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By E. F. Loiseau

Until June, 1868, it had not been attempted, either in this country or abroad, to manufacture by mechanical means, from anthracite coal-dust, artificial fuel for domestic use. Several attempts had been made to utilize coal-waste by converting it into a fuel for manufacturing purposes, but none of the processes were original, and they were merely applications of the well-known European processes and machinery, slightly modified by American ingenuity and mechanical skill. With one exception all those attempts have been failures. The great difficulty in the application of European processes and machinery has always been the limited production, and the excessive cost of the manufactured product, as compared with the cost of mining and preparing the ordinary anthracite coal for the market. The only serious and intelligent attempt to manufacture, on a large scale, artificial fuel for manufacturing purposes, has been made by the Anthracite Fuel Company, whose works are erected at Fort Ewen, near Rondout, New York. This company, organized under the auspices of the Delaware and Hudson Canal Company, had to go through the usual course of difficulties, breakages, and disappointments, which seems to be the lot of every new industry. Thanks, however, to the energy and perseverance of Mr. L. L. Crounsse, a gentleman of means, from Washington, D. C, the enterprise succeeded, and it is to-day established on a permanent basis. In order to increase the production, and to reduce its cost, the Anthracite Fuel Company was compelled to change most of its •plant, and to erect more powerful machinery, producing lumps of a larger size, almost twice the size of the lumps made previously by the same company. This increase in the size of the lumps has been resorted to in Europe as well as in this country, in order to increase

Jan 1, 1879

By L. M. Barker, E. G. Lewis

THE literature of milling is replete with papers devoted to the subject of ball milling, all of which no doubt have contributed in one way or another to progress in that art. In this paper reference will be made to only a few of the many authors, but the value of the contributions of all who have written on that subject is hereby acknowledged. With a few exceptions the efforts of most students of the subject have been devoted to laboratory investigations of principles. Davis1 was one of the first to report on plant-scale investigations and to present to mill men certain criteria for the guidance of ball-milling practices. His conclusions with respect to the significance of sizing analyses of classifier sands in their relation to the factors of mill speed and ball sizing are particularly referred to. Those conclusions were: I. If the balls are large or the speed of the mill is high, crowding will appear at the finer sizes in the classifier sands. 2. If the balls are small or the speed is low, crowding will appear at the coarser sizes in the classifier sands. 3. The indications are that best efficiency is obtained when the screen analysis of the sands show a minimum crowding at any size. The last conclusion was qualified by the statement that it had not been proved conclusively. It is surprising, however, that the literature of later years reveals little evidence that millmen have made any serious attempt to apply those criteria. This may, perhaps, be explained by the fact that the average plant-scale ball-milling problem presents so many variables that an investigation of any one of them encounters the problem of control of the others-a problem that often is unsurmountable in a small plant. In a large plant, in which there is a duplication of grinding units in parallel operation, opportunity may be afforded for determining the value of such criteria. Nevertheless, a study of published data from grinding circuits of both large and small plants suggests that either Davis' criteria have been tried and found inapplicable or have never been given consideration. For the purpose of testing Davis' conclusions and with improvement of ball-milling efficiency as the final objective, a test program was initiated in the concentrator of the New Cornelia branch of the Phelps Dodge Corporation early in 1938. The practices of that plant have already been described .2 The fine-grinding units are arranged so that any one of eight units may be operated as a test unite and its results compared with those of the remaining units. All units receive similar feed from a common storage bin, in which the product of the fine-crushing plant is bedded by traveling tripper. The ball mills are all similar in size and operated at the same speeds, and are individually metered. The feeder conveyors of each unit are equipped with Merrick weightometers. The test program as initially outlined proposed investigation of the following:

Jan 1, 1941

By C. R. Kuzell

STAFF: Editor, Gerhard Derge Carnegie lnstitute of Technology Schenley Pork Pittsburgh 13, Pa. Editorial Assistant, M. A. Redmerski Production Editor, Otto T. Johnson THE METALLURGICAL SOCIETY: C. C. Long, President; John Chipman, Past-President; J. S. Smart, Jr., Vice-President, T. D. Jones, Treasurer; R. W. Shearman, Secretary. PUBLICATIONS COMMiTTEE OF THE METALLURGICAL SOCIETY: D. J. Carney, Chairman; Robert Maddin, Past-Chairman; J. H. Hollomon, J. H. Jackson, H. H. Kellogg, T. B. King, F. C. Langen-berg, D. L. McBride, W. O. Philbrook, J. S. Smart, Jr., R. L. Smith, J. D. Sullivan, and F. L. Vogel Review and selection of manuscripts is under the supervision of the following Publications Committees: Extractive Metallurgy Division: H. H. Kellogg, Chairman; T. 8. King, Post-Chairmon; R. P. Hermsdorf, W. A. Krivsky, R. E. Lund, C. L. McCobe, Poul Queneou, A. 5. Russell, M. E. Wadsworth, and W. D. Wilkinson. Institute of Metals Division: R. L. Smith, Choirman; P. A. Beck, I. I. Bessen, J. O. Betterton, Jr., R. S. Davis, J. J. Gilmon, R. 8. Gordon, C. D. Graham, Jr., R. W. Guard, J. C. Gurlond, J. J. Heger, M. Hermon, J. N. Hobstetter, H. H. Johnson, Jr., I. R. Krarner, W. C. Leslie, R. A. Meussner, R. R. Nosh, G. E. Pellissier, T. N. Rhodin, A. U. Seybolt, L. L. Seigle, I. S. Servi, P. G. Shewmon, L. Slifkin, J. K. Stanley, C. D. Starr, and J. Washburn. Iron and Steel Division: F. C. Longenberg, Chairmon; H. L. Bishop, C. W. Sherman, J. 8. Wagstaff, and E. Whittenberger. Published bimonthly by the American lnstitute of Mining, Metallurgical, and Petroleum Engineers, Inc., 29 West 39th Street, New York 18, N. Y. Telephone: PEnnsylvania 6-9220. Subscription $20 per year for nan-AIME members in United States and North, South, and Central America; $25, foreign; $5 far AlME members. Single copies, $4.00, single copies foreign, $5.00. The AlME is not responsible for any statement mode or opinion expressed in its publications . . . Copyright 1960 by the American Institute of Mining, Metallurgical, and Petroleum Engineers, Inc. . . . Registered cable address, AlME New York ...Indexed in Engineering Index, Industrial Arts Index, and Chemical Abstracts ... Second class postage paid at New York, N. Y., and Ann Arbor, Mich. Volume 218, Number 4

Jan 1, 1961

By William Metcalf

It is the object of this paper to oppose unnecessary changes, and the introduction of new and confusing terms. From the earliest times of which we have ally record on the subject, iron has been divided into general classes. Whether iron was first known in the form of wrought iron or of steel, is a matter of no importance; but at the time when cast iron first became a prominent article of commerce, wrought iron and steel were old products— steel, at that time, being generally made from wrought iron by the process of cementation. As steel was then properly defined as iron containing more carbon than wrought iron, so cast iron was appropriately defined as iron containing more carbon than steel. Until the year 1776, when Huntsman first began the manufacture of a new kind of iron by melting wrought iron and steel in crucibles, the above definitions were all that could be desired. At first, probably, owing to imperfect appliances, only a highly carburized iron was melted in crucibles, and this led to its being called cast steel. If our ancestors had found a name for this material not involving the use of the word steel, we would have been saved the trouble of the present discussion. As the arts developed, new uses were found for steel, and the products of the crucible were varied, until at the present day it is quite common to find steel containing no more carbon than average wrought iron, and other steel containing nearly or quite as much carbon as some cast iron. All of these various products of the crucible have retained, or received, the name cast steel, usually abbreviated to the simple word steel, without caus-ing any confusion among producers or consumers in regard to terms or their meaning. In 1865, twenty-one years ago, the Bessemer process was introduced ; this was followed in a few years by the Siemens-Martin process, and the products of both were at once, and have ever since been, called steel, from the fact that they were identical in chemical and physical properties with crucible cast steel. At the present time, then, we have three subdivisions of cast steel, viz.: Crucible cast steel, Bessemer cast steel, and Siemens-Martin,

By A. Kenneth Schellinger

DURING the comminution of a brittle material in the presence of dry air, no known phase change or chemical reaction takes place. The energy changes associated with the comminution are those of the transformation of kinetic energy into heat energy and the energy absorption represented by the actual rupture of molecular and/or ionic bonds. The random nature of the actual grinding process in a tumbling-mill often precludes the effective application of a rupture force on each individual particle of brittle mineral present. The result must be a great deal of useless vibration on an atomic scale in both the brittle mineral and the grinding medium below the elastic limit, which vibration is eventually manifested as heat energy in the mill. The actual rupture of molecular, or ionic, bonds creates new surface on the brittle minerals; each square centimeter of this new surface then must possess a number of potential bonds, each of which could reform theoretically with the release of energy. The sum total of this potential energy of bonding per unit of new surface, minus bond satiation effects of the enclosing gas or liquid, must be the surface energy of the mineral. If the comminution of the brittle mineral were carried out within the chamber of a calorimeter, the energy released as heat could be determined rather accurately. Moreover, the total kinetic energy input to the comminuting mass (mineral and medium) conceivably could be derived by a suitable torquemeter and revolution counter if the whole calorimeter were revolved. The difference between these two energy figures should then represent the net energy (gross energy input—heat enerb output) used in creating new surface, gliding or slip on atomic planes, twinning, and possibly other lattice rearrangements within the mineral. If it be postulated further that with a hard, brittle crystalline material, such as quartz, the energy used to produce gliding, twinning, and other permanent lattice movements is a very small fraction of the total net energy absorbed, then this energy absorption within the grinding calorimeter can be ascribed to the creation of new surface energy alone. Such energy is, from the thermody-namic standpoint, the true effective work of the grinding device, in this case a tumbling-medium mill. The ratio of this effective work (in calories) to the total energy input (in calories) should express the thermodynamic efficiency of the comminution taking place under the conditions used in the grinding calorimeter. This approach to the measurement of the energetics of tumbling-mill grinding was suggested by some previous work by Fahrenwald and coworkers' with a laboratory ball mill and a thermometer. They measured the efficiency of grinding based on the formula: Pct Grinding Efficiency = Energy (calories) — Thermal Energy x 100 1npZ Output (calories) Energy input (calories) Efficiencies thus measured, while grinding quartz sand, ranged from 19.7 pct to 7.4 pct. Cook in 1915,' used this approach to the problem of grinding efficiencies in stamp batteries and obtained the energy input by stamp weights times drop distances and the energy output by means of thermometers and pulp flow rates. He calculated that 80 pct of the input energy to the stamp shoes was wasted as sensible heat in the ore pulp. No other studies of comminution by this method of energy differences came to the author's attention. Reasonable agreement as to the order-of-mag-nitude of comminution efficiencies in tumbling-media mills is lacking in the literature. There is a widespread impression among technical workers that the grinding efficiency of the industrial ball mill may be on the order of 1 pct, or even a fraction

Jan 1, 1952

By Willard L. Hunter

Four solvent extraction systems were studied to determine their efficiency jor extraction and separation of tantalum and columbium. Aqueous feed solutions of varying HF-HCl concentrations and metal content were contacted with equal volumes of cyclohexanone, 3-methyl-2-butanone, and 2-pentanone and solutions of varying HF-H2S04 concentrations were contacted with equal volumes of 2-pentanone. One multistage continuous test was made in a polyethylene pulse column using cy clohexanone as the organic phase. In each system studied, columbium and tantalum purities in excess of 95 pct with respect to each other were obtained in single-stage tests at low acidities in the feed solution. Separation factors ranging from 1700 to 2400 were obtained when rising HF-HCl mixtures in the aqueous phase. Best results were obtained when a solution of HF-H2S04 was used as the aqueous phase and 2-pentanone as the organic phase. A separation factor in excess of 6000 was obtained in one stage with aqueous solution concentrations of 2 _N HF and 2N H2S0,. When acid concentrations were increaszd to 52 HF and 10 _N H2S0,, 99.9 pct of the tantalum and 98.2 pct of the columbium initially present in the feed solution were transferred to the organic phase. The separation of columnbium and tantalum obtainable by means of the solvent extraction systems presented in this paper was found to corn -pare favorably with other systems, including the HF-H2SO4-methyl isobutyl ketone system currently used by most producers for the extraction and separation of these metals. TANTALUM and columbium are always found together in minerals of commercial significance, although the proportion of the two metals in ores varies within broad limits. Columbium is estimated to be 13 times more abundant than tantalum. Five methods generally employed for the separat:ion of these metals are: 1) fractional crystallization (the Marignac process),2 2) solvent separation, 3) fractional distillation of their chlorides, 4) ion exchange, and 5) selective reduction. Of these methods, the one currently used by industry to the greatest extent is that of solvent separation. One of the early technical developments in solvent separation of tantalum from columbium was reported by the Bureau of Mines: the HF-HC1-methyl isobutyl ketone system; data were presented for both laboratory and pilot-plant experimentation.3 Of twenty-eight organic solvents tested for their ability to extract tantalum from an HF-HC1 solution of columbium and tantalum, 3-pentanone (diethyl ke-tone), cyclohexanone, 2-pentanone, and 3-methyl-2-butanone were chosen for further study. Data on the HF-HC1-diethyl ketone system has been published4 and data describing the use of cy clohexanone, 2-pentanone, and 3-methyl-2-butanone as the organic phase are included in this report. RAW MATERIAL The source of tantalum and columbium oxides for this study was ('Geomines" tin slag from the Manono Smelter, Cie Geomines, Gelges, S.A., Congo. In order to extract the valuable Ta-Cb content, the slags were carbided, chlorinated, and the sublimate from chlo-rination was hydrolized and washed free of chloride with water. The washed material was air-dried and stored in a stoppered container. Throughout the paper, "feed material" refers to this mixture of hydrated oxides which was employed because of its high solubility in aqueous solutions. Typical analysis of the hydrated oxides is shown in Table I. I) HF-HC1-CYCLOHEXANONE SYSTEM Batch Separation. Effect of Acid Concentration. To determine the effect of varying the acid concentration upon the transfer of tantalum and columbium, a series of tests was made in which approximately 2.5 g of feed material was added to 25 ml solutions of 2, 4, 6, 8, and 10 N HF and 0 through 5 N HC1. Tantalum pentoxide concentration of the solu%ons was approximately 21 g per liter and columbium pentoxide was 14 g per liter. These starting solutions were shaken with equal volumes of cyclohexanone in 100 ml polyethylene bottles for 30 min. The phases were carefully separated in 125 ml glass separatory funnels. The time of contact of the solutions with the separatory funnels was kept at a minimum to reduce silica contamination. The measured phases were separated into 400 ml polyethylene beakers and the metal contents of each were precipitated by addition of an excess of ammonium hydroxide. Precipitate from each phase was filtered on ashless filter paper, ignited at 800" to 1000°C for 45 min, weighed, and analyzed by X-ray fluorescence.5 Data tabulated in Table I1 and illustrated in Fig. 1, show that maximum separation of tantalum from columbium for each HF concentration was obtained with no HCl present. The purest tantalum product was obtained with some HCl present. The highest separation factor was obtained at 2 N HF and

Jan 1, 1970

By James A. Beck

Phosphorus is essential to all life processes and therefore to the existence of man. In this role, there are no substitutes for phosphorus. In a commercial sense, phosphorus and its compounds are important to our entire economy, both in agricultural and in nonagricultural applications. The world's phosphate requirements are met by mining phosphate rock. Two general types of phosphate ore deposits are commercially important-igneous and sedimentary. Igneous deposits generally are more difficult and more expensive to mine than sedimentary deposits and are of importance mainly in the USSR, North Vietnam, and South Africa. Approximately 15% of current world production comes from these deposits. Over 80% of world production is from the pellet sedimentary deposits of Florida, North Africa, and elsewhere. Guano, the second type of sedimentary deposit, is produced in South America but is declining in world importance. Production Production of phosphate rock was reported in 31 countries during 1972. However, about 80% of world output is produced in three countries: the United States, the USSR, and Morocco (Table 15.2A.1). Throughout the past 20 years, between 75% and 80% of world output has been produced by these three leading countries. Between 1948 and 1972 world production increased at an average rate of 10% per year, from 21.5 to 103.9 million tons. Growth was quite steady at 6% per year through 1963, but in the 5 years from 1963 to 1968 production increased 11 1/2% per year. Since 1968 production has increased about 91/2 % annually. Since 1948 several new phosphate mining ventures have been developed in Senegal, Togo, Israel, and North Vietnam. In the same period, only one important phosphate deposit, on Makatea Island, has been mined out and closed. A number of other phosphate mining ventures are in various stages of planning and development. The most important new venture in phosphate mining is in the Spanish Sahara. New mining capacity is expected also in Syria, and serious investigation is in progress in Peru, India, Turkey, and Australia. Major expansion of existing operations is expected in Morocco, Russia, Tunisia, Israel, and Jordan. Consumption Historical data on world consumption of phosphate rock are not available in detail, but world consumption of phosphate has closely paralleled world production in the past two decades. The United States is the world's largest user of phosphate rock, accounting for 30%

Jan 1, 1976

By A. Eilers

THE telluride of gold and silver, the " Tellurgold-silver" of Hausmann, and " Petzite" of other mineralogists, has been found in so few localities, that a late discovery of the mineral in a new locality may not be uninteresting. So far this mineral has been found in Europe only in a few mines in Transylvania, and in Hungary ; and in the United States in the Stanislaus Mine, in Calaveras County, California, in the Golden Rule Mine, Tuolumne County, California, and in a mine in Montana, the precise locality of which I have forgotten. The new locality referred to is at the Red Cloud Mine, Gold Hill District, Boulder County, Colorado.

Jan 1, 1873

By Fathi Habashi

Nickel, copper, and elemental sulfur can be recovered from a low-grade pyrrhotitepentlandite type concentrate by leaching with HNO3 in a pressure reactor at moderate temperature and pressure. The bulk of iron is converted to an oxide. Same results can be achieved by leaching in an open vessel under a reflex condenser for an extended period of time.

Jan 1, 1974

By Stanley C. Herold

A few hates on the occurrence and significance of mud volcanoes in Colombia may be of interest at the present time, owing to the renewed activity in geological exploration of the coastal regions bordering the Caribbean Sea. The best-known volcanoes are found a few miles from the seacoast. One is situated to the south of Puerto Colombia; the second, to the east of Cartagena near the village of Turbaco; and the third, near the village of Puerto Escondido south of the Sinu River. Others are reported in more inaccessible localities. Usually they stand 2 1/2 or 3 ft. (0.762 or 0.914 m.) above the surrounding ground at the crater, though several craters from 10 to 20 ft. -(3.04 to 6.09 m.) "apart will often build up an extensive mound at low gradient. The shallow mound may cover 1/2 or 3/4 acre (0.2 to 0.3 ha.) with an elevation of 12 or 15 ft. (3.65 or 4.57 m.) at the, center. The craters are formed of hardened blue clay; the inside diameters vary from 14 to 24 in. (35.56 to 60.96 cm.). The rim is continuous, except on one side where there is usually a cut 3 or 4 in. deep, thus allowing an overflow. The craters are filled to the' rim-cut with a thick mixture of blue clay mud and water, which is kept in agitation by escaping gas. Fig. 1 shows the bubble in the act of bursting and Fig. 2 the appearance of the surface of the viscous fluid a second or so later. The frequency of the explosions is determined by the weight of the column of fluid in the neck of the volcano, consequently, such explosions are not synchronous in a group of craters. Ordinarily, there arc two or three explosions in about 3 minutes. The supply of gas is small but steady and sufficient pressure must accumulate before the bubble can enter the column of fluid. The water is derived from the surface and enters the scdirnentary strata not far distant from the volcano. During long dry seasons, as the supply of water fails the volcano dries and geyser action ceases. The temperature of the muddy fluid is normal; the gas is dry and inflammable. - No petroleum products come with the gas. On the surface of the fluid, there is sometimes a dark brown streaky scum, which

Jan 1, 1920

By R. J. Charles, G. Agar

Experiments on single particles show that the amount of material created during impact that is finer than any chosen size is proportional to the energy of the impact. As the underlying principle of comminution, it might be stated that each unit of energy input to a given comminution system tends to add to the system an identical assembly of new particles and subtract an equivalent volume of larger particles. Thus, two of the consequences of the fact that each unit of energy tends to add identical assemblies of new particles to the system are: 1) on continued application of energy the total charge in any batch comminution system tends to assume the characteristics of this assembly, and 2) the process of comminution may be described by a relationship such as E = Ak-a. Recently Schuhmannl presented a theory of comminution which puts rational perspective on the extensive controversy surrounding most of the existent theories of comminution. With hindsight the origin of controversy can be ascribed to a relatively simple circumstance. In general, a progressive shift of a size distribution curve towards finer sizes is observed as energy is added to a comminution system. It is also observed that, with continued grinding, the size distribution curves usually change and appear to approach some constant shape. Inves-tigators generally felt that an appropriate method of relating and generalizing such data would be to consider the hypothetical case where particles in the system were uniformly subjected to comminution such that each of these particles, receiving its proportion of input energy, was transformed into a number of smaller particles of uniform size. Since the changes in shape of the size distribution curves during size reduction were clearly associated with the coarse particles in the system, it was also assumed that these changes accounted for little of the input energy and one could deal solely with the equilibrium shape towards which the size distribution curves tended. Although the unrealistic nature of the foregoing points of view was realized some justification was felt for such treatments since, in most cases, the resulting mathematical formulae could, by the adjustment of at most two parameters, satisfactorily describe experimental observation. Difficulties arose, however, in that the formulae required a specific influence of the feed size on the comminution process. In actual fact, the application of a feed size term in fitting experimental data was often found to be unnecessary or contrary to the above formulae. Secondarily, much discussion arose concerning the appropriate energy number that would relate the size change of one particle to the amount of comminution energy it received. As has been previously shown3 all the above theories that treat comminution as a continuous process of size reduction may be related to a proposition of the following form: dE = -Cfn [1] where dE is the increment of energy, dx is the size change, x is the particle size, and C and n are constants. It is now clear, as pointed out by Schuhmann, that Eq. 1 is inapplicable to comminution processes, since comminution cannot be considered other than as a discontinuous mixing process in which the overall size distribution of the product results from mixing, in various proportions, finished material with unfinished, and sometimes untouched, material. A striking illustration of this mixing phenomena may be obtained by comparing the size distributions of grinds in a typical batch ball mill with size distributions calculated on the basis of mixing various proportions of feed material with a ground material which obeys a power law size distribution relationship. Figs. la and lb illustrate such a comparison and the similarity of these figures indicates that mixing plays an important role in determining the overall shape of the product size distributions. Figs. la and lb illustrate, additionally, the underlying basis of the comminution theory presented by Schuhmann.' In the preliminary grinding of relatively close sized feed particles in a batch ball mill, one may visualize that, when a successful encounter of a ball with a feed particle occurs, then the particle undergoes severe size reduction and the size range in which the resultant particles reside is far removed from the size of the feed particles. After a number of feed particles are reduced by independent but similar impacts and one examines the size dis-

Jan 1, 1961

By E. Brunner, G. L. Hassler, T. J. Deahl

The capillary effects in reservoir rock are discussed in terms of the pressures they cause in sandstones and dolomites. Data for the two-phase case (oil-gas or water-gas) and for the three-phase case (oil, water and gas in rock) are used to demonstrate that in one sense the wetting preference of a rock depends on its saturation. The nature of capillary hysteresis is described for partially stable conditions, and the concept is enlarged. Reproducibly measurable pressures include the "capillary pressure," which is the pressure difference between any two phases that are each interconnected; the "threshold pressure," necessary to force a nonwetting phase through partially saturated rock; the "displacement pressure," which is that special case of the threshold pressure in which both phases fully saturate separate portions of the rock. Displacement pressure is equal to the minimum value of the "capillary pressure." The theory of flow including capillary forces is developed at the producing surface of a well to reveal the presence there of a pressure discontinuity in the gas (or other nonwetting) phase that can be controlled to the end that more oil may be poduced from an oil field. Experiments with packed sand-flow tubes having artificial producing surfaces support the theory. Introduction The basic surface quantities acting in an oil field are two: namely, surface tensions and contact angles. These are the quantities, variously expressed, and particularized as spreading forces, adhesion tensions, heats of wetting, etc., which are measured in the laboratory by techniques mostly confined to flat or circularly cylindrical surfaces. Such measurements have not had the extensive engineering application they seem to deserve because in most practical cases they are unavoidably compounded with the complex and unapproached subject of the internal shape of the interstices of rock. In this paper it is intended that the pressure differences developed in rock by capillarity be examined, defined, and given some engineering use in terms of some new measurements that have been made. Such pressure differences—namely, the capillary pressure, the displacement pressure and the threshold pressure—seem to provide a proper contact between the basic molecular quantities and the oil field. While certain modifications of usage will be undertaken, the present effort rests upon the background of work by the U. S. Geological Survey,l by Versluys, and especially by W. 0. Smith, 3,4,5 which has been reviewed recently in papers by Leverett.=s7 The most important concept of pressure difference is the capillary pressure, a function of saturation that expresses the pressure difference between the interconnected phases in a rock. It is often measured when water and air are the fluids present, but it can be measured with other fluids. A number of curves of capillary pressure have recently been measured by a method which it is intended shall be published in a later paper. Since heretofore capillary-pressure measurements upon rock have not been

Jan 1, 1944

By G. L. Hassler, E. Brunner, T. J. Deahl

The capillary effects in reservoir rock are discussed in terms of the pressures they cause in sandstones and dolomites. Data for the two-phase case (oil-gas or water-gas) and for the three-phase case (oil, water and gas in rock) are used to demonstrate that in one sense the wetting preference of a rock depends on its saturation. The nature of capillary hysteresis is described for partially stable conditions, and the concept is enlarged. Reproducibly measurable pressures include the "capillary pressure," which is the pressure difference between any two phases that are each interconnected; the "threshold pressure," necessary to force a nonwetting phase through partially saturated rock; the "displacement pressure," which is that special case of the threshold pressure in which both phases fully saturate separate portions of the rock. Displacement pressure is equal to the minimum value of the "capillary pressure." The theory of flow including capillary forces is developed at the producing surface of a well to reveal the presence there of a pressure discontinuity in the gas (or other nonwetting) phase that can be controlled to the end that more oil may be poduced from an oil field. Experiments with packed sand-flow tubes having artificial producing surfaces support the theory. Introduction The basic surface quantities acting in an oil field are two: namely, surface tensions and contact angles. These are the quantities, variously expressed, and particularized as spreading forces, adhesion tensions, heats of wetting, etc., which are measured in the laboratory by techniques mostly confined to flat or circularly cylindrical surfaces. Such measurements have not had the extensive engineering application they seem to deserve because in most practical cases they are unavoidably compounded with the complex and unapproached subject of the internal shape of the interstices of rock. In this paper it is intended that the pressure differences developed in rock by capillarity be examined, defined, and given some engineering use in terms of some new measurements that have been made. Such pressure differences—namely, the capillary pressure, the displacement pressure and the threshold pressure—seem to provide a proper contact between the basic molecular quantities and the oil field. While certain modifications of usage will be undertaken, the present effort rests upon the background of work by the U. S. Geological Survey,l by Versluys, and especially by W. 0. Smith, 3,4,5 which has been reviewed recently in papers by Leverett.=s7 The most important concept of pressure difference is the capillary pressure, a function of saturation that expresses the pressure difference between the interconnected phases in a rock. It is often measured when water and air are the fluids present, but it can be measured with other fluids. A number of curves of capillary pressure have recently been measured by a method which it is intended shall be published in a later paper. Since heretofore capillary-pressure measurements upon rock have not been

Jan 1, 1944

By R. G. Patterson

The usual procedure in determining the magnetic susceptibilities of rocks and formations has been to take samples in the field and measure their volume susceptibilities in the laboratory, using one of numerous methods available. In none of these methods is the measuring instrument suited for field use. Usually the sample is pulverized; sometimes it is machined to a desired sue and shape, and in one method1 a cast of the sample is made and the susceptibility of the rock compared with that of a material of known susceptibility of the same size and shape, made from the cast of the original sample. Some writers assert that the difference in susceptibility of a rock sample in powdered and solid forms is negligible, and while doubtless this is true in many cases there are others in which the difference becomes appreciable. Further, the susceptibility of a small specimen may differ from that of the rock from which it is taken, owing to the stresses produced by the hammering or other forces used to obtain the sample and shape it for testing. Wilson2 found that an individual specimen of granite had about the same susceptibility in the solid as in the powdered form, but that pieces from different parts of the rock varied as much as 750 per cent because of unequal distribution of magnetite. The most accurate value of susceptibility would, obviously, be obtained from averag- ing a number of tests on the undisturbed rock instead of from one or two samples. No such procedures have been published, to the writer's knowledge. It is the purpose of this paper to describe a method by which susceptibilities of rocks may be determined in place by means of a portable instrument. Method The principle involved in this new method is that there is a change in inductance of a coil due to the presence in its magnetic field of a paramagnetic or dia-magnetic medium. In this case, however, the windings of the coil do not enclose any part of the rock under test. Instead, the coil is circular, being small in cross section as compared to its radius, and consists of several hundred turns of fine wire. It is placed flat on the rock of which the susceptibility is to be measured. Thus only part of the magnetic field from the coil penetrates the rock under test. The relation between the change in field strength or inductance of the coil and the susceptibility of the medium will be developed later. To measure the change in the inductance of the coil due to the presence of a magnetic material an alternating-current inductance bridge was chosen. Description of Apparatus Of many alternating-current bridge methods applicable,3 the one shown in Fig. 1 (Owen's bridge') was adopted for its simplicity and sensitivity. In Fig. I, the test coil is indicated by PlL1. It is connected to the bridge by about

Jan 1, 1946

By R. G. Patterson

The usual procedure in determining the magnetic susceptibilities of rocks and formations has been to take samples in the field and measure their volume susceptibilities in the laboratory, using one of numerous methods available. In none of these methods is the measuring instrument suited for field use. Usually the sample is pulverized; sometimes it is machined to a desired sue and shape, and in one method1 a cast of the sample is made and the susceptibility of the rock compared with that of a material of known susceptibility of the same size and shape, made from the cast of the original sample. Some writers assert that the difference in susceptibility of a rock sample in powdered and solid forms is negligible, and while doubtless this is true in many cases there are others in which the difference becomes appreciable. Further, the susceptibility of a small specimen may differ from that of the rock from which it is taken, owing to the stresses produced by the hammering or other forces used to obtain the sample and shape it for testing. Wilson2 found that an individual specimen of granite had about the same susceptibility in the solid as in the powdered form, but that pieces from different parts of the rock varied as much as 750 per cent because of unequal distribution of magnetite. The most accurate value of susceptibility would, obviously, be obtained from averag- ing a number of tests on the undisturbed rock instead of from one or two samples. No such procedures have been published, to the writer's knowledge. It is the purpose of this paper to describe a method by which susceptibilities of rocks may be determined in place by means of a portable instrument. Method The principle involved in this new method is that there is a change in inductance of a coil due to the presence in its magnetic field of a paramagnetic or dia-magnetic medium. In this case, however, the windings of the coil do not enclose any part of the rock under test. Instead, the coil is circular, being small in cross section as compared to its radius, and consists of several hundred turns of fine wire. It is placed flat on the rock of which the susceptibility is to be measured. Thus only part of the magnetic field from the coil penetrates the rock under test. The relation between the change in field strength or inductance of the coil and the susceptibility of the medium will be developed later. To measure the change in the inductance of the coil due to the presence of a magnetic material an alternating-current inductance bridge was chosen. Description of Apparatus Of many alternating-current bridge methods applicable,3 the one shown in Fig. 1 (Owen's bridge') was adopted for its simplicity and sensitivity. In Fig. I, the test coil is indicated by PlL1. It is connected to the bridge by about

Jan 1, 1946

Wartime geological studies by the U. S. Geological Survey and subsequent drilling carried on by the Bureau of Mines disclosed new ore in the Illinois-Wisconsin zinc field. As a result, several companies are carrying on drilling programs to locate and define new ore bodies. The Vinegar Hill company, which operates a custom mill to handle ores from various sources, now employs about fifty men in production at their Andrews mine. The ore is usually found in a 200-ft horizon below the surface. Water problems are not serious. Commercial-grade ore ranges up to 8 and 9 per-cent zinc and the cut off is approximately 41/2 percent.

Jan 1, 1948

By Geo. Otis Smith

Twelve years ago, the Director of the United States Geological Survey addressed to the Secretary of the Interior a letter calling attention to the government's need for liquid fuel for naval use and pointing out that the rate of increase in demand was more rapid than the increase in production.' This letter, in a way, inaugurated the policy of public oil-land withdrawals, which was well founded in its primary purpose of protecting the oil industry and highly desirable in its immediate effect of checking the over-development of that day in California. Unfortunately, however, through delays in legislation, this policy may be regarded now as having outlived both its intent and its usefulness. In 1908, the country's production of oil was 178,500,000 bbl., and there was a surplus above consumption of more than 20,000,000 bbl. available to go into storage. In 1918, 10 years later, the oil wells of the United States yielded 356,000,000 bb1.—nearly twice the yield of 1908—but to meet the demands of the increased consumption more than 24,000,000 bbl. had to be drawn from storage. Nor is this all of the brief comparison. In 1918, our excess of imports over exports of crude petroleum was nearly 33,000,000 bbl. whereas in 1908 we exported 3,500,000 bbl., which was net, as we had not begun to import Mexican oil. In this period, the annual fuel-oil consumption of the railroads alone has increased from 16,871,000 to 36,714,000 bbl.; the annual gasoline production from 540,000,000 gal. to 3,500,000,000 gal. This record may be taken not only as justifying the earlier appeal for Federal action, but as warranting deliberate attention to the oil problem of today. Need of Future Supply The position of the United States in regard to oil can best be characterized as precarious. Using more than one-third of a billion barrels a year, we are drawing not only from the underground pools but also from storage, and both of these supplies are limited. In 1918, the contribu-

Jan 1, 1921

By Jacques Steininger, Robert E. England

Single crystals of ZnTe and ZnTe1-,Sex with x up to 0.13 have been grown from the elements by temperature gradient solution zoning using excess tellurium as a solvent. Best results have been obtained with charges with the compositions 45/55 at. pct Zn, Te, for ZnTe and increasing amounts of selenium for ZnTe1-xSex. The temperature in the molten zone was maintained at about 1070°C with a gradient of about 10°C per cm. Chemical analyses of quenched ZnTe ingots show tellurium concentrations in the molten zone as high as 70 pct with concentration differences across the zone of 1 to 2 at. pct Dark dots which are observed by transmitted light microscopy in as-grown crystals can be removed by annealing in zinc vapor at 900 C. INTEREST in wide band gap semiconductors has led to a new study of ZnTe and ZnTel-xSex crystal growth. ZnTe is the only II-VI compound with a wide band gap (2.3 ev) that can be made p type with low resistivity. Attempts to make it n type with low enough resistivity to be useful for p-n junctions have so far been unsuccessful.1 ZnSe has a band gap of 2.65 ev but can be made n type only. However, ZnTel-xSex solid solutions with x as low as 0.36 have been made both highly n and p type2 with a minimum band gap around 2.12 ev3 at room temperature and appear to hold the best promise for efficient injection electroluminescence in the visible. ZnTe has the lowest melting point of the zinc chal-cogenides (1295°C) and consequently attempts have been made to grow crystals from both the liquid and the vapor phase.4 Complicated apparatus is required for growth from stoichiometric melts because of the high vapor pressures of the elements at the melting point of ZnTe and because of the problem of quartz devitrification. Small crystals have thus been grown in high-pressure equipment by Fischer5 and by Narita et a1.6 with pressures of the order of 50 atm of argon to prevent excessive evaporation from the melt. Large crystals of ZnTe can be obtained by growth from the vapor phase4 but they often present numerous dislocations and inclusions. An improvement in the quality of vapor- grown ZnTe crystals was reported by Albers and Aten7 by equilibration of mixtures of small crystals with compositions lying on either side of the solid single-phase field at fixed temperature. The same technique was later applied by Aten8 to the growth of ZnTe1-xSex crystals with less than 1 pct inhomo-geneity. Because of the higher liquidus temperatures of the solid solutions and the high vapor pressure of selenium, previous attempts to grow ZnTel-xSex from the melt have been limited and unsuccessful.9 The phase diagram of the Zn- Te system is reproduced in Fig. 1, based on data from Kobayashi10 and Kulwicki.11 Carides and Fishher12 have reported lower liquidus temperatures on the tellurium-rich side, but their data would require confirmation. The liquidus temperature on the tellurium-rich side decreases rapidly with increasing tellurium concentration and the Te2 vapor pressure over the liquidus also decreases accordingly.'3 The decrease in liquidus temperature and vapor pressure therefore makes it possible to use conventional apparatus if there is a sufficient excess of tellurium in the melt. Single crystals of ZnTe have thus been grown by Kucza,14 in a modified Bridgman technique, from solutions containing up to 60 at. pct of Te by lowering unsupported quartz ampoules through a temperature gradient at about 1200°C. Under these conditions, the phase diagram indicates that the entire charge is initially molten. Crystal growth can therefore proceed by normal freezing and rejection of excess tellurium into the melt. The modified Bridgman technique has several major limitations. Because of the rejection of excess tellurium into the melt during freezing, the melt composition and the temperature at the growth interface vary continuously. They tend to follow the liquidus until the eutectic which is very close to pure tellurium (447°C, >99 pct Te). Since the solidus composition also varies with temperature,15 crystals grown by this method are inhomogeneous. They present small variations from stoichiometry which may affect their structure and physical properties. The simultaneous increase in tellurium content and decrease in melt temperature also combine to reduce the rate of diffusion of tellurium away from the growth interface, thereby causing constitutional supercooling and possibly dendritic growth. To minimize these effects, the initial melt composition is in practice kept relatively close to stoichiometry (less than 60 pct Te). This however limits the possibilities of operating at low temperatures and pressures. This paper describes a modified method of crystal growth by temperature gradient solution zoning (TGSZ) which is an adaptation of the temperature gradient zone-melting technique developed by pfann16 and of the traveling solvent method of Mlavsky and weinstein.I7 The TGSZ method now applied to the growth of ZnTe and ZnTel-xSex crystals is characterized by its very simple experimental arrangement and sample preparation technique. Unlike the modified Bridgman technique, there is no increase in the tellurium concentration in the melt and therefore it is possible to operate at lower temperatures and pressures. This method is also suitable for maintaining a constant temperature at the growth interface.

Jan 1, 1969

By J. A. Knox, R. M. Lasater, J. M. Tinsley

Chemical squeeze treatments have been used to provide temporary relief from certain production problems. The chemical fracture-squeeze technique, combining the effects of a fracturing treatment and a squeeze operation, has been more successful than conventional squeeze operations. Knowledge derived from well stimulation and reservoir engineering research provides a means for predicting the theoretical effective life of such a treatment. Analysis of theoretical equations and concepts developed allows selection of improved treatment techniques based on specific formation conditioins. Theory used in this analysis was developed as an extension of previous electrical model studies made to establish the expected flow and pressure profiles adjacent to a fracture system. The chemical fracture squeeze technique can be utilized in the economic application of corrosion inhibitors, emulsion breakers and paraffin and scale inhibitors. Application of this technique is shown to be effective. The slow return rate of injected chemicals, controlled by the resultant flow profiles and treatment variables, permits extended periods of chemical effectiveness. Results of field treatments are given, showing that the concepts outlined above for chemical fracture-squeeze treatments are valid and that applying this technique can help alleviate many current production problems. INTRODUCTION Much progress has been made in the last 10 to 15 years in developing chemicals for use in stimulating wells, maintaining production and protecting well equipment from damage due to corrosion. Not too many years ago, some wells seemed to dry up or wear out. In many cases the wells were produced as long as possible without any attempt at maintaining productivity. Even with the advent of new and better stimulation techniques, a rapid decline in production was observed. Methods of removing and, in some instances, preventing damage have been developed. Among thosc factors responsible for uneconomical production are scale, paraffin, corrosion, bacteria, water blocks and emulsions. Soluble scale-prevention chemicals have been developed1,2 that can be placed in a formation along with frac- turing sand. As the water produces back across this bed, the solid material dissolves slowly and can provide long-term protection from scale. However, bottom-hole temperature and salinity of produced water vary widely and both these factors influence the rate of solubility. Scale inhibitor composition is also a controlling factor. Some of the solid material may be crushed, increasing the surface area exposed to water and increasing the rate at which it dissolves. Some of the material may never be contacted by water and can be lost. However, this type of treatment has been very successful in many instances and has helped maintain economical production for extended periods of time. Liquid scale inhibitors, which are more widely applicable and more stable, have been developed in recent years; however, because they are liquids, their use has been restricted to treatment down the annulus, using metering pumps to provide proper concentrations in the produced fluid. This has prevented use in wells containing packers, in dually completed wells and in gas-lift and flowing wells. Wells that operate with an open annulus may also experience severe corrosion problems due to introduction of oxygen. Paraffin inhibitors3 have been developed that can be fractured into a well as particulate solids to be slowly dissolved in the produced fluid. These materials are not usually effective in wells with a bottom-hole temperature in excess of 120F since solubility rate may be too fast if that temperature is exceeded or if aromatic content of the oils is unusually high. Corrosion inhibitors have been developed that can be fractured' into a well for long-term feedback, but development of a material with proper solubility or feed rate has been difficult. Corrosion inhibitors are available in many different forms. Liquids have been lubricated down the annulus or sticks or pellets dropped down tubing. Inhibitor squeeze treatments5 devcloped a few years ago led to development of inhibitors with particularly strong film-forming properties.6,7 This technique basically involves displacing a highly concentrated solution of the inhibitor into the formation through the tubing. Kerver and Hanson8 studied the adsorption properties of inhibitors on various types of formations. They showed that, even though the inhibitor was displaced radially into the true permeability, it could be produced back for a long period of time because of slow desorption from the rock. Methods developed for monitoring the return of these inhibitors generally have established 1 to 6 months as the effective limit before retreatment is necessary.9 Inhibitors displaced into the interstices of the formation sometimes cause emulsions that either hamper production or cause treating problems on the surface.

By R. Kossowsky

In the course of a study concerned with structural stability of precipitation hardening nickel base super -alloys after exposures to elevated temperatures, some interesting effects of hydrostatic pressure treatment on Rene were observed. The evidence presented below suggests that hydrostatic pressure treatment of the solution heat-treated alloy can affect the dispersion of the y' (Ni3Al) phase upon subsequent precipitation heat treatment and long time aging. Rene 41 alloy has the following nominal weight percent composition: Al B C Co Cr Fe Mn Mo Ti Ni 1.4 0.006 0.7 11.3 19.2 1.0 0.05 9.4 3.3 balance The effect of successive pressure, precipitation heat treatment, and long time aging on the microstructure of this alloy was determined by subjecting a number of alloy buttons to five different thermopressure treatments. Pressure and precipitation heat-treatment parameters are listed in Table I. Fig. 1 shows y' morphology* of specimens in groups I and 11. The treatment results in a fine dispersion with particle size on the order of 950 and 1350A, respectively, see Table I. Fig. 2 shows the morphology of y' precipitate in

Jan 1, 1967