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By D. C. Hilty, W. Crafts

L. S. Darken—Laboratory investigation of deoxidizing and other steelmaking reactions is usually centered, at least first, on the determination of the equilibrium or equilibria involved. This seems a reasonable procedure since equilibrium, if attained, depends only on composition, temperature, and pressure; hence conclusions derived from data on small experimental quantities are applicable to a heat of steel providing eauilibrium is attained in both cases. A knowledge of equilibrium serves as a useful framework even though we may know that practical conditions do not correspond to complete equilibrium. On the other hand, nonequilibrium or rate phenomena depend on a wider variety of conditions and are more difficult to interpret; conclusions applicable to laboratory conditions may or may not apply to larger scale phenomena. Hence the attainment or nonattainment of true equilibrium in the experiments here reported is of critical importance in evaluating their significance. Since some of the statements in this paper and in the closely related preceding one (on aluminum deoxidation) imply some doubt on this matter, I should first like to ask the authors whether their conditions are intended and believed to represent equilibrium. I should like to point out three considerations which seem to cast considerable doubt on the achievement of equilibrium, at least of the particular equilibrium under consideration. 1. In the experiments on manganese deoxidation the authors point out that they could not maintain the manganese-oxide slag on top of the metal in their rotating crucible, and hence they substantially dispensed with this slag. This leads to serious trouble in the interpretation of the results, for any equilibrium is, of course, a particular specific equilibrium—in this case Mn + O = MnO The experimental deletion of the upper layer of manganese oxide means that if equilibrium is attained at all it is attained between the metal and the MnO which has soaked into or adhered to the crucible (under the metal) and has dissolved substantial amounts of the crucible material including impurities. These impurities may constitute a significant portion of the slag by virtue of the small total amount of slag, even though the crucible is relatively pure. Hence there would seem to be a strong presumption that the equilibrium (if attained) involves not a pure MnO (or MnO — FeO) slag but one saturated with alumina and containing perhaps considerable impurities which substantially lower the concentration and activity of MnO, causing the above reaction to proceed to the right further than it would in the absence of alumina and impurities. Hence it is not surprising that manganese here appears as a better deoxidizer than found by other investigators. The present results may represent equilibrium with a slag of unknown composition which seems unlikely to be particularly related to plant experience. 2. The curves representing the observed silicon deoxidation (figs. 3, 4, and 5) are all drawn with a discontinuity in slope at about 0.02 pct oxygen. This point is interpreted as corresponding to the three-phase equilibrium, metal, slag, solid silica. The type of construction shown in these figures (though apparently fitting the data) is contrary to a fundamental principle of heterogeneous equilibrium as pertains to the construction of phase diagrams. According to this principle, the two solubility curves (each of the two portions of the curves in figs. 3, 4, and 5) must intersect in such manner that their (metastable) extensions must lie outside the homogeneous field rather than inside as in these figures. In other words, the "point" in these curves should be aimed in the opposite direction, if it is to be interpreted as corresponding to the three-phase equilibrium. The construction adopted is in violation of the second law of thermodynamics. This matter is discussed in detail in several texts and also by Lipson and Wilson.&apos;" The same criticism applies to the later figures representing conditions for manganese additions. The occurrence of this discontinuity or break at 0.02 pct oxygen casts further doubt on its interpretation. The earlier investigation of this system by Korber and Oelsen is in substantial agreement with the several recent findings of Chipman and coworkers that the oxygen content of iron in equilibrium with silica and silica-saturated iron oxide slag is about one third to one half that (0.24 pct at 1600") of iron saturated with pure iron oxide; thus there seems reliable evidence that iron saturated with silica and iron silicate slag at 1600" contains about 0.1 pct oxygen, or certainly much more than the 0.02 pct proposed in this paper. 3. In the quarternary system iron-silicon-manganese-oxygen one of the equilibria involved may be written 2 Mn + SiO2 (solid) = 2 MnO <slag> + Si The activity of SiO, is constant (if equilibrium is attained) by virtue of its presence as a substantially pure solid. At not too low metallic manganese content, the activity of MnO in the slag is constant by virtue of the fact that the slag is substantially pure manganese silicate saturated with silica and hence of constant composition. Thus the equilibrium constant for the above reaction is asi/a2Mn. Barring unanticipated large changes in the activity coefficients, the equilibrium constant may be adequately approximated for the composition range covered as [% Si]/[% Mn]2. Thus a plot of log [% Mn] against log [% Si] would be expected to be linear with a slope of one half as found by Kijrber and Oelsen. In the present investigation the slope (shown in fig. 15) is found to be one. It is difficult to believe that this finding represents a correct equilibrium determination, since it is at odds both with prior experimental investigation and with. theory. In view of the above points it seems that, although this paper reports many interesting findings, there is room for considerable skepticism as to the attainment of equilibrium and as to the conclusions drawn. N. A. Gokcen—The authors consider that Si% x O2% product is constant. This product is a function of the asi X a0 activity of Si02. The true constant is -------------. If the asio2 slags of this investigation were always saturated with SiO2 then Si% X O2% product would be constant,

Jan 1, 1951

By Herbert J. French

Herbert 1. French (Member 1934), vice president of the International Nickel Co. Inc., assistant vice president of the International Nickel Co. of Canada Ltd., and AIME Howe Memorial Lecturer for 1956, died in Rochester, Minn. on Aug. 17, 1955, after a long illness. Before his death, Mr. French had laid the foundation of research on which the Howe Memorial Lecture (p. 770) was based. His associates at Inco, 0. 0. Miller and J. W. Sands, were able to complete the project, present the lecture, and prepare it for publication, following Mr. French&apos;s general outline. Born in New York on May 27, 1893, he graduated from the School of Mines, Columbia University, with a degree in metallurgical engineering in 1915. Mr. French gained his early engineering experience with the American Smelting and Refining Co., serving as a chemist and as-sayer at the company&apos;s Murray, Utah, installations. He later returned east and became a metallurgical engineer for the General Vehicle Co., Long Island City, IT. Y., a subsidiary of the General Electric Co. In 1917 Mr. French was appointed civilian inspector of materials for the U.S. Army Signal Corps, and continued this work when it was later absorbed into the Bureau of Aircraft Production. Subsequently he was appointed district inspector in Philadelphia for the Pittsburgh (Ordnance Metallurgical) office, later transferring to Pittsburgh. After World War I Mr. French became an assistant physicist on the metallurgical staff, U. S. Bureau of Standards, Washington, D. C. During his years with the Bureau, he was successively associate physicist, metallurgist, senior metallurgist, and assistant chief, division of metallurgy. In 1929 Mr. French joined International Nickel as a metallurgist at the company&apos;s Bay-onne, N. J., research laboratory. Transferring to the development and research division, New York, in 1931, he took charge of alloy steel and iron development, becoming assistant manager of this division in 1943. Mr. French&apos;s appointment as an Inco vice president came in March 1947. Previously, he was appointed assistant vice president of the International Nickel Co. of Canada Ltd. in January 1947. Mr. French served the War Production Board during World War II as senior technical consultant in charge of the metallurgical and specifications section of the iron and steel branch. When this section of the WPB was organized into the steel division, he was appointed chief of the metallurgical branch. From March 1944 to September 1945 Mr. French served as assistant director. Herbert French was well known not only for his prolific contribution to the metallurgical literature, for which he received numerous awards, but also for his prolonged service to the profession through its technical societies. He was a past president of ASM, and was the Campbell Memorial Lecturer for that group in 1933. Mr. French was honored by the American Society for Steel Treating in 1931 when he was awarded the Henry Marion Howe Medal. A series of lectures he gave in 1941 before the Fourth Western Metal Congress in Los Angeles was later published in book form under the title Alloy Constructional Steels.

Jan 1, 1957

By D. T. Goettge, E. L. Robinson

The phase changes occurring in low carbon steel during hot strip mill rolling are shown to be metallurgically significant when related to commonly used temperature control points, particularly finishing and coiling temperatures. In combination, these temperatures are shown to have an important influence on the level and uniformity of hardness, grain size, and carbide characteristics of the finished hot and cold rolled sheets. PRODUCTION of wide flat-rolled products ordinarily requires a number of operations in sequence to prepare the material for shipment to the customer. Most products are tailor-made for specific end uses, with each operation contributing certain properties to the finished material. Since the characteristics imparted to the semifinished product by a given step in processing carry through to the finished product in varying degrees, it is important that the intermediate stages of production of flat-rolled strip be carried out with the same care which characterizes the last or finishing operations. The step of hot strip mill rolling is common to the production of all of the various types of flat-rolled product; therefore, the hot strip rolling is an especially important point at which to recognize and control those variables which have an effect on the surface characteristics and metallurgical properties of the finished product and which influence the ease of conducting subsequent operations. Orders entered at a producing mill usually show an end use or describe an article or part into which the ordered product is to be fabricated. Applying his experience as to the properties necessary in a finished sheet to suit the end use and to perform successfully in the fabrication involved, the metallurgist selects a steel of suitable composition and deoxidation practice, and slabs of appropriate dimensions are produced for rolling on the hot strip mill. At this stage of processing, the metallurgist faces the problem of controlling hot strip mill practice in the light of his diagnosis of the properties necessary to meet the end use, paying due attention to the accompanying problem of producing a strip which can meet processing requirements on subsequent units in the mill. It is the purpose of this paper to describe some of the factors which he must consider in solving these problems and to indicate some of the principles which guide him. Equipment, Physical Requirements of the Strip, and Temperature Measurement The metallurgist must, of course, be familiar with the physical layout of the mill, the temperature-measuring equipment available, and the physical requirements of the hot strip product before he can apply his metallurgical knowledge to the problem; hence, the first section will consist of a brief discussion of these matters. The usual hot strip mill consists of reheating furnaces, five or six roughing stands including a scale-breaker, holding table, and second scalebreaker, six-stand finishing mill, runout table with spray cooling facilities, and coilers. A schematic diagram of a typical layout is shown in Fig. 1. Slab temperatures are primarily a function of heating time and furnace temperatures, while mill speeds, spray practice, drafting practice, available water pressure, temperature of the cooling water, cross sectional dimensions of the strip, coil size, and equipment limitations, either singly or in combination, determine what rolling temperatures are practical on a given hot strip mill unit. Thus, it is possible that a set of temperatures which can be utilized successfully on one mill cannot be used on another. However, adjustments in temperatures and rolling practice can usually be made to develop the desired metallurgical properties. In addition to the metallurgical properties developed through proper temperature control, the hot strip mill must also provide strip with certain physical attributes which may be summarized as follows: Strip Cross Section—The strip contour should conform to a section which will give the best results in the cold reduction operation. This is generally recognized as a strip with 0.001 to 0.003 in. crown or shoulder-to-shoulder convexity depending on width, and freedom from concave, flat, or wedge-shaped cross sections which cause metal buildup in cold reduction. Excessive drop off in thickness at the edges can also be very detrimental in cold reducing to light gages. Gage, Width, and Camber—All of these must be controlled. For example, rundown or increasing thickness from the front to the back of the coil results in nonuniformity in the thickness of hot-rolled sheet product and in added difficulty with gage and welds in cold reduction. Similarly, excessive width variation is the cause of guide trouble and excessive edge scrap at later stages of processing, while excessive camber is the source of a variety of processing troubles. Type of Oxide—Product intended for pickling should have a predominance of the type of oxide most easily removable in sulfuric acid. It is generally recognized that this type is obtained by use of maximum table cooling water and cold coiling

Jan 1, 1957

By D. J. Carney, E. Van Meter, J. J. Oravec

A study was made of combustion-air temperatures and factors affecting air temperatures in the open-hearth regenerative systems. Air-temperature surveys in the regenerative system revealed marked thermal gradients in the air above the checkers. The design of the fantail-uptake region plays a prominent part in increasing the heat recovery of the regenerative system. THE efficiency of the open-hearth regenerative system is one of the most important factors affecting open-hearth performance. Until recently, this factor has not received the attention in the literature given to many other items affecting performance, such as the type of charge, speed of charging, and the mechanical equipment of the open hearth. J. S. Marsh&apos; emphasized the importance of the flame temperature and its dependence upon the combustion-air temperature. By means of measured air temperatures in open-hearth furnaces, data were presented which showed a remarkable degree of correlation between production rate and combustion-air temperature. This correlation was extremely good in view of the numerous factors, other than air temperature, which affect open-hearth production rates. In Marsh&apos;s work, a 100°F increase in air temperature reduced the heat time by approximately 45 min. Realizing the importance of combustion-air temperature, it is desirable to know which factors control the regenerative efficiency of the open-hearth furnace. B. M. Larsen recently discussed this subject.&apos; The present paper illustrates a few of the more important items that affect regenerative efficiency and combustion-air temperature. In the latter part of 1951, a study of open-hearth combustion-air temperatures was begun at the South Works of the United States Steel Corp. In the initial work at open-hearth shop X, which produces low carbon steel products, temperatures were measured in the uptake in a manner similar to that used by Marsh&apos; and the results obtained were very similar to the Bethlehem data. When it was decided to expand the study of combustion-air temperatures, open-hearth shop Y was selected because of the greater variety of furnace-design features, types of steel produced, and firing rates used. With the use of aspirating thermocouples, continuous gas analyzers, thermocouple and optical pyrometers, a study was made of: 1—effect of combustion-air temperature on open-hearth production rate, 2—thermal gradients present in various zones of the regenerative system, 3—effect of furnace-design variations on air temperature and heat recovery, 4-—effect of furnace-operating variables on heat recovery, and 5—variation in heat recovery with furnace age during the normal furnace campaign. Data collected on individual heats at 15 min intervals included air-flow rate, firing rate, checker temperature, combustion-air temperature, and furnace pressure. These data were collected on approximately 230 heats of steel. In addition, information was obtained at random on air infiltration and combustion-gas compositions. The data gathered have shown the desirability of closer control of open-hearth firing practices, a need for reducing air infiltration in the uptake zones, and a need for further study of design of checkers and of uptake-fantail areas. Equipment Air is practically a nonradiating medium. Consequently, in the measurement of air temperatures, the principle of heat conduction must be used rather than heat radiation. For this reason, aspirating-type thermocouple pyrometers normally are used to measure air temperatures. With these devices, air

Jan 1, 1956

By G. R. Fitterer

Trends in slag composition in acid open hearth practice, particularly the variation in iron and manganese oxides during refining, are reviewed. A procedure which is currently being used to control the refining reactions is described and partially explained through slag phase diagram considerations. In addition, the ionic nature of these slags is considered and it is proposed that silica combines with the oxide ion and forms a series of complex silicate ions. The effect of basic oxides such as FeO, MnO, and CaO is apparently additive in furnishing the oxide ion for this purpose. IT is now possible to control192 the refining of steel in an acid open hearth furnace to a surprising degree. This control has been brought about through the knowledge and use of several facts and tests. These are: 1—A planned charge analysis based on a knowledge of the type of fuel, the bath depth, etc. 2—Knowledge and control of rate of fuel input as well as its method of atomization, if any. 3—Determination of the slag fluidity. 4—Bath temperatures (use of the Pt-Pt-Rh thermocouple). 5—Periodic determination of carbon content (use of the Carb-analyzer or Carbometer). Through the use of these control methods, a heat may be made to "melt-in" with or without residual manganese and silicon. The rate of refining or carbon elimination may be controlled accurately, and the desired tapping (or "go-ahead") carbon may be approached at a rapid or slow rate according to preference and type of steel being made. Thus operating time may be predetermined and greatly reduced. Further, all of the refining can be done without any ore or other oxidizing additions, and the heat may be brought to the desired tapping temperature simultaneously with the attainment of the desired carbon analysis. This control procedure is being used in most acid plants in the United States today and has been de- scribed.&apos;, &apos; Although the slag metal relations are sufficiently well known to control the heat as stated, yet it is possible to account for only about two-thirds&apos; of the 0, which must have been used for the elimination of the carbon and other metalloids. Phase diagram studies&apos; of the slags, slag weights, the metal particle theory,&apos; ore additions, limestone additions, etc., may all be taken into consideration; yet, the mechanism of oxidation and source of all the oxygen remain to be explained. This paper reviews some of the principles upon which the control methods were based and proposes other possibilities regarding the unexplained phenomena. Old and New Acid Open Hearth Practice Some of the recent statements in the literature regarding acid open hearth operation are based on old heat data which are not typical of modern American practice. These old heat logs have been responsible for many misconceptions regarding the acid hearth practice and represent heats which do not coincide with modern methods. In recent years, American practice has been altered materially and these changes will be briefly described. Modern American Practice: A typical log of a modern American acid open hearth heat&apos; is shown in Fig. 1 which indicates that the refining time was only two hours, during which the carbon was eliminated rapidly and the bath temperature increased at a fast rate. The manganese and silicon contents of the metal were essentially eliminated and their oxides had become constituent parts of the slag at the "melt-down" period. During the course of the heat, the MnO content of the slag remained practi-

Jan 1, 1954

By Gordon H. Geiger, J. Bruce Wagner

Electrical conductavity and therrnoelectvic nzeasuretnents on synthetic hematite slabs with 0.01 to 0.90 at. pet Ti and with 0.30 at. pet Ca were made. Additions of titanium and of calcium both increased the electronic conductivity with titanium yielding greater n-type behavior and calciurn p-type behavior. Reduction studies of hematite to magnetite in CO-CO2 atmospheres between 600° and 900°C initially exhibited linear kinetics. These linear rates were increased by additions of titanium and decreased by calcium. IN recent years many studies have been reported in the literature on the kinetics of the reduction of hematite and magnetite to iron. In addition, Hansen and Josephl and Schenck and Schultz2 have reported studies on the reduction of hematite to magnetite, the first step in total reduction to iron. In order to evaluate the results of the studies of over-all reduction in terms of the actual mechanism of the reaction and to define further the important factors in the rate- controlling mechanism of the magnetic roasting reaction, the following experiments were undertaken. Specimens of undoped hematite and hematite containing titanium or calcium in solution as doping agents were reduced to magnetite in CO-CO2 mixtures. In addition, electrical-conductivity measurements were correlated with the reduction kinetics using concepts of defect solid-state chemistry. EXPERIMENTAL Fisher certified Fe2O3 powder was used to make specimens for both the electrical and kinetic studies (see Table I for analysis). Doping with titanium and calcium was accomplished by adding TiO2 and CaO powders to the Fe2O3 powder. The powders were mixed in a Waring blender for minimum times of 1/2 hr. Satisfactory blending was achieved based on comparison of analyses of individual specimens af- ter reduction. The specimens were formed in a steel die using opposed punches with a rectangular opening 10.0 by 40.0 mm. The Fe2O3-TiO, platelets were pressed cold at 16,000 psi. They were sintered for approximately 16 hr at 1075°C in air, in accordance with information in the literature3, 4 on the time and temperature needed to obtain solution of the titanium in the hematite. The Fe2O3-CaO mixtures were first cold-pressed at 20,000 psi and sintered for 3 hr at 1225°C to insure solution of CaO. This material was then ground to -325 mesh in a 6-in. ball mill and the resulting powder was used to make platelets in the same manner as above. The sintered platelets were usually between 1/16 and 1/8 in. thick. They were ground on a carborundum wheel and polished on 2/0 paper. Typical dimensions of the kinetic-study specimens were 1.6 by 0.8 by 0.05 cm, and a typical weight was 0.3 g. Conductivity and thermoelectric specimens were approximately the same size, but were subjected to further sintering in order to ensure maximum densification. Finally, all specimens were measured to the nearest 0.0005 in. and weighed on a Mettler H-15 balance to the nearest 0.0001 g and the density calculated. The average density of the specimens used for the reduction studies was 4.87 g per cc, or 7.1 pet total porosity. The standard deviation ranged from 0.14 to 0.063 g per cc within a composition group. In the present study, the apparent surface area as measured with a micrometer was taken as the true surface area. The chemical analyses for calcium and for titanium within a group showed maximum variations of 50.04 pet from the average values used in Figs. 9 and 11. In order to suspend the specimen from the balance for the kinetic studies, a hole, 0.03 in. in

Jan 1, 1965

By J. Chipman, G. G. Hatch

T. ROSENQVIST*—It is a pleasure to see the excellent way in which the experimental part of this work has been handled. There seems to be little doubt that the distribution data obtained corresponds most closely to thermodynamic equilibrium under the prevailing reducing conditions, namely equilibrium with graphite and one atmosphere CO pressure. The desulphurization curves in Fig 10 show the same general feature as the curves given by Holbrook and Joseph, but the distribution ratios are from 20 to 40 times greater—undoubtedly due to a closer approach to true equilibrium. In the theoretical discussion, the authors calculate a theoretical distribution (S) ration -jg-. which they find to be about 50 times greater than the experimental. The deviation is so great that the basis for their calculation needs a more thorough examination. The authors base their thermodynamic calculation on free energy expressions where diluted solutions of FeS and CaS are used as standard states. (The activity coefficient in diluted solutions is taken to equal unity.) Such a standard state will change when the nature of the solvent is changed. Taking the free energy of the reaction [FeS] ? (FeS), Eq 2, which is derived from the distribution of sulphur between an iron and a FeO-melt, it is very unlikely that the free energy of this reaction will be the same for a distribution between pig iron and a calcium silicate slag. Therefore a more fundamental basis for the thermodyuamic calculations seems needed, where all thermodynamic equations are referred to unambiguously defined standard states. The most natural standard states for CaO and CaS are the pure solid substances at the same temperature. As standard state for sulphur in iron, pure liquid FeS can be used. This rules out Eq 2 [FeS] ;=s (FeS) because ?F° = 0. The standard equation will then be: FeS, + CaO6 + Cgraph ?Fei + CaS8 + CO. vFo1773 = 25,000 cal It would be more universal and also simpler to refer the escaping tendency of sulphur in liquid iron to the corresponding H2S/H2 ratio which can readily be determined experimentally. As standard state a gas mixture H2S/H2 = 1/1 can be used. (This corresponds at the temperature of liquid iron closely to one atmosphere S2 vapor.) Thus the standard equation for the sulphur reaction can be formulated as follows: H2S0 + CaO3 + Cgraph ?H2o + CaS8 + COg The standard free energy of this reaction has been calculated from the best available data to AF°m3 = —35,000 cal. This gives for the equilibrium constant at 1500°C Now, the solubility of CaS in blast furnace slags has been determined by McCafferey and Oesterle* and corresponds at 1500°C to about 10 pet S (varying somewhat with the composition of the slag.) If the activity of CaS is assumed linear between 0-10 pet as curve 1, (see Fig 11), then acaO = 0.1 (S); (S) being wt. pet sulphur in the slag. For a diluted solution of sulphur in an iron melt saturated with carbon, the ratio H2S/H2 is, according to Kitchener, Bockris and Liberman,f about 0.01 [S], [S] being wt. pet sulphur in iron. Substituting these values in the expression for Kp we find The value 2.103 is only 4 times greater than the experimental coefficient found by Hatch and Chipman, but the value is very sensitive to a small error in AF°. A better agreement with the experimental distribution coefficient can be obtained if one assumes the activity of CaS to run like curve 2 (Fig 11). This (S) will give a lower theoretical W, value, a value which varies with (S) exactly as Hatch and Chipman learned. Such a shape of the activity curve, which corresponds to a positive deviation from Raoult&apos;s law, is actually to be expected from the fact that liquid silicate and sulphide phases usually show incomplete miscibility. A closer agreement between experimental and theoretical data can not be expected before we have more complete data for the individual activities of CaS and CaO in the slag. The activities acaS and Ocao referred to the solid phases as standard states, are exact defined quantities contrary to the somewhat undefined expression "free lime," and they are independent of any theory for the constitution of liquid slag. J. CHIPMAN (authors&apos; reply)—The authors wish to thank Mr. Rosenqvist for his very interesting and useful thermodynamic addition. Curve 2 of his figure offers the needed basis for explaining the increase in the ratio (S)/[S] with increasing sulphur content. Attention is called to an error in the printed paper: Fig 2 and 3 are reversed. M. TENENBAUM*—In the figures showing the relationship between excess base and sulphur distribution (Fig 6, 7 and 9) the slope of the curve tapers off in the negative basicity range. Somewhat the same thing is observed with open hearth slags. In that case, the fact that some sulphur distribution between slag and metal is obtained with negative basicity is interpreted as indicating some dissociation of the lime silicate compounds whose existence in oxidizing basic slags has been used to explain various observed phenomena with regard to other slag-metal reactions. In the case of the blast furnace slags, the reduced slope of the sulphur distribution curve with decreasing excess base is attributed to the amphoteric effect of alumina. Has the possibility of other explanations been investigated ?

Jan 1, 1950

By R. E. Boni, G. Derge

Application of surface tension measurements has been made to molten silicates in order to determine the effect of sulphur upon the surface tensions of synthetic blast furnace slags. In melts with the same molar ratios of AI2O3 + SiO2 to the basic oxides BaO, CaO, and MgO, the surface tensions increase in the order of oxides listed. Sulphur lowers the surface tensions of the basic BaO, basic CaO, acid BaO, acid CaO, and acid MgO slags in that order; and the concentration of excess sulphur at the slag surface increases in this same order of slags. The rate and amount of desulphurization of iron by these slags is favored by a low excess surface sulphur in the slag. IN a previous paper,1 the authors discussed the applications of surface tension measurements of molten silicates to problems of metallurgical interest. Of major importance is the aid that such studies lend to forming a working concept of slag structure. Since the ability of a slag to desulphurize metal depends strongly upon its composition,2"4 fundamental information about the structural differences between various slags which contain sulphur should aid the development of better desulphurizing media. For that reason, the present investigation concerns the effect of sulphur upon the surface tensions of synthetic blast furnace slags. Experimental Procedure , The maximum bubble-pressure method was used to measure the surface tensions of synthetic blast furnace slags in the temperature range 1300° to 1600°C. The method is based upon the equation which was developed by Schrödinger5 from a consideration of the forces of hydrostatic pressure and surface tension of a liquid which oppose bubble formation when a gas is forced through a tube immersed in the liquid. where y is the surface tension between argon and slag in dynes per centimeter; g is the gravitational constant, centimeters per second2; H is the manometer reading in centimeters; s2 is the density of manometer fluid in grams per cubic centimeter; S1 is the density of the medium in grams per cubic

Jan 1, 1957

By T. J. Whalen, S. M. Kaufman

Surface-tension measurements for liquid Fe-C-Co and Fe-C-Ni alloys were performed by the sesszle-drop technique at 1350o and 1425°C. Cobalt was shown to he more effective than nickel in lowering the surface tension of Fe-C alloys A minimum value for surface tension of 1640 dynes per cm was found in the Fe-C-Co system at a concentration of 1.5 pet C and 12pet Co. Analysis of these measurements in terms of adsorption and desorption behavior indicated that cobalt and nickel lower surface tension in Fe-C alloys by replacing carbon at the liquid-vapor interface. Comparison of results to date for Fe-C liquid alloys has shown that most substitutional-type elements having about the same atomic diameter as iron also have relatively the same influence on surface tension when present in dilute amounts. It has been shown previously that surface-adsorption behavior in liquid Fe-C ternary alloys is related to the manner in which the ternary addition affects the activity of carbon in the bulk solution.&apos; Certain ternary additions, such as chromium, tending to decrease carbon activity cause adsorption of carbon and chromium to the liquid-vapor interface. Additions, such as silicon, increase the carbon activity, resulting in a desorption of carbon and an adsorption of silicon. Both cases were shown to cause a decrease in surface tension due to adsorption. It is the object of this paper, as part of the writers&apos; continuing interest in the effect of alloying additions on the surface tension of Fe-C alloys, to present and discuss surface-tension data on solutions in the ternary systems Fe-C-Co and Fe-C-Ni. Available activity measurements for these systems in the solid state indicate a strong increase in carbon activity when either nickel or cobalt is added to Fe-C alloys.2, 3 EXPERIMENTAL PROCEDURE The alloy compositions used are shown in Table I. These alloys were prepared by vacuum melting in stabilized zirconia crucibles and then vacuum casting into cold-steel molds. The nominal analyses for the alloys used in this investigation are given in Table I. Surface tensions and densities were measured by the sessile-drop method4,5 in conjunction with the tables of Bashforth and bdams.&apos; Specimens were prepared by slicing 1/4-in. cubes from the center of the vacuum-cast ingots and grinding the edges of these cubes until their shapes approximated spheres with flat bottoms. Proper handling techniques, including an acetone rinse immediately before use, assured minimum contamination from sources extraneous to the actual melting. For each experimental run a sample was placed on a BeO plaque and positioned and leveled inside a vacuum induction heating apparatus. The sample and plaque arrangement sat inside a molybdenum tube which acted as the susceptor. Diagrams of this apparatus may be found in the literature.= After heating to temperatures just above the liquidus at pressures of the order of 10-4 to 10- 5 mm Hg, photographs of the drop profile were made using its natural thermal radiation as a light source. Some measurements were made with partial pressures (-1 cm Hg) of a mixture of H2 and He gases. The H2-He atmospheres proved to be necessary at higher nickel contents to retard excessive vaporization losses. Chemical analysis for carbon and the ternary addition was performed for each alloy sample after completion of the experimental run.

Jan 1, 1964

By N. A. Gokcen, E. S. Tankins, G. R. Belton

Equilibrium in the reaction H2(g) + O[in liquid iron, cobalt, or nickel] = H2O(g) has been investigated over wide temperature and composition ranges. Oxygen has been found to obey Henry&apos;s Law in each of the three metals at 1550°C. The standard free-energy changes for the above reaction are given by: (1550° to 1700°C) ?Foco = -45,360(±290) + 16.16(±0.16)T (1490° to 1700°C) ?Fo Ni = -48,170(±220) + 16.12(±0.12)T (1465° to 1700°C) where the standard state for dissolved oxygen is the I wt pet solution. ThE thermodynamic behavior of dilute solutions of oxygen in molten iron has been the subject of many investigations over the last thirty years,&apos;-&apos;4 the majority of the investigators having utilized the reaction:

Jan 1, 1964

By Robert Baschwitz, John Chipman

The distribution of silicon between liquid silver and Fe-Si-C alloys has been studied at 1420oand 1530°C. The data are consistent with earlier studies. New data of Hager on the liquidus lines of the system Ag-Si and the distribution data are used to obtain the activity coefficient of silicon in both liquid phases. Data on the heat of mixing in iron permit accurate extension to 1600°C. Equilibrium data involving SiO2 and silicon in liquid iron together with revised data on the free energy of SiO2 are used to fix the activity of silicon in the infinitely dilute solution. The binary system exhibits strong negative deviation from ideality. At infinite dilution ? Si at 1600" is 1.25 x 10&apos;3, and at concentrations up to NSi = 0.4 the slope d InySi/dNSi has a constant value of r; = 13. It is found that logysi in the ternary solutzon is approximately but not exactly the same function of Nsi + NC as of NSi in the binary. The results are consistent with currently available data on the free energy of Sic and its solubility in molten iron. LIQUID solutions of the system Fe-Si-C have acquired considerable importance as the laboratory prototypes of blast furnace hot metal. Equilibrium studies involving such solutions and slags approximating those of the blast furnace have yielded useful information concerning the thermodynamic properties of blast furnace slags. In studies of this kind great importance attaches to a knowledge of the thermodynamic activity of silicon in the solution as a function of temperature and composition. An attempt was made by Chipman, Fulton, Gokcen, and askey&apos; to evaluate all of the pertinent data on this system and to deduce the desired relation between activity, composition, and temperature. These authors published data on the solubility of graphite and Sic in molten Fe-C-Si solutions and on the distribution of silicon between liquid iron and liquid silver. They showed further how the activity of silicon in very dilute solutions in liquid iron could be calculated from equilibrium data involving the molten alloy and solid SiO,. These calculations rested on the published thermodynamic properties of SiO, in- cluding its heat of formation which at that time was recorded as -209.8 kcal. This value has been under suspicion for some time and has recently been replaced by the concordant results from two independent laboratories2,3 which place the heat of formation of a-quartz at -217.6 kcal. This revision necessitates a re-evaluation not only of the activity of SiO2 in slag but also of silicon in molten iron. It is the purpose of this paper, therefore, to recalculate the activity of silicon, and in furtherance of this objective to present new data on its distribution between liquid Fe-Si-C alloys and liquid silver. HEAT OF SOLUTION OF SILICON IN IRON In order to determine the effect of temperature upon the activity coefficient it is necessary to know the heat of solution of silicon in iron as a function of composition. This is found in the data of Korber and Oelsen4 shown in Fig. 1. The curve corresponds to the following equation, which is of a form suggested by Wagner:5 Here AH is the heat absorbed in kilocalories in forming one gram atom of molten alloy from its molten elements and the N&apos;s are atom fractions. The relative partial molal enthalpies of the components, each referred to its pureliquid state and defined as zFe = aFe - PFe and zsi = HSi — -psi, are shown graphically. At low concentrations zSi = -28.5 kcal, in agreement with Kijrber and Oelsen&apos;s computation. This is in good agreement with the value of -29.3 kcal obtained by Chipman and Grant6 using an entirely different method. ACTIVITY AT INFINITE DILUTION From the known free energy of SiO, it is possible to obtain the activity of silicon in dilute solution in liquid iron from equilibrium studies. The heat of formation of a-quartz is —217.6 kcal and the heat capacity and entropy data are given by Kelley and ~ing.&apos; The free energy of formation of ß-cristo-balite at temperatures above the melting point of silicon is expressed by the following equation: Si(Z) + O2(g) = SiO2 (crist); AF" =-226,500 + 47.50T [I] The value of the deoxidation product for silicon [%Si] x [%O]2 at 1600°C according to Gokcen and chipmans is 2.8 x 10"5, in agreement with results of Hilty and Crafts.9 More recent works of Matoba,

Jan 1, 1963

By Donald B. Evans, Robert D. Pehlke

The solubility of nitrogen in liquid Fe-A1 alloys has been measured up to the solubility limit for formation of aluminum nitride using the Sieverts method. The activity coefficient of nitrogen decreases slightly with increasing aluminum content in the range of 0 to 4 wt pct Al. Based on a nitride composition, AlN, the standard free energy of formation of aluminum nitride from fhe elements dissolved in liquid iron has been determined to be: ?F" = -59,250 + 25.55 T in the range from 1600º to 1750ºC. The solubility of nitrogen in liquid iron alloys and the interaction of nitrogen with dissolved alloying elements in liquid iron have been the subject of a number of research investigations.&apos; Most of this work, however, has been reported for concentrations well below those necessary for the formation of the alloy nitride phase. Data in the concentration region near the solubility limit of the alloy nitride, particularly for systems exhibiting stable nitrides, are important in evaluating the denitrifying power of various alloying elements. They are also useful in determining the stability of a given nitride if it is to be used as a refractory to contain liquid iron alloys. In view of the importance of aluminum as a deoxidizing agent in commercial steelmaking and the fact that its nitride, AIN, is a highly stable compound and has merited some consideration as an industrial refractory, the following investigation was undertaken. The use of the Sieverts technique provided a measurement of the equilibrium nitrogen solubility in liquid Fe-A1 alloys as a function of nitrogen gas pressure up to 3.85 wt pct A1 in the temperature range of 1600º to 1750°C. The values obtained by the Sieverts method were checked by means of a quenching method in which liquid iron was equilibrated with an A1N crucible under a known partial pressure of nitrogen gas, and the solubility of A1N in liquid iron determined by chemical analysis. EXPERIMENTAL PROCEDURE The theoretical considerations involved in determining the solubility product of a solid alloy nitride phase in liquid iron by measuring the point of departure of the nitrogen gas solubility from Sieverts law have been discussed by Rao and par lee.&apos; The principal problem is to determine the variation of nitrogen solubility in an alloy as a function of the pressure of nitrogen gas over it with sufficient precision to establish the break point in the curve at the solubility limit of the alloy nitride phase. A fairly large number of data points are required to do this. A second problem is the determination of the composition of the precipitated solid nitride phase. This is necessary in order to define completely the thermodynamic relationships. The Sieverts apparatus used to make the nitrogen solubility measurements in this investigation is of essentially the same design as that described by Pehlke and E1liott.l The charge materials were Ferrovac-E high purity iron supplied by Crucible Steel Co. and 99.99+ pct pure aluminum. Recrystal-lized alumina crucibles were used, and were not attacked by the liquid alloys. The hot volume of the system which was measured for each melt ranged from 46 to 50 standard cu cm and was found to decrease linearly with decreasing pressure and with increasing temperature. The temperature coefficient of the hot volume at 1 atm pressure of argon gas was essentially constant for all experiments at a value of -6 X 10-3 cu cm per "C. The melt temperature was measured with a Leeds and Northrup disappearing filament type optical pyrometer sighted vertically downward on the center of the melt surface. The temperature scale was calibrated against the observed melting point of pure iron taken as 1536°C. The emissivity of all melts was assumed to be that of pure iron, taken as 0.43. The charge weights ranged from 110 to 140 g and the range of aluminum contents covered was from 0 to 3.85 wt pct. Aluminum additions were made as 12 to 15 wt pct A1-Fe master alloys previously prepared in the system under purified argon. The compositions of the master alloys were checked by chemical analysis and found to be in agreement with the charge analyses. Vertical cross sections of the master-alloy ingots were used as charge material for the equilibrations in order to minimize the effect of any segregation which might have occurred during solidification of the master alloys. Determinations of the solubility product of

Jan 1, 1964

By M. L. Pearce

A comparison of the isotope-dilution, vacuum-fusion, and chemical methods of analysis for nitrogen in Si-Fe is made with particular emphasis on the effect of sample history. The superiority of the isotope-dilution method from the point of view of 1 HE analytical techniques used to determine nitrogen in Si-Fe have been subjected to close scrutiny in recent years primarily because of the marked influence of the element on the properties of the alloy. These investigations have led to a diversity of opin- both precision and accuracy is demonstrated. The solubility of nitrogen in 3.06 pct Si-Fe is investigated and the effect of silicon content on the activity coefficient of nitrogen is derived. ion regarding the reliability of the vacuum-fusion and chemical methods of nitrogen analysis when applied to si- Fe.&apos;-&apos; A majority of workers appear to favor the vacuum-fusion method over chemical methods particularly in those cases where part of the nitrogen may exist as silicon nitride or the total nitrogen content is very low. Contrary views have been expressed, however,&apos; and it has been demonstrated that for some Si-Fe alloys both methods yield results which are significantly lower than those

Jan 1, 1963

By M. G. Benz, J. F. Elliott

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

Jan 1, 1962

By Donald B. Evans, Robert D. Pehlke

The solubility of nitrogen in liquid Fe-B alloys has been measured up to the solubility limit for the formation of boron nitride. The activity coefficient of nitrogen increases with increasing boron content in the range 0 to 7 wt pct B. From experimen -tal data, values have been calculated for the B-N interaction parameter e3 at temperatures in the range 1550" to 1750°C. A value of 0.038 has been estimated for the boron self-interaction parameter eg at 1550°C. The standard free energy of decomposition of boron nitride into the elements dissolved in liquid iron has been determined to be: ?F° = 45,900 -21.25T in the range from 1550° to 1750°C. The nitride is assumed to be of composition BN. BORON nitride has an unusual combination of properties which make it appear attractive in a wide range of engineering applications. Some of its more important and most recent applications are in the nuclear area, particularly in connection with the liquid-metal cooled reactor concept now receiving considerable emphasis. Boron nitride has a high degree of stability at elevated temperatures. It also has excellent ma-chinability and the ease with which its crystals deform suggests applications as a lubricant. These properties stem from a hexagonal layer-type structure similar to the structure of graphite. One of its primary uses to date has been for seals in liquid-metal pumping systems. It is also used in nuclear reactors as an insulating layer to separate two solid metals which are not themselves compatible under the conditions of temperature and atmosphere in which they are used. Its inertness to liquid metals has also suggested use as a mold-release agent in casting processes. In addition to its excellent machinability and reported inertness to liquid metals such as iron, silicon, aluminum, copper, and zinc, boron nitride has high thermal conductivity and excellent thermal shock resistance. This combination of properties would make it appear ideal as a refractory crucible material for refining of high-purity liquid metals, for example high-quality steels. However, since it is known that concentrations of boron as low as 50 ppm can have a marked effect on the physical properties of certain steels,&apos; in particular on the creep and stress-rupture properties, an investigation was undertaken to define accurately the chemical equilibrium among boron, nitrogen, and liquid iron in the range of steelmaking temperatures. EXPERIMENTAL PROCEDURE Two experimental approaches to this problem were employed: a Sieverts&apos; method and a quenching method. In the first method, the Sieverts&apos; technique was used to measure the equilibrium nitrogen solubility in liquid Fe-B alloys of 0 to 7 pct B as a function of nitrogen gas pressure over the melt. The solubility limit of the boron nitride phase formed was determined by the point of departure of the nitrogen absorption from Sieverts&apos; Law. This technique has been applied to liquid Fe-Ti alloys by Rao and parlee,&apos; to liquid Fe-A1 alloys by Evans and Pehlke,3 and to solid Fe-V alloys by Fountain and Chipman.4 In the second method a melt of liquid iron was held in a crucible of boron nitride under a known partial pressure of nitrogen gas. After thermodynamic equilibrium was attained, the melt was quenched in a stream of helium and then analyzed by wet-chemical methods for boron and nitrogen. The Sieverts&apos; apparatus used in the first method was essentially of the same design as the one described by Pehlke and Elliott.5 The charge materials were vacuum-melted high-purity iron (Ferro-vac E) supplied by the Crucible Steel Co. and -325 mesh boron powder supplied by Cooper Metallurgical Associates of Cleveland, Ohio. The boron contained less than 0.02 wt pct O, according to supplier&apos;s analysis. Recrystallized alumina crucibles were used to contain the melt. Examination of solidified melts showed these crucibles to be satisfactory with no evidence of any reaction or physical penetration of the crucible wall by the melt. The melt temperature was measured by a disappearing filament-type optical pyrometer sighted vertically downward on the melt surface through a 1/4-in.-diam sight hole in the crucible lid. The pyrometer was calibrated against the melting point of pure iron in the same apparatus, taking the emissivity of

Jan 1, 1964

By G. W. Healy, J. C. Schottmiller

Molten silicates were found to exist in the Cr-Si-0 system at temperatures above 1450°C. one atom of oxygen is readily removed from CrzOs in the presence of Si02 at 1700°C, forming a silicate melt. Steam-hydrogen ratio measurements made at this temperature indicate that the free energy of the reaction: Cr20s(c) + Hz = 2CrO (in Si02 -saturated melt) + H20 is approximately 5600 * 1500 cal. A deep-blue chromous silicate, probably Cr2Si04, forms from these melts at about 1400" to 1500°C, and is characterized by.its distinctive X-ray diffraction pattern and optical properties—distinct pleochroism and high refractive indices. THE question of the state of oxidation of chromium in slags has vexed metallurgists for many years The experiments of Koerber and Oelsenl suggested the probable presence of divalent chromium in silica-saturated slags equilibrated with high-chromium melts. Hilty and coworkers2 had also found chromium at lower valency, as Cr304, in inclusions formed from oxygen-saturated Fe-Cr melts with as little as 10 pct Cr. In both cases, disproportiona-tion of the lower oxide to CraO3 and chromium was found to occur to a greater or lesser extent, depending upon the rate of cooling from the high temperature. The work on Cr304 was sufficiently detailed for chipmans to derive its thermodynamic properties, but Oelsen&apos;s experiments in the silicate system were not extensive enough since most of his runs were made with slags containing large amounts of manganese oxide in addition to iron and chrome oxide and silica. The present study describes experiments carried out to map out an approximate liquidus diagram in the CrzOs, "CrO", SiOa portion of the Cr-Si-0 system, and to measure the partial free energy of solution of oxygen in the system. EXPERIMENTAL 1) Approximate Melting-Point Determinations. Preliminary trials showed that when an equimolar mixture of Cr20s and SiOa was treated with hydrogen in the temperature range 1500" to 1600°C, copious amounts of steam were evolved, and a low-melting liquid formed which could be quenched to a blue, crystalline, material having a distinctive X-ray diffraction pattern. It was found that the identical material could be produced by heating intimately mixed, finely divided Cra03, Cr, and SiOa, held in a tungsten crucible, under purified argon. Thus, it was possible to prepare mixtures containing any desired proportions of chromium, silicon, and oxygen, pel-letize them, heat to temperature in the furnace shown in Fig. 1, and observe, after cooling, whether the pellet remained unchanged or showed signs of incipient, partial, or complete melting. 2) Free Energy of Solution of Oxygen. This was studied by measurement of steam-hydrogen ratios for the reaction: H20 (gas) + O (dissolved in charge) + Ha (gas) The experimental method chosen was to prepare a

Jan 1, 1964

By J. A. Cahill, A. D. Kirshenbaum

Using an alumina or zirconia crucible with an alumina sinker or a molybdenum sinker coated with zirconium dioxide, the density of liquid iron was determined by the immersed-sinker method over the temperature range of 1800" to 2500°K. The density, with respect to temperature, is ex-Dressed by the equation Dg/cm = 8.523 - 8.358 X 10 T&apos;K The molar Volumes and thermal coefficients of expansion were calculated. Iron, upon me1ting, was found to expand 3.5 pct. A basic knowledge of the physical properties of materials at high temperatures is becoming increasingly important. A check of the literature shows, that in spite of the importance of iron, very few measurements have been made of its physical properties in the liquid state. Density measurements have been made by Benedicks and his collaborators1g using the method of balanced columns, by Desch and smith4 using the immersed sinker method with an alumina sinker, by Lucas using the maximum bubble method5 and by Stott and endall&apos; who used an alumina pyknometer. In the method of balanced columns, the difference in level of molten iron in two arms of a U-tube, together with the corresponding difference of pressure had to be measured. The formation of gas bubbles in one or both arms was a great source of error. These values are very erratic. They vary from 6.83 to 7.45 g per cm3 at the melting point (1805"~) and from 6.45 to 7.15 g per cm3 at 1890°K. Stott and Rendall determined the density at 1837"K, with a reproducibility of *0.2 pct. They used an alumina pyknometer fired to 1973°K. The vessel was filled in a vacuum furnace by immersion in the liquid metal. When thermal equilibrium was attained, the pyknometer was withdrawn, cooled, the ingot removed and then weighed. The chief disadvantage of the method was the difficulty of inserting the pyknometer without cracking it. The authors have been able to determine the density of liquid iron from its melting point up to 2500°K, by using the immersed-sinker method, with A1203 or ZrOz crucibles and A1203 or molybdenum sinkers coated with Zr02, Fig. 1. EXPERIMENTAL Apparatus. In these studies the source of heat was the carbon tube resistance furnace with an argon atmosphere described previously.7 Experimental runs were made using either Ala3 or ZrOz crucibles. The sinkers used were 1) pure A1a3 and 2) molybdenum coated with ZrOz. The crucible, 2 1/8 in. in diam and 3 in. high, was centered in the furnace on an Ala3 of Zr02 pedestal. The sinker, 1/2 in. in diam and 1 1/2 in. long, together with a counter weight, was suspended from an analytical balance into the melt by a molybdenum wire. Procedure. The procedure, as described previously,&apos; consisted in measuring the weight loss of the sinker in the liquid iron while determining simultaneously the liquid iron temperature by means

Jan 1, 1962

By John Chipman

THE equilibrium between titanium in liquid iron and titanium oxides has been studied by Hadley and Derge.&apos; They have shown that a minimum occurs in the oxygen content of the metal between 0.1 and 1.0 pct Ti, but its exact level was not fixed. The oxide phase in this minimum range was principally TiO, containing some iron oxide. On the other hand, for concentrations above 5 pct Ti the oxide phase was TiO and the oxygen content of the metal increased rapidly with increasing titanium content. From their observations and the free energy of Ti0 and TiOz reported by Kelley and ah,&apos; it is possible to derive approximate values for the activity coefficients of titanium and oxygen in liquid iron-titanium alloys and the conditions for equilibrium in steel deoxidation. Neglecting possible departures from the stoichio-metric composition, the condition of equilibrium with Ti0 may be expressed as follows: TiO= Ti_ + C) log K = log NTl + log [% O] + log yTi + log fQ Here as a matter of convenience the titanium concentration is expressed in mol fraction while that of oxygen is in weight percent. The activity coefficients are yTi and fo. The value of log fo approaches zero as the concentration of titanium approaches zero, while that of log yTi approaches a limiting value of In Fig. 1 the sum of log NTi + log [% 0] is plotted for mol fractions of titanium between 0.05 and 0.50. The smooth extrapolation gives a value of —4.15 which corresponds to log K — log y:i . We therefore have the equation: According to the data of Kelley and Mah,&apos; the free energy of formation of Ti0 at 1900°K is -82,400 cal. The free energy of solution of half a mol of oxygen in iron, taking 1 pct 0 as the standard state, is -29,300 cal. From these we write: From these equations the activity coefficient of titanium at infinite dilution in iron is found to have a value of 0.011 or log y°. = -1.96. This is only an approximate value but is certainly better than the estimated 0.05 in Basic Open Hearth Steelmaking To obtain approximate values for the activity coefficient at intermediate concentrations, it is as- sumed that log yTi(l is constant and equal to -1.96. This corresponds to a value of E;: = 3 In yTi/aNTi = 9.0 which is not unreasonable We now have the value for the activity of titanium and the percentage of oxygen in equilibrium with TiO. It is therefore a simple matter to calculate the activity coefficient of oxygen which is shown in Fig. 2. The effect of titanium is rather large, being comparable to that of vanadium, but not so large as has been reported for aluminum. The slope of the line at low concentrations corresponds to E: = aln yo/ aNTi=-0.37. At concentrations below 1 pct Ti the deoxidation constant and oxygen content for equilibrium with TiO, can be calculated from the foregoing data and the free energy of formation of TiO,, which according to Kelley and Mah is -144,600 cal at 1900°K. The free energy of solution of oxygen has been given; that of Ti to form a dilute solution with 1 pct Ti as the standard state is RT ln (0.5585 y:i/47.9) = -34,800 cal. From these data we find (for concentrations in wt pct): TiO, = Ti + 2 -0; hFTgO0= + 51,200 cal log if =-5.89 The interaction coefficients, concentrations being expressed as wt pct, are e;: = alogfTi/a[% Ti] = +0.048 and e:&apos; = a logfo,/a[ojTi] = -0.187. The calculation gives the following results which, in view of the impurity of the oxide phase, must be regarded as approximate:

Jan 1, 1961

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

The activity coefficient of sulfur in Cr-Fe-S melts was determined by measuring the values of Ph3Rh,in equilibrium with such melts. The results showed that chromium has a pronounced negative effect on the activity coefficient of sulfur, which up to about 20 pct Cr may be represented by the equation: log f; = - 0.019 pct Cr It was also found that the influence of chromium was not altered by the presence of appreciable amounts of carbon or silicon. The influence of alloying elements on the activity of sulfur in molten iron has been the subject of many investigations; however the effect of one important alloying element, chromium, has not been reported, and the object of the present investigation was to determine its effect on the activity coefficient of sulfur in liquid Fe-Cr-S alloys both in the absence and in the presence of carbon and/or silicon. EXPERIMENTAL PROCEDURE The general method employed consisted of passing mixtures of hydrogen and hydrogen sulfide over the sulfur-containing melt of interest and analyzing the outgoing gas to determine the equilibrium value of which resulted from the reaction shown in Eq. 111. H, (gas) + S (dissolved in melt) = H,S (gas) 111 The activity coefficient of sulfur, fs, was then calculated with Eq. [2] in which K, is the known equilibrium constant of Eq. [I] for dilute solutions of sulfur in iron. Raw materials used in the preparation of the charges included commercial grades of electrolytic iron and chromium and carbon-reduced, acid-treated silicon of 99.9 pct purity. Oxygen in the former presented no problem since it was removed by hydrogen in the normal course of an experiment. Carbon was added in the form of premelted iron-carbon and chromium-carbon master alloys. Sulfur was charged as iron sulfide prepared by first heating powdered iron and sulfur in air in an alumina dish until reaction occurred, and then deoxidizing by melting in a hydrogen atmosphere. Commercially bottled hydrogen and hydrogen sulfide were used after being passed through purification systems containing palladium, "Drierite," and magnesium perchlorate in the case of hydrogen, and "Drierite" alone in the case of hydrogen sulfide. Lamp-grade cylinder argon served as a flushing agent without further purification. Charges weighing from 300 to 500 g were placed in a high-purity alumina crucible of 0250-ml capacity and heated in an argon atmosphere in the induction-heated carbon-tube furnace illustrated in Fig. 1. During heating, a dry hydrogen atmosphere was substituted for argon in order that deoxidation of the charge and flushing out of argon would be accomplished sooner. After the charge melted, a Pt-Pt 10 pct Rh thermocouple contained in an alumina protection tube was immersed in the melt, and the desired melt temperature (usually 1600°C) was established. Higher temperatures up to 1760°C were required for some chromium-rich alloys because of their higher melting points, and in these cases a Pt 6 pct Rh-Pt 30 pct Rh thermocouple was used. The thermocouple output was fed to an automatic controller which provided straight line temperature

Jan 1, 1961

By Nicholas J. Grant, Rolf Nordheim, Thomas B. King

Constant-load creep-rupture tests were conducted in an argon atmosphere at temperatures of 1600 to 2200°F on two heats of iron containing about 0.06 and 0.09 pct P in solid solution. The tests were conducted in the as-cast condition. Stresses were selected to give strain rates approaching those encountered in the hot working of steel, and within the limits of the creep-rupture test apparatus, namely. from about 0.001 to 50 pct per sec. FOR generations, rolling and forging practices have been developed largely by empirical methods, based on prior experience. While largely successful, difficulties are frequently encountered when new or different alloy compositions are tried for the first time. There is need to know the relationships which exist among temperature, strain rate, composition, and other variables on the deformation and fracture characteristics of steels. It has been shown for aluminum and several high-temperature alloys that the deformation and fracture characteristics follow rather well-defined laws and patterns which are closely related to the effects of strain rate, temperature, and composition.1"3 As the melting temperature of aluminum or its alloys was approached, it was possible to study the interplay of work-hardening factors and recovery or recrystal-lization, the latter resulting in improved ductility and increased resistance to intercrystalline fracture. In particular, the effects of composition are very poorly known. Within the meaning of "composition" should be included impurity elements, such as sulfur, phosphorous, lead, copper, and many others, as well as those elements which are added for alloying purposes in iron. The role of multiphase structures, in contrast to solid solutions, should also be studied in much greater detail. high strain rate creep-rupture tests would provide information regarding the deformation and fracture characteristics of metals at hot-working temperatures. It was also desired to establish the stresses which are necessary to accomplish the desired deformation, and to relate these to the strain rate and temperature. Secondly, it was the purpose of this particular study to determine the effects of phosphorus, within solid solution limits, on the deformation and fracture characteristics of iron at hot-working temperatures. EXPERIMENTAL PROCEDURE Two phosphorus levels were selected, one corresponding to the upper limit normally found for commercial steels, and one substantially higher than this, but within the region of solid solubility at the test temperatures chosen for this investigation. Twenty-pound heats were prepared by induction melting electrolytic iron in air in a magnesia lined furnace. After deoxidation with about 0.2 pct Al, ferro-phosphorus was added, and the heats were then poured into prefired silica molds. The purpose of using silica molds was to obtain a slow cooling rate during solidification to produce a relatively coarse grain size, producing a structure subject to some segregation and therefore more nearly characteristic of ingot structures. The major part of the casting assembly provided a large shrinkage head in order to produce sound castings and to promote slow cooling of the specimens. The primary austenitic grain size varied from ASTM No. 2 to No. 00. The composition of the heats, including a low phorphorus melt, used for comparison purposes, is shown in Table I. It will be noted that the oxygen content of the phosphorus containing heats is relatively high, in spite of the deoxidation practice, a condition which is difficult to control in small melts. Creep-rupture tests were nevertheless undertaken when it was noted that this quantity of oxygen did not appear to give results any different from those from a heat containing 0.01 pct 0, low phosphorus and comparable carbon Content;4 see Table 11.

Jan 1, 1961