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By G. K. Manning, A. R. Elsea, A. B. Westerman

INTRODUCTION A CONSIDERABLE number of high-temperature alloys, that is, alloys which have load-carrying ability at elevated temperatures, have been developed on an empirical basis. In order to determine why these alloys possess this particular ability, a project was started at Battelle Memorial Institute on the fundamental factors promoting high-temperature strength of alloys. At the time of inception of this study, the cobalt-base alloy, Vitallium, was widely used because of its good high-temperature properties. One phase of this study was to include an investigation of the structures observed in Vitallium after various heat treatments. However, before investigating the structural features of Vitallium, it appeared logical to examine the phase diagrams of the related binary systems in order to develop information as to which phases- might be present in Vitallium. A preliminary survey of the pertinent alloy systems was made, with particular emphasis on the cobalt-chromium system, which is the base for the Vitallium series of alloys. The early work of Lewkonja1 and Guertler2 indicated that cobalt and chromium are completely miscible in the liquid state, and, within a narrow temperature range, in the solid state; that the liquidus shows a minimum; and that the alloys containing 45 to '85 pct chromium undergo a transformation at 1200 to 1250°C. More recently, Wever and Haschimoto,3 Wever and Lange,4 and Matsunaga5 carried out experimental work which led to the diagrams shown in Fig I and 2. Both diagrams are based on thermal analysis, metallographic, magnetic, and dilatation data; in addition, X ray diffraction results were used by Wever and Haschimoto, and electrical resistance measurements by Matsunaga. It is apparent from a comparison of the two diagrams that there was a difference of opinion as to the locations of the boundaries of the various phases, and as to the existence of a phase containing approximately 47 pct chromium. With these exceptions noted, it might be pointed out that the two diagrams are similar, and that, in general, any particular reaction which is shown on both diagrams occurs at a lower temperature on the Matsunaga diagram than on that of Wever-Haschimoto-Lange. Thus, in view of the gaps in the data and the questionable features in the published diagrams, it appeared desirable to start the fundamental study of Vitallium by determining the diagram for the cobalt-chromium system. EXPERIMENTAL WORK For the convenience of the reader, the diagram as determined by the present investigation is presented in Fig g. The liquidus and solidus data for the low-chromium alloys were taken from the work of Wever and Haschimoto,3 while the, melting point for pure chromium is the

Jan 1, 1948

By Joseph B. Umpleby

PROGRESS in the petroleum industry in 1929 has been characterized by outstanding accomplishments in the fields of new discovery of supply, economic control of production, increased efficiency and reduced costs of recovery, and lowered costs and greater flexibility in manufacture. Resources have been developed in an outstanding degree in the Kettleman Hills. California, the Oklahoma City field (which adds a large potential area in central Oklahoma), the discovery of Woodbine sand production in East Texas, and the discovery of Wilcox sand production in west-central Kansas. Engineering technique has progressed both along the lines of development and production, with a net result that costs have been reduced and extraction increased in notable degree, although it is impossible to give a close measure of either. In the field of re- fining crude oils variations to the end of promoting reduced cost and greater flexibility has been more important than genera! acceptance of innovations in practice.

Jan 1, 1930

By Michael Tenenbaum

Selected characteristics of nonmetallic phases were determined in low-carbon sheet steels which had been produced by various refining; deoxidizing, and casting procedures. The results showed little influence of the refining process on the quantity, distribution, size, and character of the nonmetallic phases. The quantity of inclusions was governed by the deoxidation procedures. While the mode of casting influenced the internal structure and the pattern of inclusion distribution, it had little effect on the quantity of nonmetallics. The vast majority of inclusions were under 30 µ in diam, and there was little change in size distribution during hot and cold rolling. The composition and structure of the inclusions were expained an the basis of known equilibrium phase diagrams for the appropriate systems. Additional work is needed to explain some of the observations of this paper. HENRY Marion Howe's contributions to the metallurgical profession include his many writings, the wisdom that he imparted to his students, and the inspiration that he gave to the many scholars, teachers, and industrialists who knew him personally. It was Professor Howe's intimate colleague, Albert Sauveur,1 who, in the first Howe Memorial Lecture, could have been speaking for the metallurgist of our generation as well as his own when he wrote, "...how many of us on the point of going astray were called back to the right path by Howe's guiding torch?" More than a quarter of a century later, Francis Foley,2 one of the last in the Howe Lecture series who worked directly with the great man, delivered the ultimate tribute, "...truth, in its time is so hard to identify." While Professor Howe strove to be right, "he was content if he provoked the reader to take the next step along the path to greater knowledge." Like so many of my predecessors, I sought guidance for this lecture by referring to Professor Howe's two classic texts, Metallurgy of steel,3 and Metallography of Steel and Cast Iron: the former book interpreting the facts as he saw them near the start of his career, and the latter—published 26 years later—pointing to many fertile fields for metallurgical investigation. Those of us who harvest the fruits of Henry Marion Howe's contributions to the metallurgical profession now look with wonder at the tremendous legacy he has provided. It is rewarding to study his writings and to recognize the anticipation of such aspects of modern ferrous metallurgy as: 1) Direct reduction 2) Steelmaking reactions 3) The approaches and benefits of degassing 4) Solidification mechanisms 5) Habits and behavior of nonmetallic inclusions 6) Recrystallization phenomena 7) Slip and slip propagation 8) Dislocations 9) Discontinuous deformation 10) Microscopic and macroscopic segregation

Jan 1, 1970

By William E. Ford, Edward Salisbury Dana

In their action upon the senses a few minerals possess taste, and others under some circumstances give off odor. 444. Taste belongs only to soluble minerals. The different kinds of taste adopted for reference are as follows: 1. Astringent: the taste of vitriol. 2. Sweetish astringent: taste of alum. 3. Saline: taste of common salt. 4. Alkaline: tast'e of soda. 5. Cooling: taste of saltpeter. 6. Bitter: taste of Epsom salts. 7. Sour: taste of sulphuric acid.

Jan 1, 1922

By Walter E. Duncan

THE ores treated at the concentrating plant largely come from the blanket replacement deposits of the northeastern part of Hardin County, Illinois, and consist of complex mixtures of galena, sphalerite and fluorspar in a gangue of quartz, limestone and sandstone. The several minerals are so intimately intergrown that they are not liberated at the sizes usually treated by gravity concentration in the usual fluorspar plant. For this reason, an all-flotation method of concentration was developed in cooperation with the station of the U. S. Bureau of Mines at Rolla, Mo.1 This flotation separation made possible the commercial production of four concentrates: (I) lead concentrates, (2) zinc concentrates, (3) acid-grade fluorspar concentrates and (4) metallurgical-grade fluorspar concentrates.2,3 Although fluorspar had been floated in Canada in 1921 4 and a plant at Rosiclare had been floating fluorspar since March 1929, fluorspar flotation was given considerable impetus by the Mahoning developments, since some features of the separation were quickly adopted by other fluorspar companies. The Bureau of Mines5 reports that in the 10 years preceding 1938 only 50,552 tons of fluorspar flotation concentrates were produced in the United States. The rise from this almost nominal figure to 153,750 tons (largely acid grade) in one year (1944)6 is indicative of the activity in fluorspar flotation occasioned by the war. The industry thus proved to be in a position to expand and keep up reasonably well with the requirements imposed upon it by such developments as occurred in high octane aviation gasoline alkylation, in the use of Freon as a refrigerant and as carrier in the Aerosol "bug bomb," and in the atomic bomb project as well as in the expansion of other activities requiring hydrofluoric acid; such as, for example, the aluminum industry. Despite the fact that the greater portion of acid-grade fluorspar produced in the last few years went directly into war uses, the future of the acid-grade field still appears bright. As a result of the activity in fluorine chemistry during the war, it seems likely that in the relatively near future almost every phase of human endeavor will find some fluorine compound involved. The other three concentrates produced deserve some attention in these introductory remarks. The lead concentrates first produced contained both zinc and fluorspar but these did not interfere with their marketing. As will be pointed out later, the quality has steadily improved until today it is a relatively high-grade product. Although some zinc smelters accept concentrates containing limited quantities of fluorspar, it is a very objectionable impurity. Since flotation methods fail in the complete removal of the fluorspar, chemical methods were developed for

Jan 1, 1946

By J. E. Schiller, S. E. Khalafalla

Due to its unique surface properties, magnesium oxide (MgO) is an excellent medium to filter asbestos and other suspended solids from water. MgO operates up to twice as long as a sand filter before backwashing is required while flow rate and filtrate clarity are as good or better with MgO.

Jan 1, 1984

By E. C. Bohlen, H. l. Burghoff

THE work reported in this paper was carried out to supplement the existing information concerning directional properties and recrystallization textures of annealed brass sheet and strip. These characteristics are of direct interest when the forming and drawing properties of such material are being considered. Among those who have made contributions in this field are Bass and Glocker;1 Bauer, Göler and Sachs;2 Phillips and Samans;3 Pratt;4 Price;5 Cook;6 Richards;7 Brick;8 and Brick and Williamson.9 These investigators have found, in general, that in brass strip that shows directional variations in properties, tensile strength has a minimum value and elongation has a maximum value at 45° to the rolling direction. The most pronounced directional properties have been found in material given the greatest reductions in rolling followed by high annealing temperatures. Recrystallization texture of brass has been variously reported as (113)[112], (001)[100], and a combination of (110)[115] and traces of the primary rolling texture, (110)[112]. The directional studies have been very informative, but actual tests appear to have been confined to material in its final condition. Tests at intermediate stages have received little attention although previous history of some materials has been partly considered. Perhaps the most comprehensive investigation was made by Cook,6 who studied the directional properties of 70-30 brass strip for which the final and penultimate, or next to the last, anneals and the final reductions were varied. He found that, for any given combination of penultimate anneal and final reduction, the tendency toward the development of directional properties was reduced as the temperature of the final anneal was decreased. In addition to drawing cups and making tensile tests of the finished material at various angles to the rolling direction, he measured the frequency and the angles of twins in grains for several specimens. Plots of his twin counts showed directionality for the materials that produced eared cups. TEST MATERIALS AND EQUIPMENT For this investigation, one commercial heat of 68-32 brass was cast in the form of bars for cold-rolling, 13 ½ in. wide and 1 ½ in. thick. The analysis was as follows: 68.83 per cent copper, 0.04 per cent lead, 0.01 per cent iron, 31.12 per cent zinc (by difference). The bars were so processed to the final thickness, 0.020 in., as to obtain on this thickness all possible combinations of the variables listed below except those involving the sequence of 84 per cent penultimate reduction and 84 per cent final reduction: I. Penultimate reductions of 37 per cent, 50 per cent and 84 per cent; 2. Penultimate anneals at 800°, 900°, 1050° and 1200°F.; 3. Final reductions of 37 per cent, 50 per cent, 69 per cent and 84 per cent;

Jan 1, 1942

By Bruce W. Gonser, Robert J. Nekervis

EACH metal has a unique combination of properties that distinguishes it from other metal;. Su& a combination may account for applications that cannot be met very well by anything else. This is particularly true of tin, one of the earliest metals used by man. Table i shows the consumption of tin in the United States by usage for the years 1949 and 1950, which may be considered to be generally typical of current usage. The major applications-tinplate, solders, bronze, and babbitt-were well established a century ago. Applications for the metal and (probably later) of tin alloys started more than 5000 years ago. Fortunately for the ancients, tin is one of the metals whose oxide is easily reduced by carbon. Nature further simplified the refining problem by providing only one ore of commercial importance, cassiterite (SnO2). Tin is easily reduced from cassiterite. All that is necessary is high heat in the presence of carbon. It is quite possible that back in the dawn of history, tin was discovered when black alluvial sand was thrown on a fire, either to bank it or to put it out. SOURCES OF TIN All the important tin-producing centers are in the southern hemisphere, far away from the' industrial consuming centers. Fig 1 shows their location and 1950 production. Reserves are adequate, and the industry is able to produce considerably more tin than is

Jan 1, 1953

By R. A. Swalin

IN this paper, the results of an investigation concerning the diffusion of three elements, magnesium, silicon, and molybdenum, in nickel are presented. The work represents a continuation of a diffusion program relating to solute diffusion in nickel. The program has the dual aim of obtaining useful diffusion data and of yielding insight into the factors governing solute diffusion in close-packed metals. The first paper of this series has been published earlier? In both investigations, in agreement with recent results from other laboratories, the activation energies for solute diffusion were found to be close but not identical to that of self-diffusion in the pure solvent in question. In order to obtain valid diffusion data, certain experimental pitfalls recognized only in recent years had to be avoided. Chief among these were the necessity for minimizing short-circuiting diffusion paths such as grain boundaries and the necessity for using low solute concentration gradients. In this series of investigations the following precautions were taken in an attempt to minimize such errors. 1) Samples with large grain sizes, 0.5 to 10 mm, were prepared. 2) The diffusion coefficients were measured at relatively high temperatures, since imperfections such as dislocations play a less important role at such temperatures than at lower temperatures. 3) Alloys containing less than 1 atomic pct were chosen for study. Experimental Work Materials—A diffusion couple technique was employed in the experimental investigation. Briefly, this technique consisted of the following. A diffusion couple was fabricated by placing a flat face of a cylindrically shaped alloy disk against a similar face of a pure nickel disk, and a bond was formed at an intermediate temperature under pressure. The diffusion couple thus fabricated was subjected to a diffusion anneal at higher temperatures for a measured period of time and then sectioned perpendicular to the direction of diffusion. After analyzing the sections for solute concentration the diffusion coefficient was determined from a probability, plot of concentration vs distance from the diffusion interface. Vacuum melted Mond nickel was used in the experimental program. The chemical analysis of this nickel is listed in Table I. Alloys used were prepared

Jan 1, 1958

By John Wulff, J. H. Hollomon

THE opinion has been widely held that the corrosion of alpha brass occurs by the selective solution of zinc. As late as 1939, Fink1 and Evans2 suggested that in the initial stage of the corrosion the selective solution of zinc produces copper-rich areas, which subsequently act as cathodes that facilitate the deposition of copper. Previously Abrams3 had shown that most of the copper found on corroded brass was redeposited and not residual, although he did not consider the nature of the initiation of the corrosion process. Enough data exist to indicate that any metal surface is sufficiently heterogeneous to provide the anodes and cathodes necessary for the initiation of corrosion.4,5 Thus, for alpha brass we need postulate not an initial selective solution of zinc, but only the existence of local differences in electrochemical potential. The heterogeneity responsible for potential differences may arise from oxide and other films as well as from alloy concentration gradients. Even though selective corrosion may be possible in some alloy systems, previous data on alpha brass as well as the experimental work reported in this paper do not require this supposition. Bengough and May,6 in a discussion of Abrams' paper, first suggested the addition of small amounts of arsenic (0.03 per cent) to alpha brass to prevent the redeposition of copper (dezincification). This suggestion was later substantiated by Nixon.7 In their studies of the inhibiting influence of arsenic, Evans and Fink were led to the selective-solution hypothesis in order to explain the initial corrosion of such alloys. They believed that an arsenic film covered anode areas and prevented the formation of copper-rich spots capable of acting as cathodes for the deposition of copper. They did not consider, however, the mechanism by which the arsenical film was formed. Bengough and May,8 in another publication, suggested that the commonly found gray or black arsenical film may act to: (I) carry oxygen to the brass surface, (2) increase the discharge potential of copper on brass, (3) precipitate cuprous chloride from colloidal suspension in chloride solutions. Masing9 assumed that the film found upon arsenical brass was metallic arsenic. His measurements of hydrogen overvoltage of bulk arsenic led him to believe that the inhibition of dezincification occurs because the overvoltage of a brass surface is lowered by the arsenic film. He reasoned that this film would permit the more rapid reduction of hydrogen at the cathode, which would prevent the redeposition of copper. In a recent paper,10 we have pointed out that the film formed during the corrosion of arsenical brass and copper in stagnant solutions is essentially arsenious oxide (As203),

Jan 1, 1942

By Che-Yu Li, J. L. Gregg, W. F. Brehm

Oriented, oxygen-doped niobium bicrystals were tested in liquid lithium. The grain boundaries were attacked preferentially. The depth of the penetrated zone varies as (time)2. The penetration was aniso-tropic, had a high activation energy, and increased with the increased oxygen doping level. A possible model was proposed to account for the experimental observations. 1 HE grain boundary penetration of a metallic system by liquid metal has been studied by several investigators. Their results are summarized by Bishop.' Most of these works show that the penetration by liquid metal corresponds to the phenomenon of liquid metal wetting. In the case of a grain boundary, wetting will occur when twice the solid-liquid interfacial tension is smaller than the grain boundary tension resulting in the replacement of the grain boundary by two new solid-liquid interfaces. Other possibilities exist; for example, the atoms of the liquid metal may diffuse into the grain boundary region due to chemical potential gradient. The gradient can be produced by impurity segregation or simply be due to the increase in solubility in the grain boundary region. The penetrated grain boundary in these cases may remain solid at the test temperature. The Nb-Li system has been of considerable interest because of its possible technological applications. For fundamental interest it provides a possibility of studying the grain boundary penetration process which is not controlled by the wetting mechanism. The pure niobium is not attacked by the liquid lithium, but if niobium containing more than 300 to 500 ppm oxygen by weight is exposed to liquid lithium, corrosion occurs at the solid-liquid interface and preferentially at grain boundaries. Previous investigators2-' have proposed that this preferential corrosion at grain boundaries is caused by oxygen segregation there, with subsequent inward diffusion of lithium to form a Li-Nb-0 compound. These investigators also found that the corrosion could be retarded by adding 1 pct Zr to the niobium to precipitate the oxygen as ZrO2 upon proper heat treatment. However, there are no quantitative data on the kinetics of the grain boundary penetration process to test the validity of the proposed corrosion mechanism. In this work an investigation of this penetration process in oriented bicrystals was made as a function of the oxygen doping level in the bulk niobium and the grain boundary orientation. A possible model for the penetration process based on the experimental results was proposed. EXPERIMENTS Oriented niobium bicrystals were grown by arc-zone melting oriented single-crystal seeds.7 These bicrystals contained simple tilt boundary. The [001] directions in the two grains were tilted about a common [110]. The bicrystals were 31/2 in. long and 5 by 4 in. in cross section with the straight, symmetric, planar grain boundary longitudinally bisecting the crystal rod. The bicrystals were doped with oxygen by anodically depositing a layer of Nb2O on the surface in a 70 pct HNO solution at 100 v, using a stainless-steel cathode. The specimens were homogenized by annealing in evacuated quartz tubes at 127 5°C. Oxygen content of the niobium was measured from microhardness values, after DiStefano and Litmman.' Supplementary checks were made with vacuum-fusion analysis.7 Individual test specimens cut from the doped bi-crystal rods, about by by % in. in size, were tested inside double jacket sealed capsules. The inner jacket was niobium, the outer was stainless steel. The niobium inner jacket eliminated the problem of dissimilar-metal mass transfer.' The lithium (99.8 pct pure, obtained from Lithium Corp. of America) was handled only in a purified argon atmosphere in a Blickman stainless-steel glove box. After introduction of lithium, the capsules were sealed by welding. Further detailed experimental procedures are given in Ref. 7. The capsules were heat-treated in vertical Marshall resistance furnaces. Temperatures were controlled to When heating above 1100°C, it was necessary to seal the furnace work tube and flow argon through to prevent failure of the stainless-steel outer jacket of the capsule. Tests were made on 6" 2", 16" 2, and 33" i2" bicrystals at oxygen levels up to 2600 ppm by weight in the 6' and 16" crystals and with 1300 ppm oxygen in the 33' crystals. The oxygen levels were controlled to 100 ppm. Most of the quantitative data were obtained from 16" bicrystals between 800" and 1050°C. The capsules were quenched into water after the test and cut open with a water-cooled abrasive wheel. The capsules were then submerged in water, which dissolved the lithium and freed the specimen. Measurement of the depth of the penetrated zone in the grain boundary was done either on metallographically prepared surfaces or directly on the grain boundary plane after the specimen was fractured in tension in the grain boundary plane. The depth of penetration measured by both methods agreed well. Further details describing these techniques have been reported elsewhere.'p7

Jan 1, 1969

By AIME AIME

TRADITIONALLY, the Annual New York Meetings of the A.I.M.E. cover four days, but the program is growing on each end as well as in the middle, and this year it lasted from 3 p. m., Sunday, Feb. 16, when the Education Division got under way, to 8:40 p. m., Friday the 21st, when a trainload of electrical inspectors, pro tern, got back fro111 the General Electric plant at Schenectady. The meeting has ceased to be a mere three- ring circus: on Wednesday afternoon eight sessions were being held simultaneously in the Engineering Societies Building, if one includes the Woman's Auxiliary, and according to frequent testimony one should include the W. A. as one of the most important units in Institute affairs.

Jan 1, 1936

By T. M. Chance

THe necessity of adopting improved methods of bituminous-coal cleaning at many collieries is recognized by all familiar with the requirements of the various bituminous markets, the approaching exhaustion of the relatively small areas of inherently high-grade coal, and the difficulties encountered in maintaining a uniform grade of shipped coal. Many coals lose much of their market value by degradation in size, and, in any event, if the cleaning .process is to contemplate wetting the coal the minimum amount of fines should be produced to prevent sludge losses and the difficulties resulting from the moisture content of the wet fines. Hence, it is desirable to bypass the finer coal dry, if this can be done without too great increase in impurities in the final product. This procedure has given excellent results at washeries at Steelton and in the Birmingham district. If the raw fines are too impure to permit admixture with the washed coal, it may be desirable to use dry methods, such as the pneumatic table, rather than to wet an excessive amount of such fine material. The bituminous-coal cleaning plant should therefore: (1) Treat the raw coal in as large lump as possible and without sizing; (2) eliminate degradation of pure coal in the washing process; (3) avoid wetting the fines, if possible; (4) produce washed coal practically free from mechanically included impurities; (5) crush the refuse and retreat, if much intergrown coal and refuse are present, rather than precrush the entire feed. Ordinary gravimetric methods of concentration, whether hydraulic or pneumatic, will not meet all of these requirements, as the large lump includes those sizes now sent to the picking tables, if it is desired to treat material of such size. I do not know of any prior commercial method, based on the falling velocity, coefficient of friction or resistance to fracture, that permits the production of clean coal varying in size from, say, 10-in. lump to 1/16-in. mesh. The effect on the specific gravity of any given coal as a result of variations in ash and pyritic sulfur content is well known; in fact, it has been made use of in commercially ascertaining ash content by deter-

Jan 1, 1924

By Walter E. Duncan

The ores treated at the concentrating plant of the Mahoning Mining Co. at Rosiclare, Ill., come largely from the blanket replacement deposits of the northeastern part of Hardin County, Illinois, and consist of complex mixtures of galena, sphalerite and fluorspar in a gangue of quartz, limestone and sandstone. The several minerals are so intimately inter-grown that they are not liberated at the sizes usually treated by gravity concentration in the usual fluorspar plant. For this reason, an all-flotation method of concentration was developed in cooperation with the station of the U. S. Bureau of Mines at Rolla, Mo.1 This flotation separation made possible the commercial production of four coyentrates: (I) lead, (2) zinc, (3) acid-grade fluorspar and (4) metallurgical-grade Auorspar.2-3 Although fluorspar had been floated in Canada in 19214 and a plant at Rosiclare had been floating fluorspar since March 1929, fluorspar flotation was given considerable impetus by the Mahoning developments, since some features of the separation were quickly adopted by other fluorspar companies. The Bureau of Alines5 reports that in the 10 years preceding 1938 only 50,552 tons of fluorspar flotation concentrates were produced in the United States. The rise from this almost nominal figure to 153,750 tons (largely acid grade) in one year (1944)6 is indicative of the activity in fluorspar flotation occasioned by the war. The industry thus proved to be in a position to expand and keep up reasonably well with the requirements imposed upon it by such developments as occurred in high octane aviation gasoline alkylation, in the use of Freon as a refrigerant and as carrier in the Aerosol "bug bomb," and in the atomic bomb project as well as in the expansion of other activities requiring hydrofluoric acid; for example, the aluminum industry. Despite the fact that the greater portion of acid-grade fluorspar produced in the last few years went directly into war uses, the future of the acid-grade field still appears bright. As a result of the activity in fluorine chemistry during the war, it seems likely that in the relatively near future almost every phase of human endeavor will find some fluorine compound involved. The other three concentrates produced deserve some attention in these introductory remarks. The lead concentrates first produced contained both zinc and fluorspar but these did not interfere with their marketing. As will be pointed out later, the quality has steadily improved until today it is a relatively high-grade product. Although some zinc smelters accept concentrates containing limited quantities of fluorspar, it is a very objectionable impurity. Since flotation methods fail in the complete removal of the fluorspar, chemical methods were developed for

Jan 1, 1948

By Walter E. Duncan

The ores treated at the concentrating plant of the Mahoning Mining Co. at Rosiclare, Ill., come largely from the blanket replacement deposits of the northeastern part of Hardin County, Illinois, and consist of complex mixtures of galena, sphalerite and fluorspar in a gangue of quartz, limestone and sandstone. The several minerals are so intimately inter-grown that they are not liberated at the sizes usually treated by gravity concentration in the usual fluorspar plant. For this reason, an all-flotation method of concentration was developed in cooperation with the station of the U. S. Bureau of Mines at Rolla, Mo.1 This flotation separation made possible the commercial production of four coyentrates: (I) lead, (2) zinc, (3) acid-grade fluorspar and (4) metallurgical-grade Auorspar.2-3 Although fluorspar had been floated in Canada in 19214 and a plant at Rosiclare had been floating fluorspar since March 1929, fluorspar flotation was given considerable impetus by the Mahoning developments, since some features of the separation were quickly adopted by other fluorspar companies. The Bureau of Alines5 reports that in the 10 years preceding 1938 only 50,552 tons of fluorspar flotation concentrates were produced in the United States. The rise from this almost nominal figure to 153,750 tons (largely acid grade) in one year (1944)6 is indicative of the activity in fluorspar flotation occasioned by the war. The industry thus proved to be in a position to expand and keep up reasonably well with the requirements imposed upon it by such developments as occurred in high octane aviation gasoline alkylation, in the use of Freon as a refrigerant and as carrier in the Aerosol "bug bomb," and in the atomic bomb project as well as in the expansion of other activities requiring hydrofluoric acid; for example, the aluminum industry. Despite the fact that the greater portion of acid-grade fluorspar produced in the last few years went directly into war uses, the future of the acid-grade field still appears bright. As a result of the activity in fluorine chemistry during the war, it seems likely that in the relatively near future almost every phase of human endeavor will find some fluorine compound involved. The other three concentrates produced deserve some attention in these introductory remarks. The lead concentrates first produced contained both zinc and fluorspar but these did not interfere with their marketing. As will be pointed out later, the quality has steadily improved until today it is a relatively high-grade product. Although some zinc smelters accept concentrates containing limited quantities of fluorspar, it is a very objectionable impurity. Since flotation methods fail in the complete removal of the fluorspar, chemical methods were developed for

Jan 1, 1948

By R. F. Mehl, R. W. Parcel

THE rate of the decomposition of austenite in eutectoid steels, forming only pearlite, may be expressed fundamentally in terms of the rate of nucleation and the rate of growth of pearlite nodules. This matter has received much attention in recent years. (The basic references are listed in ref. 1; references of particular import to the present work will be given separately.) Systematic data have been developed for plain carbon eutectoid steels.:! Although the physical factors affecting the rate of nucleation, N, in case of plain carbon steels have presumably been identified, they cannot as yet be evaluated quantitatively.' Several somewhat successful attempts, however, have been made to calculate the rate of growth, G. In the latter case the important factors determining the edgewise growth of pearlite have been assumed to be: 1—the interlamellar spacing; 2—the concentration extremes and concentration contours of carbon in austenite in front of the growing pearlite interface; and 3—the rate of diffusion of carbon in austenite.* The only systematic data on N and G for pearlite in alloy eutectoid steels are those for Co-steels;6 there are no data on alloy eutectoid steels in which the alloying element is known to decrease the rate of formation of pearlite, apart from a few scattering data reported earlier' for steels containing manganese. This paper reports a systematic study of N and G for eutectoid alloy steels containing molybdenum and nickel, respectively. In order to provide information of help in understanding the results, new data are presented on the effect of molybdenum on the interlamellar spacing of pearlite, So; data on the effect of nickel on So have already been published.' The alloys used were in five groups: 1—Pure Fe-C-Mo alloys (Table I) were supplied by the Climax Molybdenum Company of Michigan, Detroit. They were made from Armco ingot iron of standard analysis, Acheson graphite, and ferro-molybdenum, melted in silica-lined crucibles in a high frequency induction furnace. The ferromolyb-denum was added to the melted steel, followed in 5 min by 0.08 pct Al. The ingot as-cast measured 23/4x 31/4x10 in.; it was hot-forged at 1150°C to a bar 1 in. sq.

Jan 1, 1953

By N. Tiner

In an article on magnesium and its alloys, Gann and Winston! stated that manganese has a limited solubility in the liquid state. W. Schmidt2 showed a diagram according to Joseph Ruhrmann indicating that the solubility of manganese in liquid magnesium falls from about 2.65 per cent at 790°C. to about 0.5 per cent at 675°C. The curve was extrapolated to show zero solubility at the melting point of pure magnesium (Fig. I). This work suggested that at the lowest manganese contents it was not possible to detect either a eutectic or the formation of a solid solution, so that manganese was stated to be present in the structure as large individual crystals. Two years after the presentation of, these results, Gann3 brought evidence to show that some manganese is capable of dissolving to form a solid solution, any excess of manganese present then assuming chiefly the form of small blue-gray particles scattered throughout the primary magnesium crystals, occasionally in clusters but seldom at the boundaries. He presented micrographs of cast alloys containing 0.1, 0.4 and 1.0 per cent manganese that show a small amount of coring around the individual particles due to solid solution, and indicate that the location of the manganese particles is closely associated with the original dendritic structure of the primary crystallization. He also pointed out that the amount of manganese that can be dissolved in magnesium depends on the amount of other alloying elements present, the effect of the second alloying element being to decrease the amount of manganese retained in the alloy. E. Schmid and G. Siebe14 have determined the solid solubility of manganese and its variation with temperature by means of precision X-ray diffraction measurements. They found that the solubility is 3.4 per cent at 645°C. and decreases to practically zero at 200°C. It is apparent that the X-ray diffraction measurements of Schmid and Siebel are not in agreement with the results of Ruhrmann as presented by Schmidt. This disagreement, and also the lack of data on magnesium-aluminum-manganese and magnesium-zinc-manganese systems, led the author to the present investigation, to determine accurately the liquid solubility of manganese and its variation with temperature. Experimental Method The experimental method for making solubility determinations consists of saturating the molten magnesium or the alloys with manganese at various temperatures and analyzing the dip samples taken from these melts. Melting is carried out in a cylindrical steel pot heated by an electric resistance furnace. The pot had a metallic outside coating to protect the steel against oxidation, and a graphite inside lining to prevent the contamination of the melt by prolonged contact with iron. The inside diameter of the pot was 4 in. and the depth 12 inches.

Jan 1, 1945

By Blake M. Loring

RECENTLY the S-curves for 30 to 40 alloy steels have been published.1,2 These steels show individual characteristics, which make each additional S-curve of great interest. There are important differences in the mechanism of the transformation process, the type of transformation product, and the influence of alloying elements. Steels of the same general alloy composition may possess such variable characteristics with regard to the length of time of isothermal transformation that an S-curve for each heat of steel may be desirable. In the present work the isothermal transformation of a steel having the following composition and grain size was studied: 0.20 percent carbon; 0.21 manganese; 0.026 phosphorus; 0.017 sulphur; 0.056 silicon; 1.45 chromium; 3.25 nickel; austenite grain size, 7. The progress of the isothermal transformation was followed by several different methods, including hardness measurements, dilatometer observations, and examinations of the microstructure. It was not expected that these methods would be in precise agreement.3 Accordingly, the changes in microstructure and hardness were given additional weight in determining the initial stage of transformation and the dilatometer measurements were relied on in estimating the completion of the process. The beginning of transformation was indicated by I per cent of transformation products and the end of transformation by about 99 per cent. The reproducibility of the various methods in the ranges of highest sensitivity was checked by several observations at each time and temperature. The steel used in this investigation was annealed for 24 hr. at 925°C. Macroetching revealed no serious segregation. The specimens for the metallographic and hardness investigations were 1 1/4 by 1/2 by 1/8 in. Wires attached to the samples were used for handling, instead of tongs, to avoid chilling. The specimens were heated at 845°C. for 1/2 hr. and quenched into constant-temperature salt baths held at various temperatures from 205° to 650°C. The time required to transfer the specimens was found to be about x 1 1/2 sec., and nearly 5 sec. more was required for them to come to the temperature of the bath. After various lengths of time in the constant-temperature baths the specimens were quenched in water at 21°C. The specimens were cut in half for the metallographic examination, to provide a surface free from decarburization. To determine the beginning and end of the transformation the percentage of transformation determined metallographically and by hardness was plotted against time. A planimeter was used in the metallographic determination. The hardness and metallographic determinations made at room temperature were confirmed reasonably well by dilatometer measurements taken during the process of transformation at the various temperatures. Two dilatometers were used to

Jan 1, 1941

By Strathmore R. B. Cooke, Paul B. Queneau

The kinetics of the dissolution of scheelite in basic solutions of carbonate and fluoride were investigated. Work was also done with solutions of alkali metal chloride, hydroxide, phosphate, and mixtures of phosphate and fluoride. The study was conducted at 90 psig and at temperatures ranging from 100" to 155"C, and both natural and synthetic scheelite single crystals were used. The interaction of scheelite with carbonate solutions generally followed a parabolic rate law, and resulted in the formation of calcite crystals on the attached surface. The transport of the CO3 through the calcite to the scheelite surface was probably rate -controlling between 115" and 135°C. Positive deviations from Parabolic behavior were observed at 100" and 155?C, presumably due to the calcite grain growth, and to the formation of a noncoherent calcite layer, respectively. The leaching of scheelite with alkaline fluoride solution produced a calcium fluoride reaction-product which covered the surface as a sheet-like layer. Below 110°C the dissolution rate was parabolic; at 115" and 135°C it was linear. In the linear region, the periphery of the calcium fluoride layer lifted from the sample. Only the lower layers, braced by the scheelite substratum, remained unbroken. This bound layer, approximately constant in thickness, limited the rate at which the fluoride could attack the scheelite. The phosphate and phosphate-fluoride leaches dissolved scheelite at a linear rate; solid reaction products were respectively hydroxyapatite and fluorapatite. Sodium hydroxide and chloride were not effective leachants, and did not produce observable solid reaction products. THE feasibility of pressure leaching of scheelite pulps with basic solutions containing either carbonate or fluoride ions, as indicated by the following equations, has been established by previous investigators:1-3 200°C CaWO4s + CO37q - CaCO3s+WO4aq [1] 200°C CaWO4s + 2Faq ^ CaF2s+WO4aq [2] It is to be noted that a commercial process employing reaction [I] is in use at Union Carbide's operation near Bishop, Calif. In the earlier work referred to, it was apparent that the precipitation of the solid reaction-product on the scheelite particles sharply reduced contact of the leachant with the scheelite. We have extended this work by studying the kinetics of dissolution employing single crystals of scheelite of known exposed surface area. In addition, the effectiveness of solutions of phosphate, of phosphate with fluoride, and of chloride and hydroxide as leachants for scheelite have been investigated. EXPERIMENTAL Apparatus. The low-pressure autoclave used in this wo (100 psig maximum) is essentially that of J. Halpern4 as modified by F. A. Forward.5 Constructed entirely of 316 stainless steel, its maximum capacity is 4000 ml. The temperature in the autoclave was regulated to *0.5?C by a Wheelco thermocouple controller. A 4-in. diam, three-bladed impeller, circulated solution upward against the sample, and a strobo-scope permitted holding the stirring rate to *15 rpm. A check valve and a "pop" type safety valve were installed, a sample holder was fixed to an externally adjustable rod, and a water-cooled condenser was placed in series with the sampling valve. The stainless steel sample holder, Fig. 1, held the epoxy-mounted sample (f) five mm above the impeller. Tightening the tapered sleeve (d) positioned the epoxy-resin specimen-mount by forcing it back against the spacer (c). The mount (e) was 1 in. diam. Sample Description and Preparation. Both synthetic and natural scheelite crystals were leached. The former were single crystals of 99.95 pct purity which were leached approximately perpendicular to the "c" axis; they were supplied by the Gallard-Schlesinger Chemical Manufacturing Corp. The natural crystals, supplied by Minerals Unlimited, were transparent, analyzed 99.8 pct CaWO4, and in ultraviolet illumination exhibited the characteristic blue glow of substantially molybdenum-free scheelite. To permit exposure of an essentially constant surface area of scheelite to the leachant, the samples were mounted in Scotchcast Brand Resin No. 250 (Minnesota Mining and Manufacturing Co.). The mount-

Jan 1, 1970

By G. L. Craig

In order to meet the unprecedented demand for copper it has proven necessary not only to develop every primary source, but also thoroughly to exploit the vast reservoir of metal in use that is not directly serving the war effort. To accomplish this, industry has been called upon to use its resourcefulness for developing methods of recovery that have not been previously utilized. It is in this connection that we have been asked to review the methods suggested for recovering the basic constituents of various types of the so-called clad or composite steels. As a background for a discussion of recovery processes, it seems appropriate to consider clad materials in general and their processes of manufacture. A composite steel has been defined as one consisting of two or more component parts of which the smallest shall comprise at least 3 per cent of the total mass. Clad materials or composites are produced commercially by several different methods of which the most important may be classified as: I. The Blacksmith or Forge Weld Method. This method is limited to carbon steels or low-alloy steels as the presence of even small amounts of common alloying metals prevent the formation of a satisfactory weld. The principle is the application of pressure to sections in contact at elevated temperatures. Because of the tendency of the iron to oxidize, borax is generally used as a flux to absorb the iron oxide. 2. Casting Process-In this method a composite ingot, billet or cake is produced by pouring one metal onto or about another. The bond may be accomplished by the action of the molten metal against a solid, in which case the bond may be referred to as mechanical; while in other instances alloying occurs at the interface producing an anchor by the formation of component parts of the two materials. 3. Cementation Process.-In this process any number of combinations of metallic and nonmetallic constituents which are mixed together may be used as a bonding agent. The combinations, whatever they may be, are placed between the materials to be joined and subjected to pressures at elevated temperatures to produce the desired bond. 4. Fusion Welding Processes.-Gas and electric joining for direct use or subsequent fabrication. 5. The, Assembly Process.-This method involves the joining together of prefabricated bars or plates followed by hot and/or cold working the assembly to the desired finished form. This method is advantageous in many cases because of its flexibility on small quantities as compared to the casting method. It is also possible to control the relative proportion of components more accurately. In this discussion we are concerned only with the scrap resulting from the manufacture of clad materials and our interest,

Jan 1, 1943