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By Perry G. Harrison

The increased use of sintering for the beneficiation of iron ores and the reclaiming of flue dust creates a lively interest in sintering costs and economics. The character of material sintered and geographical location of plants so radically alter sintering costs and economics that it is well.to understand at least the basic elements which control such changes. The following cost factors are believed to be roughly approximated for large-scale Dwight-Lloyd continuously operated sinter-machine installations located anywhere. Per Crude Ton Labor, supplies and repairs 0.15 Power 6.5¢ X kw-hr. rate ? Plant overhead and administration 0.05 Depreciation per ton annual capacity 0.05 Fuel: 6 per cent coke breeze or equivalent minimum ? 1 per cent coke breeze additional for each 5 per cent free and combined water in ore or dust ? Ignition distillate at 0.6 gal. per ton ? Per Sinter Ton Royalty on ore 0.10 Royalty on flue dust 0.15 Per Crude Ton "Winter expense"; i. e., the cost of the five months enforced idle . period for plants tied in to Great Lakes transportation season 0.03 Using the foregoing data, it is possible to roughly approximate the cost of efficient sintering at any location for any ore, viz: Per Crude Ton Per Ton Handled Sinter 1. Flue Dust—Steel Plant Locations Sinter recovery, 15 per cent moisture and carbon 85 per cent Labor, supplies and repairs 0.15 0.18 Power 6.5¢ X 1¢ kw-hr. 0.065 0.08 Plant overhead and administration 0.05 0.06 Depreciation per ton 0.05 0.06 Dust handling and preparation 0.10 0.12 Fuel: free, contained in dust Ignition: blast-furnace gas free Royalty 0.15 Total $0.65 Note:—Cost increased by either deficiency or considerable excess of carbon in dust.

Jan 1, 1932

By Perry G. Harrison

The first autlientic description of an iron bath for the deposition of iron is probably that of Bottger in 1846, who used a bath containing ferrous sulfate and ammonium chloride. In 1861, Kramer deposited iron from ferrous chloride solution. Electrolytic iron was produced in 1869 by Bietz, who used it for making some magnetic tests. In the same year, Klein is. said to have worked out his process. Jacobil in 1869 described the results obtained in electroplating with iron on copper for making dies and plates for bank notes, by Klein's process. A letter from Klein to Jacobi describes the bath more fully. It consisted of FeS04 + (NH4)2SO4. Lenz2 described some properties of electrolytically precipitated iron. He used Klein's bath, FeS0, + MgSO4 + MgCO3, to neutralize and obtained fine-grained and hard iron. His conclusions were as follows: 1. Electrolytic iron and copper contain gases, notably hydrogen. 2. The volume of gas absorbed by iron varies within wide limits, but it is easy for iron to take up very considerable quantities of gas. 3. The absorption of gas is principally in the first formed layers of iron. 4. When iron is heated, gas begins to come off below 100°, principally hydrogen. 5. Heated to redness, reduced iron oxidizes in water, in part at least at the expense of the oxygen of the water, decomposing it and setting free hydrogen, which is partly or wholly absorbed. Siemens,3 in 1889, was the first to propose a general process embodying a step for leaching a sulfide mineral with ferric chloride or sulfate and a step for regenerating the leach and depositing iron on a cathode in a diaphragm cell. So far as is known, Siemens did not carry out his patent

Jan 1, 1930

By R. C. Good

Slag control for any kind of steel, rimming, straight carbon or alloy, should start with the charge and be developed well in advance of the tap because its composition, viscosity and temperature will unquestionably govern the physical and chemical properties of the steel when tapped. In the majority of plants producing alloy steels, primary consideration is given to the chemical specifications; physical characteristics usually occupy secondary place in the melter's mind. Recently, however, buyers have indicated limits of machinability, hardenability, grain size and, of course, always wanted steel free from foreign nonmetallic inclusions. It is these latter specifications that require the attention of the operator to the slag and its control. The slag must act as a vehicle for oxidized elements originating from the metallic portion of the charge; it should hold the oxides of phosphorus, silicon, manganese, iron and chromium that come into contact with it either before or after the refining and finishing stage of the heat. It must be used as a transferring medium of oxygen from the atmosphere or oxide additions to the metal and should permit a free escape of gas generated within the charge. Finally, the slag is the principal controlling factor in regulating the rate of oxidation which in turn eventually determines the quality of the steel as measured for the various characteristics mentioned above. With pig iron of uniform composition, the iron oxide in the slag increases as the limestone is increased but with the same addition of stone in every heat, the iron oxide decreases as the silicon is increased in the charge, and vice versa.

Jan 1, 1935

By R. C. Good

Slag control for any kind of steel, rimming, straight carbon or alloy, should start with the charge and be developed well in advance of the tap because its composition, viscosity and temperature will unquestionably govern the physical and chemical properties of the steel when tapped. In the majority of plants producing alloy steels, primary consideration is given to the chemical specifications; physical characteristics usually occupy secondary place in the melter's mind. Recently, however, buyers have indicated limits of machinability, hardenability, grain size and, of course, always wanted steel free from foreign nonmetallic inclusions. It is these latter specifications that require the attention of the operator to the slag and its control. The slag must act as a vehicle for oxidized elements originating from the metallic portion of the charge; it should hold the oxides of phosphorus, silicon, manganese, iron and chromium that come into contact with it either before or after the refining and finishing stage of the heat. It must be used as a transferring medium of oxygen from the atmosphere or oxide additions to the metal and should permit a free escape of gas generated within the charge. Finally, the slag is the principal controlling factor in regulating the rate of oxidation which in turn eventually determines the quality of the steel as measured for the various characteristics mentioned above. With pig iron of uniform composition, the iron oxide in the slag increases as the limestone is increased but with the same addition of stone in every heat, the iron oxide decreases as the silicon is increased in the charge, and vice versa.

Jan 1, 1935

By Francis B. Foley

Fundamentally, slag control in acid open-hearth steelmaking cannot be considered from any different viewpoint than can that in basic open-hearth melting. The same laws of mass action and distribution apply in both cases, so that while most, if not all, of the recent intensive study of slag-metal reactions have been carried on in basic furnaces the principles evolved are nevertheless applicable to acid open-hearth steelmaking and it is therefore not our intention to discuss the various possible chemical reactions in the slag and between slag and metal. The points we have to carry in mind, in considering acid melting practice, are the differences in the type of steels produced and the difference in the chemistry of both the steel and the slag. The acid furnace is used to produce, let us not say "quality" steel, for, after all, a "quality" steel for one purpose is not a "quality" steel for another, but steels that require acid melting practice to be of proper "quality." Steels that are required to have high physical properties in tests taken transversely from forgings are peculiarly the product of acid furnaces. In this class may be placed various ordnance materials, notably gun forgings and projectiles and large commercial forgings requiring high transverse ductility. Forgings requiring an extremely hard surface, polished and free from imperfections, are also typical acid-steel products. Of course, such forgings can be made of basic open-hearth steel, but not with the same assurance of success. At the start, the preparation of the slag in the acid and basic furnaces differs. Lime is charged in the beginning of a basic heat to form a slag, but in the acid furnace nothing is added for the special purpose of producing a slag when the heat is melted down. The result is that the acid furnace has much less volume of slag than the basic. The slag formed upon melting down is made up almost entirely of the oxides of elements contained in the metallic charge, notably oxides of iron, manganese and silicon, the amount of silica being augmented somewhat by erosion of the furnace lining. A typical acid open-hearth slag, when the bath is completely melted, will have an analysis about as follows: CaO, 3.40 per cent; SiO2, 51.9; Fe2O3, 1.25 ; FeO, 28.86; Al2o3, 1.82; MnO, 12.22. The high iron oxide content of the slag gives it a black appearance. The metal is high in carbon and some manganese and silicon will be present, depending on the amount in the original charge, the amount of

Jan 1, 1935

By Francis B. Foley

Fundamentally, slag control in acid open-hearth steelmaking cannot be considered from any different viewpoint than can that in basic open-hearth melting. The same laws of mass action and distribution apply in both cases, so that while most, if not all, of the recent intensive study of slag-metal reactions have been carried on in basic furnaces the principles evolved are nevertheless applicable to acid open-hearth steelmaking and it is therefore not our intention to discuss the various possible chemical reactions in the slag and between slag and metal. The points we have to carry in mind, in considering acid melting practice, are the differences in the type of steels produced and the difference in the chemistry of both the steel and the slag. The acid furnace is used to produce, let us not say "quality" steel, for, after all, a "quality" steel for one purpose is not a "quality" steel for another, but steels that require acid melting practice to be of proper "quality." Steels that are required to have high physical properties in tests taken transversely from forgings are peculiarly the product of acid furnaces. In this class may be placed various ordnance materials, notably gun forgings and projectiles and large commercial forgings requiring high transverse ductility. Forgings requiring an extremely hard surface, polished and free from imperfections, are also typical acid-steel products. Of course, such forgings can be made of basic open-hearth steel, but not with the same assurance of success. At the start, the preparation of the slag in the acid and basic furnaces differs. Lime is charged in the beginning of a basic heat to form a slag, but in the acid furnace nothing is added for the special purpose of producing a slag when the heat is melted down. The result is that the acid furnace has much less volume of slag than the basic. The slag formed upon melting down is made up almost entirely of the oxides of elements contained in the metallic charge, notably oxides of iron, manganese and silicon, the amount of silica being augmented somewhat by erosion of the furnace lining. A typical acid open-hearth slag, when the bath is completely melted, will have an analysis about as follows: CaO, 3.40 per cent; SiO2, 51.9; Fe2O3, 1.25 ; FeO, 28.86; Al2o3, 1.82; MnO, 12.22. The high iron oxide content of the slag gives it a black appearance. The metal is high in carbon and some manganese and silicon will be present, depending on the amount in the original charge, the amount of

Jan 1, 1935

By George E. Beavers

It is well to understand at once that converter gas is always mixed with copper blast-furnace gas at Copperhill before entering the Glover tower, and, at times, roaster gas is also added along with the converter and blast-furnace gas. Fig. 1 is introduced to show the variations in the sulfur dioxide content of the gas and the ability of the acid-plant operator to control the variations, resulting in a very even grade at the Gay-Lussac tower entrance. The sulfur dioxide content of the gas entering the Gay-Lussac tower must be low and regular to assure low niter consumption. The blast-furnace gas alone is rather uniform as regards sulfur dioxide content and the variations, as shown in Fig. 1, are chiefly caused by converter changes—out for charging, slag pouring, copper pouring, and, of course, the "finish." The combined gas during the converter finish is, at times, almost free of oxygen and the sulfur dioxide content reaches 13.0 per cent. At such times air is added at the Glover tower.

Jan 1, 1934

By A. G. Suydam

Ancient as is the art of producing copper, so ancient is one of its eternal problems: refractories. Looking backward, in the light of present knowledge, clouded though it be, one cannot avoid a sense of profound respect for the patience, acumen and courage of those who have wrought so successfully despite difficulties, a more accurate understanding of which seems merely to accentuate. The problem of refractories arises from the necessity for constructing containers in which to bring natural ores into thermal solution in order to effect reduction and separation of the valuable metal content and free it of undesirable contamination while producing a waste slag. The very forces known to produce thermal solution of sufficient liquidity are necessarily destructive of exposed refractory linings in proportions varying inversely with thermal conductivity, directly with the porosity and ease of fluxing of the refractories used, and directly with the temperatures employed. Beyond this, mechanical forces are set up within the refractory lining incident to rapid heating or cooling, shrinkage at high temperatures, and unequal or excessive loading, that frequently pass the elastic limit, causing spalling or distortion. The effects of these forces are often accentuated by the necessity of providing at the same time as hot a bath and as cool a container as are consistent with fuel economy. Evolution in the Use of Refractories Clay Brick.—Fireclay and clay refractories had to yield wherever they were in contact with slags rich in basic oxides, first because of the combining power of those oxides with free silica and secondly because of the tendency of alumina to form either aluminates or alumina-silicates of varying complexity. Of no less importance, the incipient fusion point was low as compared with good clay brick of today, while the brick lacked strength at high temperatures. Expansion was slight, therefore it was difficult to make and maintain tight walls, roof, or bottom. However, the spalling tendency was low because of some of these properties and clay brick have retained their place in roasting furnaces, boiler furnace linings, and in the upper walls of some of the reverberatory types such as some refining, anode and wire-bar furnaces. They have served often and most efficiently for hot patching.

Jan 1, 1934

By L. W. Kemph, K. R. VanHorn

During the recent development of aluminum alloys for free-cutting screw-machine rod, it became desirable to know something of the solubility of lead and bismuth in liquid aluminum and in some aluminum alloys. The literature is not particularly helpful in supplying this information. These portions, therefore, of the constitutional relationships of aluminum-bismuth and aluminum-lead alloys were investigated by thermal analysis and by chemical analysis of samples taken from aluminum-rich melts in equilibrium with precipitated lead or bismuth. The solubility of lead and bismuth in some liquid aluminum-copper alloys was also investigated. Some consideration was also given to the solubility of these elements in solid aluminum. Among the earliest investigators of the aluminum-lead and alunlinum-bismuth systems was Wright,' who reported that melts of aluminum and lead formed two layers indicating limited liquid solubility. Under his conditions, the aluminum-rich layer was reported to contain 1.91 per cent Pb and the lead-rich layer, 0.07 per cent Al. Subsequently, Pecheau2 found that in aluminum-rich alloy melts with more than 10 per cent Pb three layers were distinguishable. He reported that the middle layer contained from 3 to 10 per cent Pb. He also found that the melting point of aluminum appeared to be lowered slightly by the addition of lead. Gwyer3 investigated these alloys and found evidence of a slight lowering of the freezing point of aluminum by the addition of either lead or bismuth. He found no evidence of solid solubility in either case and made no attempt to determine the liquidus curves. Hansen and Blumen-tha14 reported that the addition of lead distinctly lowered the solidification point of aluminum. They also found that bismuth lowered the melting point of aluminum. Guillet5 reported almost complete mutual immiscibility for the aluminum-bismuth alloys in the liquid state. Bohner6 examined the effect of various concentrations of lead and bismuth on the electrical conductivity of aluminum. He found decreases in conductivity on annealing at 500' C. as compared with the conductivity of the same alloys on annealing at 300' C.

Jan 1, 1939

By L. W. Kemph, K. R. VanHorn

During the recent development of aluminum alloys for free-cutting screw-machine rod, it became desirable to know something of the solubility of lead and bismuth in liquid aluminum and in some aluminum alloys. The literature is not particularly helpful in supplying this information. These portions, therefore, of the constitutional relationships of aluminum-bismuth and aluminum-lead alloys were investigated by thermal analysis and by chemical analysis of samples taken from aluminum-rich melts in equilibrium with precipitated lead or bismuth. The solubility of lead and bismuth in some liquid aluminum-copper alloys was also investigated. Some consideration was also given to the solubility of these elements in solid aluminum. Among the earliest investigators of the aluminum-lead and alunlinum-bismuth systems was Wright,' who reported that melts of aluminum and lead formed two layers indicating limited liquid solubility. Under his conditions, the aluminum-rich layer was reported to contain 1.91 per cent Pb and the lead-rich layer, 0.07 per cent Al. Subsequently, Pecheau2 found that in aluminum-rich alloy melts with more than 10 per cent Pb three layers were distinguishable. He reported that the middle layer contained from 3 to 10 per cent Pb. He also found that the melting point of aluminum appeared to be lowered slightly by the addition of lead. Gwyer3 investigated these alloys and found evidence of a slight lowering of the freezing point of aluminum by the addition of either lead or bismuth. He found no evidence of solid solubility in either case and made no attempt to determine the liquidus curves. Hansen and Blumen-tha14 reported that the addition of lead distinctly lowered the solidification point of aluminum. They also found that bismuth lowered the melting point of aluminum. Guillet5 reported almost complete mutual immiscibility for the aluminum-bismuth alloys in the liquid state. Bohner6 examined the effect of various concentrations of lead and bismuth on the electrical conductivity of aluminum. He found decreases in conductivity on annealing at 500' C. as compared with the conductivity of the same alloys on annealing at 300' C.

Jan 1, 1939

By Robert D. Pehlke, Robert G. Blossey

The solubility of nitrogen in liquid cobalt and a number of dilute cobalt alloys Was measured in the temperature range 1550" to 1700°C at nitrogen pressures to 1 atm. At 1600°C and 1 atm nitrogen pressure, the solubility in pure cobalt is 0.0047 wt pct [3.8 cu cm (stp) per 100 g Co]. The standard free- energy change for the solution reaction 1/2 N,(g) = gout pct in Co) is iF - 10,000 + 5.24 T cal per g atom N. The alloying elements Cv, Cu, Mo, Nb, Tu, W, and V increase the nitrogen solubility, while Al, Fe, Ni, and Si decrease the nitrogen solubility. THE solubility of nitrogen in cobalt was studied previously by Sieverts, Busch and Dodd,2 and Schenck, Frohberg, and Graf.3 Sieverts investigated the solution below the melting point of cobalt, and Busch and Dodd worked with the liquid metal; however, neither study found any solubility for nitrogen in cobalt. Schenck et al, reported a solubility of 0.005 wt pct N in cobalt at 1600°C. Seagle et al. 4 reported residual nitrogen in cobalt after electron-beam melting, although no reasons were ventured for the presence of this interstitial impurity. This investigation was undertaken to clarify these inconsistencies, and to provide additional data on atomic interactions in dilute metallic solution. EXPERIMENTAL PROCEDURE This study was well-suited to the Sieverts' method, which has not changed significantly since its introduction by Sieverts. 5 The apparatus was of the same design as that described by Humbert and Elliott, 6 with a reaction bulb similar to that reported by Weinstein and Elliott. 7 The buret was not water-jacketed, but the measured gas volumes were corrected for small changes in room temperature. The melt temperature was measured by a disappear ing-filament optical pyrometer sighted through a prism onto the melt surface. Temperature calibration was made based on a measurement of the melting point of pure cobalt taken as 1495°C. The difference between the reciprocal of the observed and the true temperatures was assumed to be a constant, neglecting the changes in emissivity with small additions of alloying elements. The total error in gas-volume measurement caused by accuracy limitations in reading the mercury level in the buret, variation in ambient temperature, and variation in melt temperature was about 0.5 cu cm. This represents approximately 10 pct of the total solubility, and is a larger relative error than in previous studies6-' because of the small nitrogen solubilities encountered in the present investigation. The source and purity of the materials used are listed in Table IA. Recrystallized alumina crucibles were used throughout the investigation. Examination of the crucibles after solidification of the melts showed no reaction or penetration. Alloying of the cobalt melt was accomplished with the dropping technique described by Humbert. 6 The investigation was started using cobalt from African Metals Corp. in shot form, but this material was not of sufficient purity and did not yield consistent solubility results. Sherritt Gordon Mines Ltd. cobalt was then used throughout the investigation. In experiments involving alloying elements which could react with oxygen dissolved in the melt, the cobalt was further refined by annealing at 1400°C in a dry-hydrogen atmosphere. This treatment, described by Woolley and Pehlke, 8 markedly reduced the oxygen content. The oxygen and nitrogen analyses of the cobalt used in this study are presented in Table IB. RESULTS Hot Volume. The hot volume was measured prior to each run and was 50 to 55 cu cm (stp) at 1600°C. It increased linearly with increasing pressure and decreasing melt temperature. Pure Cobalt. Measurements of the solubility of nitrogen in pure cobalt and the temperature coefficient of solubility are summarized in Table 11. At 1600°C and 1 atm nitrogen pressure, the solubility was found

Jan 1, 1967

By E. N. Skinner, Arthur Philliops

During the course of an experimental program concerned with the hydrogen embrittlement of copper containing oxygen in concentrations within the solubility limits it became necessary to make a critical appraisal of the literature dealing with the solubility relationships of oxygen and solid copper. The latest determinations, and perhaps the only data obtained on "spectroscopically" pure copper, are those of Rhines and Mathewson' who reported that the solid solubility increases from 0.007 per cent oxygen at 600°C. to about 0.01; per cent at 1500ºC. Hanson, Marryat and Ford2 had previously placed the solubility limit at less than 0.009 per cent oxygen at 1000ºC. and Allen and Street3 had suggested, on the basis of an unpublished research by T. Hemitt, not over 0.005 per cent oxygen at 500°C. In the introductory stages of the investigation indirect evidence accumulated to suggest that the solubility limits were significantly lower than those previously reported. For this reason it was deemed essential to clarify this point before proceeding with a program intended to establish a quantitative relationship between hydrogen embrittlement and oxygen concentrations positively known to be within the solid solution range. Furthermore, the increasing production and the highly selective applications of the commercial "oxygen-free" coppers inevitably direct attention to the practical necessity for exact knowledge regarding the effects of mini-tie concentrations of the elements ordinarily found in the high-purity coppers now available. Of these elements oxygen occupies a unique position, not only by virtue of its specific effects on copper but more particularly in view of its important reactive tendencies toward the other impurities with which it is associated. Rhines and Mathewson considered several methods for measuring the solubility of oxygen and finally adopted the simple plan of saturating the specimens, obtained from redeposited cathode copper, by heating at the desired temperature in air. After the removal of surface oxide by mechanical and chemical means, the oxygen content was determined in the underlying metal. In general, this process of saturation, with a few modifications, was followed by the present writers. Although the procedure is direct and has obvious advantages, its effectiveness, unfortunately, is reduced by an excessive scaling of the copper, particularly at the higher temperatures. After saturation treatments above 900°C. the writers found that the specimens, necessarily rather thin in the original condition, consisted largely of scale and yielded too little metal for a satisfactory analytical sample. Furthermore, great difficulty was experienced in effecting complete removal of the scale. Needless to say, it is necessary to exercise extraordinary care in the preparation of the surface of the analytical sample in order to eliminate submicro-scopic fragments of cuprous oxide which ordinarily are lodged in the crevasses and

Jan 1, 1941

By E. N. Skinner, Arthur Philliops

During the course of an experimental program concerned with the hydrogen embrittlement of copper containing oxygen in concentrations within the solubility limits it became necessary to make a critical appraisal of the literature dealing with the solubility relationships of oxygen and solid copper. The latest determinations, and perhaps the only data obtained on "spectroscopically" pure copper, are those of Rhines and Mathewson' who reported that the solid solubility increases from 0.007 per cent oxygen at 600°C. to about 0.01; per cent at 1500ºC. Hanson, Marryat and Ford2 had previously placed the solubility limit at less than 0.009 per cent oxygen at 1000ºC. and Allen and Street3 had suggested, on the basis of an unpublished research by T. Hemitt, not over 0.005 per cent oxygen at 500°C. In the introductory stages of the investigation indirect evidence accumulated to suggest that the solubility limits were significantly lower than those previously reported. For this reason it was deemed essential to clarify this point before proceeding with a program intended to establish a quantitative relationship between hydrogen embrittlement and oxygen concentrations positively known to be within the solid solution range. Furthermore, the increasing production and the highly selective applications of the commercial "oxygen-free" coppers inevitably direct attention to the practical necessity for exact knowledge regarding the effects of mini-tie concentrations of the elements ordinarily found in the high-purity coppers now available. Of these elements oxygen occupies a unique position, not only by virtue of its specific effects on copper but more particularly in view of its important reactive tendencies toward the other impurities with which it is associated. Rhines and Mathewson considered several methods for measuring the solubility of oxygen and finally adopted the simple plan of saturating the specimens, obtained from redeposited cathode copper, by heating at the desired temperature in air. After the removal of surface oxide by mechanical and chemical means, the oxygen content was determined in the underlying metal. In general, this process of saturation, with a few modifications, was followed by the present writers. Although the procedure is direct and has obvious advantages, its effectiveness, unfortunately, is reduced by an excessive scaling of the copper, particularly at the higher temperatures. After saturation treatments above 900°C. the writers found that the specimens, necessarily rather thin in the original condition, consisted largely of scale and yielded too little metal for a satisfactory analytical sample. Furthermore, great difficulty was experienced in effecting complete removal of the scale. Needless to say, it is necessary to exercise extraordinary care in the preparation of the surface of the analytical sample in order to eliminate submicro-scopic fragments of cuprous oxide which ordinarily are lodged in the crevasses and

Jan 1, 1941

By H. W. Gillett

Unlike most previous Howe lecturers, I had not the good fortune to be associated with Henry Marion Howe, nor to be directly one of his students. Yet, through his writings, he has been my teacher, as he has of all American metallurgists. Instructive as his writings are—I use the present tense because Howe thought so keenly and reasoned so surely, seeing clearly, as if by intuition, what was hazy to lesser minds, that his writings are still vital—it is not those books and papers, nor even the minds he trained in his classes, that were his most outstanding service. It was the spirit of Howe in his approach to the problems of metallurgy, his broad-mindedness and fairness, his recognition of the need for theories and hypotheses to explain metallurgical phenomena, his willingness to use them as servants, as well as his questioning attitude—his refusal to accept them as masters—that comprise his greatest service. This most thoroughly warrants the honor the Institute pays each year to his memory. These traits I so respect and honor in any man that I glory in this opportunity to do reverence to him in whom they were so notably united. Howe's Discussion of a Creep Problem I have often wished that Howe were still with us to turn his keen insight upon the problems of the use of metals at high temperatures, a field much studied but still very hazy. Indeed, 53 years ago, in a paper1 before this Institute, Howe stated a problem closely allied to some that still perplex metallurgists and engineers dealing with the high-temperature field. Howe was intrigued by a report2 from another old master, Robert Henry Thurston, on the behavior of annealed vs. cold-drawn iron wire, and in order to broaden the foundation for metallurgical generalization, Howe made experiments of his own on copper and silver. In these tests by Thurston and by Howe, the wires were rapidly loaded to determine the

Jan 1, 1939

By B. M. Larsen, L. S. Darken

Some years ago we collated all laboratory data then available to us on the distribution at equilibrium of manganese and of sulphur between metal and simple slags, and used the results in setting up an equation, which proved to be in accord with determinations of the distribution ratio of manganese and of sulphur between liquid steel and open-hearth slag, over a wide range of operating conditions. We now present an outline of our calculations and inferences on these two closely related questions, which are of especial importance because of the advisability of conserving manganese wherever possible. In general, our results show that in the open-hearth furnace equilibrium between metal and slag, with respect to both manganese and sulphur, is substantially attained during the finishing period of the heat, or in about a half hour to an hour after any additions were made. This implies that the end result will be identical whether manganese is added as alloy or metal to the liquid steel or as oxide to the slag. The proportion of total manganese retained by the steel is favored: (I) by use of the minimum amount of lime, consistent with other operating limitations, required to give a lime-silica ratio of about 2.4, which usually corresponds to a minimum practical slag volume; (2) by a high concentration in the slag of MnO relative to FeO; (3) by high operating temperature. Absorption of sulphur by the slag from the liquid metal is favored: (I) by large slag volume; (2) by a high concentration of active (or "free") lime and of manganese oxide dissolved in the slag; (3) by low concentration of silica, iron oxide, and phosphate dissolved in the slag. Distribution 02 Manganese between Slag and Metal at Equilibrium On the basis that the distribution of manganese between liquid steel and slag is controlled by the reaction FeO + Mn -& MnO + Fe [A] slag metal slag metal the distribution at equilibrium, at a given temperature, is expressed by the equilibrium constant for this reaction, which is defined as K,, _ aMnO' afe aFeO ' aMn where a is the activity of the molecular species denoted by the subscript. The activity of each of the several components, although it is not known precisely, is approximately equal to the concentration of each component expressed as its mol fraction; that is, as the ratio of the number of mols of the given component to the total number of mols of all the molecular species present in the metal or slag, as the case may be. Moreover, since the activity, or concentration, of iron in the liquid metal is in fact substantially constant, the term afe may be combined with K" to give a new constant K'. Making these changes, 7

Jan 1, 1942

By B. M. Larsen, L. S. Darken

Some years ago we collated all laboratory data then available to us on the distribution at equilibrium of manganese and of sulphur between metal and simple slags, and used the results in setting up an equation, which proved to be in accord with determinations of the distribution ratio of manganese and of sulphur between liquid steel and open-hearth slag, over a wide range of operating conditions. We now present an outline of our calculations and inferences on these two closely related questions, which are of especial importance because of the advisability of conserving manganese wherever possible. In general, our results show that in the open-hearth furnace equilibrium between metal and slag, with respect to both manganese and sulphur, is substantially attained during the finishing period of the heat, or in about a half hour to an hour after any additions were made. This implies that the end result will be identical whether manganese is added as alloy or metal to the liquid steel or as oxide to the slag. The proportion of total manganese retained by the steel is favored: (I) by use of the minimum amount of lime, consistent with other operating limitations, required to give a lime-silica ratio of about 2.4, which usually corresponds to a minimum practical slag volume; (2) by a high concentration in the slag of MnO relative to FeO; (3) by high operating temperature. Absorption of sulphur by the slag from the liquid metal is favored: (I) by large slag volume; (2) by a high concentration of active (or "free") lime and of manganese oxide dissolved in the slag; (3) by low concentration of silica, iron oxide, and phosphate dissolved in the slag. Distribution 02 Manganese between Slag and Metal at Equilibrium On the basis that the distribution of manganese between liquid steel and slag is controlled by the reaction FeO + Mn -& MnO + Fe [A] slag metal slag metal the distribution at equilibrium, at a given temperature, is expressed by the equilibrium constant for this reaction, which is defined as K,, _ aMnO' afe aFeO ' aMn where a is the activity of the molecular species denoted by the subscript. The activity of each of the several components, although it is not known precisely, is approximately equal to the concentration of each component expressed as its mol fraction; that is, as the ratio of the number of mols of the given component to the total number of mols of all the molecular species present in the metal or slag, as the case may be. Moreover, since the activity, or concentration, of iron in the liquid metal is in fact substantially constant, the term afe may be combined with K" to give a new constant K'. Making these changes, 7

Jan 1, 1942

By R. W. Gurry

Thermodynamic calculations indicate that boron is a better deoxidizer than silicon but probably is not quite as effective as aluminum. Boron should, therefore, be readily oxidized out of the open-hearth bath, which implies that it is not recovered in significant concentration from any scrap charged; also that, if added in the ladle, it tends to oxidize out during teeming unless protected by the presence of a better deoxidizing agent. These conclusions do not apply to liquid cast iron, in which the oxygen content is much lower than in liquid steel. The possibility of conserving certain strategic alloying elements widely used in steelmaking, notably manganese, chromium and molybdenum, by the use of boron, which in small concentration appears to be extraordinarily effective in promoting hardenability, raises a question as to what extent any boron present in the scrap charged into the open hearth is oxidized out during melting and subsequent refining. This question is significant because the optimum concentration of boron in the finished steel, which is fairly critical, would be very difficult to attain if the boron in the charge were largely retained in the metal. Moreover, unless boron is substantially eliminated in the open-hearth process its use on a large scale would eventually make it impossible to produce boron-free steel except by restricting the charge to virgin material. There is at present, unfortunately, virtually no satisfactory direct evidence to provide an answer to this question; but there are indications from practice that boron is oxidized out in the open hearth in the production of medium or low-carbon steel, although it may be retained if the carbon content remains fairly high; that is, if the oxygen is kept fairly low. In the absence of direct data, it is necessary to rely upon the indications of indirect evidence, the best approach now available being a thermodynamic calculation of the deoxidizing power of boron in liquid steel by the general method used so successfully by Chipman1 in his study of the reactions in the open-hearth process. The thermal data for boron, upon which such a calculation must be based, are reasonably satisfactory; the only quantities not directly determined are the entropy of melting of boron, the activity coefficient of boron in liquid steel, and the activity coefficient of B2O3in an open-hearth slag; but these values may be estimated with ample accuracy. The results of this calculation, which is presented later, are given in Table I, together with corresponding data for other deoxidizing elements. This table shows the calculated residual content of oxygen in equilibrium with different residual concentrations of the deoxidizer in the metal;

Jan 1, 1944

By R. W. Gurry

Thermodynamic calculations indicate that boron is a better deoxidizer than silicon but probably is not quite as effective as aluminum. Boron should, therefore, be readily oxidized out of the open-hearth bath, which implies that it is not recovered in significant concentration from any scrap charged; also that, if added in the ladle, it tends to oxidize out during teeming unless protected by the presence of a better deoxidizing agent. These conclusions do not apply to liquid cast iron, in which the oxygen content is much lower than in liquid steel. The possibility of conserving certain strategic alloying elements widely used in steelmaking, notably manganese, chromium and molybdenum, by the use of boron, which in small concentration appears to be extraordinarily effective in promoting hardenability, raises a question as to what extent any boron present in the scrap charged into the open hearth is oxidized out during melting and subsequent refining. This question is significant because the optimum concentration of boron in the finished steel, which is fairly critical, would be very difficult to attain if the boron in the charge were largely retained in the metal. Moreover, unless boron is substantially eliminated in the open-hearth process its use on a large scale would eventually make it impossible to produce boron-free steel except by restricting the charge to virgin material. There is at present, unfortunately, virtually no satisfactory direct evidence to provide an answer to this question; but there are indications from practice that boron is oxidized out in the open hearth in the production of medium or low-carbon steel, although it may be retained if the carbon content remains fairly high; that is, if the oxygen is kept fairly low. In the absence of direct data, it is necessary to rely upon the indications of indirect evidence, the best approach now available being a thermodynamic calculation of the deoxidizing power of boron in liquid steel by the general method used so successfully by Chipman1 in his study of the reactions in the open-hearth process. The thermal data for boron, upon which such a calculation must be based, are reasonably satisfactory; the only quantities not directly determined are the entropy of melting of boron, the activity coefficient of boron in liquid steel, and the activity coefficient of B2O3in an open-hearth slag; but these values may be estimated with ample accuracy. The results of this calculation, which is presented later, are given in Table I, together with corresponding data for other deoxidizing elements. This table shows the calculated residual content of oxygen in equilibrium with different residual concentrations of the deoxidizer in the metal;

Jan 1, 1944

By J. W. Spretnak, G. Sachs

The: iron-rich iron-nickel alloys have attracted considerable academic interest in recent years. The carbon-free alloys are of minor practical importance, but they are the base of many alloys with various outstanding properties. The iron-nickel alloys, therefore, have been investigated extensively regarding both their structures and their properties. The researches on these alloys up to 1938 have been collected and critically reviewed by J. S. Marsh,l and will be discussed in some detail in the sections of this paper dealing with specific subjects. These numerous investigations have not succeeded in establishing the equilibrium conditions in this system. Alloys containing more than a certain amount of nickel (8 to 10 per cent Ni) undergo the allotropic transformation extremely sluggishly, both on heating and cooling, showing a large hysteresis," which is not dependent upon the rate of cooling and persists even with very slow rates of cooling.3 Honda4 and Merica4 have therefore resigned themselves to proposing a diagram (Fig. I) for practical use, illustrating the structural relations under commercial conditions instead of attempting to establish the true equilibrium diagram. Marsh is less pessimistic and suggests an equilibrium diagram (Fig. 2) which conforms approximately to the facts known about this system. Recent X-ray investigations by Owen-Sully5 and Bradley-Gold-schmidt6 on powdered alloys indicate that the previous work on the iron-nickel system yielded very incomplete results. These investigators agree (Figs. 3 and ,+) that alloys in the powdered form containing more than 8 per cent and up to about 35 per cent Ni decompose into a stable heterogeneous mix-

Jan 1, 1941

By G. Sachs, J. W. Spretnak

The: iron-rich iron-nickel alloys have attracted considerable academic interest in recent years. The carbon-free alloys are of minor practical importance, but they are the base of many alloys with various outstanding properties. The iron-nickel alloys, therefore, have been investigated extensively regarding both their structures and their properties. The researches on these alloys up to 1938 have been collected and critically reviewed by J. S. Marsh,l and will be discussed in some detail in the sections of this paper dealing with specific subjects. These numerous investigations have not succeeded in establishing the equilibrium conditions in this system. Alloys containing more than a certain amount of nickel (8 to 10 per cent Ni) undergo the allotropic transformation extremely sluggishly, both on heating and cooling, showing a large hysteresis," which is not dependent upon the rate of cooling and persists even with very slow rates of cooling.3 Honda4 and Merica4 have therefore resigned themselves to proposing a diagram (Fig. I) for practical use, illustrating the structural relations under commercial conditions instead of attempting to establish the true equilibrium diagram. Marsh is less pessimistic and suggests an equilibrium diagram (Fig. 2) which conforms approximately to the facts known about this system. Recent X-ray investigations by Owen-Sully5 and Bradley-Gold-schmidt6 on powdered alloys indicate that the previous work on the iron-nickel system yielded very incomplete results. These investigators agree (Figs. 3 and ,+) that alloys in the powdered form containing more than 8 per cent and up to about 35 per cent Ni decompose into a stable heterogeneous mix-

Jan 1, 1941