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By Marcus A. Grossmann

The Institute has established this lectureship to honor the memory of a great American metallurgist, one whose fame has continued long after his passing. As one scientist recently stated it, "All metallurgical texts gradually become outdated and outmoded, except those of the great Henry Marion Howe." It seems fitting, then, that, once every year, we shouId review, in his honor, some aspects of the science in which he was such a distinguished leader, and also discuss any new data that may help to clarify our concepts. It is my privilege, for which indeed I express the deepest appreciation to this Institute, to offer for consideration a few thoughts on the toughness and fracture of hardened steels. Before proceeding to the data, I wish to express my great indebtedness to many associates whose stimulating discussions, generous contributions of data and cooperation in experiments are gratefully acknowledged. (But I wish to absolve them of any blame that may arise from the way in which their discussions and data have been used!) First, Dr. Edgar C. Bain, Vice President, Carnegie-Illinois Steel Corporation, whose amiable but merciless criticisms and always constructive and thoughtful suggestions help unfailingly to guard against pitfalls. Then to associates at Gary Steel Works, especially Mr. H. B. Wishart, Mr. W. K. Smith and Mr. V. Elliott, for great assistance in securing data. Also to Col. C. H. Greenall, Director of Laboratories, Frankford Arsenal, and his metallurgical staff, including Messrs. J. K. Desmond, H. Markus, D. F. Armiento, H. Rosenthal and Henry George, for numerous data and illustrations. Further to Dr. J. R. Low and Dr. M. Asimow, for helpful discussions of effects of states of stress during deformation and rupture, to Mr. J. M. Hodge for discussions and data, to the staff of the U. S. Steel Corporation Research Laboratory for advice and data, and to the Metallurgical Staff at Duquesne Steel Works. The individual acknowledgments will also be found under illustrations. Acknowledgment is also due to Mr. S. C. Snyder for incredibly meticulous scrutiny of manuscript. To all of these, grateful thanks. Introduction The discussion to be offered here will deal with quench-hardened steels only, and may perhaps be considered under three headings: 1. It was found that, when ferrite was precipitated in the (prior austenite) grain boundaries of hardened steel, the notch-bar toughness was much less than in pieces fully hardened. The fracture took place in the ferrite, and the loss in toughness is attributed to the lower cohesive (cleavage) strength of the ferrite, as cornpared with martensite. 2. When notch-bar impact test pieces of quenched and tempered steels were examined as to their mode of fracture, it

Jan 1, 1947

By Marcus A. Grossmann

The Institute has established this lectureship to honor the memory of a great American metallurgist, one whose fame has continued long after his passing. As one scientist recently stated it, "All metallurgical texts gradually become outdated and outmoded, except those of the great Henry Marion Howe." It seems fitting, then, that, once every year, we shouId review, in his honor, some aspects of the science in which he was such a distinguished leader, and also discuss any new data that may help to clarify our concepts. It is my privilege, for which indeed I express the deepest appreciation to this Institute, to offer for consideration a few thoughts on the toughness and fracture of hardened steels. Before proceeding to the data, I wish to express my great indebtedness to many associates whose stimulating discussions, generous contributions of data and cooperation in experiments are gratefully acknowledged. (But I wish to absolve them of any blame that may arise from the way in which their discussions and data have been used!) First, Dr. Edgar C. Bain, Vice President, Carnegie-Illinois Steel Corporation, whose amiable but merciless criticisms and always constructive and thoughtful suggestions help unfailingly to guard against pitfalls. Then to associates at Gary Steel Works, especially Mr. H. B. Wishart, Mr. W. K. Smith and Mr. V. Elliott, for great assistance in securing data. Also to Col. C. H. Greenall, Director of Laboratories, Frankford Arsenal, and his metallurgical staff, including Messrs. J. K. Desmond, H. Markus, D. F. Armiento, H. Rosenthal and Henry George, for numerous data and illustrations. Further to Dr. J. R. Low and Dr. M. Asimow, for helpful discussions of effects of states of stress during deformation and rupture, to Mr. J. M. Hodge for discussions and data, to the staff of the U. S. Steel Corporation Research Laboratory for advice and data, and to the Metallurgical Staff at Duquesne Steel Works. The individual acknowledgments will also be found under illustrations. Acknowledgment is also due to Mr. S. C. Snyder for incredibly meticulous scrutiny of manuscript. To all of these, grateful thanks. Introduction The discussion to be offered here will deal with quench-hardened steels only, and may perhaps be considered under three headings: 1. It was found that, when ferrite was precipitated in the (prior austenite) grain boundaries of hardened steel, the notch-bar toughness was much less than in pieces fully hardened. The fracture took place in the ferrite, and the loss in toughness is attributed to the lower cohesive (cleavage) strength of the ferrite, as cornpared with martensite. 2. When notch-bar impact test pieces of quenched and tempered steels were examined as to their mode of fracture, it

Jan 1, 1947

By Eugene McAuliffe

THE last obtainable figures of the value of the coal mining investment are those contained in the U. S. Census Reports, from data gathered in 1919. The values shown therein and set forth below cover lands and equipment and do not include distribution and marketing facilities. The working capital necessary to meet pay rolls to purchase material and supplies and workmen's compensation insurance are likewise excluded.

Jan 1, 1926

By Westwater, J. S.

The Mather mine of The Negaunee Mine Co. embraces nearly all of Sections 1 and 2, T47N, R27W. within the limits of the cities of Negaunee and Ishpeming on the Marquette iron range of Michigan's Upper Peninsula. Operations of the Negaunee Mine Co., the stock of which is jointly owned by Bethlehem Steel Co. and The Cleveland-Cliffs Iron Co., are under the direction of the latter company. The opening of the Mather mine was described by C. W. A1len. Mather "A" shaft was completed to an initial depth of 2352 ft in early 1943. The shaft capacity of over one million tons yearly is in prospect of being realized by orderly development and mining, and sinking of the second or "B" shaft then started in accordance with previous planning. Mather " B, " also a vertical shaft, was designed as a twin to Mather "A" shaft and the sinking technique developed at Mather "A" was utilized in "B" shaft operation.

Jan 1, 1949

By F. G. Smith

A FEW years ago, the writer encountered a, problem that, at first, seemed to be due to peculiar conditions affecting grain growth. Large cups made from heavy metal failed in the first drawing operation in the process of making seamless tubes. The metal, as cast, appeared to be sound and strong; it rolled successfully and withstood the first cupping operation, but on the first draw it failed, with a crystalline fracture. The failure appeared in the slightly worked part of the bottom of the cup, and microscopic examination revealed exceptionally large grains. Knowing the general conditions governing recrystallization of brass, which were later published by Matthewson and Phillips, an investigation was outlined with the idea of including various conditions under which new grains might form, and which would include the effect that a previous anneal might have upon the anneal following. These conditions were produced by annealing specimens of brass at five different temperatures, indenting them with a 10-inn. ball under four different pressures, and then reannealing at each of the five temperatures five specimens each of which had been annealed at one of the five temperatures.

Jan 8, 1919

By J. Ruben Velasco, Roland B. Mulchay

CANANEA has long been recognized as a remarkable field for geologic study. The copper deposits and rocks of the district have been described by many geologists and engineers, but only the most general correlations have been made between Cananea sedimentary rocks and other known sedimentary sections in the southwestern United States and northern Mexico. The present paper describes the Cananea sediments in greater detail than has been done before and attempts to fit the Cananea sedimentary section more closely into the geologic time table. The lack of well-preserved fossils has made it difficult to date the sediments accurately in geo- logic time, but it is possible to make tentative correlations between the Cananea sediments and the southeastern Arizona sections, based largely upon lithology and general position in the geologic column. It appears that sedimentation at Cananea and Bisbee may have been closely similar during Paleozoic time. Even such generalized correlations, however, may be subject to considerable modification in the future. The present study has led to the recognition of other problems of age and mineralization relationships in the Cananea district. Cananea is located in the north-central part of the state of Sonora, Mexico, at an elevation of 5270 ft. It is about 135 miles northeast of Hermosillo, the state capital, and 25 miles south of the international boundary. By road Cananea is 40 miles from the twin towns of Naco, Ariz., and Naco, Sonora, and about 50 miles from Bisbee, Ariz. It is served by the Nogales-Naco branch of the railroad, F.C. Pacifico, and is connected with Chihuahua and Mexico City by the Aeronaves airline.

Jan 6, 1954

By F. F. Aplan

Mineral processing engineers have recorded an- other year of active research and development work. Most gratifying was the broadly based attendance at the Mineral Processing Fundamental (formerly Basic Science) Committee sessions at the 1968 Annual Meeting of the AIME. Because of the availability of good papers, the active discussion and the growing attendance, sessions have grown from one to three at the annual meeting. Prof. M. C. Fuerstenau of the University of Utah will chair the Mineral Processing Fundamentals Committee for the next two years and we may thus be assured of continued active leadership. The name change from "Basic Science Committee" to the more descriptive "Mineral Processing Fundamentals Committee" approved by the MBD executive council is a welcome improvement. Our profession continues to attract the interest and cooperation of those in other professional groups. The 1968 Engineering Foundation Particulate Matter Conference, under the chairmanship of John Karpinski of Bethlehem Steel, was devoted exclusively to comminution this year. It attracted conferees from five continents and served as a particularly stimulating source of interchange of knowledge from many technical fields. Next year's conference will be under the chairmanship of Professor L,. G. Austin of The Pennsylvania State University. This conference plus the Symposium on Wettability and Flotation to be held at the annual American Chemical Society meeting in Minneapolis in April indicates the success achieved in the inter-disciplinary approach to problems. Other evidence of this spirit of professional cooperation is the forth- coming book on Size Reduction edited by D. W. Fuerstenau. This is the outgrowth of an AIChE symposium on size reduction held in 1965.

Jan 2, 1969

By A. Hultgren, G. Phragmén

Page Outline of Progress of Knowledge and Theories about Gas Evolution in Steel Ingots. and Its Influence on Crystallization and Segregation................ 134 Object of Present Investigation........................................... 148 Theoretical Discussion of Process of Solidification........................... 149 Gas Given Off from Rimming Steel during Solidification................... 149 Equilibrium Diagram of the Iron-carbon-oxygen Alloys................... 151 Solidification of Pure Iron-carbon-oxygen Alloys.......................... 157 Solidification when Carbon Monoxide Is Given Off at Constant Pressure... 157 Solidification when Gas Evolution Is Suppressed....................... 158 Schematic Application on Solidification of Rimming-steel Ingots.......... 159 Influence of Manganese, Sulphur and Phosphorus......................... 160 Experimental work..................................................... 162 Liquid Steel and the Mold Gas......................................... 162 Ingots Investigated and Methods Used.................................. 165 Ingot structure....................................................... 174 Structure of Rim Zone.............................................. 174 Structure of Core................................................... 181 Structures Obtained under Special Conditions of Freezing................ 182 Distribution of Metalloids............................................. 187 Other Observations Made............................................. 192 General Discussion of Solidification Process................................. 195 Condition of Liquid Steel before Casting................................. 195 Rimming Period...................................................... 202 Composition of Rim Zone............................................. 225 Freezing after Top Is Closed........................................... 228 Slag Inclusions and Ingot Scum........................................ 234 Reaction between Gas in Blowholes and Surrounding Solid Steel during Cooling 235 Summary.............................................................. 237 Appendix—Preparation and Etching of Ingot Sections....................... 238 References............................................................. 239 In 1934, Jernkontoret (The Swedish Ironmasters' Association) appointed a committee for the study of the structure of rimming-steel ingots and the various phenomena associated with their solidification. The members of the committee, including those who have joined it later, have been: I. Bohm, B. D. Enlund, B. Kalling, M. Tigerschiöld, S. Wohlfahrt and the authors. The present paper‡ is a somewhat

Jan 1, 1939

By G. Phragmén, A. Hultgren

Page Outline of Progress of Knowledge and Theories about Gas Evolution in Steel Ingots. and Its Influence on Crystallization and Segregation................ 134 Object of Present Investigation........................................... 148 Theoretical Discussion of Process of Solidification........................... 149 Gas Given Off from Rimming Steel during Solidification................... 149 Equilibrium Diagram of the Iron-carbon-oxygen Alloys................... 151 Solidification of Pure Iron-carbon-oxygen Alloys.......................... 157 Solidification when Carbon Monoxide Is Given Off at Constant Pressure... 157 Solidification when Gas Evolution Is Suppressed....................... 158 Schematic Application on Solidification of Rimming-steel Ingots.......... 159 Influence of Manganese, Sulphur and Phosphorus......................... 160 Experimental work..................................................... 162 Liquid Steel and the Mold Gas......................................... 162 Ingots Investigated and Methods Used.................................. 165 Ingot structure....................................................... 174 Structure of Rim Zone.............................................. 174 Structure of Core................................................... 181 Structures Obtained under Special Conditions of Freezing................ 182 Distribution of Metalloids............................................. 187 Other Observations Made............................................. 192 General Discussion of Solidification Process................................. 195 Condition of Liquid Steel before Casting................................. 195 Rimming Period...................................................... 202 Composition of Rim Zone............................................. 225 Freezing after Top Is Closed........................................... 228 Slag Inclusions and Ingot Scum........................................ 234 Reaction between Gas in Blowholes and Surrounding Solid Steel during Cooling 235 Summary.............................................................. 237 Appendix—Preparation and Etching of Ingot Sections....................... 238 References............................................................. 239 In 1934, Jernkontoret (The Swedish Ironmasters' Association) appointed a committee for the study of the structure of rimming-steel ingots and the various phenomena associated with their solidification. The members of the committee, including those who have joined it later, have been: I. Bohm, B. D. Enlund, B. Kalling, M. Tigerschiöld, S. Wohlfahrt and the authors. The present paper‡ is a somewhat

Jan 1, 1939

By E. R. Kaiser

COAL research during 1942 was directed in an important degree toward the solution of problems of wartime importance. A wider selection of coals for carbonization to meet the increased demand for coke, and the improved utilization of lower-grade coals for boiler fuel were made possible by fundamental studies on cod and ash behavior that had been started several years ago. The coal industry's interest in the work of the various laboratories brightened significantly as results were demonstrated on smokeless combustion in stoves, on stokers without coke trees, and on pulverized firing of forge furnaces. Despite the limitations of priorities and scarcity of materials, the mineral industries building of the West Virginia University was completed and equipped with facilities for research on coal min

Jan 1, 1943

Remarks Of Mr. Robert W. Hunt, General Superintendent, Albany And Rensselaer Iron And Steel Company., Troy N. Y. - In discussing Dr. Dudley's two most interesting papers, I feel a natural hesitancy in disagreeing with conclusions formed after such careful and conscientious work. But I think he has made his deductions from too meagre premises. The analyses of but twenty-five samples are entirely too few to justify the establishment of so important a formula. When we consider that he indirectly proposes to regulate an interest amounting, even at the present low prices, to over $20,000,000 per annum, we may well hesitate before accepting a formula based upon the chemical and physical analyses of but twenty-five steel rails. Dr. Dudley touches the keynote in referring to the proposed labors of the Government Test Commission. They based their hopes of attaining success upon the chemical and physical analyses of a very large number of samples, and in the only branch of investigation which the short-sighted policy of Congress has allowed them to complete, i.e., chain cables, we find that a dozen, twenty-five or one hundred tests gave no satisfactory results. It was only after many hundreds that they were enabled to draw conclusions. There are so many circumstances bearing upon the life of a rail, that the task of extracting a correct result seems herculean. I presume I am right in stating that in our Northern latitudes early winter and spring months witness the breaking of the greatest number of rails, thus seeming to prove that an unstable road-bed has much to answer for. Then, again, broken and flattened wheels must be taken into account, but I am convinced that more rails have been broken by the treatment which they received before leaving the rolling-mill * The remarks of the participants in this debate have been written out by the speakers, and are here given without any attempt to retain the order of the dis¬cussion. While the report does not, therefore, preserve the vigor and spontaneity of the debate, it is believed that it gains in value by giving the matured views of the speakers. The continuation of this discussion at the Pittsburgh Meeting, May, 1879 (beginning with remarks of Mr. Cloud on page 401), is appended for convenience of reference.-T. M. D., Sec'y

Jan 1, 1879

By AIME AIME

L H. DUSCHAK gave an interesting talk at a recent meeting of the. San Francisco Section, based -011 experimental work with a variety of ores at the laborator of the Treadwell-Yukon Co., in Berkeley, Cal. He was of the opinion that the customary "cut and try" method of flotation testing was still in evidence and that the flotation process was more of an art than an exact science. Propounded theories have enabled investigators to' classify reagents as well as to suggest new ideas both in the metallic and nonmetallic fields, but the application of theory has riot as yet been able to solve many of the unknown factors in operation.

Jan 1, 1932

By Koert D. Burnham, John G. Broughton

WOLLASTONITE in Essex County, New York, occurs as a typical contact mineral in a series of rocks metamorphosed by anorthosite. Sole current use is in various types of electric welding fluxes. Its uniform lathlike shape suggests its use as a specialized filler.

Jan 1, 1944

By J. D. Doherty

That America's great coal deposits eventually will be our principal source of liquid as well as solid fuels is generally accepted. Moreover, the day when synthetic oil from coal will begin to supplement our petroleum supplies does not appear to be far off. The American petroleum industry has not spared effort or expenditure in its attempt to keep pace with the demand for oil, and recent production has exceeded expectations. However, the rapidly rising demand for liquid fuels plus the increasing difficulty of finding and developing the new oil needed even to maintain present production rates make it highly unlikely that oil from domestic wells can fully meet future oil requirements. Therefore, it appears that one or more of the following courses must be followed: 1. Curtail oil consumption. 2. Increase imports. 3. Develop new sources such as synthetic liquid fuels.

Jan 1, 1949

By Robert F. Mehl

EXTENSION of physical and chemical methods of research in the study of metallic behavior continues rapidly, particularly in the correlation of behavior with crystal structure, and in the analysis of elastic and plastic properties. The growth of the science of metals during 1933 calls for special comment; the need for special reviews and for textbooks and monographs is now acute, as might he supposed from the number of references appended to this article, a list which is much abbreviated.

Jan 1, 1934

By Edwin B. Eckel

This paper, based on brief field examination and on data supplied by the operators, records the condition of the Italian mercury industry as of March 1945, not long after Italy's collapse. Except for the once-Italian but now Yugoslavian Idria mine near Trieste, virtually all the known mercury deposits are in the Monte Amiata district in Siena and Grosseto Provinces, 75 miles north of Rome. This district contains the Abbadia San Salvatore. the Siele. the Argus, and the Cerreto Piano mines besides numerous prospects and unproductive mines. Under pressure from Germany the principal mines were highly productive during the early part of the war, but production fell off long before its end. All of the mines were damaged in some way at the German withdrawal but by September 1944 the Abbadia had resumed production and several others were only lacking power by the early spring of 1945. The Monte Amiata district is characterized geologically by a thick series of sedimentary rocks that range from Triassic to Eocene in age . and are surmounted on Monte Amiata itself by a thick cap of extrusive trachyte. Bodies of travertine and of landslide detritus, younger than the trachyte, are rather widespread. The structure is complex and little known but most of the ore deposits seem to lie along or near a major, north-trending fault or on associated cross-fractures. Cinnabar is the only important ore mineral and clay minerals are by far the most abundant products of hydrothermal alteration. A southward increase in the amount of stibnite, relative to cinnabar, suggests horizontal zoning. The grade of ore ranges from 0.60 to 3.0 Pet and the reserves, as compared with those in American mines, are enormous. Even in the face of war-time scarcities, the mines are remarkably self-sufficient and labor is plentiful, but the costs of production are estimated to be not greatly below those of the better American mines. Notes on the principal mines, on the mining and metallurgical methods, and on the manufacture of synthetic cinnabar are included in the paper. Introduction With but few brief interludes, Spain and Italy, including the Idria mine near Trieste, which has passed from Austrian to Italian to Yugoslavian hands in the Past 3 decades, have led the world in the production of mercury, or quicksilver, for many centuries. Despite their enviable position with respect to the supplies of a metal so essential in both war and peace, there is a notable lack of up-to-date information in America on the mercury industry of either country. Duschak and Schuette' and Schuettez,3 give by far the best summaries in English known to the writer, but the latest firsthand report cited by them on the Italian mines was published in 1915.' Having been deeply interested in the geology and economics of mercury for several years, the writer naturally felt most fortunate in being the to obtain enough firsthand information on the Italian industry to fill at least a few of the gaps in our knowledge. The opportunity came during the war, soon after this industry, together with the rest of Italy, had capitulated to the Allies. Many of the facts presented here are thus definitely "dated," but others are of less transitory nature, and even the dated facts should be of interest in showing the strength and

Jan 1, 1949

By Edwin B. Eckel

This paper, based on brief field examination and on data supplied by the operators, records the condition of the Italian mercury industry as of March 1945, not long after Italy's collapse. Except for the once-Italian but now Yugoslavian Idria mine near Trieste, virtually all the known mercury deposits are in the Monte Amiata district in Siena and Grosseto Provinces, 75 miles north of Rome. This district contains the Abbadia San Salvatore. the Siele. the Argus, and the Cerreto Piano mines besides numerous prospects and unproductive mines. Under pressure from Germany the principal mines were highly productive during the early part of the war, but production fell off long before its end. All of the mines were damaged in some way at the German withdrawal but by September 1944 the Abbadia had resumed production and several others were only lacking power by the early spring of 1945. The Monte Amiata district is characterized geologically by a thick series of sedimentary rocks that range from Triassic to Eocene in age . and are surmounted on Monte Amiata itself by a thick cap of extrusive trachyte. Bodies of travertine and of landslide detritus, younger than the trachyte, are rather widespread. The structure is complex and little known but most of the ore deposits seem to lie along or near a major, north-trending fault or on associated cross-fractures. Cinnabar is the only important ore mineral and clay minerals are by far the most abundant products of hydrothermal alteration. A southward increase in the amount of stibnite, relative to cinnabar, suggests horizontal zoning. The grade of ore ranges from 0.60 to 3.0 Pet and the reserves, as compared with those in American mines, are enormous. Even in the face of war-time scarcities, the mines are remarkably self-sufficient and labor is plentiful, but the costs of production are estimated to be not greatly below those of the better American mines. Notes on the principal mines, on the mining and metallurgical methods, and on the manufacture of synthetic cinnabar are included in the paper. Introduction With but few brief interludes, Spain and Italy, including the Idria mine near Trieste, which has passed from Austrian to Italian to Yugoslavian hands in the Past 3 decades, have led the world in the production of mercury, or quicksilver, for many centuries. Despite their enviable position with respect to the supplies of a metal so essential in both war and peace, there is a notable lack of up-to-date information in America on the mercury industry of either country. Duschak and Schuette' and Schuettez,3 give by far the best summaries in English known to the writer, but the latest firsthand report cited by them on the Italian mines was published in 1915.' Having been deeply interested in the geology and economics of mercury for several years, the writer naturally felt most fortunate in being the to obtain enough firsthand information on the Italian industry to fill at least a few of the gaps in our knowledge. The opportunity came during the war, soon after this industry, together with the rest of Italy, had capitulated to the Allies. Many of the facts presented here are thus definitely "dated," but others are of less transitory nature, and even the dated facts should be of interest in showing the strength and

Jan 1, 1949

By H. Margolin, E. Ence

Two versions of the Ti-Mn binary diagram have been published recently.' , -0th diagrams show two compounds in the region between 40 and 70 wt pct Mn, but disagree as to the reaction in which these compounds are involved. The investigation of the manganese-rich portion of the Ti-Mn binary diagram was undertaken at New York University as part of an investigation of ternary systems with titanium and manganese in order to determine which of the proposed diagrams is correct. A number of alloys between 31 and 70 pct Mn were prepared in a manner similar to that described by Cadoff and Nielsen; except that low currents (110 amp in argon atmosphere) and long melting times (up to 20 min) were used to prepare the alloys. Compositions were determined from weight-loss data, assuming all loss as due to manganese. Heat treatments were carried out with relatively large pieces, since there was a tendency for manganese to be lost during heat treatment. When X-ray diffraction data was to be obtained, the central parts of heat-treated specimens were used to make filings or powders which were not heat treated. Specimens were heat treated from the as-cast state. Heat-treatment times were as follows: 1150°C, 1 day; ll00°C, 2 days; 1000°C, 5 days; and 900°C, 15 days. It should be noted that equilibrium was not attained at 900°, 1000°, and in one case, at 1150°C. Metallographic specimens were electrolytically polished and strain etched by a technique described elsewhere.' At least four, and possibly six, phases were found in the region investigated. On the basis of information available at this time, a completely self-consistent diagram cannot be constructed, and therefore data are presented only for those phases which have been identified by both X-ray and microstruc-ture. Of the compounds detected, the one highest in manganese is the Laves phase, TiMn,, which is hexagonal with a MgZn, type of structure.V he diffraction data for TiMn2 from a 70 pct Mn alloy annealed at 1150°C are shown in Table I. The c/a ratio and parameters of TiMn2 agree well with those of Wall-baum hnd Rostoker et al. The values obtained here are c/a = 1.641, a = 4.825A. Another compound is the y-phase which is estimated to contain about 60 pct Mn. The y-phase has a structure which is identical to that of TiMn, with c/a = 1.639, a = 4.906Å. The fact that y has a Laves-type lattice would suggest that TiMn, has a range of solubility which extends from the composition of TiMn2 (69.6 Mn) to that of y (60 pct Mn). However, this could not account for microstructures which, in the 60 to 70 pct Mn region, show several phases in both the as-cast state and after annealing at 1150°C. Fig. 1 shows a two-phase structure of a 60 pct Mn alloy annealed at 1150°C. The phases present are y (white) and e (dark). If y were TiMn, then, according to Rostoker et al.,' the second phase of Fig. 1 should be P-Ti. The diffraction data for the 60 pct Mn alloy of Fig. 1 are shown in Table I. The starred d-values are from the e-phase and these lines do not correspond to those of &Ti. Comparison of as-cast and 1150°C microstructures of the 60 pct Mn alloy indicates that e precipitated from y. Since y has a

Jan 1, 1955

By John Chipman

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

Jan 1, 1961

[A Aamodt, H. C., A55 C Sales, Great Lakes Carbon Corp., 18 E. 48th St., New York, N.Y. Aamot, Olav Crone, M29 2126 M4, Galveston, Texas Aaronson, Hubert I., M47 E Prin Res Engr, Ford Motor Co., Met. Dept., Sci. Lab., Engrg. Staff, P. O. Box 2053, Dearborn, Mich. Aase, Glenn D., M54 D Prin Engr, Air Pollution Control Dist., 1480 Mission St., San Francisco 3, Calif. Abbett, W. A., Jr., M56 8629 Beverly St., Duluth 8, Minn. Abbey, Robert G., M56 138 Dartmouth Rd., Bala Cynwyd, Pa. Abbott, A. G., Jr., J52 E Test, Dev Engr, Chrysler Corp. Missile Div., P. O. Box 2628, Detroit 31, Mich. Abbott, Mark L., A58 Rep, General Refractories Co., 208 S. LaSalle St., Chicago, Ill. Abbott, W. K., J58 E Dev Met, Int'l Nickel Co., Inc., 67 Wall St., New York 5, N.Y.]

Jan 1, 1961