolation, and how the Gibbs-Schuhmann method is applied to obtain activities in ternary systems. The rigorous derivation of the latter, requiring considerable facility in handling partial differential equations, tends to mask the real simplicity of the method, and repel the very engineers and experimenters who would benefit the most from its use. I) GENERAL PROCEDURE Deoxidation of steel with silicon and manganese results in the formation of two phases, metal and oxide. The number of components is four—Fe, Mn, Si, and 0. The phase rule then gives the number of degrees of freedom: If temperature and pressure are fixed, 2 deg of freedom remain. Consequently, it suffices to fix the concentration of two of the components of the system for all the concentrations to be determined and, at least in principle, calculable. The practical problem is then to discover a straightforward method of calculation with a minimum of trial and error solutions. The type of reactions to be dealt with are like the following: Si (in steel) + 2 O(in steel) = SiO2(in oxide phase) The standard free energy of this reaction is readily obtained from the literature, so that the equilibrium constant can be calculated by the expression: Since the metallurgist is concerned with percentages rather than activities, a real solution requires information that will permit activities to be converted to concentrations. This information is fairly adequate for the elements dissolved in molten steel, but is not available for the FeO-MnO-SiO2 oxide system. Therefore, the first step in this study was to find the relation between activity and concentration for the three oxides making up the system. The next step was the calculation of slag and metal compositions that are in equilibrium with one another. As shown by the phase rule, it is sufficient to assume the values of two composition variables in order to calculate the rest. But which two are picked makes a vast difference in how difficult the calculation turns out to be, so that it is necessary to make preliminary trial of several routes to find the easiest one. A convenient method is to begin with the slag, and to pick FeO concentration and that of one of the other oxides. Starting with the relation between oxygen dissolved in the liquid steel and FeO in the slag permits a good first estimate to be made of the oxygen content of the steel in equilibrium with FeO, because the iron content being fairly close to 100 pct, Fe has an activity close to unity. Using this first estimate of oxygen activity, approximate values of the manganese and silicon contents of the melt are readily calculated from the appropriate equilibrium constants. A minor correction for the depar-

Jan 1, 1963

By J. F. Peters

The term solution loss is discussed and defined. Examples are given showing that solution loss may either have a favorable or unfavorable effect on blast furnace performance. A theory is advanced explaining the contradictions encountered during earlier studies of the problem. MANY papers have been written and numerous theories advanced concerning the chemical reactions in the iron blast furnace. Richards, discussing the utilization of fuel in the blast furnace, said: "All the carbon burnt in the furnace should be first oxidized at the tuyeres to CO and all the reduction of oxides above the tuyeres should be caused by CO, which thus becomes CO,. This dictum is not Gruner's own words, but expresses their sense, and from the point of view of the present discussion, it is the correct principle upon which to obtain the maximum generation of heat in the furnace from a given weight of fuel." Richards also said the cubic feet of wind per pound of coke does not express how efficiently a furnace is running, but it will be shown later where Howland paid much attention to this figure. Richards pointed out a shortcoming of Grun-er's discussion in that Richards claimed there is not enough CO generated in a good working blast furnace to possibly combine with the oxygen of the ore, so some of it must be reduced by solid carbon. Mathesius2 made two important contributions. First, he wrote the direct and indirect reduction equations showing the heats of formation in each case and stressed that the indirect reduction reaction produces heat while direct reduction absorbs heat. Secondly, he substantiated Richards' conclusion that there may be a deficiency of CO gas and that some direct reduction is required, but he pointed out that "direct reduction in the hearth has often been confused with direct reduction in the stack, which more correctly should be termed 'premature combustion'." Then he said that "as this carbon is consumed partly by economical (direct reduction in the hearth) and partly by wasteful reactions in ever varying proportions, it is evident that the relation of this total carbon gasified above the tuyeres to the fuel consumption of a furnace cannot possibly have a direct bearing on the economy of furnace operation. The premature combustion of carbon (CO2+C?2CO) must therefore in all cases be considered a detrimental reaction." Johnson3 discussed this whole problem. Through experience Johnson found that when departure from Gruner's ideal working is considerable, the fuel economy is poor, and when the quantity of blast goes up, the fuel economy goes up in the same proportion. Johnson said that the wind per pound of coke is a measure of fuel economy, which will be shown to be wrong. Howland4 established the fact from operating data that there was no relationship between the coke consumption of a furnace and the percentage of coke burned at the tuyeres. But some of his calculations have led to questionable conclusions, such as "it is practically impossible to obtain low coke consumption unless we keep our wind low." Howland made an important contribution when, in his concluding paragraphs, he reached certain negative decisions as to why one coke works better than another. He said the reason one coke works better than another in a blast furnace is not because: 1—there is any difference in the percentage gasified at the tuyeres, or 2—there is any difference of wind required per pound of coke. Korevaar5 propounded a new theory on combustion which disagrees with Gruner because "as far as we can see, this is sufficient proof for the invalidity of Gruner's ideal, for if it was valid, the Low coke consumption should always be accompanied by a higher percentage of carbon burned at the tuyeres. This not being the case, we must deliberately give up our belief in Gruner's ideal." The part in italics will be proved to be wrong. Martin" contended that there was not enough reducing capacity in the blast furnace unless solution loss occurs. He came to a series of conclusions, such as: 1—The greatest efficiency of the blast furnace may not be attained when the reduction is performed entirely by carbon monoxide as demanded by Gruner's definition of the ideally perfect working of the blast furnace. 2—The so-called solution loss reactions, which should more properly be termed direct reduction reactions, promote furnace efficiency. 3—In modern blast furnace practice, the carbon consumption of the process is determined primarily by the carbon needed for reduction purposes, any thermal deficiency created by the reduction process being balanced in practice by the use of blast heat. From a practical standpoint further discussion of the theory of chemical reactions is of little moment. There is however one phase of the general theory of chemical reactions which is very important and that is the combustion of coke in the blast furnace. The purpose of this paper is to show that the reaction

Jan 1, 1955

By A. B. Kinzel

IT is with sincere appreciation and a deep sense of responsibility that I accept the honor of delivering the Howe Memorial Lecture. In our time metallurgical research has delved into phenomena ever more complex in character, so that much of this work must be done by organized teams. We, of the Union Carbide and Carbon Research Laboratories and the Electro Metallurgical Co., are truly a team and the lecture which is to follow is due largely to a few of the outstanding members of that team here cited and well known to you in their own right: John Lamont, whose work deserves special recognition, Walter Crafts, William Forgeng, William Binder, Robert Fowler, and David Swan. Thus it is a fitting pleasure to accept this honor for the research institution which I represent. Henry Marion Howe was truly inspirational and his breadth of view was such that he could use either the method of rigid proof or implied mechanism to further the broad understanding. But perhaps his outstanding characteristic was his sound judgment and his ability to weigh observations. The following is replete with observations and judgment as to their implication. We would like to feel that it is the type of dissertation which Howe, himself, would have enjoyed. Chromium carbides in stainless steel have, in a sense, been a key to the progress of the stainless steel industry. Brearley's first stainless steel, containing approximately 0.30 pct C, was successful because it differed from previous Fe-Cr alloys in that the carbides were present in such amount and form as to provide the stainless and cutting properties. Again, the 12 pct Cr die steels with a carbon content of 1.5 pct or more achieved their properties by virtue of the form and distribution of the chromium carbides. In the straight chromium steels with from 12 to 25 pct Cr, chromium carbide amount and distribution are once more the determinants with respect to physical properties and corrosion resistance. In each of the cases just cited the role of the carbide is in essence similar to that of iron carbide in carbon steel and this story is so well known that we need not dwell on it. In the austenitic stainless steels, the chromium carbide plays only a minor positive role with respect to mechanical properties, and for corrosion resistance the objective is to achieve maximum homogeneity. Thus the tendency has been to ever lower the carbon and correlatively the chromium carbide content of the austenitic steels. Today stainless steels with carbon less than 0.03 pct are beginning to find their true place, and this is being aided in major degree by our Company's introduction of a new type of ferrochromium having negligible carbon. The role of carbon in these austenitic steels has long been recognized, and a truly enormous amount of research has been devoted to the subject. Much has been learned about corrosion resistance, but the attack on the problem from the point of view of carbide precipitation and the nature thereof has left much to be understood. Because of its fundamental importance to the future of stainless steels, further study of the mechanism of carbide formation in austenitic steels is of interest. In the 18-8 Cr-Ni steels, which are typical of the austenitic class of steel, carbon is soluble in the aus-tenite to the extent of approximately 0.15 pct at 1832°F (1000°C). The solubility becomes less with decreasing temperature, so that at 1652°F (900°C) the solubility limit is approximately 0.06 pct, at 1472°F (800°C) it is about 0.03 pct, and at 932°F (500°C) it is approximately 0.01 pct. Obviously this is the ideal situation for the classical precipitation phenomenon. It is true that, in a sense, 18-8 austenite resulting from annealing is in a metastable state, and the phenomenon of ferritic precipitation from this austenite should be considered. However, in a so-called fully austenitic 18-8 steel this is secondary with respect to the carbides and can be neglected. A wide variety of chromium carbides is known. Only one chromium carbide, Cr,,C,,, frequently referred to as Cr,C, has been found in unmodified low carbon 18-8 steel. This, fortunately, simplifies the study of the precipitation phenomena. For this study an A.I.S.I. type 304 stainless steel of commercial quality was selected. Analysis showed C 0.07 pct, Mn 0.49 pct, Si 0.33 pct, Ni 9.34 pct, Cr 18.91 pct, and N 0.033 pct. As expected with this composition the steel was homogeneous after annealing except for a few pools of ferrite, which were disregarded in that their location was not coincident with subsequent carbide precipitation areas. On corrosion testing the steel was normal and typical of good commercial quality. Specimens 1/2xlx4 in. were annealed and subjected to precipitation heat treatment for 100 hr at 100" temperature intervals from 1000° to 1500°F and for ten selected intervals ranging from 5 min to 64 hr at 1300°F. These blocks were then cut into small pieces for metallographic studies. The first problem

Jan 1, 1953

By R. F. Mehl

Jan 1, 1961

By J. H. Swisher

An experimental study has been made of the possible mechanisms for foam stability in the system CaO-SiO2-Cr2O3, where Cr2O3is the foaming agent. The degree of lowering of surface tension by Cr2O3 was determined at 1600 "C for high -silica melts. Measurements were also made of foam stability under standardized conditions. The results of the two sets of measurements then were correlated by applying the Gibbs and Marangoni theories of film elasticity. It was demonstrated that the Marangoni elasticity effect is probably the largest single contributor to foam stability, although the high uiscosity of' silicate melts makes some contribution in controlling the rate of drainage of liquid from bubble lamellae. ThE tendency of metallurgical slags to foam has frequently been observed during steel-refining operations. In the open-hearth furnace,this tendency is considered undesirable because it slows down the rate of heat transfer from the burners to the molten-metal bath. On the other hand, it is sometimes desirable to have a "foamy" slag in the basic oxygen converter.' A more effective blanket over the steel bath is made by a "foamy" slag, and loss in yield of metal due to splashing is minimized. In addition, a flush slag can be removed more easily in this condition. Since slag-foaming problems in the field have been attacked largely on an empirical basis, it appeared desirable to obtain a better basic understanding of the mechanism of foam stability. The experimental work was directed almost entirely toward the behavior of Cr2O3 as the foaming agent in CaO-SiO,-Cr2O3 melts. In the first stage of the investigation, the degree of lowering of surface tension by Cr2O3 was determined at 1600°C. The second stage consisted of measuring foam stabilities under standardized conditions. The two sets of experimental results then were correlated by applying various theories of foam stability. For convenience in interpreting the surface-tension and foam-stability results reported here, a portion of the CaO-SiO2-Cr2O3 phase diagram2 is reproduced in Fig. 1. EXPERIMENTAL 1) Surface-Tension Measurements. Very little information is available in the literature on the lowering of surface tension of slags by foaming agents. Kozakevitch 3 mentioned that the addition of 1.5 pct Cr2O3 lowered the surface tension of FeO slightly. In another system, some data on the lowering of surface tension of foaming slags by P2O5 were reported by Cooper and Kitchener.4 The technique used for the surface-tension measurements was the maximum bubble-pressure method,' using a single tube immersed to various depths in the melt. This method has been used extensively in high-temperature systems, such as in liquid metals, slags, and glasses.6,7 It has the advantage that the contact angle between the liquid and the tube material need not be known. The equation used for calculating surface-tension values from maximum bubble-pressure measurements is the Schroedinger equatioq5 which can be written as follows:

Jan 1, 1964

By S. Y. Ogawa

The effects of sulfur (up to 0.1 pet) on the deformation and fracture characteristics of iron, in cast form, were studied at strain rates up to 100 pct pcr sec and at temperatures of 1600o to -3300 oF. The effects of oxygen and manganese additions on the behavior of Fe-S alloys were studied under comparable test conditions. Brittle fracture characteristics, evident at all strain rates, resulted from the presence of the liquid iron sulfide phase at grain boundaries. Ductility could be restored in three ways: solution of the sulfide in solid y iron at higher temperatures, spheroid-zzation of the liquid sulfide, and increase. in the melting point ot the sulfide. THE literature shows that most previous studies of deformation and fracture at hot working temperatures have been based on measurements of energy absorption, reduction of height in forging upset tests, torsion tests of bar or wire samples, and so forth,' but that relatively few tension tests have been used at high temperatures and strain rates. The present work was initiated to study the ef- fects of temperature, strain rate, composition, and structure on the deformation and fracture characteristics of iron, utilizing cast specimens tested in tension. As in a previous study,' strain rates up to 100 pct per sec were chosen for the temperature range 1600° to 2400° to provide data which might be useful in the interpretation of the deformation and fracture behavior of steels under hot working conditions. The previous work was with Fe-P solid solution al10ys;2 this work is concerned with Fe-S alloys, and with the effects of oxygen and manganese additions. MATERIALS AND PROCEDURE Cast tes! specimens were employed throughout, since most of the difficulty during hot working occurs in the initial breakdown of the ingot. Alloy Systems. Ten 25 lb. heats containing sulphur were prepared. Of these, three had manganese additions, and two had oxygen additions. The sulfur content varied from 0.023 to 0.10 pct. Manganese contents were intended to be ten to twenty times the sulfur content of the particular alloy. Oxygen, being more difficult to control in small melts, was varied by the amount of solid deoxidizer added, but poor control of the oxygen content was experienced in most instances. Table I shows the chemical analyses of the heats. Melting and Casting. Electrolytic-iron chips were melted by high frequency induction in a prefired, clay-graphite crucible lined with rammed magnesite.

Jan 1, 1962

By R. G. Ward, P. L. Sachdev

Using an improved maximum bubble pressure technique, the densities of iron silicates at 1400°C have been measured under nitrogen. At the wiistite composition the density has been measured by bubble-blowing experments with both argon and nitrogen and calculated from the measured volume of a known mass of melt under nitrogen. The densities under nitrogen are significantly different from those measured under argon for melts containing less than 28 wt pct SiO2. THE constitution of liquid slags is not well understood, largely because no single property or parameter can be measured which gives conclusive evi- dence of the types and packing of the ions present. Of the many property measurements which can provide information leading to a picture of the constitution of slags, density gives the most direct evidence and has been studied extensively. The work reported here is part of a program of study of densities in multicomponent melts in which the iron oxide-silica system is the solvent. These melts are important as they are fundamental to basic steelmaking, and they allow the study of basic silicate compositions which have hitherto been largely neglected. As considerable disparity exists

Jan 1, 1965

By R. G. Ward, John Henderson. R. G. Hudson, G. Derge

Densities of melts of the iron oxide-silica system in contact with solid iron have been measured by the maximum hubble pressure method in the composition range O to 37 wt pct SiOz and the temperature range 1255 to 1410C. The constitution of the melts is discussed and it is postulated that the structure changes from a dislribution of iron ions in an oxygen ion network at pure "FeO" to a distribution. of iron ions in a network of silicate tetrahedra at the orthosilicate composition. JOHN HENDERSON, Junior Member AIME, was formerly with the Metals Research Loborotory, Carnegie Institute of Technology, Pittsburgh, Pa., on leave from Broken Hill Proprietary Co., Ltd., Research Division, Shortland, Australia. R. G. HUDSON, formerly with Metals Research Laboratory, is now with the John Jay Hopkins Loborotory for Pure and Applied Science, General Atomic Division, General Dynamics Corp., LaJolla, Calif. R. G. WARD, was formerly with the Department of Metal lurgical Engineering, Carnegie lnstitute of Technology, while on leave from the Department of Metallurgy, University of Sheffield, England. G. DERGE, Member AIME, is Jones and Laughlin Professor of Metallurgical Engineering, Carnegie lnstitute of Technology. Manuscript submitted January 19, 1961. ISD The system iron oxide-silica is an important one metallurgically because it forms the basis of several complex slag systems in use for industrial smelting and refining processes. In recent years considerable work has been done on liquids of this system but there are still many points of difference among workers using different experimental techniques and theoretical approaches. Phase equilibria/"3 activity,4-6 electrical conductivity,' current efficiency,' transference number,8 viscosity,9 surface tension,'' and density" measurements have all contributed to an understanding of the problem. Measurement of density is one procedure which is directly indicative of liquid structure since any deviation from ideality must be a result of structural interactions. Liquids of the iron oxide-silica system are of special interest because this is one of the few metal oxide-silica systems on which measurements can be carried out conveniently over the entire composition range from pure oxide to silica saturation. This includes the range of high basicity which has received relatively little attention in other systems. Although one investigation of density in this system has previously been undertaken," the results seem of sufficient importance to warrant the independent redeter-mination reported here.

Jan 1, 1962

By Ottar Dragge, C. Danielsson, Bo Kalling

THE desulphurizing of pig iron has been accomplished with a number of different additions. The oldest and still most commonly used agent is soda, the extensive use of which commenced about 1925, when it was used principally for cupola furnace iron. More recent experience' seems to show that better results can be obtained with sodium hydroxide. The well-known desulphurizing properties of lime have also been exploited in different technical processes. Another material with even more powerful effect is calcium carbide.' The desulphurizing ability of manganese, when added to the ladle in sufficient quantity, should also be mentioned in this connection. During recent years increasing attention has been paid to the desulphurizing properties of metallic magnesium." An addition of a suitable alloy of magnesium is now in use purely for the purpose of sulphur elimination. Of the desulphurizing agents mentioned, lime is by far the cheapest, provided that the reaction can be brought about rapidly and completely. Therefore, a method that makes full use of the desulphurizing ability of lime may be able to compete with other processes. A method developed at the Dom-narfvet Iron and Steel Works (Sweden) will be described, which enables pig iron to be rapidly desulphurized to very low sulphur contents by using a burnt lime powder. as the desulphurizing agent. Lime in Older Processes In cases where lime has been used for the desul-phurization of pig iron, it has generally not been used alone, but mixed with other substances such as fluorspar, to obtain the formation of a molten slag during the process. This method has been tried by Tigerschiold,' who treated the iron with a lime-fluorspar mixture, the stirring of the iron being brought about inductively with low frequency alternating current. Very good results were obtained. A process of this type has also been suggested by R. P. Heuer, U. S. A. The principles of this method, which has been tested in Great Britain by Newell. Lanener. and Parsons." re that a mixture of lime and fluoispar is added to the hot metal in the ladle, while a powerful stream of nitrogen gas is blown into the bath to produce the required intermixing. The results of the tests were unsatisfactory, however. A similar process has been developed at The Steel Co. of Canada, according to a statement by H. M. Griffith.' Here the tests were carried out in a carbon-lined ladle provided with carbon tuyeres in the side wall for blowing nitrogen into the bath. The addition consisted of about 20 lb of a mixture of burnt lime and fluorspar per ton of pig iron. Good results appear to have been achieved. The sulphur content of the pig iron is stated to have been reduced from 0.025 to 0.050 pct down to 0.006 pct. Various methods of desulphurizing pig iron have been tried using lime powder without fluxing material for fusing. Eichholz and Behrendt7 have experimented with blowing a powdered limeicoke mixture with air into the ladle. Their results were, however, not conclusive and the experiments do not appear to have been continued. Similar experiments have been carried out at Domnarfvet, using nitrogen instead of air in order to avoid oxidation. But these attempts were not particularly successful. It appears to be difficult to achieve the required agitation by this means. The strong cooling effect of the gas on the iron is also a serious drawback. A method in many respects similar to that tried at Domnarfvet was tried by Eulenberg and Krus at the end of the 1930's. Here again desulphurization was carried out with lime alone, brought into contact with the molten iron in a rotary furnace. The temperature was kept at the required level, 1400" to 1500°C, by the introduction of a pulverized coal burner in one end of the furnace. The speed of rotating was not given. A paper by Bading and Krus states that, in one of the first experiments, the sulphur content in 56 tons of pig iron was brought down from 0.186 to 0.035 pct in 117 min, but that a considerable shortening of the time would be possible. According to later reports by Eichholz and Behrendt,' it should be possible by this process to achieve a desulphurization speed of 0.35 pct S per hr for a consumption of 6 to 10 pct limestone and 2 to 3 pct coke, as fuel exclusively. The final sulphur content is, however, not stated. Domnarfvet Method After a number of different procedures had been investigated, the tests at Domnarfvet were directed to desulphurization with lime in a rotary furnace. Before going into the practical details of the method, the theoretical aspects will be discussed briefly. If the pig iron does not contain alloying elements other than carbon, the reaction can be expressed most simply by the usual equation: FeS + CaO + C = Fe + CaS + CO [I] 4H,. ~ 34,000 cal That this reaction can be carried through to a very complete desulphurization of pig iron has been shown by OelsenD in a discussion in connection with the Eulenberg and Krus' method. He mentions two laboratory tests, in one of which the sulphur content in the pig iron at 1400°C was reduced from 0.540 to 0.006 pct after treating with 3.35 pct lime. The pig iron had a low manganese content, but other analysis is th. given. Mention also should be made of the recently published investigations by Fischer and Cohnen'" dealing with the influence of the carbon content of the iron on desulphurization with lime, although in this case fluorspar was added also. The tests show that efficient desulphurization is possible with lime in the steel bath, provided that the carbon content is sufficiently high. The temperature employed in these tests was considerably higher (1620") than that normal for treatment of pig iron. The author concludes that the product S% X C% - 0.011 at the temperature in question.

Jan 1, 1952

By S. D. Baumer, P. M. Hulme

IN the late thirties, the National Carbide Co. cooperated with C. E. Wood, of the U. S. Bureau of Mines, in his investigation of the relative merits of various desulphurizers, including soda ash, caustic soda, and calcium carbide. Laboratory tests showed that carbide, when it could be made to react, is an excellent desulphurizing agent for molten iron. Sulphur content can be driven to lower levels and higher extractions obtained with carbide than with actionsany of the more common reagents. Wood's results1 are shown in Table I. Unfortunately, as the Handbook of Cupola Operation puts it, the chemical fact that carbide is a good desulphurizer was of only academic interest because it was found to be extremely difficult to devise a practical means to make it react with molten iron. Calcium carbide is formed in the electric furnace at 4000°F and above, and its softening point is probably at least 500 °F above the usual working temperatures encountered in iron and steel practice. Consequently, carbide does not form a true slag but floats as a dry powder on top of the metal and only a very small portion of it ever comes in actual contact with the iron. Stirring with a rabble, or pouring the metal over the carbide, increases the efficiency only slightly. Extractions of 20 to 30 pct can be obtained in this manner, but conventional soda slag treatment can do better than this and do it more cheaply. All attempts to lower the melting point of carbide in order to obtain a reactive, liquid slag have so far proved fruitless. Directly under the arc in a metallurgical electric furnace, carbide becomes highly reactive. Excellent sulphur removal can be obtained without any slag other than a thin layer of carbide." imilarly, good results are obtained by adding small amounts of carbide to the finishing slag in double-slag arc furnace practice. To react a liquid with a solid, it is axiomatic that the liquid has to wet the solid before anything can happen. If the solid is heavier than the liquid, the problem is easy, but it becomes more difficult when the solid is much lighter than the liquid, as in the case of carbide and liquid iron. Wood recognized this problem and solved it in a unique fashion. The results shown in Table I were obtained by spinning the carbide beneath the surface of the molten iron by means of a refractory centrifuge. This technique allowed each particle of the finely divided carbide to come into intimate contact with the metal and to be wetted thereby. Wood's centrifuge technique was successful in the laboratory where it achieved excellent and consistent results. Some attempts were made to expand this method to commercial practice, but serious difficulty was encountered in obtaining a refractory centrifuge head that would be economically feasible. About this time the war intervened and the project lay dormant for several years. In 1944, it was revived. It was suggested that the carbide could be blown into the metal with a carrier gas in an attempt to eliminate the necessity for the expensive and brittle centrifuge. The idea was first tried out in a fairly large ladle of iron using natural gas as the carrier. Considerable sulphur was removed, but it was quite obvious that the use of natural gas was not practical. Attempts then were made to blow carbide into molten iron using, in turn, nitrogen, argon, carbon dioxide, air, and oxygen. The latter two gases proved unsatisfactory. Calcium evidently prefers oxygen to sulphur because in the tests calcium oxide and carbon dioxide were produced, the sulphur still being untouched in the iron. Nitrogen, argon, and carbon dioxide gave much better results, although the efficiencies and extractions were erratic, and only a few isolated tests approached the results obtained by Wood. Table II shows typical results obtained with these gases. The sulphur removals were interesting, sometimes even encouraging, but it is evident that such erratic behavior could not be tolerated in commercial practice. A number of different types of equipment, such as sand blasting machines, refractory guns, and the like can used to blow the solid into the metal. All types required relatively large quantities of gas in order to maintain the flow of solid carbide through the system and into the metal. It was observed that the bubbles of gas breaking through the surface of the metal contained quantities of unreacted carbide. The liquid metal never came in contact with these particles and if it cannot wet them it cannot react with them. The initial work had shown that carbide had great possibilities as a desulphurizer. In practice

Jan 1, 1952

By C. R. Masson, M. L. Pearce

The nitrogen contents of seven specimens of iron and steel were determined by the three methods. Good agreement won generally observed between the results of the isotope -dilution and Kjeldahl determinations, tltzts establishing the reliability of the isotope -dilutzon technique. For some specimens, the vacuum-fusion values at 1650 °C were lower than the corresponding Kjeldahl values by up to 0.0015 pct absolute. These differences were eliminated for a specimen of "pure" iron by performing the vacuum-fusion analyses at 2100 ° to 2240 °C. The reason for this relatively high temperature required m the vaczium-fusion analyses is discussed. ThE determination of nitrogen in iron and steel has been the subject of numerous investigations and a concise review of the extensive literature in this field has recently appeared.' Two methods of analysis are most commonly employed, the vacuum -fusion and the chemical or Kjeldahl method. Except in special cases where the presence of certain alloying elements may present difficulties, both methods are generally regarded as applicable, although the vacuum-fusion method is more sensitive and is often preferred for samples of very low-nitrogen content. The method of isotope dilution, first employed for the determination of gases in metals by Kirshenbaum and Grosse,2 has recently been applied to the determination of nitrogen in iron and steel.3,4 The method is attractive in that it does not require the quantitative extraction of gas from the metal specimen. Staley and Svec3 modified the standard Kjeldahlpro-cedure by introducing, along with the steel sample, a measured amount of ammonium sulfate enriched in the isotope 15N. The nitrogen content was obtained by measuring the isotopic ratio 15N/14N in the resultant solution. The technique involved the distillation of nitrogen as ammonia from alkaline solution and subsequent oxidation of NH4+ in the distillate to gaseous nitrogen. The results for iron and steel samples of commercial origin were often in reasonable agreement with values quoted by the suppliers, although occasional marked discrepancies were observed, particularly with the results of vacuum-fusion analyses. Preliminary work in this laboratory4 on the determination of nitrogen by isotope-dilution in the gas phase yielded results for three samples which were significantly higher than the values obtained by vacuum-fusion. The present paper describes an extension of this work to a wider variety of samples. Analytical results by the Kjeldahl method are also reported. EXPERIMENTAL The technique employed for the isotope-dilution determinations was similar to that described elsewhere.4 Several minor modifications were made to the apparatus. These included the use of molybdenum instead of platinum-rhodium suspending wires when crucibles were degassed at temperatures above 1600°C. The circulatory system used previously for converting CO to CO2 was replaced by a single chamber, the walls of which were cooled directly in liquid nitrogen. Temperatures were measured with an optical pyrometer which had been recently calibrated and, as in the previous study, were minimum values obtained by sighting on the center bottom of the crucible. Temperatures obtained by sighting on the interior walls were always higher by 100' to 130°C with the design of crucible employed. Flat-bottomed crucibles exhibited an even larger temperature difference. To check the efficiency with which crucibles were degassed in the isotope-dilution apparatus, several experiments were done in the vacuum-fusion apparatus, suitably modified4 for isotope-dilution studies. Faster pumping speeds and higher degassing temperatures were possible, the latter due to the use of a generator with a higher power output (10 Kva at 398 kc per sec). In these experiments the combustion of CO was omitted and a correction4 was made for the contribution of CO to the ion current at m/e 28, used in determining the isotopic ratio R = l5NP4N. This correction did not seriously influence the re-

Jan 1, 1962

By O. Cuscoleca

The Austrian plants at Donawitz and Linz were the first to blow steel with high purity oxygen. The paper shows how the process was developed and gives a survey of the results achieved to date. Compared with open hearth steel of equal quality, the obvious advantages of oxygen steel are the low investment and conversion costs. The nitrogen content of oxygen steel is not higher than that of good open hearth steel. Rimmed and killed steel products made by the oxygen process are superior to rimmed and killed steel products made by the best open hearth process. TWO new steel plants using the principle of making steel with high purity oxygen went into operation in Austria, one at Linz (Vereinigte oster-reichische Stahlwerke) in November 1952 and the other at Donawitz (dsterreichisch-Alpine Montan-gesellschaft) in May 1953. An estimated 330,000 metric tons were produced by the two plants in 1953, the first year of operation. In 1954 production by Austrian plants- using the high purity oxygen approach will be raised to 450,000 metric tons. This will be in addition to facilities in Huckingen (Man-nesmann A. G., Düsseldorf, Germany), those planned and under construction at Hamilton, Ontario, Canada (Dominion Foundries and Steel, Ltd.), and elsewhere. It is expected that by 1955 a total capacity of one million tons of high purity oxygen steel will be available. At the close of the last century, because of increasing availability of scrap, open hearth steel production forged ahead at an ever increasing pace. This caused world steel production to rise faster than pig iron production and finally to overtake it. In 1911 65 million tons of steel were produced against 64 million tons of pig iron. World steel production was 209 million tons in 1951, while pig iron output was only 147 million tons. The 1951 breakdown for steel shows 118 million tons made from pig iron, while the balance, 91 million tons or 44 pct of the total tonnage of steel produced, was made from scrap. This increase in crude steel production on a basis of high scrap consumption led to the world market scrap shortage and soaring scrap prices. In the United States and other nations, production of converter steel has fallen far behind that of open hearth steel. The surplus of processing scrap, un-absorbable by converting mills and thus a welcome source for open hearth and electric melting shops in the past, together with regular scrap purchases, no longer can meet requirements of both open hearth and electric steel production in Europe. In addition, recent modification of the basic bessemer process, blowing with oxygenated blast, substantially raised the scrap capacity of these plants. Any further expansion of world steel production will necessitate utilization of self-containing processes in regard to scrap because of the shortage.

Jan 1, 1955

By J. Chipman, H. Towers, M. Paris

A simple radioactive tracer technique is used to measure the diffusion coefficient of calcium ion in molten slags. In a slag of 40 pct Ca0-40 pct Si0,-20 pct Al203, Dc " at 1450°C is 1.3x10-6 cm' sec-'. THE application of the principles of thermodynamics to steel and iron making problems has proved so fruitful that the kinetic approach has tended to be neglected. It seems probable that in some reactions the rate-determining step is the dif-fusivity of the reactants or of the products. But knowledge of the diffusion coefficients of the constituents of liquid slag and metal is singularly lacking. The present work was undertaken as a first step toward supplying such data for slags. Furthermore, any additional information on the physical properties of liquid slags might be expected to help in elucidating their structure. It is essentially a preliminary investigation, the course of which was determined more by the necessity of establishing a method than by the immediate intrinsic interest of the results. For example, the selection of calcium ion to be studied was dictated by the suitability of the isotope Ca45 in that it is a simple emitter with a long half-life. Of the other ions commonly encountered in slags, the isotopes of iron and manganese have relatively complex radiations as well as the normal disadvantage of requiring control of the oxygen potential of the atmosphere; Mg27 and Al29 have half-lives measured only in minutes; Si3' has a simple decay process but its half-life of 2.8 hr is too short for preliminary studies; the only useful oxygen isotope is the stable O18; and there remain only sulphur and phosphorus both of which have suitable isotopes but were rejected as being of less fundamental interest than calcium. Similarly a lime-alumina- silica slag was used in preference to calcium silicate primarily because of its low melting point and its capacity to form a glass on fairly rapid cooling. Literature Review Very few studies of diffusion in liquid silicate systems have been reported. In order to determine the origin of diopside inclusions in felspathic rocks, Bowen1 investigated the diffusion between diopside and various mixtures of albite and anorthite. Platinum crucibles were used with diopside, the heavier of the two liquids, forming the lower half of the cell and diffusion taking place against gravity. Change in concentration along the diffusion path was found by measuring the refractive index of the quenched glass. Nearly thirty years later McCallum and Barrett2 used essentially the same method to determine the diffusion coefficient of lime in lime-alumina-silica slags. In this case the interest was to find the rate-determining step in the process of slag attack on refractory materials. In an investigation of the kinetics of the sulphur reaction, Derge, Philbrook, and Goldman8 determined the diffusion coefficient of sulphur in a typical blast furnace slag by the simple procedure of melting a slag containing 2 pct S over an identical slag sulphur-free. They make no claim to a high degree of accuracy but suggest that D, is of the order of 10-6 cm2 sec-l. Other high temperature liquid diffusion studies have been concerned with metals. Holbrook, Furnas, and Joseph4 determined the diffusion coefficients of silicon, phosphorus, sulphur, manganese, and carbon in liquid iron by immersing a small carbon crucible containing pure iron-carbon alloy in a large vessel containing iron with a high concentration of the particular element. Their results were confirmed by Paschke and Hauttmann5 using a similar method. Diffusion coefficients in silicates in the glassy state have been studied by Johnson, Bristow, and Blau6 Both Na24 and Ca45 were used as tracers but only the

Jan 1, 1954

By K. L. Komarek

Based on theoretical and experimental evidence a discussion follows of the behavior of phosphorus -bearing iron ores in the R-N Direct Reduction Process and suggestions are made of methods of reducing the amount of phosphorus in the metallic end product. In ferrous metallurgy a direct reduction process is one in which iron ores are reduced to metallic iron with gaseous or solid reductants without the appearance of a liquid phase. A number of attractive features have induced several companies and government agencies to invest in the development of direct reduction processes. A summary of all direct reduction processes up to 1954 has been given by Barrett,' and Wiberg,2 and Willems3 have reviewed the most recent developments in this rapidly expanding field. Many difficulties have been encountered in direct reduction processes and the nature of these difficulties has varied from process to process. One problem common to almost all of them is the removal of phosphorus which is one of the reasons for the rather pessimistic outlook given by some government publications4'5 to direct reduction processes. In this paper an attempt is made to give a theoretical explanation of the variations in phosphorus removal observed in the R-NY Direct Reduction Process. However, many conclusions are general enough to be applicable to other processes. Most iron ores treated by the R-N process yield products lower in phosphorus than the original ore. A qualitative account of the factors has been given by Stewart, Reed, and Herasymenkoe but the erratic removal of phosphorus from some ores and the general importance of this problem make a more careful analysis of the theoretical aspects desirable. In the R-N process mixed ore or balled fines, ex-

Jan 1, 1963

By G. W. Healy

G. W. Healy (union Carbide Metals 0.)-The author's paper is a useful contribution to the store of maps of chemical activities of oxides in multi-component slag systems. It is also a good example of the utility of the Gibbs-Schuhmann technique for calculating activities in a system where that of one of the components has been measured. This paper Koh and Caugherty. This plot is reproduced by alor in X-ray Metallography. Because of this nonlinearity, preparation cf suitable standards and/or correction for absorption and enhancement are essential in microanalysis. However, our objection is not the conclusion that Dr. Aaronson has arrived at nor the technique he has used; but only to the foot-note credited to V. Macres. The level of chromium that he was concerned with (less than 3 pet) is so low that the deviation of uncorrected Cr-curve will be negligible. Besides Dr. Aaronson has used chromium intensity from martensite and set it equal the bulk chromium content of the alloy. Using this chromium-intensity as a reference, he has calculated the amount of chromium in the ferrite. This amounts to the same as using an internal standard. Since the chromium content in austenite and ferrite are almost the same, enhancement due to iron in both will be the same and therefore does not need to be corrected. together with the author's recently published one1 on the CaO-FeO-Fe2O3 system will be most helpful to others learning to apply Schuhmann's method, which merits a far wider application than it has received to date and should greatly aid our understanding of equilibria between metal and oxide phases. As shown by okcen" its use may even be extended to sections of systems with any number of oxides. I have some questions as to the selection of equilibrium constants made by Dr. Turkdogan. He has chosen one for the formation of Fez03 from FeO and oxygen which gives Fea3 activities 50 pct higher

Jan 1, 1963

By P. T. Carter, A. B. Murad, H. B. Bell

N. A. Gokcen (Michigan College of Mining and Technology, Houghton, Mich.)—The activities of silica, represented in Fig. 5 for the systems MnO-SiO2 and CaO-SiO2, are in disagreement with the established binary phase diagrams. At Ns102 = 0.50 in MnO-SiO2, and at Ns102, = 0.65 in CaO-SiO2, each binary system is saturated with respect to silica at 1550°C, and therefore as102, is unity in each case. The curves for as102 (FeO-SiO2) and as102, (MnO-SiO,) should nearly co-

Jan 1, 1953