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By Nev A. Gokcen

PUBLISHED data on the solubility of nitrogen in liquid manganese are widely discordant. Ochsenfeldl observed that a Mn-N alloy with 3.6 pct N consisted of solid and liquid phases at 1260°C but at 13 00° to 1340°C the solid phase disappeared and the liquid contained 0.1 to 0.13 pct N. In contrast Saito's measurements at approxhately 1400°C yielded an average value of 0.97 pct N. Sieverts3 volumetric method is not suitable for the determination of gas solubility in manganese because the liquid metal vaporizes readily and condenses in the cooler parts of the apparatus where it can absorb large amounts of nitrogen. The purpose of this investigation was, therefore, to determine the solubility of nitrogen in manganese accurately in the range of 1273" to 1500°C. The experimental method used in this study was as follows. Electrolytic manganese of 99.9 pct purity, and weighing 50 g, was melted in a pure alumina crucible placed in a tubular furnace. Temperature was measured with a Pt-10 pct Rh thermocouple and controlled within ± 5°C. Pure nitrogen was bubbled through the melt for 1 hr at constant temperature and then a sample was taken by sucking the metal into a 2-mm clear silica tube and immediately quenching in water. The sample was broken into small pieces and found to be sound to the naked eye. The entire sample was then dissolved and the resulting solution was analyzed for nitrogen by the well-known solution-distillation method. The experimental results are presented in Fig. 1. All the nitrogen solubility data refer to 1 atm of nitrogen pressure; hence the observed values are slightly corrected by using Sieverts' equation when the atmospheric pressure differed more than 5 mm Hg from 760 mm, and further, in the case of the runs at 1500°C the correction arising from the presence of Mn vapor has been made. (Cf. Eq. [3]). Scattering in the data is within ±5°C in temperature measurement and ±3 pct in total nitrogen analysis. The straight line in Fig. 1, correlating the percentage of dissolved nitrogen, %N, with the inverse temperature in OK-1, can be expressed by:

Jan 1, 1962

By N. A. Gokcen, R. A. Dodd

Solubility of nitrogen in liquid iron-manganese system at 1550°C and one atmosphere pressure has been determined by a simple method. Results show that the solubility increases from 0.040 pct for pure iron to 1.41 pct for pure manganese. DETERMINATION of the solubility of gases in volatile metals. and alloys by the well-known Sievertsl method is unreliable. This is particularly true for the Fe-Mn system since Mn vaporizes readily from the alloys containing as little as 2 pct Mn, and, upon condensing on the cooler parts of the apparatus, it absorbs large amounts of nitrogen. Further, the condensing Mn vapor interferes with the usual method of temperature measurements with an optical pyrometer.

Jan 1, 1962

By O. D. Gonzalez, H. A. Wriedt

Alloys ranging from pure iron to pure nickel were saturated with nitrogen gas at 918°, 999°, and 1217°C and analyzed. The solubility of nitrogen at 1-atm pressure was obtained as a function of nickel content for the whole range of iron-nickel alloys and the temperature dependence of solubility is shown for the experimental alloy compositions. The heat of solution and the entropy of solution of nitrogen in the alloys as func-tiom of composition up to 41 pct Ni are given. 1 HE acquisition of more exact thermodynamic information for systems composed of iron with various alloying elements continues to interest ferrous metallurgists. The interstitial alloying elements, especially carbon, hydrogen, and nitrogen, comprise a field of particularly intense study. A recent investigation of carbon solubility in Fe-Ni alloys held at 1000°C in gases of fixed carbon activity showed an unpredicted minimum in the solubility near 72 pct Ni.1 The present investigation was undertaken to see if a similar anomaly in solubility existed for nitrogen in Fe-Ni alloys. The solubility of nitrogen in ? iron at known nitrogen activities has been measured several times.&apos;-&apos; Corresponding information for the solubility of nitrogen in solid Ni and Fe-Ni alloys is not available. Juza and sachsze9 reported that metallic nickel dissolved 0.07 pct N in equilibrium with Ni3N at 445°C. This result was regarded as dubious by Turkdogan and Ignatowicz10 who found less than 0.0004 pct N in nickel specimens equilibrated at 600°C with ammonia-hydrogen mixtures having fugacities of N2 gas up to 35,000 atm. Such fragmentary reports indicate only that nitrogen gas has a very much lower solubility in nickel than in iron. MATERIALS A purified iron from Battelle Memorial Institute was used for solubility measurements. This grade contained more than 99.95 pct Fe, the highest content of any measured individual impurity being 50 ppm for each of As, C, Cu, and Pb. The nickel and iron-nickel alloys, supplied by the International Nickel Co., contained 0.02 to 0.04 pct C, 0.17 to 0.19 pct Mn, 0.04 to 0.08 pct Si, < 0.01 pct P, <0.03 pct S, and <0.20 pct Co as principal impurities. The Fe-0.59 pct Mn alloy was of zone-melted quality, the highest concentration of any individual impurity being 15 ppm Al. The "prepurified" grade of nitrogen gas from Matheson Co. had a nominal nitrogen content of 99.996 pct. An "electrolytic" grade of hydrogen gas from National Cylinder Gas. CO. in which the principal impurity is water vapor was admixed with the nitrogen to prevent oxidation of these specimens. This grade was preferred to a purer grade because the presence of some oxygen helps in suppressing contamination of the specimens, for instance, by silicon from the porcelain furnace tube. EXPERIMENTAL PROCEDURE The specimens were equilibrated in vertical tube furnaces through which a 99 pct N2-1 pct H2 gas was passed at ambient pressure. For the 915", 918", and 999°C runs, a wound-resistance furnace was used, and for the 1217°C runs, a furnace with a tubular silicon carbide element was used. The temperature control system on both furnaces was similar: a Weston "Celectray" controller with a modulator, responding to the electromotive force of a thermocouple with its hot junction in the furnace, switched the furnace current between high and low settings. The temperature distributions in the working zones of the furnaces were determined with calibrated Pt/Pt-10 pct Rh thermocouples. The overall uncertainty in temperature was estimated to be ±3° at 915° to 999°C and ±5° at 1217°C . Consideration of the small temperature coefficients of the equilibria studied, together with the error limits in the method of analyzing for nitrogen, showed that further refinement in temperature uniformity would give no improvement in resultant accuracy. The reactive gas was generated by mixing together "prepurified" nitrogen and "electrolytic" hydrogen directly from cylinders commercially supplied. The flow rates of nitrogen and of hydrogen were fixed by setting with bleeders the pressure drops across the individual calibrated flow meters of constant resistance. For any given alloy, the solubility of nitrogen at 1-atm pressure (% N) was obtained from the analyzed nitrogen content of equilibrated specimens (% Na)according to Sieverts&apos; law, thus

Jan 1, 1962

By D. C. Hilty, W. Crafts

Determination of the solubility of oxygen in iron containing silicon, or manganese, or both, has confirmed the earlier work on silicon, shown that manganese is more effective than expected, and has demonstrated that the combination of silicon and manganese is a much stronger deoxidizer than might have been inferred from their individual effects. SILICON and manganese are of primary impor-tance in the deoxidation of steel, and a study has been made at the Union Carbide and Carbon Research Laboratories, Inc. of the solubility of oxygen in iron in the presence of silicon and manganese, singly and in combination, as a basis for more effective control of inclusion formation. The investigation was carried out with the same equipment and experimental procedure that were used in the determination of the oxygen solubility of iron containing aluminum&apos;. The heats were melted in a rotating crucible furnace under an argon atmosphere. Bath temperatures were controlled by platinum/platinum +10 pct rhodium thermocouples to attain equilibrium at 1550°, 1600°, and 1650°C, so that oxygen solubility isotherms were determined directly without requiring calculation from a temperature coefficient. A detailed description of the furnace and procedure is given in the paper on aluminum deoxidation1. Oxygen solubility in the presence of more than 0.10 pct silicon was found to approximate earlier determinations closely, but some deviation was observed at lower silicon contents. Manganese appeared to be more effective than had been anticipated. The combination of silicon and manganese lowered the solubility for oxygen markedy as compared with either silicon or manganese alone. Although the solubility for oxygen in the presence of both silicon and manganese represents only a part of the information needed to control inclusion formation, it suggests a partial explanation of the benefits of this combination that have been observed in practice. Manganese and Oxygen in Liquid Iron: The study of oxygen in iron in the presence of manganese was carried out in magnesia crucibles of the type furnished commercially for laboratory induction furnaces. Alumina crucibles were unsatisfactory, because the work on the aluminum-oxygen equilibria in iron&apos; had shown that merely melting iron in an alumina crucible limited the solubility of oxygen to a level considerably below that anticipated for moderate concentrations of manganese. Silica crucibles appeared unsuitable because of the dangers of excessive fluxing by the melt. Moreover, as will be shown later, melting iron in a silica crucible also limits the oxygen content below that in equilibrium with

Jan 1, 1951

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 T. L. Joseph

A study is made of the amount of solution loss necessary to maintain the reducing power of the gas stream in the blast furnace. Curves are presented to show the effect of solution loss, moisture in the blast, and carbon dioxide from the flux on the nitrogen in the THE blast furnace process is based upon the counter flow of gases and solids. As CO, N, and H, flow upward from the combustion zones, oxygen is acquired from the descending charge. In the reduction of iron ore, a portion of CO is converted to CO, and similarly a portion of H, is converted to water vapor. The inert N,, from the air used in combustion, passes through the furnace with little change. Its concentration is, however, decreased by reactions such as direct reduction and solution loss which increase the volume of CO in the gas stream; Similarly the evolution of C02 from the limestone also dilutes the nitrogen. he purpose of this paper is to illustrate an idealized and simplified method of studying furnace processes by following changes in the gas phase between the tuyeres and the stock line. A more specific objective is to evaluate the effect of solution loss upon the CO/CO, ratio in that region of the furnace in which FeO is reduced to metallic iron. This last stage of reduction requires relatively high CO/CO, ratios to exceed the equilibrium requirements. Solution loss or the reaction of COZ with C to produce CO has a pronounced effect upon the ratio of the carbon gases and is necessary to maintain the reducing power of the gas stream if the consumption of coke is low. It will be explained later that indirect reduction followed by solution loss is stoichiometri-cally equivalent to direct reduction. Calculations will be made to show how the composition of the gas in the region of the mantle varies with coke consumption and with different amounts of solution loss. Such calculations show the condi- tions under which gasification of C with oxygen in the charge is needed to maintain the reducing power of the gas. Equilibrium conditions for FeO and the carbon gases will be used to establish a minimum CO/CO, ratio below which reduction will not proceed. The manner in which carbon is gasified in the furnace, at the tuyeres with oxygen in the air or above the tuyeres with oxygen from the charge, will be a basic feature of all calculations. It is hoped that greater interest in the use of top gas as a means of following furnace reactions will be aroused by the calculations and generalized curves which are presented. Bosh Gas Equations Subject to some alteration by the amount of moisture in the blast and by direct reduction, the gas leaving the combustion zones of a blast furnace has a definite composition. Because a relatively small amount of oxygen is acquired from the charge in the bosh and in the crucible, the products of combustion undergo little change until they enter the shaft. Bosh gas is, therefore, essentially the products of combustion of carbon in a deep fuel bed with air. The relative weights and volumes of reacting materials are expressed by the equation: 2~ + 0? + 3.76N, = 2C0 $ 3.76NZ [I] Air Bosh Gas -air = 79% N? = 3.76) 21% 02 Starting with a known mass of C consumed largely by air, Eq 1, but partly by water vapor, Eq 2, the volume and C + H2O = CO $ H? [21 composition of the bosh gas can be calculated and subsequent changes followed as reactions take place at various elevations in the furnace. As shown in

Jan 1, 1952

By T. L. Joseph

S. T. Killian (Johnstown, Pa.)—This is one of the finest papers I have read. Tying in stoichiometric calculations with furnace performance and practice is a step which had to be taken sooner or later. The noteworthy difference between Dr. Joseph&apos;s type of calculations and regular blast furnace calculations is that the Ib mol system is used as a basis. With the Ib mol system, weights, volumes, and chemical reactions can all be expressed in the same equation. In the paper, wind, ore, flux, and fuel are all expressed as lb or lb mols. Probably Dr. Joseph does not realize it, but the vague word coke appears only twice in the entire paper. Lb of C and Ib mols of C are followed through reactions but the word coke appears only as 1560 lb coke per ton of pig and 1700 lb of coke per ton of iron. Obviously in order to understand furnace reactions, the coke should be expressed as lb or lb mols of C. Furnaces can also be compared more easily. In some respects the paper is too thorough and too complete. The effects of the metalloids reduced into the iron upon the top gases represents a difference of less than 3 pct of the CO formed in the bosh. Due to the completeness of the calculations in relation to the CO/CO2 ratio, this was included and was necessary. However, the exclusion might have enabled more furnace men to follow the lb mol system of calculations through the blast furnace to a better degree. By considering only irons of similar analysis, this part of the calculations might have been omitted. However, if this had been done, total rewriting of the paper later would have been necessary in order to make the work complete as it is now. It also would not have been nearly as authoritative. In the paper, there appears the reaction: H2O + CO ? CO2 + H2 [I] Dr. Joseph states that he did not take this reaction into consideration in any calculations pertaining directly to the paper. The piobable reason- for this is that although it contains all the main reacting top gases except N2, it is rather inflexible since it is monomolecular in relation to each of the reacting gases and does not tie in with the gasification of C. Actually the reactions: H2O + C ? CO + H2 [2] 2H2O + C ? CO2 + H2 [31 and the solution loss reaction: CO2 + c ? 2c0 [41 tend to assume an equilibrium through the reaction: H2O + CO ? CO2 + H2 [I] which should be considered a balancing or equilibrium reaction. Reactions 2, 3 and 4 permit furnace conditions to balance with the CO/CO2 ratio and H2 formation. They tie in with the solution loss. Reaction 1 unites them chemically. Probably the best calculation to make at this time would be to try to find the relative importance of the CO2 from the flux and the H2 in the dilution on an actual furnace gas analysis. For this purpose the Dob-scha-Carnegie-Illinois paper—"Effect of Sized and Sintered Mesabi Iron Ores On Blast Furnace Performance" is chosen. This paper was presented before the blast furnace section of the AIME in 1948. This represents the best large scale furnace operation available to me. Unfortunately the changes were brought about by beneficiation of the burden and not by changes on one burden. In choosing the basis for the calculation in relation to the furnace, 100 mols of dry top sgas is chosen. This leaves something to be desired inasmuch as the nitrogen basis is changing but I believe it will be better understood than any other type and it is the easiest to use.

Jan 1, 1952

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 Arnlf Muan, Bert Phillips

The quenching technique has been used for- a study of phase velntiorzs within the composition triangle 2CaO.Fe2O3-FeO.Fe2O3 Fe2O3 of the system Ca-Fe-O. Desired total compositions of sanzples were attained by weighing of starting materials in required proportions and keeping them in sealed 80 pct Pt 20 pct Rh tubes during equilibration .runs. The liquidus surface has been delineated. the existence of two ternary compounds has been established, and seven ternary inwariant situations have been determined. ONE unit within the research program on refractory oxides in progress in our laboratories is the study of phase relations in the system Ca-Fe-Si-O. The present paper deals with the ternary system 2CaOFe2O3-FeO.Fe2O3-Fe2O3, which is only a small part of the enormously complex quaternary system. Many of the phases occurring in iron ore sinter products have compositions which can be closely approximated within this ternary system, and a knowledge of stability relations existing among these phases may be expected to be a useful guide for improving sintering operations. Two fundamentally different experimental approach es are commonly used in studies of systems containing iron oxides, both permitting control of the oxidation state of Fe. One method consists in keeping constant the oxygen partial pressure of the gas phase in equilibrium with condensed phases (liquid and crystalline). In the other method, which is the one used in the present investigation, the total composition of condensed phases is kept essentially constant by keeping the samples in a gas-tight container. The details of this experimental procedure will be described in a later section. PREVIOUS WORK Extensive studies of phase relations in the bounding binary system FeOFe2O3-Fe2O3 have been reported by Greig, Posnjak, Merwin, and Sosman,&apos; by Darken and Gurry,2, 3 and recently by Phillips and Muan.4 A diagram summarizing the results of these studies is shown in Fig. 1. Particular attention is

Jan 1, 1961

By M. V. Nevitt

In the systems Ti-Mn-O, Ti-Fe-O, Ti-Co-O, and Ti-Ni-O the bounda.r-ies of the Ti2Ni-type phases were determined at one or more temperatures and the variation of the lattice parameter with oxygen content was determined. Densities were calculated from the lattice parameters and compared with measured density values. The: results indicate that the occurrence of the phase in these systesms can be correlated qualitatively with valency electron concentration, and that the role of oxygen is that of an electron acceptor. The lower limit of oxygen solubility appears to be determined by the valencies of Mn, Fe, Co, and Ni, while the maximum oxygen concentration coincides with the filling of the 16 (c) positions of the O 7h - Fd 3m space group. THE suggestion has been made by several investigators&apos;" that the phases having the cubic E9,-type structure, and known as 17-carbide-type, double-carbide-type and Ti,Ni-type, are members of a family of electron compounds. This concept has been given additional support by recent work8 in which new isostructural phases involving second and third long period combinations were found, and which provided further evidence of the regularity of occurrence of the phase in terms of periodic table relationships. In this laboratory attention has been focused on the isomorphs containing titanium, zirconium, or hafnium, and the role that oxygen plays in their occurrence. In some binary systems Ti,Nitype* phases occur having the formula A,B where A is the titanium group element. Based on previous workq and the present investigation, oxygen is known to be soluble in two of these binary phases, Ti,Co and Ti2Ni. It is probable that oxygen is also soluble in the other phases of this kind. In other binary systems the Ti,Ni-type phase does not occur, but does occur in the corresponding ternary systems with oxygen .3-5 The experiments described here were performed to determine whether the occurrence and composition of certain of the Ti,Ni-type phases could be related to an electronic effect and whether oxygen&apos;s stabilizing role is exerted through an influence on the electron: atom ratio. The ternary systems Ti-Mn-O, Ti-Fe-O, n-Co-O, and Ti-Ni-O were selected for study for two reasons: First, several schemes have been proposed for first long period elements which, although not in quantitative agreement, show a generally consistent trend for the variation of valency with atomic number. Although for a transition metal the term valency is difficult to define and is generally not a constant number which can be applied to all alloys, it is usually assumed to be an index of the number of electrons per atom involved in metallic cohesion. Second, the determination of the Ti2Ni-type phase boundaries was facilitated by the fact that the phase relations in several of these ternary systems have been investigated by other workers."&apos; EXPERIMENTAL PROCEDURE___________________ The alloys were prepared by arc melting crystal-bar titanium, reagent grade TiO, and electrolytic manganese, iron, cobalt, and nickel. Each button was remelted at least three times. The metals had a minimum purity of 99.9 pct except the nickel whose purity was 99.4 pct, the major impurity in this instance being cobalt. The preparation of the manganese alloys was attended by the customary difficulties associated with the vaporization of manganese. The technique used in this case was to add approximately 10 pct extra manganese to the original charge and to continue remelting the button until the final weight was in agreement with its intended weight. At least three alloys in each system were analyzed chemically and the results, even for the manganese alloys, were in good agreement with the intended compositions. A few additional alloys in the Ti-Mn-O system were prepared by the sintering of mixed powders in evacuated quartz tubes followed in some cases by arc melting. For annealing, the alloys were wrapped in molybdenum foil and placed in fused silica tubes containing zirconium chips. The fused silica tubes were evacuated at room temperature to a pressure of 1 x l0-6 mm of Hg and sealed. These capsules were then annealed for 72 hr at an external pressure of 5 x 10-5 mm of Hg in a vacuum furnace whose temperature could be controlled to + 1°C. The success of this procedure in avoiding significant oxygen or nitrogen pickup was indicated by the bright, ductile condition of the molybdenum foil and by the complete absence of a microscopic reaction layer on the specimens. This method did not permit rapid quenching of the specimens but in no case did metal-lographic examination indicate that a solid-state transformation had occurred on cooling. Metallo-

Jan 1, 1961

By C. D. King

DURING the 30-year period spanned by these annual Howe Memorial presentations, many lecturers could proudly claim a kinship either as a student or an associate of the man whose memory we honor. Although it has been my good fortune to have attended many of these annual lectures, it was not my privilege to have known Henry Marion Howe personally. However, his great repute as teacher and scientist was known to all undergraduates of my day and the later years have enhanced my appreciation of his wisdom and foresight. Those who knew him well have said he derived particular pleasure from speculations on the future world of metallurgy. For this reason, I feel that perhaps he would not be unsympathetic to a lecture in his honor which departs from the highly instructive scientific presentations made in the past by so many able Howe Memorial lecturers, and which is concerned more with the practical phases of various steelmak-ing processes and some speculations on their future form and relative importance. The word "revolutionary" is frequently applied to each seemingly important improvement in the production of steel ingots, but in retrospect these changes, impressive as they appear at the time, are merely steps of progress. In the hundred years from the inception of tonnage steelmaking, only three processes can be truly classified as revolutionary. They are the pneumatic process, known in this country as the bessemer process; the reverberatory method called the open hearth process; and, the electric furnace process. There have been many variations and combinations of the three fundamental methods, but they remain truly the only revolutionary methods in steelmaking since its early history. Everything else has been evolutionary, in effect. doing the same things that we have done in the past but doing them better, correcting our errors through experience, and slowly but inevitably reaching a higher state of accomplishment. It has often been said that coming events cast their shadows before, and the production of steel ingots is no exception. As a result of the unrelenting demands of World War I1 and the years that followed, truly impressive progress has been made in steel ingot production. The incessant pressure for immediate results during this period required the employment of initiative and daring, as in few past decades, and many developments were brought to fruition. Of equal importance is the possible effect on future steelmaking methods of the many ideas initiated but still in formative stages. Fig. 1 portrays ingot production in the United States by the three fundamental processes over a period of 75 years and is interesting because it poses some questions as to future trends. The early ascendancy of the bessemer, its replacement in importance by the open hearth process, the amazing growth of the latter, and the recent challenge of the electric furnace are evident from the chart. Management is fully aware of these changes, but is even more interested in the future trends. Our concepts of the relative importance of the more recent developments and their possible effect on future processes may perhaps be best exemplified by a specific, hypothetical problem. Let us assume management is contemplating a new ingot producing plant with an output of 100,000 net tons per month, located in an area where some purchased scrap may be obtained but where by far the largest component will be own-produced blast furnace iron. Management requires a process or combination of processes which will yield highly uniform quality characteristics in the ingot form, and represent the soundest selection in investment and operating cost. Under these conditions, the obvious selection for the past four decades has been the open hearth process but, in view of more recent developments, management may believe that it is no longer permissible to disregard other possibilities with impunity. Accordingly, to be assured of the best possible selection, they request that you review not only the possibilities of utilizing the conventional open hearth, duplex, bessemer, and electric furnace methods, but also the more recent developments, such as the turbo-hearth, the Linz-Donawitz method, the Perrin modifications, and other possibilities. With this background, one might then appraise the relative importance of these methods to meet a specific need, and concurrently speculate on the forms that future ingot processes will assume and the relative importance of these processes.

Jan 1, 1955

By G. Sachs, A. W. Dana, C. C. Chow

A great number of the investigations on the plastic flow of metals have been concerned with the establishment of a "universal" stress-strain relation. In such a relation some stress function when plotted against a strain function should yield identical curves for the various stress states. In the first investigation of this type, Ludwik and Scheu1 plotted the maximum shearing stress as a function of the maximum principal strain. Later Ros and Eichinger2 introduced two universal stress-strain relations, the one relating the maximum shearing stress to the maximum shearing strain, and the other relating a stress invariant, suggested by von Mises and Haigh, to the corresponding strain invariant. (In more recent investigations the stress and strain invariants are frequently supplemented with some factor to render their meaning more lucid.) A further suggestion which has not attracted appreciable attention is that by Baranski³ who used stress and strain deviators. The most common means of experimentation to determine the relation between stress and strain consists in subjecting thin walled tubes to combined internal pressure and axial tension.4a,4b,4c This method allows the study of plastic flow under stresses which are variable in two directions. However, the plastic flow which can be obtained in this manner is comparatively small, being limited by either tension failure or instability. For copper,&apos;. only the relation between maximum shearing stress and maximum shearing strain yielded good agreement. On the other hand, tests on a stee14b and on an aluminum alloy4c. resulted in systematic deviations if any of the discussed universal stress-strain relations were used. It would seem, therefore, that the agreement mentioned above for copper is only incidental and explained by its high rate of strain hardening compared to that of other metals. Much larger strains than experienced in the tube tests can be obtained by subjecting a thin membrane of a ductile metal, which is restrained at its periphery, to a uniform hydraulic pressure. The thin sheet forms a deep bulge before it fails. The stresses and strains in such a bulge increase with increasing distance from the edge of the clamping "die," the maximum stresses and strains occurring at the pole (crown) of the bulge. While the stress and strain states are determined by the contour of the bulge, the absolute magnitude of the stresses and strains depends upon the hydraulic pressure. The bulge contour is in turn correlated with the geometry of the die opening. The deformation and fracture characteristics of circular bulges, that is, bulges formed with circular clamping dies, have been the subject of numerous experimental and analytical investi-gations.5,6,7 It has been shown that plastically deformed circular bulges develop large and comparatively uniform strains before failure by instability"6b,6c,6d and closely assume a spherical shape.6d Also the distribution of strains across the contour of the bulge is dependent on the metal being investigated and is correlated with, but cannot be predicted from, the metal&apos;s stress-strain characteristics. On the other hand, oblong or elliptical bulges, that is, bulges formed with elliptical clamping dies, are not as susceptible to analytical analysis and have not been investigated to the extent that circular bulges have. The few available data6c,7c indicate that stress states are obtained at the poles of the bulges, varying between plane strain and balanced biaxial tension, depending upon the geometry of the die opening. In this paper, the strain state and curvatures exhibited by three bulge shapes, a circular and two elliptical bulges, Fig 1, are analyzed experimentally using methods described in previous publications.6a,6c An attempt is made to derive the stress-strain relations for these bulges, which represent strain states in which the ratio of the two positive principal strains varied between 1.0 and 0.35. In addition, tension tests yielded data for a value of —0.5 for this strain ratio. Such an analysis should indicate the applicability of the various laws correlating stress with strain to the stress and strain states occurring in bulged shapes. Definitions and Nomenclature The definitions of the major stress and strain quantities used in this paper are as follows: s1, s2, s3 = principal normal stresses Sl > s2 > S3 t = shear stress e = conventional (unit) strain e = In (1 + e) El, E2, E3 = principal natural strains 7 = shear strain The maximum shear stress: , _ S1 — S3 lmax = 2 Frequently, the flow stress, s1 — s3 = 2lmax rather than the maximum shear stress is used.

Jan 1, 1950

By John Henderson

FOR some time now the most commonly accepted description of liquid silicate structure has been the "discrete ion" theory, proposed originally by Bockris and owe.&apos; This theory is that when certain metal oxides and silica are melted together, the continuous three dimensional silica lattice is broken down into large anionic groups, such as sheets, chains, and rings, to form a liquid containing these complex anions and simple cations. Each composition is characterized by "an equilibrium mixture of two or more of the discrete ions",&apos; and increasing metal oxide content causes a decrease in ion size. The implication is, and this implication has received tacit approval from subsequent workers, that these anions are rigid structures and that once formed they are quite stable. The discrete ion theory has been found to fit the results of the great majority of structural studies, but in a few areas it is not entirely satisfactory. For example it does not explain clearly the effect of temperature on melt structure,3 nor does it allow for free oxygen ions over wide composition ranges, the occurrence of which has been postulated to explain sulfur4 and water5 solubility in liquid silicates. In lime-silica-alumina melts the discrete ion theory is even less satisfactory, and in particular the apparent difference in the mechanism of transport of calcium in electrical conduction8 and self-diffusion,&apos; and the mechanism of the self-diffusion of oxygen8 are very difficult to explain on this basis. By looking at melt structure in a slightly different way, however, a model emerges that does not pose these problems. It has been suggested5" that at each composition in a liquid silicate, there is a distribution of anion sizes; thus the dominant anionic species might be Si3,O9 but as well as these anions the melt may contain say sis0:i anions. Decreasing silica content and increasing temperature are said9 to reduce the size of the dominant species. Taking this concept further, it is now suggested that these complexes are not the rigid, stable entities originally envisaged, but rather that they exist on a time-average basis. In this way large groups are continually decaying to smaller groups and small groups reforming to larger groups. The most complete transport data 8-10 available are for a melt containing 40 wt pct CaO, 40 wt pct SiO2, and 20 wt pct Al2O3. Recalculating this composition in terms of ion fractions and bearing in mind the relative sizes of the constituent ions, Table I, it seems reasonable to regard this liquid as almost close packed oxygens, containing the other ions interstitially, in which regions of local order exist. On this basis, all oxygen positions are equivalent and, since an oxygen is always adjacent to other oxygens, its diffusion occurs by successive small movements, in a cooperative manner, in accord with modern liquid theories." Silicon diffusion is much less favorable, firstly because there are fewer positions into which it can move and secondly, because it has the rather rigid restriction that it always tends to be co-ordinated with four oxygens. Silicon self-diffusion is therefore probably best regarded as being effected by the decay and reformation of anionic groups or, in other words, by the redistribution of regions of local order. Calcium self-diffusion should occur more readily than silicon, because its co-ordination requirements are not as stringent, but not as readily as oxygen, because there are fewer positions into which it can move. There is the further restriction that electrical neutrality must be maintained, hence calcium diffusion should be regarded as the process providing for electrical neutrality in the redistribution of regions of local order. That is, silicon and calcium self-diffusion occur, basically, by the same process. Aluminum self-diffusivity should be somewhere between calcium and silicon because, for reasons discussed elsewhere,&apos; part of the aluminum is equivalent to calcium and part equivalent to silicon. Consider now self-diffusion as a rate process. The simplest equation is: D = Do exp (-E/RT) [I] This equation can be restated in much more explicit forms but neither the accuracy of the available data, nor the present state of knowledge of rate theory as applied to liquids justifies any degree of sophistication. Nevertheless the terms of Eq. [I] do have significance;12 Do is related, however loose this relationship may be, to the frequency with which reacting species are in favorable positions to diffuse, and E is an indication of the energy barrier that must be overcome to allow diffusion to proceed. For the 40 wt pct CaO, 40 wt pct SiO2, 20 wt pct Al2O3, melt, the apparent activation energies for self-diffusion of calcium, silicon, and aluminum are not significantly different from 70 kcal per mole of diffusate,&apos; in agreement with the postulate that these elements diffuse by the same process. For oxygen self-diffusion E is about 85 kcal per mole,&apos; again in agreement with the idea that oxygen is transported,

Jan 1, 1963

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. M. Dahl, L. H. Van Vlack

STAFF: Editor, Gerhard Derge Associate Editor, Paul G. Shewman Carnegie lnstitute of Technology Schenley Park Pittsburgh, Pa. 15213 Editorial Assistant, M. A. Redmerski Production Editor, Otto T. Johnson THE METALLURGICAL SOCIETY: Jack H. Scoff, President; Richard C. Cole, Post-President; Harold B. Emerick, President-Elect; Ralph L. Hennebach, Treasurer; Robert W. Shearman, Secretary; Donald A. Parks, Assistant Secretary; Leslie S. Wilcoxson, Assistant Secretary. PUBLICATIONS COMMITTEE OF THE METALLURGICAL SOCIETY: R. E. Lund, Chairman; T. E. Dancy, H. B. Emerick, P. R. Gouwens, R. E. Grace, J. H. Jackson, H. H. Johnson, A. E. Lee, Jr., R. R. Nosh, R. D. Pehlke, and Paul Queneau. Review and selection of monuscripts is under the supervision of the following Publications Committees: Extractive Metollurgy Division: R. E. Grace, Chairman; G. M. Bell, D. W. Bridges, J. M. Cigon, G. W. Healy, T. A. Henrie, R. D. Holli-day, C. E. O&apos;Neill, C. S. Sami s, A. W. Schlech-ten, and Charles Shull . Iron and Steel Division: R. D. Pehlke, Chairman; T. P. Floridis, Arnulf Muon, G. R. St. Pierre, E. T. Tuckdogon, L. H.Von Vlack, and J. M. Uys. Institute of Metals Division: H. H. Johnson, Jr., Chairman; J. B. Clark, Vice Chairman; M. R. Achter, G. F. Bolling, J. O. Brittain, G. P. Conard, II, L. A. Girifolco. G. T. Hahn, J.P. Hirth, L. Himmel, G. T. Horne, George Krauss, C. F. Leitton, Jr., J. D. Livingston, R. D. Monning, H. M. Otte, S. V. Radcliffe, R. E. Reed-Hill, H. C. Rogers, O. Sherby, M. T. Simnod, G. R. Speich, E. A. Steigerwold, R. A. Swolin, W. A. Tiller, W. R. Upthegrove, J. B. Wagner, Jr., Derek Walton, H. W. Weart, W. W. Webb, and D. WiIsdorf. Published monthly by the American lnstitute of Mining, Metollurgicol, and Petroleum Engineers, Inc., 345 East 47th Street, New York, N. Y. 10017. Telephone PLAZA 2-6800. Subscription $30 per year for non-AIME members in United States and North, South, and Central America; $32, foreign; $7.50 for AlME members. Single copies, $6.00, single copies foreign, $6.50. The AlME is not responsible for any statement mode or opinion expressed in its publications . . . Copyright 1965 by the American Institute of Mining, Metallurgical, and Petroleum Engineers, Inc. . . . Registered cable address, AlME New York . . . Indexed in Engineering Index, lndustrial Arts Index, and Chemical Abstracts . . Second class postage paid at New York, N. Y., and Ann Arbor, Mich. Volume 233, Number 1.

Jan 1, 1965

By J. M. Dahl, R. J. Warrick, O. K. Riegger, H. Van Vlack

A liquid which is rich in oxygen (and silicon) develops at steel rolling temperatures in resulfurized and plain-carbon steels. This liquid fluxes solid manganese sulfide. The composition of the liquid and the resulting microstructures vary with the manganese/silicon/oxygen ratios in the steel. The observations and conclusions zuhich are presented are used 1) to suggest a mechanism for MnS deformation in resulfurized steels, and 2) to rationulize hot-shortness anomalies between plain-carbon and resulfurized steels. 1 HIS is a summary of the dependence of sulfide inclusion microstructures upon steel composition, and an interpretation of the behavior of sulfide inclusions at steel-rolling temperatures. Sulfide inclusions are known to have several metallurgical effects upon steel. Their effects upon hot-shortness are best appreciated. Although hot-shortness is well known, it is questionable whether its mechanism is fully understood because there are several anomalies in our interpretation. For example, why should not high sulfur contents produce extensive hot-shortness in free-machining steels ? A second metallurgical consequence of sulfide inclusions appears because sulfide inclusions improve machinability. Furthermore, globular inclu- sions are to be desired over elongated inclusions. To date, we know that lower silicon contents (< 0.010 pct) favor the globular sulfides, but we do not know why this interrelationship between silicon content and inclusion shape exists. Finally, the evidence is strong that the surface quality of a hot-rolled steel is particularly sensitive to the sulfur content. SUMMARY OF PREVIOUS WORK The role of sulfur in hot-shortness was first suggested during the past century. It is uncertain who was the first to conclude that sulfur was less deleterious in the presence of manganese, and that manganese altered the sulfide phase from a liquid FeS to a solid MnS at steel-rolling temperatures. However, Urban and chipman&apos; emphasized that liquid FeS may accumulate as an interdendritic film during solidification. More recently, Keh and Van lack&apos; showed that the intergranular liquid does not completely surround the metal grains at all rolling temperatures. Rather, a small finite dihedral angle exists when geometric equilibration is attained at

Jan 1, 1962

By E. T. Turkdogan, L. S. Darken

Calcium ferrite melts were equilibrated with sulfur and oxygen-bearing gases at temperatures within the range 1290°C to 1620°C. The results show that at oxygen partial pressures below 10-4 atm the sulfide-reaction occurs and at higher oxygen pressures the sulfur dissolves in the melt principally as sulfate ion. It is also observed that when the product increases, sulfate ions are converted to pyrosulfate ions and the results permit the evaluation of the pyrosulfate/sulfate ratio. It is shown that the ratio y CaSO,/rCaO increases with decreasing concentration of calcium oxide in calcium ferrite, silicate and aluminate melts. Indications are that oxy-acids, e.g. silica, alumina and ferric oxide, increase yCaS0,. A few experiments were carried out within the sul-tide range and the results are in accord with those obtained by other investigators on aluminate and silicate melts. BECAUSE of the industrial importance and theoretical interest, many investigators have studied the reactions between molten oxides, silicates or alumi-nates, and gases containing oxygen and sulfur. The early work reviewed by Schenckl and studies made by Bardenheuer and Geller2 indicates that solution of gaseous sulfur in an oxide melt resulted in the replacement of the oxide ions by the sulfide ions. Measurements made by Grant and Chipman3 on the equilibrium partition of sulfur between molten iron and complex silicate melts also demonstrated that, for a given temperature and silicate composition, the distribution of sulfur between slag and metal increased with decreasing oxygen content of the metal. Fincham and Richardson4 studied the effects of temperature and partial pressures of sulfur and oxygen on the solubility of sulfur in simple silicate and alumino-silicate melts. They observed that at oxygen partial pressures below about 10-5 atm sulfur in the gas dissolved in the melt as sulfide ions, replacing an equal number of oxide ions of the melt. At oxygen partial pressures higher than 10-3 atm, sulfur entered the melt as sulfate ions. Similar studies were made by St. Pierre and Chipman5 using calcium ferrite and calcium silico-ferrite melts. The experimental data presented in this paper were obtained in this Laboratory about 10 years ago; this is the first formal presentation although a preliminary report was given previously.6 In each of these experiments, a pure synthetic CaO-Fe2O3 melt in a platinum crucible was equilibrated with a gas mixture (SO2-O2, SO,-air, SO2-CO, or SO2-CO2-CO) at a temperature ranging from 1296°to 1620°C. The experimental technique was essentially the same as that reported by Darken and Gurry,7 the main difference being that the atmosphere in the reaction chamber contained sulfur dioxide together with oxygen, or carbon dioxide-carbon monoxide

Jan 1, 1962