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By Edward P. Barrett

DURING the past few years numerous references have been made in the technical press and Bureau of Mines Bulletin 270 to sponge iron' and so-called "direct metal" processes. The idea has been prevalent that sponge iron and "direct metals" are cheap commodities. In many instances it has been proposed that these processes be used to treat low-grade ores, utilizing low-grade coals as reducing agents. It is questionable whether or not high-grade sponge iron can be made from low-grade materials. Particles contain¬ing iron oxide and gangue become, upon almost complete deoxidation, particles containing metallic' iron and gangue. The possibility of mechanically separating the metallic iron from the gangue in these particles depends . on the physical characteristics of the particular ore under treatment. Some ores, in which the minerals constituting the gangue break free from the iron oxide upon crushing, may be concentrated magnetically after the iron oxides have been reduced to metal. The finely disseminated ores are least amenable to concentration. In general, high-grade sponge iron can only be made from high-grade raw materials. Sponge iron containing small amounts of sulfur can only be made from raw materials containing small amounts of sulfur or by

Jan 1, 1930

By Robert M. Grogan, Gill Montgomery

Fluorspar, the commercial name for fluorite, is a mineral composed of calcium fluoride, CaF,. Its valuable properties are due to its content of fluorine, and it is the principal commercial source of that element. The name is derived from the Latin word "fluere," to flow, because the mineral has a low melting point and is used in metallurgy as a flux. Cryolite is a sodium aluminum fluoride, Na,AlF,. It is a rare mineral which has been found in commercial quantities in only one place in the world, Greenland. Small amounts of it are shipped from stock in that country, and its place in industry has been taken over almost completely by synthetic cryolite. Because of the relative unimportance of cryolite, discussion of it has been relegated to a short section at the end of this chapter, which is principally concerned with fluorspar. History Fluorspar was used for ornamental purposes by the Greeks and Romans, who fashioned such things as vases, drinking cups, and table tops from it. Various peoples including the Chinese and the American Indians carved ornaments and figurines from large crystals. Its usefulness as a flux was known to Agricola (1564), who wrote about it in 1546. Mining began in England about 1775 and at various places in the United States during the period 1820 to 1840. Production became substantial following the development and widespread adoption of the basic open hearth method of making steel, in which fluorspar is used as a flux. After that, production and usage were stimulated by growth in the steel, aluminum, chemical, and ceramic industries and were accelerated by World Wars I and II. Fluorocarbons entered the picture in 193 1 and the use of anhydrous hydrogen fluoride (HF) as a catalyst in the manufacture of alkylate for high octane fuel blends began in 1942. The development of the froth flotation process in the late 1920s, a differential flotation scheme for separating fluorspar from galena, sphalerite, and common gangue minerals in the 1930s, and the application of heavy-media concentrating methods to the treatment of low grade ores in the 1940s were outstanding technological contributions that enabled increased production of fluorspar concentrates. In recent years the development of pelletizing and briquetting processes for making flotation concentrates into gravel-size particles for use in steel furnaces and the development of more efficient and selective flotation schemes for treating crude ores containing abundant dolomite and barite have been major improvements in the industry.

Jan 1, 1975

By G. O. Hiers

THE object of the experiments reported in this paper is to determine the eutectic composition of copper and tin and to determine the location of the part of the liquidus line immediately above the eutectic composition in copper. Three methods were used in the investigation: (1) the method of dissolving copper in a bath of molten tin at constant temperature, with the idea that when the bath was saturated with copper its copper content, by analysis, together with the temperature at which the saturation took place would locate a point on the liquidus line (2) the method of the differential cooling curves, and (3) the method of microscopic examination. This paper is principally concerned with the results of the last two methods mentioned. The results of the first method, that of dissolving copper in molten tin, did not agree with the .results of Miller,1 by the same method, nor with the results of other investigators by other methods, nor yet with the results of the cooling-¬curve experiments and microscopic examination reported here.

Jan 1, 1929

By J. L. Ratliff, R. I. Jaffee, H. R. Ogden, D. J. Maykuth

An experimental program was carried out to improve the low-temperature ductjlity of tungsten through the combined use of dispersed oxides for grain-size control and Groups VII and VIII metal additions for matrix softening. Separate binary -alloy studies showed that increasing amounts of finely dispersed thoria or zirconia and critical amounts of rhenium, osmium, and iridium were effective in significantly reducing the ductile-to -brittle bend transition temperature of tungsten as well as in increasing its re crystallization temper - LIKE most of the high-melting point bcc metals, tungsten undergoes a marked transition from ductile to brittle behavior with decreasing temperatures. The material factors which influence the transition temperature include grain size, metal purity, and the presence of dispersed phases. ature and decreasing its recrystallized grain size. The beneficial effects shown by each of these additions on transition temperature and grain size in binary combinations appeared to be additive in tevnary combinations. Thus, combined additions of 2 to 8 vol pct thoria with 5 pct Re, 0.87 pct Os, or 0.30 pct Ir were effective in lowering the transition temperature of tungsten pom 2000 to 75"C, increasing its re crystallization temperature from 1600 to 1800°C, and decreasing its recrystallized gain size from 1175 to 6800 grains per sq mm. The mechanism by which these factors are operable in tungsten is not yet clearly understood. Nevertheless, it has become increasingly apparent that the interrelationship of grain size and matrix composition governs to a large extent the degree of low-temperature ductility which can be achieved. Though it is not possible to accurately assess the relative importance of these variables, the available evidence suggests that, at low temperatures, grain-size effects predominate over purity effects. This was indicated in recent studies by Allen, Maykuth, and Jaffee,' involving single crystals containing 20 to 40 ppm 0 and 1 to 30 ppm C. Thus, while each

Jan 1, 1964

By H. Reiss

The zone-melting process in which redistribution of solute in a solid bar is effected by the passage of a molten zone is considered mathematically. Simple approximate techniques are developed for computing the manner in which redistribution occurs as molten zones continue to pass. The introduction of the "zone-melting flux" provides valuable insight into the nature of the phenomenon, as well as a central mathematical theme in terms of which the process can be discussed. Curves are presented for typical and general cases. AN extremely efficient purification technique was described recently by Pfann.1 Known as zone refining, it consisted of the slow passage of a series of molten zones, produced by external heaters, through a long solid ingot of the substance to be purified. Equations were given for the maximum separation attainable, and a numerical computation method was described for obtaining the concentration in the ingot after a given number of zone passes. The present paper offers an interpretation of the physical nature of zone melting in terms of a transport process in which formal diffusive and convec-tive flows occur. This interpretation, in addition to providing insight into the physical nature of the process, also provides a basis for its mathematical treatment. From this basis, useful equations are developed for the solute concentration in the ingot as a function of the number of zone passes. These are applicable particularly where large numbers of passes are necessary and where numerical computational methods might be laborious. All considerations will deal with the limiting form of the process, described by Pfann,' in which: 1—Diffusion in the solid is considered negligible. 2—Mixing in the liquid is supposed, complete. 3—The distribution coefficient, k, measuring the ratio (at equilibrium) of solute concentration in the solid to that in the liquid is supposed, independent of composition. In general, this paper will be concerned with a bar of uniform (actually unit) cross section, ex- tending in the x-direction from x = 0 to x = L, where L may be infinite. Zone melting is a transport process, and as such must admit of interpretation in terms of a flux of transported quantity. However, the progress of operation is not measured in units of time but in terms of the number of completed zone passes. Consequently, the zone-melting flux will be a rate, per unit pass, rather than per unit time. The description of this flux and the examination of its properties is given below. Zone-Melting Flux Fig. 1 represents an intermediate stage of the nth pass. Concentration C is plotted against distance, x. The molten zone with its back at the point x and front at x + I moves in the direction indicated by the arrow. As it moves, it leaves behind the nth

Jan 1, 1955

By John Hall

THE Fremont test for measuring the energy consumed in breaking a notched bar of steel is not so well known in this country as it deserves to be. The test specimen used in this test is about 3/8 by 1/4 by about 1 1/4 in., notched with a hack saw on the lower side to cause the piece to break at a fixed point. A weight of 10 kg. falling 4 m., and provided with a knife or chisel which strikes the specimen, breaks the test piece by impact. The residual force in the falling weight after it has broken the specimen is recorded by a suitable device, and the difference between the total energy and the residual energy of the weight (in kilogrammeters) is the force consumed in breaking the specimen. An experience of several years with the Fremont testing machine has shown its great value in readily detecting brittleness not revealed by tensile testing or slow bending testing. I this paper it is proposed to discuss (1) the supersensitiveness of the test as applied to cast steel and (2) its value in revealing the effect of heat treatment under certain conditions. .

Jan 7, 1913

By AIME AIME

COAL occupied a large place in the technical sessions of the Institute at its annual meeting for in addition to three sessions specifically de- voted to coal the two sessions on mine ventilation and the two on ground movement and subsidence, which are reported under their own headings, were primarily concerned with coal. The first session on coal was a joint one with the Iron and Steel Division, on Wednesday afternoon, with F. H. Crockard and J. R. Campbell presiding as joint chairmen and the latter actually officiating. The principal topic of discussion was G. S. Scott's paper "Evaluation of Coal for the Making of Blast- Furnace Coke," which has been published as T. P. 159. The author made a brief statement of its con- tents to start the discussion and the chairman, after briefly reviewing it himself, called on C. A. Meissner to start the discussion. He briefly reviewed the economic factors in the use of coal for coke-making, saying that not only .does the removal of 1 per cent of ash from the coal reduce the cost of pig iron 12 or 13c. per ton, but it also permits coke of satisfactory structures to be made from a coal which otherwise could not be used. He stressed the importance of uniformity in blast-furnace fuel and discussed the benefit of mixing different coals as raw material for the coke oven and cited experience with Illinois coals.

Jan 1, 1929

By A. C. Watts

FOR several years, a mine in Colorado experienced considerable trouble from small fires caused by the blasting of coal. Although a well-known make of permissible powder was used, it was first thought that the powder ignited gas that might be present and that this, in turn, set fire to line brattices or to the coal. Experiments were, therefore, conducted with another make of powder, but the results convinced the superintendent of the mine, Robt. Williams, Jr., that the fires were not caused by the powder but by the high-voltage electric current used for detonating the shots. The mine "makes" gas very freely, giving off from three-fourths to a million cubic feet of methane per 24 hours. The coal is a good grade bituminous of a very free burning quality. Electric shot-firing from the outside after all men and animals were outside had been practiced for a number of years. The shooting circuit was connected with the main power circuit at the mouth of each entry. Shooting circuit switches were mounted in boxes, which were kept locked with the handle of the switch, in open position, showing through the bottom of the box. The door of the box could not be shut and locked when the shooting switch was closed. At the entrance to each room, or working place, a small switch, called the miner's switch, was placed on the shooting line. It was the duty of the miner, when entering his place at the beginning of the shift, to see that this switch was open and that it was kept open until he left the place at the end of the shift to go out of the mine. Grounded return was used for main power lines. The current was 500 volts, direct current, with 100 to 300 amp. The nearest working face was 9600 ft. from the shot-firers' switch outside the mine and the most remote working face was 2 ½ miles. The various working faces were scattered over a wide area between these two points.

Jan 9, 1925

By V. H. Gottschalk

THE solubility of gases in metals has been of interest since Graham's time in 1866, but, although the subject was actively studied by iron and steel metallurgists during the eighties, the era of painstaking laboratory investigation begins in 1907 with the publication of Sieverts'1 thesis on the occlusion and diffusion of gases in metals. Since then, Sieverts has worked almost continuously in this field, and his views on the subject are the prevailing ones at the present time.2 Probably the most important result obtained by Sieverts, and frequently verified since by other observers, is the discovery that at a constant temperature the solubility of almost all gases in both the liquid and solid state of most of the metals is proportional to the square root of the pressure (for pressure above 100 mm.). The obvious explanation of this fact is that the gas dissolves as atoms and not as molecules, although it has been pointed out a number of times, first by Donnan and Shawl in connection with their work on the solubility of oxygen in silver at 1075° C., that the formation and solution of a compound of the metal and gas would also be indicated by a variation of the solubility with the square or higher root of the pressure. Sieverts4 himself raised the question whether the usual explanation (i. e., that the gas dissolves as atoms) may not be wrong, when he found that the square root law held also for the solubility of sulfur dioxide in molten copper; in which case dissociation into simpler molecules or atoms does not take place. Stubbs5 subsequently showed that Sieverts and Krumbhaar's "constant" for sulfur

Jan 1, 1932

By Henry E. Colton

NeaR the town of Christiansburg, Va., occurs a singular feature in topographical as well as geological structure, which may be said to have an important bearing on a large area to the southwest. The great water-shed ridge, which divides the waters flowing into the St. Lawrence from those flowing into the Atlantic ocean, coming southwestward, forms all of what was the boundary of Maine as agreed upon by the treaty of 1783, and a part of the present boundary, all of the northern New Hampshire boundary, and entering Vermont, continues south of Lake George. Passing irregularly through New York, it enters Pennsylvania, and there bifurcating, sends one prong to the west as a divide between the waters of the lakes and the Ohio, while the other becomes the steady, regular ridge which gave it the name of Alleghany, and thus passes on southwestward through Virginia. At no point has it ever been the geological divide. Its course, commencing in the Archean rocks, has passed through nearly every series of formation, and comes into Virginia in the Carboniferous strata. The geological divide—the line between the fossiliferous and the non-fossiliferous rocks—lies, in Canada, to the west of it, but from New York south into Virginia is far to the east. Reference to Dr. Hitchcock'k map will show this. But at the locality noted these positions are changed; the water-divide becomes the eastern chain, and the geological divide is the western, returning, it may be said, to the positions occupied in the region where they originated. These relations are shown on the large map accompanying the present paper. For several miles, the track of the Norfolk and Western Railroad

Jan 1, 1888

By O.W. Ellis

Recently there has been a considerable revival of interest in the effects of the various elements commonly added to brass for the purpose of increasing its strength. For many years the work of Guillet2 alone gave reliable information in this regard. Even today his determinations of the coefficients of equivalence of the various elements relative to zinc in brass are those universally employed in industry. This is so because these coefficients have stood the test of time—their substantial correctness has been proved in almost universal practice. It is not our intention to discuss here these coefficients or their use. Rather do we wish to emphasize the need for further systernatic studies of the mechanical properties of the ternary systems of copper, zinc, and other individual elements. Since Guillet published the results of his first investigations Millington, 16 Smalley33 and Thiband 45 have added somewhat to our information. In general they have confirmed the findings of Guillet, which may be stated in the following rather general terms: 1. The addition of aluminum to the 70:30 and 60:40 brasses progressively increases their hardness and strength and reduces their ductility and resistance to shock. 2. The addition of small amounts of iron to a 60:40 brass improves its strength without affecting its ductility. 3. The addition of small amounts of manganese to a 60:40 brass causes a progressive increase in its strength and reduction in its ductility. A considerable amount of information has been amassed in regard to the effect of nickel on brass (9, 22, 41) which it is unnecessary to refer to here, in view of the scope of this paper. The situation in regard to these alloys in 1926 was very clearly stated by an anonymous writer,47 in The Metallurgist of February of that year, whose remarks were so to the point that they are well worth quoting: It will he seen that there are still large fields remaining to be studied in each of these systems (those of the aluminum, iron, nickel and manganese brasses) before our knowledge is adequate. When we come to the more complicated systems the position is even less satisfactory, and on account of the very incomplete nature of the work which has been

Jan 1, 1929

By O. W. Ellis

Recently there has been a considerable revival of interest in the effects of the various elements commonly added to brass for the purpose of increasing its strength. For many years the work of Guillet2 alone gave reliable information in this regard. Even today his determinations of the coefficients of equivalence of the various elements relative to zinc in brass are those universally employed in industry. This is so because these coefficients have stood the test of time—their substantial correctness has been proved in almost universal practice. It is not our intention to discuss here these coefficients or their use. Rather do we wish to emphasize the need for further systernatic studies of the mechanical properties of the ternary systems of copper, zinc, and other individual elements. Since Guillet published the results of his first investigations Millington, 16 Smalley33 and Thiband 45 have added somewhat to our information. In general they have confirmed the findings of Guillet, which may be stated in the following rather general terms: 1. The addition of aluminum to the 70:30 and 60:40 brasses progressively increases their hardness and strength and reduces their ductility and resistance to shock. 2. The addition of small amounts of iron to a 60:40 brass improves its strength without affecting its ductility. 3. The addition of small amounts of manganese to a 60:40 brass causes a progressive increase in its strength and reduction in its ductility. A considerable amount of information has been amassed in regard to the effect of nickel on brass (9, 22, 41) which it is unnecessary to refer to here, in view of the scope of this paper. The situation in regard to these alloys in 1926 was very clearly stated by an anonymous writer,47 in The Metallurgist of February of that year, whose remarks were so to the point that they are well worth quoting: It will he seen that there are still large fields remaining to be studied in each of these systems (those of the aluminum, iron, nickel and manganese brasses) before our knowledge is adequate. When we come to the more complicated systems the position is even less satisfactory, and on account of the very incomplete nature of the work which has been

Jan 1, 1929

By Otto H. Henry, J. J. Cordiano

THOUGH powder metallurgy is one of the oldest of metallurgical processes, it is in its infancy as a branch of the modern field of metallurgy. As early as 3000 B.C., the ancients produced implements and weapons of iron by reducing iron ore in a charcoal fire and forging the resultant sponge while still hot into the desired shape. Melting and casting soon superseded the powder metallurgy practice, and it was not until the turn of the twentieth century that powder metallurgy was applied to the commercial manufacture of tungsten lamp filaments. From this beginning, the use of the powder metallurgy process spread to the manufacture of porous oil-impregnated bearings, cemented carbide tools, contact points, diamond grinding wheels, clutch facings, starter brushes, resin-bonded radio cores, magnets, metallic filters, and other parts. More recently, and particularly during the present war, there has been a definite trend toward the manufacture of machine parts by this process in competition with the more conventional fabricating methods. Notwithstanding these many developments, scientific progress has been slow. While many articles on powder metallurgy have appeared in the press and various publications, there have been too few contributions to our technical societies, with the result that there is a dearth of the type of information necessary for the full development of this science. It is of primary importance that the results of research and development be freely disseminated if powder metallurgy is to realize its fullest potentialities. PURPOSE OF INVESTIGATION Excluding the refractory metal field, all commercial powder metallurgical products made by a cold compressing and sintering operation contain voids. These voids can be substantially eliminated by subsequent severe working and heat-treatment, but such practice has not proved economical in most applications. By applying heat during the compressing operation, plastic deformation of the powder particles is substantially increased, and the resultant compact or briquette is practically free of voids. However, hot-pressing has many attendant problems, which at present preclude its use in the manufacture of precision parts. The more important of these are to devise: I. A die steel capable of withstanding high pressures at elevated temperatures. 2. A high-temperature lubricant capable of preventing excessive die wear and welding of the compact to the die walls. 3. A method of retaining a neutral or reducing atmosphere in the compacting zone of the die assembly. 4. A means of ejecting the hot-pressed specimen into a neutral atmosphere until reasonably cold.

Jan 1, 1945

By M. C. Dow

INTRODUCTION BELT conveyors generally are conceded to be the most economical method yet devised for the transportation of large quantities of bulk materials within plants. Belts are coming into greater use for transportation over long distances and are replacing other forms of long-haul conveyance. It is not the intent of the writer to comment on the design of belt conveyors, but to offer some suggestions for improvement in the operation of conveying belts, based on many years experience with belts in several stonecrushing plants. It is the contention of this writer that opportunities for improvement not fully realized by most operators exist in many plants and that a study of the individual conveyors can result in lower unit belt costs. GENERAL RELIABILITY It is the fool-proof nature and general reliability of the belt conveyor that is responsible for its neglect. Even when abused, a belt will carry large tonnages and last a long time, often outlasting the personnel responsible for its care. Some operators look upon the purchase of a new belt as an expensive outlay every so many years, rather than a constant and steady cost amounting in belt wear alone to several dollars every operating day. This belt wear for all conveyors in one stone-crushing plant known by the writer costs 1 1/2 cents per ton or $12 to $15 per hour, based on the present cost of belt replacements. The fact that these replacement costs are double those of prewar quality emphasizes the necessity of improving the conditions that make belts wear out. Some of those conditions are the responsibility of the conveyor designer, and if a serious original error has been made, this handicap cannot be overcome by the operator. If the belt is too narrow, too steep, or too fast for good loading, the operator finds that he has an inherently expensive belt. The other factors that decrease the life of a belt are more or less under his control. The two factors of most importance are the loading conditions and the alignment. Most of the cover wear and carcass cutting occurs at the loading point and if the alignment is not good under all conditions, edge wear or damage may result, Fig I. LOADING THE BELT It is difficult to load a belt in an ideal manner; that is, to flow the material on the moving belt at a steady rate, without impact, without turbulence, and with a velocity equal to and in the same direction as the belt. An inclined belt is especially difficult to load and particularly when its speed is over 300 or 350 fpm. Inclined conveyors require longer skirt plates to prevent spillage until the load settles. It does not seem reasonable to expect an inclined conveyor to carry the same load as a horizontal belt of the same width and speed, because of the difficulty in loading

Jan 1, 1947

By Howard Eavenson

PRIOR to 1907 nearly all coke was made in beehive ovens, and most of the gas produced was made in the old-style gas retorts, and while there were a few coke plants in southern West Virginia, southwest Virginia and Kentucky operating on high-volatile coals the proportion of the total product made by them was small and was usually used locally. The greater part of the coke made, and the coal gas produced, came from the Pittsburgh seam of western Pennsylvania and northern West Virginia-which was then regarded as the standard coking and gas coal of the coun, try, and the best coal available anywhere for these purposes. With the advent of the by-product oven and the building of coke plants at the furnaces, the restriction of the use of one grade of coal for making coke was removed and the use of mixtures of low-volatile and high-volatile coals began. The change in the locations of the coke plants removed the necessity of using Connellsville coal and also made sources of gas available to the public utilities other than of their own manufacture. Most of the first oven plants were built at points distant from the Connellsville region and this afforded an opportunity for the use of coals from the southern Appalachian fields, which were at approximately equal distances from the ovens. Since that time development has been made on a number of seams of coal of great purity in southern West Virginia, southwestern Virginia and eastern Kentucky, which have been largely used for cokemaking, gas and other metallurgical purposes where low amounts of ash, sulfur and phosphorus are determining factors. These coals are much lower in the objectionable elements than the best of the coal from the Pittsburgh seam, or than any northern coal, and in by-product ovens produce coke that is not excelled for any purpose by any coal mined in this country, and is equaled very seldom. Coal from several of these seams is shipped in great quantities without beneficiation and is lower in ash and sulfur than the best washed product from any seam mined in the north.

Jan 1, 1932

By Milton E. Wadsworth, R. Ted Wimber

Cobalt sulfate solutions containing ammonium acetate and chloroplatinic acid were reduced by hydrogen in a pyrex-glass lined autoclave in the temperature range of 170o to 232°C and hydrogen partial pressure range of 115 to 830 psia. The reduction rate was directly proportional to the hydrogen partial pressure and surface area of the pyrex glass and was independent of the quantity of chloroplatinic acid added initially. Experiments involving the variation of the relative concentration of ammonium acetate indicated that the reducible cobalt complex was probably the diacetate complex of cobalt, Co(AC)4H20, or a new mononcetate complex Co Ac, which was in solubility equilibrium with a pink precipitate of CO(AC)-4HzO. THE reaction in which a metal is dissolved by an acid to produce gaseous hydrogen and a salt solution was discovered early in the history of chemistry. In 1859 Beketoff found experimentally that this reaction could be reversed; i.e., a salt solution could be reduced by gaseous hydrogen to produce a metal and an acid. A review of work done on this phenomenon since that time may be found elsewhere., The hydrogen reduction of a cobalt salt solution is facilitated by complexing the cobalt ion. An ammonia complex of cobalt has been reduced commercially in the recovery of cobalt metal. A new reducible complex of cobalt was discovered5 when it was found that a co-baltous sulfate solution containing ammonium acetate could be reduced by hydrogen at temperatures in the region of 200°C. When a cobalt sulfate-ammonium acetate solution was heated to a temperature below its normal boiling point, a violet color became apparent, indicating complex formation. The nature of this complex was investigated5 by the addition of NH4Ac to a CoSO4 solution maintained at 85o. During the first additions of NH, Ac, the pH of the solution remained fairly constant at about 5.85. However, as the ratio of NH,Ac to CoSO, approached two, the pH rose and then leveled off at about 6.05. The absorption spectra of a Co(Ac), solution and a CoSO,, NH Ac solution were obtained at 85°C and were compared and found to be the same. These findings suggested that the diacetate complex of cobalt, Co(Ac),.4H20, was formed at 85°C. When a cobalt sulfate-ammonium acetate solution was heated to a temperature above about 165o, a finely divided pink precipitate appeared. The X-ray diffraction pattern of this precipitate indicated that it was Co(Ac), - 4H,O. In addition, it was discovered that when chloroplatinic acid, H,PtCl;, was added initially to the cobalt sulfate-ammonium acetate solution, a faster reduction was obtained. The roles of the solution complex, pink precipitate and chloroplatinic acid in the reduction process were then investigated. APPARATUS The experimental work was carried out in a two-liter stainless-steel autoclave. Adetailed description of the autoclave and the auxiliary equipment used in maintaining constant temperature and pressure may be found elsewhere.= Because the stainless steel was corroded, and also because it acted as a hydrogena-tion catalyst, an all-glass liner was fabricated such that the solution came only into contact with flame-polished pyrex glass. EXPERIMENTAL PROCEDURE The solutions used in the experimental work were prepared by dissolving reagent grade chemicals in distilled water. Although variation of the brand of ammonium acetate appeared to have no effect on the experimental results, CoSO, 7H O from the J. T. Baker Chemical Co. of Phillipsburg, N. J.,was found to give faster reductions than that prepared by Allied Chemical and Dye Corp., N. Y. The former was used throughout the course of the experimental work and was weighed up at the outset of each experiment. The ammonium acetate was dissolved to form a 6M stock solution, which was stored under refrigeration. A 10 pct solution of chloroplatinic acid (J. T. Baker Chemical Co.) was diluted to a 1.15 x 1Q2 M stock solution, which was standardized by precipitation of K,PtCl, as outlined by Scott. The appropriate volume of the chloroplatinic acid, H,PtCl,, solution was pipetted into the clean, dry glass liner. The cobalt sulfate-ammonium acetate solution, which had previously been saturated with

Jan 1, 1962

By C. M. Loeb, T. E. Norman

The use of ball, rod and tube mills for grinding ore, cement and other materials has grown so rapidly during the past forty years that the world's annual consumption of ferrous grinding media for these mills is now estimated to be between one half million and one million tons per year. Ferrous grinding balls constitute the major portion of this tonnage. Obviously they represent suficient value to justify thorough studies of the factors governing their performance. The selection of grinding balls is governed principally by: I. Quality (wear resistance, impact resistance, soundness, and the like). 2. Sources of supply and delivered cost. 3. Grinding characteristics or efficiency in the ball mill. This paper deals principally with the quality of ferrous grinding balls. In the study of these factors certain data relative to the fundamental nature of ball wear in ball mills have been obtained. These data are also presented and discussed briefly. The Development of a Suitable Wear Test A study of the fundamental factors governing the quality of grinding balls has been hampered seriously by the fact that a competent test has, in the past, involvetd the purchase of several hundred tons of halls of a specific type which were then run in one or more ball mills for a period ranging from several months' to several years' duration. Often, during the period of test, it became necessary to change operating conditions or the character of the ore fed to the test mill with the result that the rate of ball consumption changed and the test figures became of little value. Under such circumstances, progress in the development of better grinding balls, has been necessarily slow. Economic factors and variations in the quality of balls produced by different sources of supply generally make it necessary for each mill operator to determine for himself the most suitable type of balls for his mills. In our own ball mill grinding operations at Climax, Colo., we were faced with this problem. After we had run a few large scale wear tests at considerable expense we decided to investigate the possibilities of a small scale wear test which would be capable of testing numerous types of balls within a relatively short time. The most important requirement of any test is, of course, that it give results which can be used to predict accurately the wear in full scale operations. It was known that Ellis and his associates1'2 had developed a method of testing grinding balls by small scale tests run at the Ontario Research Foundation. Ellis' method of testing was used as a starting point in our investigations. In the course of our tests a number of modifications of the original method were found to be desirable so that, by an evolutionary procedure, a method of small scale

Jan 1, 1949

By C. M. Loeb, T. E. Norman

The use of ball, rod and tube mills for grinding ore, cement and other materials has grown so rapidly during the past forty years that the world's annual consumption of ferrous grinding media for these mills is now estimated to be between one half million and one million tons per year. Ferrous grinding balls constitute the major portion of this tonnage. Obviously they represent suficient value to justify thorough studies of the factors governing their performance. The selection of grinding balls is governed principally by: I. Quality (wear resistance, impact resistance, soundness, and the like). 2. Sources of supply and delivered cost. 3. Grinding characteristics or efficiency in the ball mill. This paper deals principally with the quality of ferrous grinding balls. In the study of these factors certain data relative to the fundamental nature of ball wear in ball mills have been obtained. These data are also presented and discussed briefly. The Development of a Suitable Wear Test A study of the fundamental factors governing the quality of grinding balls has been hampered seriously by the fact that a competent test has, in the past, involvetd the purchase of several hundred tons of halls of a specific type which were then run in one or more ball mills for a period ranging from several months' to several years' duration. Often, during the period of test, it became necessary to change operating conditions or the character of the ore fed to the test mill with the result that the rate of ball consumption changed and the test figures became of little value. Under such circumstances, progress in the development of better grinding balls, has been necessarily slow. Economic factors and variations in the quality of balls produced by different sources of supply generally make it necessary for each mill operator to determine for himself the most suitable type of balls for his mills. In our own ball mill grinding operations at Climax, Colo., we were faced with this problem. After we had run a few large scale wear tests at considerable expense we decided to investigate the possibilities of a small scale wear test which would be capable of testing numerous types of balls within a relatively short time. The most important requirement of any test is, of course, that it give results which can be used to predict accurately the wear in full scale operations. It was known that Ellis and his associates1'2 had developed a method of testing grinding balls by small scale tests run at the Ontario Research Foundation. Ellis' method of testing was used as a starting point in our investigations. In the course of our tests a number of modifications of the original method were found to be desirable so that, by an evolutionary procedure, a method of small scale

Jan 1, 1949

By J. T. Eash, N. B. Pilling

As a group, the alloys of iron, nickel and carbon are, in application, one of the most versatile of the ferrous alloy family, and while many investigations have been made of their properties and structure only a few attempts have been made to show the microstructural relation over a wide range of composition. It is necessary at once to be clear about the kind of structural relation with which we are concerned. The equilibrium diagram provides quantitative data regarding structural make-up and its variation with temperature, but equilibrium structures often are far different from the technologically significant ones. This is particularly true of steels and cast irons, and some of the most important components of their structure may have no place in the diagram of equilibrium. The fugitive phases that result from transformation are dealt with in a highly detailed and descriptive manner in the S-curves originated by Bain. The present effort lies in a still different field, which is to portray the relation between sweeping changes in composition and in resultant structure, under controlled but nonequilibrium conditions of thermal treatment. The Guillet1 diagram presented in 1903 was the initial attempt at such a correlation and frequent references to this diagram can be found in the literature even though later work has shown it to require considerable modification. Kase2 published in 1925 a diagram that was based upon observations of furnace-cooled melts. At low carbon contents this diagram agreed fairly well with experience in showing pearlite to exist in alloys containing up to 6 per cent nickel, and completely austenitic steels at 24 to 28 per cent nickel. At high carbon contents, however, irons were indicated as being martensitic at around 2 per cent nickel and austenitic at 12 per cent nickel; these interpretations are open to serious question. Based upon experience with steels and cast iron, Wickenden3 suggested a diagram that agreed fairly well with Kase's in the steel range but which presented a wide departure from it in the higher-carbon, high-nickel regions. In its broad picture, the Wickenden diagram is an approach to "practical" structures. [ ] Reference may be made at this point to the efforts of Marshy to construct an iron-nickel-carbon equilibrium diagram by the coordination of scattered data, which are described at length in the monograph cited. None of these preceding attempts has appeared to meet the need for an exposition of the structural sequence that is encoun-

Jan 1, 1942

By L. Seigle, R. Resnick

An inert-marker movement experiment indicates that the ratio of the intrinsic diffusion coefficients DC:DTa = 80:l in TaC at 2500°C. Measurements of the diffmion coefficient of carbon in nonstoichiometric TaC at temperatures from 1700° to 2700°C reveal that Dc increases with decreasing carbon content, but much less than expected from the probable change in vacancy concentration with carbon content. A diffusion process involving two simultaneously operating mechanisms is postulated, and shown to be theoretically feasible. The average value of the carbon diffusion coefficient is given by DC = 0.18 exp[(-85,000 ± 3000)/RT] sq cm per sec over the composition range 46 to 49.5 at. pct C. BECAUSE of their high melting points and hardness, the carbides of the IV, V, and VI group transition metals, along with those of uranium, have attracted considerable interest for applications at high temperatures. In these applications the reactivity of the materials is important, and, since rates of diffusion within the compounds influence reactivity, a knowledge of diffusion kinetics and mechanisms is desirable. While many investigations of the mechanical and electrical properties of these compounds have been made, only two fundamental investigations of diffusion in the carbides are known. Chubb, Getz, and Townleyl measured the diffusivity of carbon and uranium in UC, and Gel'd and Liubimov2 measured the diffusivity of carbon and niobium in NbC. This paper describes an investigation of the diffusion of carbon in tantalum monocarbide and, in particular, the influence of carbon deficiency on this process. Tantalum carbide melts at approximately 3800°C, which makes it one of the highest melting materials known. The compound exists over a rather wide range of carbon Content.3-7 At the peritectic temperature, 3240°C, the phase extends from about 36 to 50 at. pct C. Although the compound can exist with a substantial carbon deficiency, the high carbon phase boundary remains near the stoichiometric composition over the entire temperature range; i.e., no carbon excess is observed. The structure of TaC is the NaCl type wherein carbon atoms normally occupy the octahedral sites in a somewhat expanded fcc lattice of tantalum. Decrease of the lattice parameter with decreasing carbon suggests that the removal of carbon introduces octahedral vacancies into the lattice. I) EXPERIMENTAL DETAILS AND RESULTS Inert-Marker Experiments. In a compound such as TaC the interstitial element would be expected to diffuse more rapidly than the metal. This was confirmed by an inert-marker experiment, following Srnigelskas and irkeendall.8 Ideally, the markers should be placed at the interface between a slab of low-carbon TaC and graphite, and their movement during subsequent inter-diffusion measured. Unfortunately, no solid could be found which is unreactive in contact with carbon at the high temperatures employed in these experiments. In order to circumvent this problem, a specimen was designed in which the markers consisted of several small canals running just below the surface of a tantalum slab. This specimen was prepared by machining grooves on the surface of the tantalum slab and then diffusion-bonding a thin plate of tantalum to the slab over the grooves. The surface of the plate was then ground down until the distance between the canals and surface was as small as possible (about 0.01 cm). Thus, the canals would lie entirely within the TaC phase after a short period of diffusion. The diffusion anneal consisted of immersing the metal sample in high-purity graphite powder and heating for approximately 10 hr at 2500°C under vacuum. At this temperature, the vapor pressure is sufficiently high and the transfer of carbon from graphite sufficiently rapid to allow the surface of the diffusion sample to attain the stoichiometric carbon concentration very quickly. Conclusions regarding the relative diffusion rates of carbon and tantalum in the compound layers (TaC and Ta2C) can be drawn from the location of the canals after the diffusion anneals. If the growth of the layers is governed mainly by the diffusion of carbon, as expected, the canals should remain close to the sample surface. If the diffusion of tantalum contributes appreciably to formation of the compound layers, the distance from the markers (canals) to the surface should increase. Fig. 1 shows, diagrammatically, the appearance of the specimens after diffusion, and Table I presents the depth below the surface at which the

Jan 1, 1967