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By L. S. Darken

IT has long been recognized that the driving force in an isothermal diffusion process may be regarded as the negative gradient of the chemical potential (partial molal free energy) of the diffusing substance. This equivalence is exactly analogous to the fact that a mechanical force is the negative gradient of the potential energy. Nernst1 in 1888 expressed these driving forces in terms of osmotic pressure, which is directly related to the chemical potential and free energy. The relationship between the diffusivity, mobility and activity coefficient of electrolytes in aqueous solution has been developed in great detail by Onsager and Fuoss2 with results which have recently been confirmed experimentally by Harped and Nuttall.3 This interpretation of the driving force in isothermal diffusion has been discussed earlier by the author 4.6 who pointed out4 that "for a system of more than two components it is no longer necessarily true that a given element tends to diffuse toward a region of lower concentration even within a single phase region"; departure from the behavior of an ideal solution may be so great that the concentration gradient and the chemical potential gradient, or activity gradient, may be of different sign, thus giving rise to "up hill" diffusion. Since, in the discussion of that paper,4 some skepticism as to the validity of this conclusion was expressed, it seemed desirable to adduce experimental evidence to support it. Evidence of such diffusion in nonmetallic systems has already been reported. For example, it was observed by Hartley11 in a series of experiments in which sodium chloride diffused from a saturated solution in about 5 pct acetone in water into a solution virtually free of salt but with essentially the same acetone concentration. Specifically, a wine glass containing crystalline salt and saturated solution was totally immersed in a large glass cylinder containing the acetone-water solution without salt; the difference in specific gravity was such as to prevent convection. Diffusion of salt was accompanied by a marked depletion 0f acetone in the wine glass; after 3 days the acetone concentration decreased from 5.37 pct at the top of the glass, where the salt concentration was low (0.93 pct), to 1.84 pct at the bottom where the salt concentration was high (21.64 pct). This "uphill" diffusion was found to be such that the partial pressure (activity) of acetone was essentially equalized throughout the system when a steady state gradient of sodium chloride was maintained. In order to demonstrate the existence of such diffusion in metals, a series of four weld-diffusion experiments was made. In these measurements pairs of steel of virtually the same carbon content, but differing markedly in alloy content, were welded at the end and held at 1050°C for about two weeks. Subsequent analysis showed that carbon had diffused so as to produce an inequality

Jan 1, 1948

By D. M. Deason, R. M. Chhatre, G. Y. Onoda

INTRODUCTION The treatment of colloidal suspensions is a subject of increasing interest in mining and benefication (1). Colloidal suspensions are not readily operated upon by mechanical and physical methods useful with coarse suspensions, such as filtration, thickening, and flotation. This is because colloids are strongly affected by interfacial and interparticle forces that may be large compared with, and resistant to, external forces. The degree and type of interactions between colloids can be modified by small additions of reagents such as coagulants, flocculants, dispersants, and immiscible liquids. These alterations in turn change the properties of the suspension and provide possible opportunities for transforming suspensions to a more favorable condition for a given processing operation. Phosphate slimes are an example of a colloidal system of interest today. In the mining and beneficiation of phosphate rock in Florida, slimes are a waste product. The phosphate ore (called matrix in the industry) is slurrified hydraulically and pumped to a beneficiation plant, where the -150 mesh material is removed by cycloning from the coarser phosphate rock and silica. The resulting -150 mesh slurry, called phosphate slime, is pumped to large impoundments. The solid content of the slime entering the impoundment is around four weight percent, and over 80% of the solids is less than one micron in size. The immediate problems with phosphate slime relate to their disposal (2, 3). The disposal problem is associated with the very large volumes and the poor dewatering characteristics of the slimes. To have sufficient impoundment volume, large earthen dams are built around the mined areas. The volume above ground level approaches and

Jan 1, 1980

By D. L. Katz

The critical phenomena have been studied during the past century but our knowledge of the critical temperatures and pressures of complex hydrocarbon mixtures still is very limited. The critical temperatures and pressures of pure substances have been examined in large num-bers,20 and in great detail.11,17 No experimental determinations of the critical phenomena have been reported on such complex hydrocarbon systems as a reservoir fluid. The critical temperature is defined by Taylor18 as follows: "there is some temperature for each gas above which the gas cannot be liquefied. This temperature is called the critical temperature." The critical pres-sure of a pure substance is the vapor pressure at the critical temperature. It should be noted that these definitions refer to a given substance in the pure state and do not mean that the pure substance cannot be liquefied in the presence of a second constituent. The normal procedure for obtaining the critical temperature of a substance is to heat it in a glass tube 1,20 under pressure until the meniscus between the liquid and vapor phase disappears, although other methods, especially for mixtures, have been used. 11,14 However, when considering oil and gas reservoirs, it is more enlightening to consider a critical phe-nomenon that occurs when a mixture of oil and gas are compressed at a reservoir temperature until the meniscus disappears because the two phases become equal in composition. This conception, along with erroneous applications of the definition of the critical phenomena of a pure substance to that pure substance when it is part of a complex mixture, has caused confusion even among persons familiar with the classical theories.

Jan 1, 1938

By Jamie Deuel

The a ad on Connection" For the purpose of this paper, we will concentrate on the ubquitous radon gas as the principle, low-level radiation effect from uranium tailings piles. Standards are also proposed for gamma radiations but, by most accounts, this is much less of a low level problem than is radon. I am also aware of some just completed research at Oak Ridge National Laboratories that suggest polonium may be a major concern in tailings, but those data are preliminary at this time. What is radon gas? In the first place it is not a gas in the accepted sense in that it has no driving pressure head. It might prove a more convenient description to call it radon vapor. Radon vapor, then, is 7-1/2 times heavier than air. Radiologically, it is an alpha emitter which means it spontaneously gives off high ionizing potential but low penetrating power particles. In fact, the alpha particle has such low penetrating power that this sheet of paper will completely shield a person. The problem, though, is breathing the radon decay products, called radon daughters. If radon daughter products are ingested into the lungs, their alpha emissions may cause cancer. The principle carcinoma associated with breathing radon, or more basically, associated with radiological effects is oat cell car- cinoma of the undifferentiated mall cell type. Radon has a 3.8 day half life which means in less than four days half of its initial radioactivity has decayed away. In less than a month it essentially becomes inert or non-radioactive. The Tailings Situation The NRC, in its April 1979 Generic Environmental Impact Statement

Jan 1, 1983

By C. S. Barrett

WhEN a collimated beam of protons or other energetic particles is scattered by a single crystal, the emerging particles produce patterns that contain much crystallographic information. Calculations of the trajectories of individual particles can predict with reasonable accuracy the complete pattern (which is related reciprocally to channeling, now studied in detail6) but the task is a lengthy one which has been completed for very few cases. A many-beam dynamic diffraction calculation of the patterns would be even more difficult and in some cases may be invalid. Because of these complexities, simple methods that will predict to a rough approximation the relative intensities of the lines in films of the back-scattering patterns of a given crystal are wanted. I have found a method which, although it is not a valid computation of intensities or of film darkening by either dynamic or kinematic diffraction principles or by trajectory calculations, nevertheless is found to be useful in practice. It has been tested on several crystal types,7 and is here tested on additional ones. The method consists in first calculating the structure factor F(hk1) for the (hkl) plane, of spacing d, by the familiar equation: where the summation extends over the atoms in the unit cell and fj is the atom scattering factor of the jth atom (using tables computed for electron diffraction, preferably those computed without exchange). Then the F values are squared and summed over all the orders, n, for which F2 has an appreciable value, giving a quantity: Finally, I, is expressed as a percentage of Ic for the

Jan 1, 1970

By Frank R. Milliken

SCOPE THIS paper is a running commentary on metallurgical problems and developments, stressing ilmenite flotation, since the start of operations five years ago, at the mill of National Lead Company, Titanium Division, Maclntyre Development, Tahawus, New York. [ ] GENERAL In early 1941, when, world conditions threatened to cut off the supply of ilmenite (obtained largely from India) to this country, the National Lead Company started to develop and bring into production their Maclntyre Development. This operation supplied the bulk of the ilmenite used during the war period for the manufacture of the much needed titanium pigments. Maclntyre Development is at Tahawus, New York, on the headwaters of the Hudson River in the center of the scenic Adirondack Mountains. A general description of the operation was given in the Adirondack Issue of Mining and Metallurgy for November 1943. Operating tonnages and production have increased since 1943, however. Nearly 10,000 tons of ore and waste is broken and loaded daily in the open-pit mine. About half of this tonnage is ore, from which is produced nearly 800 tons of ilmenite concentrate and 1600 tons of magnetite concentrate daily. ORE-TYPES From an ore-dressing standpoint, there are five rather distinct ore types and two waste-rock types in the mine. The ore types are shown in Table 1. The anorthosite waste is a coarse-grained white rock, largely labradorite feldspar. The gabbro waste is generally finer grained, and contains, in addition to feldspar, 35 to 75 pct iron silicates such as hornblende, pyroxene, garnet and biotite. A minor mineral mineralogically, but important metallurgically, is apatite. A few calcite

Jan 1, 1947

By Frederic Benard

THE treatment of Balbach-Thum slimes at Copper Cliff by the Ontario Refining. Co. is of interest because it differs considerably from methods usually employed for the recovery of fine gold from parting-plant slimes. Owing to the comparatively high percentages of pal-ladium and platinum, wet methods are used to remove the greater proportion f these metals before electrolytic refining in the Wohlwill cells. THE PLANT The platinum-metals department, Wohlwill room, and gold-melting room extend along the north side f the silver refinery and are separated from the parting plant by a glass partition (Figs. 1 and 2). The platinum-metals department resembles a laboratory built on a large scale, with the various pieces of equipment laid out on terraces to facilitate handling. Because of the corrosive nature of the solutions, chemical stoneware is used throughout. Elevation of acids is accom-plished by means of Mariotte bottles. On the top level are three steam-jacketed stoneware kettles of 50-gal. capacity, also a packed tower. One kettle is used for digesting the slimes while the remaining kettles are used for precipitating the gold. The dissolver is equipped with a treated concrete hood, which is connected to the flue system. Gases are drawn off through the packed tower by means of a 6-in. stoneware exhaust fan. A 15 per cent solution of sodium carbonate is continually circulated through the tower. On the intermediate level are two suction filters, one for removing silver chloride and the other for the gold sand. The filter medium consists of an asbestos pad covered with a filter paper on which is a layer of twill.

Jan 1, 1938

By Luther Wagoner

HAVING given in a former paper1 the results of assays of sea-water, bay-mud, dredgings from San Francisco bay, etc., and' believing it might be interesting to extend the work to include' some deep-sea dredgings, I procured from the Smithsonian Institution six samples taken by the U. S, steamer Albatross, and marked as follows

Jan 9, 1907

By James Terry Duce

Production of oil in Bahrein for the war years was as follows: YEAR BBL PER YEAR Prior to 1939 . . . . . . . . . . . . . . 22,287,055 1939 . . . . . . . . . . . . . . . . . . . . . . 7,588,554 1940 . . . . . . . . . . . . . . . . . . . . . . 7,073,919 1941 . . . . . . . . . . . . . . . . . . . . . . 6,794,157 1942 . . . . . . . . . . . . . . . . . . . . . . 6,240,627 1943 . . . . . . . . . . . . . . . . . . . . . . 6,571,609 1944 . . . . . . . . . . . . . . . . . . . . . . 6,713,795 1945 . . . . . . . . . . . . . . . . . . . . . . 7,308,938 Total to Jan. 1, 1946 . . . . . . . . 70,578,654

Jan 1, 1946

By George M. Enos, Robert J. Anderson

An impoRtant factor affecting the rate and nature of corrosion of metals and alloys is the film, or coating, formed on the surface; and this may accelerate or retard corrosive action once started. The formation of films and coatings is intimately associated with the chemical composition and physical constitution of both the metal and the corroding medium. A film or coating may be either the corrosion product resulting from oxidation; that is, an oxide or salt, or a deposition of suspended matter from the corroding media upon the surface of the metal, or a mixture of both. The coating may adhere tightly or loosely to the surface of the corroded metal. In short, a film or coating is the reaction product of the corroding medium and the metal, which adheres to the surface of the metal and with which may be intermingled material from the attacking media not concerned in the chemical reactions. As the terms film and coating are used by different writers for very different things, distinction is made between the two, by the present writers, on the basis of thickness. Thus, a film is defined as a corrosion product or deposition, on the surface of a corroded metal, that is of such thickness that it cannot be measured by the metallurgical microscope. A coating, on the other hand, is of such thickness that it can be measured. If the resolving power of the 2-mm. (equivalent focal length) apochro-matic oil immersion objective (N.A. 1.4) is taken as the limit of the microscope, the limiting resolution is two lines that are 0.0002 to 0.0004 mm. apart. It is thus possible to measure coatings that are greater than 0.0002 to 0.0004 mm. thick. This thickness is equivalent to 50,000-

Jan 1, 1925

By H. I. Kaplan, C. Laird

Pulsating contpresslon experiments have been carried out on coppev single crystals in order to test the adequacy of mechanisms which have been suggested for stage I cvack grouth when tension-compression loading is the mode of- applying stress. Although dejorrrzation continues slowly for many millions 01 cycles under Pulsating compression stresses both within slip bands formed in the first cycle and by the creation of new bands, the morphology of these bands is not typical of fatigue slip bands in general and neither initiation of cracks nor propagation of artificially induced cracks was observed. It is therefore concluded that 1) initiation and growth of cvacks in fatigue is a consequence of repeatedly reviersed, microplastic deformation rather than intermittent, unidirectional deforma-tion, 2) gvowth of- cracks in polycrystalline specimens FAILURE of a plain specimen subjected to cyclic tension-compression stresses is known to take place by two stages of cracking.1,2 The first stage is characterized by propagation along slip planes roughly at 45 deg to the stress axis, in the outermost layers of the specimen, and at a rate of the order of angstroms per cycle. The average macro orientation of a stage I crack is normally at right angles to the stress axis,3 however, except in a few cases, e.g., single crystals in suitable orientation, when both the micro and macro directions of propagation are at 45 deg to the axis. After a stage I crack has penetrated to such a depth that the stress on the remaining section of metal is significantly increased, stage II crack propagation succeeds stage I, at right angles to the stress axis both micro and macroscopically. Direct evidence of the processes occurring during a subjected to pulsating compression stresses is caused by the setting-up of local tensile stresses due to interactions between grains, and 3) both unslipping mechanisms and operation of the "plastic blunting process " within a single slip band are adequate descriptions 01- stage I growth, being fundamentally similar. The slip mode of a material, however, is considered to control whether unslipping or the plastic blunting process takes place. Thus materials of planar slip mode fauor unslipping while those hacing a wavy mode, and capable of cross slip, can fail in stage I by the plastic blunting process. Similarly, and perhaps more importantly, reversed torsion and tension-compression modes of applying stress may be expected to cause the unslipping mechanism and the plastic blunting process, respectively. single stress cycle4,5 shows that stage II crack propagation takes place by a repetitive plastic rounding and closing of the crack tip. This mechanism has come to be called the "plastic blunting process".6 On the other hand, the extreme smallness of the phenomena occurring in stage I growth prevents elucidation of its mechanism by direct observation. Many suggestions have been proposed for this mechanism,'"-" most of them involving some kind of random or systematic unslipping process. It is possible, however, that the mechanism of stage I growth is essentially the same as that of stage 11, but occurring on a much smaller scale.6 In this situation, it has been observed that cracks propagate along slip bands comprising dislocation cell structures and bounded on either side by regions of different dislocation density and distribution." Since there is evidence that such bands are softer than their matrix, * it may be expected that the plastic blunting process occurs within a single slip band during stage I growth, rather than on two gross bands as in stage 11, when the acting stress is greater.= The blunting of the crack tip allowed by coordinated

Jan 1, 1968

By G. H. Bruce, C. E. Williams

The trend toward deeper drilling, together with the attcndant increase in power requirements for circulation of the drilling fluid, has emphasized the need for a critical examination of the factors affecting the removal of bit cuttings from the hole by the drilling fluid. The ability of drilling fluids to lift cuttings is called their carrying capacity. A series of laboratory and field experiments has been conducted to determine the minimrim annular velocity necessary to remove cuttings, and to investigate the effects of properties of drilling fluids on their carrying capacities. Consideration of the results of these experiments led to the following conclusions: 1. Turbulent flow in the well annulus is most desirable from the standpoint of cutting removal. 2. Low viscosity and low gel are advantageous in removing cuttings. 3. Increase in mud weight is effective in increasing carrying capacity. 4. The carrying capacity is higher when the pipe is rotated than when it is not. 5. If turbulent flow can be maintained, an annular velocity slightly higher than the slip velocity of the largest cuttings to be transported should keep the bore hole clean. This implies velocities of 100 to 125 ft per minute rather than the presently used 175 to 225 ft per minute. INTRODUCTION Power Savings by Reduction of Annular Velocities A large portion of the power expended in drilling operations is consumed in circulating the drilling fluid. An important factor in establishing the rate of mud circulation is the minimum velocity in the annulus necessary to remove bit cuttings. Empirically, it has been found that average annular mud velocities of about 200 ft per minute will remove cuttings. It was not definitely known, however, whether annular velocities of about 200 ft per minute were just above the minimum necessary to remove cuttings, or whether such velocities could be materially reduced without sacrifice of the ability of the mud to remove cuttings. It is apparent that if annular velocities could be reduced without impairment of cutting removal, a considerable saving in power requirements would result. Need for Research on Carrying Capacity The ability of a drilling fluid to transport cuttings is called its carrying capacity. Although it has been recognized that the carrying capacity of a mud is affected by mud properties such as viscosity and density1,2,3,4 there have been various views in the industry as to the effects of these mud properties on carrying capacity. The economic importance of the problem of carrying capacity and the scarcity of information on the subject indicated that research on the problem was needed. THE FACTORS AFFECTING CARRYING CAPACITY Qualitative Determination of Factors The mechanism of cutting transport is closely related to that involved in the separation of material by settling processes. A considerable amount of research has been done on settling problems, and discussions of sedimentation theory can be found in standard texts.5,6 Consideration of the information available from these sources, together with consideration of the mechanism of cutting transport, leads to the conclusion that the factors affecting carrying capacity are the dimensions of the system, the physical properties of the cuttings. and the physical properties of the drilling fluid. system Dimensions and Their Effect The dimensions of the fluid circulating system of importance to carrying capacity are the bore hole size, drill pipe size, pump capacity, and pump speed. These dimensions determine the annular velocity of the drilling fluid. Physical Properties and Their Effects The physical properties involved in the interaction between mud and cuttings are the density and shape of the cuttings and the density, viscosity and gel strength of the drilling fluid. The effect of the density factor on carrying capacity is fairly obvious; high density difference between cuttings and fluid results in a low buoyant force and therefore decreases carrying capacity. The effect of cutting shape is less obvious. Although

Jan 1, 1951

By C. E. Williams, G. H. Bruce

The trend toward deeper drilling, together with the attcndant increase in power requirements for circulation of the drilling fluid, has emphasized the need for a critical examination of the factors affecting the removal of bit cuttings from the hole by the drilling fluid. The ability of drilling fluids to lift cuttings is called their carrying capacity. A series of laboratory and field experiments has been conducted to determine the minimrim annular velocity necessary to remove cuttings, and to investigate the effects of properties of drilling fluids on their carrying capacities. Consideration of the results of these experiments led to the following conclusions: 1. Turbulent flow in the well annulus is most desirable from the standpoint of cutting removal. 2. Low viscosity and low gel are advantageous in removing cuttings. 3. Increase in mud weight is effective in increasing carrying capacity. 4. The carrying capacity is higher when the pipe is rotated than when it is not. 5. If turbulent flow can be maintained, an annular velocity slightly higher than the slip velocity of the largest cuttings to be transported should keep the bore hole clean. This implies velocities of 100 to 125 ft per minute rather than the presently used 175 to 225 ft per minute. INTRODUCTION Power Savings by Reduction of Annular Velocities A large portion of the power expended in drilling operations is consumed in circulating the drilling fluid. An important factor in establishing the rate of mud circulation is the minimum velocity in the annulus necessary to remove bit cuttings. Empirically, it has been found that average annular mud velocities of about 200 ft per minute will remove cuttings. It was not definitely known, however, whether annular velocities of about 200 ft per minute were just above the minimum necessary to remove cuttings, or whether such velocities could be materially reduced without sacrifice of the ability of the mud to remove cuttings. It is apparent that if annular velocities could be reduced without impairment of cutting removal, a considerable saving in power requirements would result. Need for Research on Carrying Capacity The ability of a drilling fluid to transport cuttings is called its carrying capacity. Although it has been recognized that the carrying capacity of a mud is affected by mud properties such as viscosity and density1,2,3,4 there have been various views in the industry as to the effects of these mud properties on carrying capacity. The economic importance of the problem of carrying capacity and the scarcity of information on the subject indicated that research on the problem was needed. THE FACTORS AFFECTING CARRYING CAPACITY Qualitative Determination of Factors The mechanism of cutting transport is closely related to that involved in the separation of material by settling processes. A considerable amount of research has been done on settling problems, and discussions of sedimentation theory can be found in standard texts.5,6 Consideration of the information available from these sources, together with consideration of the mechanism of cutting transport, leads to the conclusion that the factors affecting carrying capacity are the dimensions of the system, the physical properties of the cuttings. and the physical properties of the drilling fluid. system Dimensions and Their Effect The dimensions of the fluid circulating system of importance to carrying capacity are the bore hole size, drill pipe size, pump capacity, and pump speed. These dimensions determine the annular velocity of the drilling fluid. Physical Properties and Their Effects The physical properties involved in the interaction between mud and cuttings are the density and shape of the cuttings and the density, viscosity and gel strength of the drilling fluid. The effect of the density factor on carrying capacity is fairly obvious; high density difference between cuttings and fluid results in a low buoyant force and therefore decreases carrying capacity. The effect of cutting shape is less obvious. Although

Jan 1, 1951

By H. N. Mead

In a reservoir when gas comes out of solution and rises, additional pressure is created because of the change in position of this gar in the bounded volume. If this pressure effect is not taken into account as a pseudo-influx ill mate rial balance calculations on reservoirs in which there is evolving gas, an error is introduced that is directly proportional to the length of oil column and amount of gas evolved and inversely proportional to the reservoir pressure. In reservoirs with small oil column this pseudo-influx is of little importance. The larger the oil column the more important the effect becomes. The most important application, however, will be for reservoirs with declining pressure in which increasing water entry has been indicated by material balance calculations. It could be that this indication is the result of the cited pseudo-influx and not water entry at all. This paper attempts to explain this phenomenon in relation to material balance calculations and prevents an approximate method of determining tile pseudo-influx. INTRODUCTION Only recently has the pressure-volume relationship of gas rising in a liquid appeared in engineering literature, although its effect has been discussed for several years—especially among engineers engaged in drilling operations. The writer published a paper in 1957 in which this phenomenon was examined in relation to blowouts in drilling wells.' Also, in 1957 Stegemeier and Matthews' authored a paper in which the relationship was presented with respect to pressure build-up tests when shutting in producing wells. In this paper the effect will be called "pressure inversion" which is descriptive of the phenomenon. Fundamentally, the effect just mentioned is the result of changing the position of a quantity of energy contained within the gas itself (as a result of its compression) within the bounded volume in which the gas exists. If the gas were allowed to expand "beyond all bounds" there could be no pressure inversion effect. This is because all of the energy contained within the gas as a result of compression would have been re- PRESSURE INVERSION A phase that has not been discussed in the literature is the effect of pressure inversion upon material balance calculations in reservoirs in which the reservoir pressure drops with reservoir withdrawal and is below the bubble point. This action releases solution gas which, after the critical gas saturation has been reached, will tend to rise and collect at the top of the reservoir. The pseudo-influx caused by this effect could be great enough in reservoirs of large oil column and high permeability to render invalid any analyzer studies made on them — if pressure inversion has not been taken into account. Most suspect would be those reservoirs with large oil column in which increasing water entry has been predicted but the bottom wells have not yet produced water. Example 1 Simply stated, this phenomenon exists in oil reservoirs because of the difference in density and expansibility between gas and oil. For example, if a bubble of gas exists at the bottom of a 1,000-ft column of oil having a gradient of 0.30 psi/ft with the pressure at the top of the column zero, the bubble of gas will be compressed to a pressure of 300 psi. If temperature and the combined volume of the oil column and the gas bubble remain constant, as the gas bubble rises in the oil column it will have the same volume and consequently the same pressure at any point. Under these conditions when thc bubble reaches the top of the oil column, the pressure will be approximately 300 psi at the surface and approximately 600 psi at the bottom of the oil column. If it is assumed that the oil is incompressible the pressures will be exactly 300 and 600 psi, respectively.

HIGH-GRADE manganese ore, from which manganese is obtained commercially, is not found in large quantities in any major steel-producing nation in the free world. The U. S. is a "have not" nation with respect to deposits of directly mineable high-grade manganese ore. Known resources of 48 pct Mn or better grade ore amount to less than 200,000 tons. In 1950 the U. S. steel industry consumed 1.8 million short tons of metallurgical grade manganese ore that contained about 800,000 tons of manganese. About 16 pct of the manganese content was lost in processing, so that about 650,000 tons, or 13 pounds per ton of steel actually entered into steel production. Under present practices use expands directly with steel output, and by 1975 the demand in both the U. S. and the rest of the free world is expected to be roughly 60 pet greater than in 1950. In peacetime about 80 pet of manganese consumption goes into steel production; high-manganese steel, dry cells, and chemicals account for the remainder. The manganese supply problem centers around high-grade ore for ferromanganese production. Use of ores containing less than 35 pet Mn sharply increase the costs of making ferromanganese. Use of ferro-manganese of grade below 70 pet in turn requires changes in steelmaking that increase steel cost. Under normal conditions the present small domestic production cannot be expected to increase. Major resources in the U. S. consist of 12 low-grade deposits. The cost of mining and treating these ores to extract a product as good as that yielded by imported ores is at least twice and in some cases more than four times the 1951 price of foreign ores delivered to the U. S. However, as long as trade relations and overseas shipping are not interrupted, deposits in India, Africa, and Brazil can meet steadily increasing demand at approximately present costs. Cost considerations indicate that the U. S. should continue to rely upon overseas sources for its peace-time supply, and that this situation is satisfactory. But, this does not take into account the question of how the U. S. will be able to meet its needs in war. Position of the Rest of the Free World In 1950, free world steel producers outside the United States, with a steel output of 70 million ingot tons, consumed about 1.3 million tons of metallurgical-grade ore. Their manganese ore demand, expected to increase directly with steel production, will by 1975 be about 2.3 million tons. Russia possesses over half the known manganese ore reserves of the world and is producing twice the tonnage of any other country. It supplied more than a third of the U. S. manganese requirements up to 1938 and again in 1948, but by 1950 Soviet manganese exports to the free world had virtually ceased. The free world's supply of manganese now comes mainly from India and Africa. Somewhat over 10 pet of U. S. imports came from Brazil and Cuba. Security Considerations In the event of war the U. S. might be substantially cut off from 90 pet of present sources. Reduction in manganese specifications might cut consumption by over 10 pet without seriously affecting steel quality. By elimination of losses in the production of ferromanganese savings as high as 10 pet might be possible. But, wartime manganese requirements cannot be met through conservation alone. To meet possible future emergencies the U. S. should continue its comprehensive security program for manganese, including stockpiling and research on the economic use of low-grade ore, domestic ores, the recovery of manganese from slag and the reduction of manganese requirements in steel production. If this work, including additional pilot plant operation is pursued vigorously, it should be possible in an emergency to get an adequate supply of manganese from domestic sources. The national stockpile then can be looked upon as a source of supply during the period of at least 2 years required to reach full-scale production from low-grade resources. Ferromanganese Smelting In comparison with smelting of pig iron, ferro-manganese smelting is a very wasteful process. Under present ferromanganese blast-furnace smelting practice, about 8 pet of the manganese in the furnace charge is lost to the slag, and roughly the same amount is lost to the stack gases; the total loss approaches 15 pct. Present practice is a compromise between excessive slag loss and excessive stack loss. In fact, it may be seriously questioned whether conventional blast furnace design is suitable for manganese smelting. U. S. Resources The known manganese deposits of the U. S. contain a total of 3500 million long tons of raw material and 75 million long tons of metallic manganese. More than 98 pct of this contained metal is in 12 large low-grade deposits of which the most important are those at Chamberlain, S. Dak; Cuyuna, Minn.; Aroostook County, Maine; and Artillery Peak, Ariz. Reserves of high-grade ore (48 pct Mn) amount to less than 200,000 tons. About 20 million tons of ore average over 15 pct Mn, and when grade is decreased to 10 pct Mn reserves amount to about 100 million long tons. If cut-off grade is decreased to 5 pet Mn, resources amount to 800 million long tons. Many of these low-grade ores may be beneficiated by flotation or other concentration methods. Pyrometallurgical Methods For smelting ferromanganese, it is essential to have an ore containing at least 50 pct manganese, with an Mn:Fe ratio of about 8:1. Direct smelting of 20 pct Mn concentrates is not promising. The only method that offers any promise involves two-step smelting.

Jan 1, 1952

By R. E. Smallman

R. E. Smallman (University of Birmingham, England)—Recently, Tedmon and Ferriss11 have determined the yield stress parameters oi and ky for tantalum by measuring the lower yield stress as a function of grain size 2d and fitting the results to a relationship of the form They report that although ky , which is taken to be a measure of the dislocation locking strength, is small (- 2 to 4 x 106 cgs units) a substantial yield drop is nevertheless observed in a normal tensile test. Niobium gives a similar result,12-14 as pointed out in the original work by Adams et a1.,12 and in order to check this apparent anomaly the yield-stress parameters of electron beam-melted niobium have recently been reanalyzed15 by the Luders strain technique. In this method the strain hardening part of the stress-strain curve is extrapolated to zero plastic strain; the intercept on the preyield portion of the curve is taken to give oi, whilst the difference between oi and the lower yield stress gives kyd-1/2. The results indicate that ky increases with increasing grain size and hence, a plot of vs d-112 yields an apparent ky, which is lower than the true value. A similar effect could account for the small ky found in the relatively pure tantalum used by Tedmon and Ferriss. The variation of ky with grain size shows that dislocations are more strongly locked in coarse-grained specimens than in fine-grained samples. In niobium, this may be attributed to the fact that the dislocation density in the fine-grained material is higher than that found in the coarse-grained samples which are given a sufficiently prolonged anneal to remove any residual substructure and, since the metal contains only a small amount of interstitual impurity, a variation in locking occurs. By contrast, application of both the grain size analysis and the Luders strain method to yield-stress data from commercially pure vanadium containing a large amount of interstitial impurity gives consistent values of oi and ky, with ky independent of grain size and temperature. Electron microscope observations show minor variations in dislocation density from grain size to grain size, but in any case in this material the dislocations are heavily locked with precipitate. On yielding new dislocations are generated and, as a consequence, the importance of any differences in dislocation density between the various specimens of different grain size is considerably reduced. It is perhaps significant that Adams and lannucci,16 working with a grade of tantalum containing a higher interstitial content than that used by Tedmon and Ferriss, prepared the specimens of different grain size by annealing in the temperature range 1500" to 2000° C to minimize any differences in dislocation structure, and found that ky had a value of 1.04 x 107 cgs units, independent of testing temperature. Such behavior is consistent with the dislocations being locked by carbide precipitates so that the generation of free dislocations is an athermal process. The recent work of Gilbert et al.17 also shows that in tantalum there is no significant variation of ky with grain size provided it contains 150 ppm of oxygen. In this case, however, the dislocations are not locked by precipitate and ky is temperature dependent. C. S. Tedmon and D. P. Ferriss (authors' reply)— We would like to thank Dr. Smallman for his interesting comments and discussion to our paper, "The Dependence of Yield Stress on Grain Size for Tantalum and a 10 pct W-90 pct Ta Alloy".18 It was suggested that perhaps the relatively small values obtained by us for ky of tantalum could be attributed to the same cause that accounts for the apparently small values of ky that result when it is determined by the Luders Strain technique. Since our values were obtained by plotting the lower yield stress vs the reciprocal of the square root of the grain size, it is not clear how this could be the case. The values of ky in this experiment have been calculated, using the Luders strain technique. With this method, values for ky on the order of 2 x 105 to 5 x lo6 cgs units were obtained. In spite of this rather large variation, the magnitudes are still small, and there appeared to be no good correlation between ky and the grain size or the yield stress, probably because of the difficulty in accurately extrapolating the work-hardening portion of the curve back to zero plastic strain. As was shown in the original data,18 there was little work hardening in any of the curves, at any temperature. In his discussion, Dr. Smallman also points out how ky has been observed to increase with increasing grain size, when determined by the Luders strain technique. There are at least two possible explanations for this. In the first case, if it is assumed that the bulk of the interstitial impurities are concentrated at the grain boundaries, then, of course, the available grain boundary area would decrease with increasing grain size, thus presenting less area for the interstitials, which would then presumably increase the concentration within the grains, thereby increasing the locking of the dislocations. In the second case, the increase in ky with increasing grain size would be attributed to the nature of the grain boundary itself. One of the several ways of deriving the Hall-Petch equation19 is based on the stress concentration arising from a pile-up of dislocations at the boundary. The ability of the stress concentration to unlock a source in a neighboring grain would depend on the strength of the grain boundary. As is well-known, the nature and struc-

Jan 1, 1963

By R. E. Hummel, J. W. Koger

SINCE the first report about a diffusionless transformation of bcc p1 brass to tetragonal p" in 1936 by Kaminski and Kurdjumov,' a series of papers have been published about this transformation, mainly dealing with the temperature range of the martensitic-start temperature (M,) and with the crystallographic structures of the parent and product phases .s In the

Jan 1, 1969

By W. P. Sykes

In an earlier paper1 the composition-temperature limits of the gamma iron phase in the iron-tungsten system were reported as approximated by thermal analyses. At that time no attempt was made to develop metallographic evidence of the coexistence of two phases in the iron-rich solid solution at temperatures between 900" C. and 1400" C.

Jan 1, 1931

1-Iron and Steel JOHN A MATHEWS, Chairman Ralph H SWEETSER Vice-chairman WILLIAM CAMPBELL, Vice-chairman MAX ROESLER, Secretary Iron Ore CHARLES B MURRAY, Chairman R C ALLEN W O HOTCHKISS MAX ROESLER ERNEST F BURCHARD THOMAS T READ DWIGHT E WOODBRIDGE M M DUNCAN WILLIAM KELLY CARL ZAPFFE C T FAIRBAIRN CHARLES F RAND

Jan 1, 1923

By K. P. Gupta, P. C. Panigrahy

The stabilization of the R, a-Mn, and 0-Mn phases have been studied in the Mn-Ti-Fe and Mn-Ti-Co systems. Iron and cobalt both appear to stabilize the (Mn-Ti) R phase to almost the sarne extent. The R-phase region was found to extend from the lowest e/a to slightly beyond the maximunz e/a limit known for this phase. But, while iron appears to stabilize the a-Mn phase, cobalt tends to stabilize the p-Mn phase. In the two systems manganese appears to get replaced by iron and cobalt in each of the mentioned phases. The instability of the a-Mn phase in the Mn-Ti-Co system and the /3 -Mn phase in the Mn-Ti-Fe system cannot be explained on the basis of adverse size effects because atomic diameters for both iron and cobalt (C.N. 12 at. diam) are ziery similnr and not much different from manganese which they replace. Qualitatively, the reason for the stability of the a-Mn and the p-Mn phases can be traced to the more favorable e/a ratio prevailing in the respective systems and to a competing tendency between the two phases. In transition metal alloy systems the o, p,P, R, a- Mn,' and p-Mn2 phases have been claimed as electron compounds. A large volume of work has been done to establish the criterion for the formation of the o phase but until very recently practically no systematic work was done on the a-Mn and the /3-Mn phases. A recent investigation on the P-Mn phase3 indicates the e/a criterion for p-Mn phase stabilization. Since the R phase was first known to appear only in certain ternary systems1 no detailed work was then possible for this phase. The R phase has been recently discovered as a binary intermetallic compound in the Mn-Ti~ and Mn-si~-' binary systems. The existence of binary R phases opens up the possibilities of studying the effect of alloying elements on the stabilization of the R phase. Of the two binary systems possessing an R phase, the Mn-Ti system appears to be more interesting because at a suitable high temperature it is possible to find the three electron compounds, the a-Mn, p-Mn, and R phases, side by side and it is possible to study the effect of a third transition element on these three electron compounds. For the present investigation iron and cobalt, so called B elements for the formation of electron compounds, have been used as the third element to study the stabilization of the a-Mn, P-Mn, and R phases. EXPERIMENTAL PROCEDURE The alloys were prepared by using 99.9 pct pure electrolytic Fe and Mn, 99.5 pct Co, and crystal bar titanium, supplied by Semi Elements Inc., New York and Gallard Schelsinger Mfg. Co., New York. Weighed amounts of the components were melted in recrystal-lized alumina crucibles in an inert atmosphere (argon) high-frequency induction melting unit. Titanium was made into fine chips for easy dissolution and a special charging procedure was adopted to avoid contacts of titanium chips with the alumina crucibles. Up to 20 at. pct Ti, the maximum titanium content in the investigated alloys, there was no visible sign of reaction of titanium with the alumina crucibles. With a careful control of melting time and temperature the losses were minimized and were always found to be below 0.1 pct. Because of such small and almost constant weight losses, the alloys were not finally analyzed. The alloys were wrapped in molybdenum foil and annealed in evacuated and sealed silica capsules at 1000" * 2°C for 72 hr and subsequently quenched in cold tap water. Annealed samples were examined metallographically and by X-ray diffraction. For all high manganese alloys oxalic acid solutions of various concentrations and 1.0 pct HN03 solution were found suitable as etching reagents. Best contrast between the a-Mn and the R phases could be obtained by using freshly prepared 60 pct glycerine + 20 pct HN03 + 20 pct HF solution. For high iron and cobalt containing alloys, especially for alloys containing the a-Fe, y-Fe, and P-Co phases, 15 cc HNOJ + 60 cc HC1 + 15 cc acetic acid + 15 cc water solution was found to be the best etching reagent. All X-ray diffraction work was carried out (using specimens prepared from annealed powders) with a 114.6 mm diam Debye-Scherrer camera using unfiltered FeK radiation at 25 kv and 10 ma. All calculations for X-ray diffraction work were carried out using an IBM 7044 digital computer RESULTS AND DISCUSSION The two ternary systems, MnTiFe and MnTiCo, were investigated near the manganese rich end, Figs. 1 and 2, and show some common features. In both alloy systems large extensions of narrow R phase regions occur at almost constant titanium contents. At titanium contents higher than that of the single phase R-phase alloys, the same unidentified X phase was found in both ternary systems. The extensions of the X phase close to the Mn-Ti binary indicate that this phase could be the TiMns phase. Too few X phase diffraction lines were present in the diffraction patterns to make positive identification of the X phase. In contrast to this similarity the two systems show opposite behavior in the extensions of the a-Mn and 8-Mn phase regions; while iron tends to stabilize the a-Mn phase, cobalt

Jan 1, 1970