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By R. W. Raymond

(Cleveland Meeting, October, 1912.) UNDER the names of Conservation, Social Justice, the New Nationalism, and Progressive Democracy, many earnest reformers are calling for a new system of Federal government to replace the one which they ascribe to our fathers, and declare to have been outgrown. They are proposing the lease by the United States of certain natural resources on the public domain, for the profit of the U. S. Treasury, instead of the sale of such resources to private citizens or associations of citizens. In the present paper, I shall try to show that this notion is neither new nor good. It is clear that the United States is owner, as well as sovereign, of public lands acquired through conquest or purchase from other nations, as it was owner of the public lands expressly ceded to it by the original thirteen States. Its policy with regard to such lands involves, therefore, two entirely distinct questions: What shall it do as owner ? and, What shall it do as sovereign ? The latter question, it must be confessed, has played but a small part in our history. All the prerogatives of sovereignty which were not explicitly conferred upon the Federal government by the original States were retained by them. The ownership or control of precious or other metals or minerals in the earth, for instance, was thus reserved to the several sovereign States. New York, South Carolina, and other States have passed laws on this subject, without regard to Federal authority. As new States have been successively admitted to the Union, the tacitly accepted theory has been,. that they thereby acquired all the reserved rights of the original States. These newer States largely outnumber the first. thirteen; and it is inconceivable that they would submit to any deprivation of sovereignty based on historical grounds. One of them-Texas-came into the Union by its own voluntary

Oct 1, 1912

By Tong Guangxu

INTRODUCTION Throughout the world, the caving mining methods of ore-draw under the overlying waste rock are sublevel caving in Sweden, block caving in U.S.A. and forced block caving and sublevel caving with sill-pillar in U.S.S.R. These caving methods are of high efficiency, low cost and large production (especially the block caving method) when compared to opencast mining. From the ore production of all under- ground mines, the largest annual production of underground metalliferous mines in the world is caving methods. The sublevel caving in Kiruna Iron Mine of Sweden has reached annual ore production over 20 million tons in 1974. The block caving in Climax Molybdenum Mine and San Manuel Copper Mine of U.S.A. both have produced about 40 thou- sand tons of ore per day in 1971. At the same time, the productivity of Kiruna was 12 thousand tons of ore per man-year, Climax 42.8 tons (48.3 short tons) per man-shift and San Manuel 29.01 tons (32.1 short tons) per man-shift. The main feature of this group of mining methods is the underground extraction of ore from beneath overlying caveable waste rock. Since the loss and dilution of ore are inherent (sometimes to a great extent), the control of ore-draw in these methods as com- pared with other methods is very important. Consequently, concerned Universities and Research Institutes have devoted great amounts of research on ore-draw theory and control management which has provided positive results to mine production, and has apparently promoted the development of the caving methods. During 1979 in China, metalliferous underground mines accounted for 15.22% of the total iron ore produced, while also accounting for 56% of total non-ferrous production. According to the mining methods, sub level caving in the principal underground iron mines counted for about 56.74% of total principal underground iron mine production, but only about 1% of total non-ferrous underground mine production. Relative to forced block caving and sublevel caving with sill pillar, the Chinese non-ferrous under- ground mines estimated about 35% of total non-ferrous underground mine production from these two methods, mainly from the latter. From the trend of development of underground metalliferous mines in China, the percentage of production in caving will be increased in the future, especially in block caving and forced block caving which have already been given great attention in the mining circle. In these types of mining methods the ore is drawn from the stope under a large area of overlying waste rock, which complicates the basic regulation and control of ore-draw, but provides lower loss and dilution than sublevel caving. Because of these reasons, the Kiruna Iron Mine in Sweden is intending to change its sublevel caving by testing a sublevel shrinkage caving method and considering a large area of ore-draw beneath the stope as an advantage. Therefore, the basic regulation and control management of ore-draw under a large area, as practiced in China, will be discussed in this paper. BASIC REGULATION OF ORE- DRAW FROM CAVING STOPE The aim of studying ore-draw under a large area of overlying waste rock is to se- cure a planned draw schedule that guarantees a certain plane of interface between ore and waste rock, and controls the change of its shape in spatial position for reducing ore loss and dilution during the draw process. Presently, the ellipsoid theory is comparatively near the actual attitude of ore-draw from the cave. 1. Ore Drawn Out from Single Drawpoint Laboratory testing and practical experience all show that after a certain amount of ore has been drawn out from a drawpoint, its original shape in the stope before drawing is more or less similar to an ellipsoid, hence the name "draw ellipsoid." This draw ellipsoid is cut at the bottom by a horizontal plane corresponding to the raise of the drawpoint, and its volume can be calculated by the following formula:

Jan 1, 1981

By R. B. Adair, J. S. Browning

The laboratory batch and continuous flotation pilot plant tests demonstrated the technical feasibility of recovering high grade mica concentrates from weathered mica pegmatite ores of Alabama and Georgia. The research indicated that combinations of anionic and cationic collectors may be used effectively for flotation of fine size mica from weathered pegmatite ores. In continuous tests, concentrates containing 98.5% mica were obtained from the Georgia pegmatite ore; the Alabama pegmatite ore concentrates contained 98.4% mica. The recoveries were 91 and 89% respectively. INTRODUCTION The principal uses of fine ground mica are as a filler in wallboard joint cement, as a filler and surface coating for roofing, as an ingredient in paints, and in oil well drilling mud. The mineral has other uses in the manufacture of rubber, wallpaper, plastics, welding rods, electric insulation, house insulation, and textiles, and as an annealing agent in metal treatment. In recent years, more than 99% of the domestic mica produced has been scrap and flake mica (mica which does not meet specifications for sheet mica and is used for producing fine ground mica). There has been a continued increase in mica production for several years, the 1963 production of scrap and flake mica totaling 117,251 tons.1 Ground mica is obtained primarily by crushing and milling pegmatites and schists. To a lesser extent, mica is produced as a byproduct of kaolin washing and feldspar and spodumene flotation operations. The processes used in recovering mica by crushing and milling pegmatites are generally simple, consisting of various combinations of alternate roll crushers and trommel screens that separate the mica and gangue at screen sizes coarser than 6-mesh. As these processes are designed to recover only coarse mica, high losses in the plant rejects are common. Large tonnages of tailings from the crushing and screening plants have been accumulated in a number of areas. Methods for treating such products were developed by the Bureau of Mines in 1941,2 but have not been generally applied. More recently, mica flotation research has been completed and published by the Bureau of Mines.3 These methods required complete removal of 150- to 200-mesh materials from the flotation feed with consequent fine mica losses. Later, the Bureau of. Mines investigated methods for-recovering fine size mica from pegmatite ores after desliming sufficiently to remove clay materials, but not so drastically as to remove the fine sands. This report summarizes the results of these studies. The process developed was effective on pegmatite ores from two locations and should be applicable to the commercial treatment of other mica-bearing pegmatite ores and fine rejects that have been accumulated at various mica-milling operations. DESCRIPTION OF ORES The ores used in the investigation were obtained from the Dixie Mines, Inc., Heflin, Alabama, and the Ruberoid Corporation, Hartwell, Georgia. The sample from Alabama contained muscovite and quartz, with a high percentage of clay, and minor amounts of biotite, kaolin, limonite and tourmaline. The mica in the ore was essentially all minus 4-mesh in size and was free of attached mineral grains. The Georgia sample contained muscovite and quartz, with minor amounts of biotite, kaolin, and limonite. The mica in the ore, which was essentially all minus 4-mesh, was liberated. Petrographic analyses of the two samples are given in Table I. THE ANIONIC-CATIONIC MICA FLOTATION METHOD Previous investigators2,3 have reported that complete desliming of mica ores at 150- to 200-mesh was required prior to flotation with cationic collectors to obtain satisfactory selective separation of the mica from the other mineral components. Numerous tests were made at the Tuscaloosa Metallurgy Research Center to determine if some reagent combination could be used to selectively float finer size mica without complete desliming. The investigation led to development of a process using a simple reagent com-

Jan 1, 1967

By R. G. Jones, W. L. Kinney, R. E. Schilson, R. S. Wilson, G. A. Clark, H. Suralo

This paper discusses the results of the Fry conventional or cocurrent in situ combustion test, which was conduct-ed in a 3.3-acre inverted five-spot. The depth of the formation was between 880 and 936 ft; the oil had a specific gravity of 28.6° APl and a viscosity of about 40 cp at the reservoir temperature of 65°F. Preceding the combustion test, air injection tests were conducted which, in conjunction with geological studies, were used to evaluate the characteristics of the reservoir. Combustion was initiated on Oct. 13, 1961, with ignition being accomplished by a 40 kw electrical heater. The test phase of the project ended on Oct. 1, 1963. During the test, the average air injection rate was 1,520.-000 scf/D. Throughout the test, production of all fluids— gas, oil, and water—was monitored. Cumulative oil production credited to the project was 100,586 bbl. The cumulative air-oil ratio was 11,500 scf/bbl oil, and the oxygen uti1ization efficiency was 87 per cent. INTRODUCTION The Marathon Oil Co. conducted a successful in situ combustion test, beginning Aug. 22, 1961, at the Fry unit, Crawford County, 111. The purpose of the project was to test the feasibility of cocurrent in situ combustion as a means of oil recovery in the Fry type reservoir. Interest in in situ combulstion as an oil recovery tool has been stimulated mostly by the existence of large reserves of heavy viscous crudes with low expected recovery, usually less than 10 per cent. These are the so-called unrecoverable reserves, and most combustion tests to date have been conducted in this type of reservoir.1-4 In contrast, the Fry combustion test was conducted in a reservoir with a relatively high gravity oil having a relatively low viscosity. This paper discusses the performance of the test. The geology of the reservoir and the field operations are discussed in separate papers.5 TEST SITE The Fry combustion test was carried out in a 3.3-acre inverted five-spot portion of a lenticular body of Robinson sandstone. Net sand was 50 ft thick, porosity averaged 19.7 per cent, oil saturation was 68 per cent of pore volume, and water saturation was 20 per cent of pore volume. The oil in place was estimated at 1,040 bbl/acre-foot, or 171,600 bbl within the 3.3-acre pattern. The water in place was 326 bbl/acre-foot, or 53,800 bbl. The oil has a specific gravity of 28.7° API and a viscosity of 40 cp at the reservoir temperature of 65°F. AIR INJECTION PERFORMANCE Air injection took place in two phases, the phases separated by ignition of the reservoir. In the pre-ignition phase, air injection tests were conducted in the summers of 1960 and 1961. These indicated that the Fry reservoir was confined, and a high return rate of injected air could be expected. This proved to be an outstanding characteristic of the project, as cumulative gas production was 95.3 per cent of the air injected. The difference between the cumulative air injected and the total gas produced can be largely accounted for by the quantity of air stored in the reservoir. An estimated 16 X 10 cf of air remained in the burned-out portion of the reservoir and an indeterminate amount of gas was stored in the unburned but pressurized reservoir. Hence, a complete material balance of gases would account for nearly 100 per cent of the air injected. At times during the test, the daily gas production rate was 98 per cent of the daily air injection rate. Fig. 1 presents the air injection history of the Fry com-

Jan 1, 1966

By Donald A. Brobst

The minerals barite (BaSO4 barium sulfate) and witherite (BaCO3 barium carbonate) are the chief commercial sources of the element barium and its compounds whose many uses are nearly hidden among the technical complexities of modern industrial processes and products. Barite, the major ore mineral, is extremely vital to the petroleum industry which in 1973 consumed at least 80% of the world's produc¬tion of 4.4 million tons as a major ingredient of the heavy fluid, called mud, that is circulated in rotary drilling of oil and gas wells. The re¬maining 20% of the barite production was consumed chiefly in the manufacture of barium chemicals and glass and as a pigment, filler, and extender. Barite occurs throughout much of the world and is available from three major geologic types of deposits-vein and cavity fill¬ing, residual, and bedded-in sufficient quantity at competitive prices to meet current demands. The world's demand for barite is expected to increase, and geologic circumstances are favor¬able for the discovery of new deposits of com¬mercial value. Witherite is much less common and abun¬dant than barite, although it is more desirable in many ways as a raw material for the pro¬duction of barium chemicals. The United States has not produced witherite since about 1950; England is currently the chief producer of witherite. End Uses Most of the world's barite production since 1926 has been used as a weighting agent for the muds circulated in rotary drilling of oil and gas wells. The muds fundamentally are mixtures of water, clay, and barite in different proportions that vary according to local reservoir condi¬tions. Muds with a specific gravity as great as 2.5 are used. The mud is pumped down the hollow drill stem, passes through the bit at the bottom of the hole, and rises to the surface in the space between the drill stem and the wall of the hole. In the course of this circulation the drill bit is cooled, cuttings are removed, the drill stem is lubricated, the walls of the hole are sealed, and the hydrostatic head of the column of weighted fluid helps to confine high oil and gas pressures. The latter feature aids in prevention of gushers, thus reducing both environmental pollution and waste of oil and gas resources as well as conserving the natural reservoir pressure for greater production and rate of recovery of the products contained in the rocks. Barite is particularly well suited for drilling mud because it is clean, easy to handle, soft (nonabrasive), heavy, virtually inert chemi¬cally, and relatively inexpensive compared to many other available heavy materials. Barite is used in the manufacture of glass in continuous tanks. The addition of barite ho¬mogenizes the melt and gives greater brilliance and clarity to the finished glass. Ground barite, both unbleached and bleached by sulfuric acid, is a common industrial filler, extender, and weighting agent. The rubber in¬dustry is a major consumer of barite as a filler. Barite also is added to bristolboard, heavy printing paper, playing cards, rope finishes, brake linings, clutch facings, plastics, and li¬noleum, to name but a few uses. Bleached barite has long been an extender in white lead paint because of its weight. The low index of refraction of barite, however, makes its ability to cover marks poorer than some other sub¬stances, but its low capacity for absorption of oil is a good feature. Off-color or unbleached barite can be used as a filler in colored paints. In the construction industry, some lump barite is used in concrete aggregate to weight down pipelines buried in marshy areas and to shield nuclear reactors. Because barite absorbs gamma radiation well, its use reduces the amount of expensive lead shielding otherwise

Jan 1, 1975

By R. E. Ogilvie, J. I. Goldstein

The a and y solubility limits in the Fe-Ni phase diagram have been redetermined at temperatures above 500°C. Both a diffusion-couple and a quench and anneal technique were used. The solubility limits were measured with an electron-probe micro-analyzer. The nickel concentration at the phase boundary is increased below 700°C and the a solid-solubility range is much larger than had been previously measured. The solubility limits are also extrapolated to 300°C. It is suggested that the solubility of nickel in a FeNi reaches a maximum in the temperature interval 400o to 500°C. THE equilibrium diagram has been of great use in the field of meteoritics, where the phase relations between kamacite (a) and taenite (?) in metallic meteorites can be described by means of the Fe-Ni diagram. The study of metallic meteorites by electron-probe microanalysis has cast some doubt on the accuracy of the presently available Fe-Ni diagrams.1, 2 Recent thermodynamic studies of the Fe-Ni system also suggest that the diagram may be in error.3 For these reasons the high-temperature (800o to 500°C) part of the diagram was redetermined. INTRODUCTION The currently accepted Fe-Ni diagram is that of Owen and Liu.4 Above 910°C, there is a region of complete solid solubility, ? (fee). Below 910°C, the a (bee) phase is stable in pure iron. The effect of increasing amounts of nickel is to stabilize the y phase. The phases that form when Fe-Ni alloys are heated or cooled bear little relation to the equilibrium diagram. If an alloy is cooled from the y state and held at a temperature within the a + y field, no evidence has been found for the occurrence of the y - a transformation.5 If the alloy is cooled to low enough temperatures the y phase breaks down into a supersaturated bee phase called a2. In fact, in alloys over 27 pet Ni the y phase is retained at room temperature.6 The a, phase has the same composition as the original y. The temperature at which a2 forms, the M, temperature, has been determined experimentally.' A state of equilibrium can be approached by cooling below M, to form a2 and then reheating the alloy into the two-phase region of the diagram. The y phase will then begin to precipitate out of the a2 phase and grow. The growth of the phase, however, is quite slow. Using the interdiffusion coefficients -Da of Goldstein et al.,8 it is estimated that it takes about 1 year to grow a 10-µ-wide region of ? at 700°C in a 5 pet Ni alloy. Owen and Liu4 used the technique just described to form the equilibrium phases. The phases present were determined by means of X-ray analysis. The accuracy of their diagram depends on the number of alloys available near the phase boundary at a given temperature. In this study two different techniques were used to determine the a/a + ? and ?/a + ? solubility limits. The inherent accuracy of both techniques was greatly improved over that used by previous investigators because the phase-boundary compositions were measured with an electron-probe microanalyzer. PROCEDURE The two methods used to determine the Fe-Ni diagram are the diffusion couple (D.C.) and the quench-and-anneal (Q.+A.) techniques. In the first method, diffusion couples whose diffusion path goes through a two-phase region of the phase diagram were used. A description of the technique used for making the diffusion couples has been described in a previous paper.' After the diffusion treatment a discontinuity in the resultant concentration vs distance profile was measured. The nickel concentrations in the a and ? phases at the interface of the discontinuity are the solubility limits of the a and ? phases in the phase diagram at the diffusion temperature. If the interface com-

Jan 1, 1965

By R. Simon

The sources of energy dissipation for concentrated loadings on rock are considered in an attempt to account for the experimentally measured magnitude of the work required to break out a unit volume of rock from the free surface of an essentially semi-infinite medium. It is concluded that most of this work probably represents the elastic strain energy developed by the loading in a much larger volume of rock beneath the loaded region than the volume of the rock fragment broken out to the side of the loaded region. This strain energy is largely dissipated in the form of stress waves generated by the high rate of unloading produced by the propagating cracks. The energies associated with the formation of the new surfaces of the cracks and with the stress waves generated directly by the loading process are computed to be negligibly small. Possibilities for improving the utilization of energy to drill rod. subject to the geometrical limitations imposed by down-hole operation, are discussed. It is pointed out that any such possible improvements would probably have to be differential ones, since each rock configuration of more favorabIe loading geometry that can be created down the hole is accompanied by a complementary configuration of less favorable loading geometry. INTRODUCTION Dislodging each cubic inch of rock from the bottom of the hole by the action of a bit requires the expenditure of an amount of energy that varies from approximately 5,000 in.-lb to approximately 100,000 in.-lb, depending on the hardness of the rock, or, more technically, upon its fragmentation strength.1 In this paper we will discuss (I) why the energy expended in drilling is so large, (2) what happens to this energy upon completion of the drilling process, and (3) what are the possibilities for reducing the magnitude of the energy required to drill rock. DETERMINATION OF ROCK DRILLING ENERGY The volume of rock removed per unit time from the bottom of a hole of diameter D is evidently (7/4)D2R, where R is the rate of penetration of the bit. If P is the rate at which work is done by the bit on the rock at the bottom of the hole, the energy required to break out a unit volume of rock is given by: Ev =(4/p) P/D2R............(i) For rotary drilling, of either the rolling-cone or drag-bit varicty, P = 2pLN, where L is the torque resistance to rotation at the bottom of the hole and N is the rate of rotation of the bit. L is essentially the same as the torque measured at the rotary table only when drilling in shallow holes. The energies expended in rotating the drill string against the frictional resistance of the walls of the hole and and against the viscous drag of the drilling fluid are extraneous to the subject under consideration, although these may be much greater in magnitude than E, when drilling in a deep hole. For percussion drilling, P = fE where f is the percussion frequency and E is the work done on the rock per impact. The latter quantity can be both computed and measured for a percussion drilling machine. 2 (Under satisfactory drilling conditions, defined in terms of ranges of numerical values of certain dimensionless parameters, E is only 30 to 50 per cent less than the impact energy of the striker.2) Alternatively, E, may be measured directly by dropping chisels shaped like bit edges, backed by rigid weights, onto the surfaces of laboratory rock samples of effectively semi-infinite extent. Under these circumstances, essentially all of the impact energy is converted to work done on the rock, and the relationships among volume of rock broken out, chisel shape, impact energy and indexing distances can be obtained.3 The values of the energy required to break out a unit volume of rock under favorable circumstances are substantially in agreement for rotary drilling, percussion drilling and drop testing at atmospheric pressure. The energy per unit volume is a quantity of the order of magnitude of roughly twice the com-pressive strength of the rock as measured by a uniaxial loading test. The phrase "order of magnitude" in this paper means from about 1/3 as much to 3 times as much; i.e., the energy per unit volume may range from roughly the same up to several times

By John E. O’Rourke, Kevin M. O’Connor, Pamela H. Rey

INTRODUCTION The resurgence of coal mining activity in the United States, brought on by the spiraling costs of fossil fw1 energy in the Seventies, has come at a time of intense public concern for the quality of the environment. Notwithstanding pressure on our economy to develop alternate sources of fue1 energy to the import of oil, the legislatures of several states have reacted to public concern over the environment by passing strict regulations aimed at con- trolling the subsidence effect s of underground mining. Agencies of the federal government charged with assistance to the mining industry, including the Department of Energy and the Bureau of Mines, have sponsored a number of instrumentation and field measurement projects aimed at the development of subsidence prediction models that can aid the mine operator's task of subsidence control. There are good empirical models developed in Europe for subsidence prediction, but they were made possible by a large body of mining-induced subsidence data collected there over a long period of time. No com- parable subsidence data base exists in the United States, and consequently empirical modeling of subsidence is not a realistic approach for our near term needs. Moreover, the geologic and topographic diversity of the several coal regions in the United States is expected to necessitate the development of several empirical models, each one expected to be relevant to its own region. Because of the time and costs that are likely to be involved in an empirical modeling approach, it is considered more expedient and cost effective to develop a general, mechanistic model for subsidence prediction purposes. In order to develop such a model, it is necessary to investigate and quantify the mechanics of the subsidence process from the mine level up to the ground surface. The series of projects discussed in this paper are designed to achieve this objective and include the following work: (1) the identification of geotechnical instrumentation that will pro- vide mine level overburden and surface subsidence data. (2) a field demonstration of selected instruments, and (3) documentation of case histories for complete subsidence mechanics, using the demonstrated and preferred instruments. An identification of feasible instrumentation and monitoring techniques was completed by Woodward-Clyde Consultants (WCC) in 1977 (O'Rourke and others). This paper discusses a demonstration of those instruments at a mine in Utah, and at two subsequent projects, currently underway at longwall mines in Colorado and West Virginia. 'he latter two projects when complete will provide documented case histories of subsidence mechanics. The process of optimizing subsidence instrumentation and monitoring techniques to the conditions encountered during installation and monitoring for these underground mines is shown to be an evolving one, and one which has had some notable successes to date. INITIAL DEMONSTRATION The initial design and demonstration of selected monitoring systems was carried out at the SUFCO No. 1 mine, near Salina, Utah. The instrumented panel was approximately 152 m wide. 640 m long. and was 290 m to 320 m deep. The mined height of coal. seam averaged 2.4 m. The mining method was room and pillar using continuous mining machines. This method allowed some monitoring of the supported condition during development, and eventually allowed monitoring of a caved system when both chain pillars and room pillars were extracted on retreat. The two instrument systems shown on Table 1 were selected from the earlier feasibility report for demonstration at SUFCO No. 1. Collectively, the two systems, one for a fully-supported mining method and the other for a fully-caved method, incorporate most of the instrumentation to be found within all five systems listed in the earlier feasibility report. The instrumentation includes surface, subsurface and mine monitoring installations. All of the SUFCO instruments selected to meet the specifications of the general instrument types listed on Table 1 were manually operated. That is, data from the installed system could only be obtained while a person was there to physically observe or operate the system readout. Automatic data recording equipment was available for some installations, but the objectives were to keep the systems as simple as possible for the demonstration project. A complete description of the surface, sub- surface and mine level instruments, and the demonstration project results are given in WCC (1982), and selected features are discussed in this paper.

Jan 1, 1982

By John Riegle

To date. utility company underground storage of gas has generally been restricted to depleted dry gas fields. The Playa del Rey project is probably the first to successfully store gas in a partially depleted oil reservoir with the recovery of large volumes of pas at high rates as the main objective. Oil recovery has been a secondary consideration. Problems encountered unusual to those of storage in a dry gas zone were: (1) the removal and retardation of formation of emulsion. (2) the upstructure movement of fluid during withdrawal periods which formed fluid blocks, and (3) reservoir shrinkage resulting from encroachment of edgewater. The solution of these problems as outlined in the paper has resulted in increasing the withdrawal rate from the original design capacity of 4,000 Mcf per hour to the current 10.000 Mcf per hour. Additional increase is anticipated as the operations continue. Migration. reservoir performance. operational procedure and a historical record are included to make this a resume of the project from its war-time inception in 1942 to the first of 1952. INTRODUCTION The Playa del Rey underground gas storage project is probably the first project in which gas has been stored in a partially depleted oil reservoir, with the recovery of large volumes of gas at high rates as the main objective and the recovery of oil a secondary consideration. Problems unusual to those of storage in dry gas zones have made this a pioneer endeavor. The total storage capacity of approximately 1,500,000 Mcf of this reservoir is small in comparison with other underground gas storage projects. However. by study and experiment the deliverability into transmission lines. operating at pressures in excess of 150 lbs., has been nearly tripled in the past three years. to the current 10.000 Mcf per hour late, without the use of compression. It is anticipated this rate will gradually increase as additional fluid is removed from the formation. LOCATION AND HISTORY Playa del Key is located on Santa Monica Bay about two miles south of the beach commuity of Venice and 15 miles southwest of the renter of the City city Los Angeles. Fig. 1. The discovery well was completed at 6,194 ft in 1929. An upper zone at 3,905 ft was found on June 18. 1930. Townlot development was very rapid and by the end of 1930 there were 141 producing wells in the field. The Union Oil Co. completed a lower zone well south of the Townlot Field in May, 1931, which was believed to be an extension, until additional drilling of about 50 wells during 1934 and 1935 indicated this area to be a separate accumulation as shown on Fig. 2. The lower oil horizon, which is now the storage zone, had no original gas cap and is believed to be a continental detrital deposit of conglomerate that accumulated in valleys and depressions of a weathered schist high. which later subsided and was overlain by an impervious nodular shale. This type of formation has rapid variation of porosity. permeability and thickness due to lack of sorting action common to marine deposition. and the uneven surface of the original schist high. Production was limited on the upstructure sides by the pinching out of the conglomerate, and downstructure by edgewater. Unrestricted production, together with high permeabilities, led to large wastage of gas from this new area as facilities were not available for transport of gas to market. The decline was very rapid and by 1942 the portion of the new area south of Ballona Creek was nearly depleted. ACQUISITION OF PROPERTY The rapid increase in industrialization of Southern California during World war 11 forced upon the local gas com-

Jan 1, 1953

By Francis R. Conley, John A. Sievert, John N. Dew

A brief review is presented of the past performance of a number of large, thin, highly permeable reservoirs with low dips in the Bolivar Coastal fields of Venezuela. The performance of these reservoirs indicates that the fluids are segregated vertically within the sand section by gravity. With this assumption, equations are developed which describe the performance under pressure maintenance operations. Methods of solving these equations and results of simple example calculations are presented. Example calculations indicate that under pressure maintenance conditions injected gas tends to {tow preferentially along the top of the sands and that encroaching water has a tendency to flow preferentially along the bottom. The expected performance of segregated fluids is discussed and compared with that of fluids which are uniformly distributed in any sand section. INTRODUCTION The field performance of a number of reservoirs described herein indicates that the fluids are segregated vertically within the sand section by the force of gravity. Thus, it was felt that any method used to predict the future performance of these reservoirs should consider the effects of segregation in the sand sections. A study of the available information on some of the reservoirs suggests that increased recoveries may be expected if the reservoir pressure is maintained by either crestal gas injection or flank water injection. To predict future performance of reservoirs under pressure maintenance operations, a method of analysis was needed which would account for segregation of fluids in the sand sections. Several methods of analysis have been developed to take into account the segregation of fluids in the reservoir as a whole1,3 To our knowledge no method considers segregation of the fluids within sand sections in the manner indicated by the past performance of several reservoirs in the Mara-caibo Basin. This paper outlines part of the work done in studying some of these reservoirs and contains a description of their performance characteristics. The analysis presented is restricted to pressure maintenance conditions, since space limitations prevent a full discus- sion of the development of the mathematical relations and the various methods of solving them. Only a sketch of the development of the mathematical relations is given. The various methods of solving these relations are pointed out, but the actual determination of solutions to various problems are omitted except for one example. It is felt that these results may aid in the study of reservoirs outside the Maracaibo Basin. Some concepts on which the present analysis is based are outlined by D. N. Dietz. However, the analysis presented herein includes several factors not considered by Dietz: (1) variations in permeability and in the cross section, (2) various shapes of the cross section, and (3) the production of fluids. Also, the mathematical development presented by Dietz differs considerably from our corresponding analysis. RESERVOIR CHARACTERISTICS The reservoirs under consideration, large and thin, with low dip and high permeability, are large to the extent that they contain from 0.5 to over four billion bbl of oil initially in place. The section thicknesses vary from 100 to 400 ft and the lengths from 10,000 to 40,000 ft. Thus, a length-wise cross section of the producing formation appears to be long and thin. The dip angles vary from 0 to 6 degrees and the average permeabilities vary from 0.5 to over three darcies. The reservoirs contain from 20 to 50 per cent shale inter-laminated with the productive sands. Most shale breaks within the major sands do not correlate from one well to the next, and correlation is often difficult, even between wells drilled from the same location. However, it is often possible to correlate the shale breaks between major sands for some distance. Herein we are concerned with the performance of reservoirs containing oil of gravities over 20" API. Past reservoir performance indicates good pressure communication and, in cases where pressure sinks have developed, large amounts of fluid migration have occurred. Few of the reservoirs have had initial gas caps, but also, few have been found to be highly under-saturated. Due to gravity segregation, secondary gas caps usually form before the pressure has been reduced more than 25 per cent of its initial value. The effect of gravity has not only been apparent on a reservoir-wide basis, but has also caused segregation of the reservoir fluids in productive sections. Proof of this is found from the results of selective well tests, workovers, and electric and various other types of logs. Evidence that

By Nicholas J. Grant, John S. Benjamin

A series of composite alloys containing a high volume of NiAl, Ni3Ah or CoAl, bonded with 0 to 40 vol pct of a ductile metal phase, were prepared by powder blending and hot extrusion. The binder metals were of four types: pure nickel or cobalt, near saturated solid solutions of aluminum in nickel and cobalt, type 316 stainless steel, and niobium. Sound extrusions were obtained in almost all instances. Studied or measured were the following: interaction between the alunzinides and the binders, room-temperature modulus of rupture values, 1500° and 1800°F stress rupture properties, hardness, structure, and oxidation resistance. Stable structures can be produced for 1800°F exposure, with interesting high-temperature strength and good high-temperature ductility. Oxidation resistance was excellent. A large number of experimental investigations have been made of the role of structure on the properties of cermets and composite materials. Gurland,1 Kreimer et al.,2 and Gurland and Bardzil3 have indicated the preferred particle size in carbide base cermets to be about 1 µ, with a hard phase content of 60 to 80 vol pct. The optimum ductile binder thickness was noted to be 0.3 to 0.6 µ.1 Complete separation of the hard phase particles by the binder is important in reducing the severity of brittle fracture.' The purpose of the present study was to produce structures comparable to the conventional cermets, using a series of relatively close-packed intermetal-lic compounds rather than carbides as the refractory hard phase, and to study the effects of binder content and composition on both high- and low-temperature properties. The selected intermetallic compounds were particularly of interest because of the potential they offered in yielding room-temperature ductility. The highly symmetrical structures are known to possess high-temperature ductility and room-temperature toughness. Based on a ductile binder, the alloys were prepared by the powder-metallurgy route to avoid melting and subsequent alloying of the matrix, and were extruded at relatively low temperatures. It was expected that the composite alloy would retain useful ductility. In contrast, infiltration and high-temperature sintering led to alloying of the matrix and to decreased ductility. The systems Ni-A1 and Co-A1 were selected for this study. In the Ni-A1 system the compounds NiA1, having an ordered bcc B2 structure, and Ni3Al(?1), having an ordered fcc L12 structure, were chosen. In the system Co-A1 the intermetallic compound CoAl with an ordered bcc B2 structure was used. ALLOY PREPARATION The intermetallic compounds, see Table I, were prepared by using master alloys of Ni-A1 and CO-A1, with additions of either cobalt or nickel to achieve the desired compositions. The master alloy in crushed, homogenized form, was melted with pure nickel or cobalt in an inert atmosphere, cold copper crucible, nonconsumable tungsten arc furnace. The resultant intermetallic compounds were homogenized at 2192°C in argon, crushed, and dry ball-milled in a stainless mill to -100 and -325 mesh for the Ni-A1 compounds and to -325 mesh for the CoAl compound. Finer fractions were separated for some of the composite alloys. Several ductile binders were utilized. These included Inco B nickel, 5µ ; pure cobalt, 5 µ, from Sher-ritt Gordon Mines, Ltd.; fine (-325 mesh) niobium hydride powder; fine (15 µ) type 316 stainless-steel powder; and near-saturated Ni-A1 and Co-A1 solid-solution alloys, also in fine powder form. The niobium hydride was decomposed above about 700°C in processing of the compacts in vacuum to produce niobium powder. The Ni-7.1 pct A1 and the Co-5.3 pct A1 solid-solution alloys were prepared from pure nickel or cobalt and pure aluminum by nonconsumable tungsten arc melting under an inert atmosphere. The ingots were homogenized, lathe-turned to fine chips, and dry ball-milled in air to -325 mesh powder. These solid-solution alloys are designated NiSS and CoSS; see Table I. Subsequently the hard and ductile phases were dry ball-milled as a blend. Experiments clearly established the need to coat the hard particles with the ductile binder to optimize subsequent hot compaction by extrusion. Ordinary dry mixing usually resulted in nonhomogeneous alloys which were quite brittle. Conventional cermets are consolidated by liquid phase sinteiing or infiltration, which resulis in undesirable and uncontrolled alloying of the binder phase. For this study, a loose (unsintered) powder-extrusion process was emploved, minimizing reactions between binder and hard particle, thereby permitting much greater control of composition and structure. The constituent powders were first mixed in the desired

Jan 1, 1967

By E. Miller, J. M. Eldridge, K. L. Komarek

The thermodynamic properties of liquid Mg-Ge alloys have been determined between 1000°and 1500°K by an isopiestic method. Germanium specimens, heated in a temperature gradient and contained in covered graphite crucibles of special geometry, were equilibrated with magrtesium vapor in closed titanium tubes. The crucible design allowed free access of magnesium vapor to the samples during the equilibration to form alloys of magnesium and germanium, but prevented magnesium losses from the crucibles on quenching the titaniuin tubes to terminate the experimental runs, thus preserving the equilibrium alloy compositions. The activities and partial molar enthalpies of magnesium and the integral thermodynamic properties of the system were calculated from the experimental data. THE Mg-Ge phase diagram' shows one congruent melting compound, Mg2Ge, of essentially stoichio-metric composition, two eutectics, and very limited terminal solid solubilities. Very little information is available on the thermodynamic properties of the Mg-Ge system. The free energy of formation of Mg,Ge was recently deter-mined2 by a Knudsen cell technique in the temperature range 610° to 760°C. The standard enthalpy of formation of Mg,Ge was measured calorimetrically by Bever and coworkers.3 The present study was undertaken as part of a general investigation of the thermodynamic properties of the homologous series of Mg-Group IVB systems, i.e., Mg-Pb,4 Mg-Sn,5 Mg-Ge, and Mg-Si. An isopiestic technique was used which was developed by the authors5 for investigating the thermodynamic properties of liquid Mg-Sn alloys. Specimens of the nonvolatile component, contained in covered graphite crucibles, are heated in a temperature gradient in an evacuated and sealed titanium reaction tube, and equilibrated with magnesium vapor of known pressure. The method employs crucibles of special geometry which preserve the high-temperature equilibrium composition of liquid alloys having a highly volatile component such as magnesium on termination of the experimental runs by quenching the crucibles to room temperature. EXPERIMENTAL PROCEDURE First reduction germanium of 99.999+ pct purity (Eagle-Pitcher Co., Cincinnati, Ohio) and 99.99+ pct magnesium metal (Dominion Magnesium Ltd., Toronto, Canada) were used. The graphite crucibles were machined from high-density (1.92 g per cu cm) graphite rods (Basic Carbon Corp., Sanborn, N.Y.) which had a maximum ash content of less than 0.04 pct. The non-reactivity of graphite with germanium at the temperatures used in this study had been previously established by Scace and Sleck.6 The experimental procedure has been previously described in detail.5 The selection of a particular crucible geometry for a run was determined by a combination of imposed experimental conditions, the principle being that more tightly covered crucibles were required to preserve alloy compositions during quenching when higher magnesium pressures and higher specimen temperatures were used. Depending upon the composition range of the equilibrated alloys the source of the magnesium vapor was either pure magnesium or a two-phase mixture of Mg2Ge + Ge-rich liquid of known magnesium pressure. The experimental runs can be divided into the following three groups on the basis of crucible geometry and magnesium source material. Crucibles with Small Holes and Pure Magnesium Reservoirs. The crucible dimensions were identical to those of the Mg-Sn investigation5 except that the hole diameters were reduced to 0.010 in. because of the higher temperatures and higher magnesium pressures involved in the Mg-Ge system. During an equilibration run, magnesium vapor diffused from the reservoir to each specimen through the small holes, one drilled through the crucible lid and two others drilled through graphite baffles positioned vertically inside the crucible between the lid hole and the specimen. Since the magnesium pressure was high, i.e., in the range 117 to 277 Torr, during the equilibration time of approximately 24 hr, equilibration was not impeded by these holes. A specimen composition at equilibrium was fixed by the relative temperatures of the specimen and the reservoir, and by the thermodynamic properties of the system. Upon brine quenching the titanium reaction tube to end a run the vapor pressure of magnesium above the liquid alloys decreased exponentially with decreasing temperature, and the small cross-sectional areas of the holes (4.9 x 10"* sq cm) drastically reduced magnesium losses from the crucibles. Because of its low vapor pressure, germanium losses from crucibles during a run were at most 0.2 mg for pure germanium and correspondingly less for the alloys. This crucible geometry satisfactorily retained the equilibrium alloy compositions on quenching for magnesium-rich (from 3 to 33 at. pct Ge) alloys provided their temperatures were below the melting

Jan 1, 1967

By Donald B. Evans, Robert D. Pehlke

The solubility of nitrogen in liquid Fe-A1 alloys has been measured up to the solubility limit for formation of aluminum nitride using the Sieverts method. The activity coefficient of nitrogen decreases slightly with increasing aluminum content in the range of 0 to 4 wt pct Al. Based on a nitride composition, AlN, the standard free energy of formation of aluminum nitride from fhe elements dissolved in liquid iron has been determined to be: ?F" = -59,250 + 25.55 T in the range from 1600º to 1750ºC. The solubility of nitrogen in liquid iron alloys and the interaction of nitrogen with dissolved alloying elements in liquid iron have been the subject of a number of research investigations.' Most of this work, however, has been reported for concentrations well below those necessary for the formation of the alloy nitride phase. Data in the concentration region near the solubility limit of the alloy nitride, particularly for systems exhibiting stable nitrides, are important in evaluating the denitrifying power of various alloying elements. They are also useful in determining the stability of a given nitride if it is to be used as a refractory to contain liquid iron alloys. In view of the importance of aluminum as a deoxidizing agent in commercial steelmaking and the fact that its nitride, AIN, is a highly stable compound and has merited some consideration as an industrial refractory, the following investigation was undertaken. The use of the Sieverts technique provided a measurement of the equilibrium nitrogen solubility in liquid Fe-A1 alloys as a function of nitrogen gas pressure up to 3.85 wt pct A1 in the temperature range of 1600º to 1750°C. The values obtained by the Sieverts method were checked by means of a quenching method in which liquid iron was equilibrated with an A1N crucible under a known partial pressure of nitrogen gas, and the solubility of A1N in liquid iron determined by chemical analysis. EXPERIMENTAL PROCEDURE The theoretical considerations involved in determining the solubility product of a solid alloy nitride phase in liquid iron by measuring the point of departure of the nitrogen gas solubility from Sieverts law have been discussed by Rao and par lee.' The principal problem is to determine the variation of nitrogen solubility in an alloy as a function of the pressure of nitrogen gas over it with sufficient precision to establish the break point in the curve at the solubility limit of the alloy nitride phase. A fairly large number of data points are required to do this. A second problem is the determination of the composition of the precipitated solid nitride phase. This is necessary in order to define completely the thermodynamic relationships. The Sieverts apparatus used to make the nitrogen solubility measurements in this investigation is of essentially the same design as that described by Pehlke and E1liott.l The charge materials were Ferrovac-E high purity iron supplied by Crucible Steel Co. and 99.99+ pct pure aluminum. Recrystal-lized alumina crucibles were used, and were not attacked by the liquid alloys. The hot volume of the system which was measured for each melt ranged from 46 to 50 standard cu cm and was found to decrease linearly with decreasing pressure and with increasing temperature. The temperature coefficient of the hot volume at 1 atm pressure of argon gas was essentially constant for all experiments at a value of -6 X 10-3 cu cm per "C. The melt temperature was measured with a Leeds and Northrup disappearing filament type optical pyrometer sighted vertically downward on the center of the melt surface. The temperature scale was calibrated against the observed melting point of pure iron taken as 1536°C. The emissivity of all melts was assumed to be that of pure iron, taken as 0.43. The charge weights ranged from 110 to 140 g and the range of aluminum contents covered was from 0 to 3.85 wt pct. Aluminum additions were made as 12 to 15 wt pct A1-Fe master alloys previously prepared in the system under purified argon. The compositions of the master alloys were checked by chemical analysis and found to be in agreement with the charge analyses. Vertical cross sections of the master-alloy ingots were used as charge material for the equilibrations in order to minimize the effect of any segregation which might have occurred during solidification of the master alloys. Determinations of the solubility product of

Jan 1, 1964

By S. Nakajima, H. Okazaki

Quantitatiue studies of the deformation texture in drawn tungsten wives were made by the X-vay dif-fractottletetr. Experimental results show that the diffraction Intensities are equal to tilose pvedicted from the (1 10). fiber lexlure but the angxla), spreads of. diffraction peaks in the pole distribution curres are different for different diffraction planes and directions. For this reason a modified (110) fiber lextuve model, in which a kind of anisotropy is assumed, is proposed to explain the results. According to this model the poles lying on a line directing front the (110) to the (110) poles in the (1 10) standard stereograpllic projection should show spreads which are different from those lyitlg on a line directing from the (001) to the (001) poles, which is confirmed by the experiments. The anisolvopy and the spveads of the pole positions are large at the outer part of the wires and decrease gradually lowards the inside of the wire. The possibilily of occurrence of such anisolropy in irrelals with fcc stvuctures is discltssed. THE deformation texture of drawn tungsten wires has been assumed by different investigators to be the simple ( 110) fiber texture.' Recently, however, Leber2,3 has shown that a swaged tungsten rod has a cylindrical texture. It changes gradually to the (110) fiber texture by drawing through dies. However, even after drawing to 0.25 mm in diam, the cylindrical texture can still be found in wires together with the (110) fiber texture. This was deduced from the pole figures obtained from the longitudinal section of these wires. Use was made also of quantitative measurements of the pole distribution curves. Leber stated that the angular spread of the pole distribution curves (henceforward called dispersions) are quite different for (400) 45 deg and (400) 90 deg: the former is always larger than the latter. This inequality is accompanied by deviations of the diffraction intensities from the theoretical values for the ( 110) fiber texture. Bhandary and cullity4 have reported similar results on iron wire and explained them by assuming a cylindrical texture. Both Leber3 and Bhandary4 used only the results of the (400) reflection for the determination of the dispersion. The pole figures found by Leber3 and by Rieck5 are largely different. The model given by Leber to explain the effects is in the authors' opinion in some respects unsatisfactory, especially if one looks at other than the (400) reflections. Intensities and dispersions of diffraction peaks are conclusive factors for the determination of the fine structure in wire textures. For this reason we studied them extensively to come to a model which is more suitable to fit the facts. In the following, after giving the experimental set-up, we report about measurements of X-ray diffraction on drawn tungsten wires. Different models to describe the experimental results will be discussed. EXPERIMENTAL GO-SiO2-A12O3 doped tungsten wires drawn to 0.18 mm in diam were used for the measurements. The wires were chemically etched to various diameters down to 0.03 mm. Measurements were carried out for the different wires in order to determine the dependence of the texture on the radius. The wires were cut to pieces of 10 mm length and fixed with paste closely against each other on a flat, polished glass plate. Parallelism of the wires with the surface of the glass plate should be adequate. For the diffraction studies three different X-ray sources were applied, respectively, giving the CuK,, FeK,, and FeKp emission. The measurements were carried out with a diffrac-tometer with a GM counter. The latter was fixed to a certain diffraction angle 20hkl and the diffraction intensity was recorded as a function of the angle of rotation of the specimen around the axis, lying in the specimen surface and perpendicular to the wire axis, as shown in Fig. 1. Measurements were also done with the detector at angles slightly deviating from the diffraction maxima The measured intensities in this case were taken to be equal to the background level. The deviations were chosen as small as possible but large enough to eliminate the influence of the diffraction maxima. The useful range of the rotation angle x of the specimen is generally limited by the wavelength of the X-rays. We have: where and cp is the angle between the wire axis and the normal of the diffraction plane. Intensity measurements were made to find the necessary corrections for counting loss of the GM counter and for distortion resulting from such effects as absorption of X-rays and from inclination of the reflection plane under study with respect to the surface of the specimen. The counting loss was esti-

Jan 1, 1968

By Allan E. Martin, Harold M. Feder, Irving Johnson

The cadmium-uranium system was studied by thermal, metallographic, X-7-ay and sampling techniques; special emphasis was placed on the establishment of the liquidus lines, The single inter metallic phase, identified as the compound UCd11 melts peritectically at 473°C to form a-umnium and melt containing 2.5 wt pct uranium. The cadmium-rich eutectic (0.07 wt pct uranium) freezes at 320.6°C. Solid solubilities in uraizium and cadmium appear to be negligible. Between 473°C and 600°C the liquidus line is retograde. NO publication relating to the cadmium-uranium phase diagram was found in the literature. The establishment of this diagram was of considerable interest to us because of a possible application of the system to the pyrometallurgical reprocessing of nuclear fuels. Analysis of liquid samples, metallographic examination, thermal analysis, and X-ray diffraction analysis were used to establish the phase diagram from about 300° to 670°C. Particular emphasis was placed on the establishment of the liquidus lines. The same system was concurrently studied in this laboratory by the galvanic cell method.' Both studies benefited from a continual interchange of information. MATERIALS AND EXPERIMENTAL PROCEDURES Stick cadmium (99.95 pct Cd, American Smelting and Refining Co.) contained 140 ppm lead as the major impurity. Reactor grade uranium (99.9 pct U, National Lead Co.) was most often used in the form of 20-meshspheres. This form was particularly suitable because it does not oxidize as readily as finer powder. The liquidus lines were determined by chemical analysis of filtered samples of the saturated melts. The liquid sampling technique is described elsewhere2 alumina crucibles (Morganite Triangle RR), tantalum stirring rods, tantalum thermocouple protecthecadmiumtion tubes, Vycor or Pyrex sampling tubes, and grades 60 or 80 porous graphite filters were used. Uranium dissolves in liquid cadmium rather slowly. In order to achieve saturation of the melts it was necessary to modify the procedure of Ref. 2 by the use of more vigorous stirring and longer holding periods (at least 3 hr) at each sampling temperature. The samples were analyzed for uranium by spectro-photometry (dibenzoyl methane method) or by polar- ography. The analyses are estimated to be accurate to 2 pct. Thermal analysis was performed on alloys contained in Morganite alumina crucibles in helium atmospheres. Standard techniques were employed; heating and cooling rates were about 1°C per min. For the determination of the peritectic temperature, Cd-10 pct U charges were first held for at least 50 hr at temperatures in the range 435° to 460°C to form substantial amounts of the intermediate phase. For the determination of the effect of cadmium on the a-p transformation temperature of uranium, charges of Cd-25 pct U (-140+100 mesh uranium spheres) were first held near the transformation temperature, with stirring, to promote solution of cadmium in the solid uranium. The holding times and temperatures for these treatments were 18 hr at 680°C for the cooling run and 28 hr at 630°C for the heating run. Alloy specimens for X-ray diffraction and metallographic examination of the intermediate phase were prepared in sealed, helium-filled Vycor or Pyrex tubes. Ingots from solubility runs and thermal analysis experiments also were examined metallographically. Crystals of the intermediate phase were recovered from certain cadmium-rich alloys by selective dissolution of the matrix in 20 pct ammonium nitrate solution at room temperature. Temperatures were measured with calibrated Pt/Pt-10 pct Rh thermocouples to an estimated accuracy of 0.3°C. However, the depression of the freezing point of cadmium at the eutectic is estimated to be accurate to 0.05°C because a special calibration of the thermocouple was made in place in the equipment with pure cadmium just prior to the measurement. EXPERIMENTAL RESULTS The results of this study were used to construct the cadmium-uranium phase diagram shown in Fig. 1. This diagram is relatively simple; it is characterized by a single intermediate phase, 6 (UCd11), which decomposes peritectically, and which forms a eutectic system with cadmium. The solid solubilities in the terminal phases appear to be negligible. An unusual feature of the diagram is the retrograde slope of the liquidus line above the peritectic temperature. The Liquidus Lines. The liquidus lines above and below the peritectic temperature are based on three separate solubility experiments. The data are shown in Fig. 1 and are given in Table I. It is apparent from the figure that the solubility data obtained by the approach to saturation from higher temperatures fall on substantially the same lines as those obtained

Jan 1, 1962

By R. A. Wolfe, H. W. Paxton

Self-diffilsion coefficients for cr51 and Fe55 in 12 pct Cr-Fe and 17 pct Cr-Fe for Fe55 in chromium, and for Cr51 in vanadium have been measured. The results are compared with other values for the Fe-Cr system, and with the various theories of diffusion in hcc metals. Some empirical correlations are discussed between Do and Q in hcc systems, or, expressed differently, the constancy of ?G*/T solidus for seveval bcc metals and alloys is noted. It appears very probable that a vacancy mechanism is operative in bcc metals, hut this cannot he stated with certainty. THE great bulk of work on diffusion in metals, both experimental and theoretical, was for many years concentrated on those with close-packed and, in particular, fcc lattices.1,2 There appears to be little doubt that the mechanism of diffusion in these solids is vacancy migration, leading to mass transfer and in substitutional solid solutions to a Kirken-dall effect.3,4 For bcc metals, the picture is much less clear. The Kirkendall effect certainly occurs in several alloys.5-10 However, attempts to understand the factors contributing to the pre-exponential in the usual expression for the diffusion coefficient D =D, exp {-Q/RT) by extension of ideas useful in close-packed lattices have not always been successful. Zener,11 Leclaire,12 and Pound, Paxton, and Bitlerl3 have suggested that various forms of ring diffusion may be important in some bcc metals. For close-packed metals, Do is usually about 1 sq cm per sec and Q - 35Tm kcal per mole (Tm = melting temperature in OK). The theory of Pound et al. suggests for ring diffusion that Do may be about 10-4 and Q, although difficult to calculate with any precision, would be significantly less than 35 T,. The experimental results on self and solute diffusion in ? uranium14,15 and ß zirconium,10 and for solutes in 0 titanium,17 and possibly for self-diffu- sion in chromium below about 0.75 T,," gave some credence to this theory. However, not all bcc materials display low values of DO and Q, and the exceptions were not predicted by any theory. Furthermore, it has recently become apparent that, in bcc materials, log D is not always linear with T-l if a sufficiently wide range of temperature is studied.16,18 This variation may be such that Q may increase18,19 or decrease20 with increasing temperature. The present work was undertaken in an attempt to provide further diffusion data on bcc metals, and to try to understand the factors which contribute to differences in behavior between the various elements. For part of this work, the Fe-Cr system was chosen since it is of considerable technological importance, and data on 12 pct Cr and 17 pct Cr alloys appeared well worthwhile to supplement that existing for the remainder of the stern.18,22 The diffusion of Fe55 in chromium was studied as an example of a more or less "normal" tracer element in a possibly abnormal host lattice. Finally, no data were available for vanadium, the neighbor of chromium in the periodic table, because of lack of a suitable isotope so cr55 was used as a tracer in a few preliminary experiments. For convenience, we shall refer to elements whose Do and Q are low compared to those predicted by Zener's theory as "anomalous". PROCEDURE This investigation determined self-diffusion rates by means of radioactive tracers and the integral-activity method first utilized by Gruzin.23 In this method a thin layer of radioisotope of the diffusing element is plated or coated onto a planar surface of the diffusion sample, which is then given an isothermal-diffusion annealing treatment. The determination of an activity-penetration curve involves measuring the residual activity of the specimen after each successive layer or section has been removed parallel to the original planar surface. The method used here is essentially the same as that used by Gondolf18 and Kunitake.21 Two radioactive tracers, cr51 and Fe55, were used in this investigation. Diffusion coefficients were determined for the diffusion of one or both of these tracers in four different materials, viz., Fe-12 wt pct Cr alloy, Fe-17 wt pct Cr alloy, chromium, and vanadium. The diffusion samples had nominal dimensions of 1.5 cm diameter and 0.5 cm thickness. The grain size was several millimeters for the Fe-Cr alloys and at least 1 mm for the chromium and vanadium samples. Accurately planar surfaces

Jan 1, 1964

By A. S. Yue, A. G. Guy

A study was made of the effects of a prolonged flux of zinc atoms through the a solid solution of zinc in copper. The experimental arrangement consisted essentially of a copper disk about 0.01 in. thick, at one of whose surfaces a gaseous atmosphere containing zinc atoms was maintained, and at the other surface a gaseous atmosphere with a minimum of zinc atoms was maintained. During prolonged theothersurfaceexposure at high temperatures the zinc content of the copper disk gradually built up to the steady-state concentration distribution and then remained at this value. The concentration-distribution curves for various conditions were determined by chemical analyses. The results showed that the condition of steady-state diffusion was achieved. The diffusion coefficients calculated from the experimental data, although not of high precision, agreed with the values obtained by other workers using unsteady-state methods. Relatively slight porosity developed in the specimens in the course of diffusion. A LTHOUGH most diffusion studies have been made under unsteady-state conditions, it is known' that the steady-state method is often superior with respect to the directness and accuracy of interpretation of the data. Steady-state diffusion of gases through metal diaphragms is well known. Also, Harris' and Smith" have used the steady-state method in studying the diffusion of carbon in aus-tenite. The accepted mechanism in this system involves the motion of the interstitial carbon atoms in the rigid framework of the lattice of iron atoms. Thus, there is little difficulty in visualizing the steady flow of the small carbon atoms through the austenite. The situation in substitutional diffusion is quite different. Here the atoms are comparable in size, and it is not evident how a steady flow of one of the atoms through the solid solution might be achieved. At the time the present research was started, it was known that a previous exploratory attempt to produce steady-state diffusion in a substitutional alloy, the Au-Ag system,' had been unsuccessful and had indicated that perhaps there were basic difficulties that could not be ovei-come. Therefore, the present research began as a study of the effect of a prolonged flux of metal atoms through a substitutional solid solution. Eventua.lly, it was possible to produce actual steady-state diffusion in the system chosen for study, the a Cu-Zn alloys. Experimental Procedure The aim in the experiments was to maintain a high zinc content, about 30 pet, at one surface of a copper sheet, and to maintain a low zinc content, near 0 pet, at the opposite surface. The zinc would then diffuse into and through the copper, first building up to the steady-state concentration distribution and then maintaining this distribution. The three types of specimens that were used are shown in Fig. 1. In type A specimens the copper disk through which diffusion occurred was welded to the top of a cylindrical molybdenum tube, the bottom of which also was sealed by welding. At the diffusion temperature the brass chips in the molybdenum container were the source of the zinc vapor which maintained the lower surface of the copper disk at 30 pet Zn. The upper surface was maintained at 0 pet Zn by the vacuum in which type A, and also type B, specimens were diffused. Since the molybdenum container was impervious to zinc vapor, it was intended that the only path of escape for the vapor from the brass chips would be through the thin copper diffusion disk. However, it was found that small leaks often developed at the welded joints during the diffusion treatment, and in most specimens some of the zinc was lost in this manner. Although even small losses of this kind were a serious handicap in attempting to determine the flux through the disk, they did not prevent the maintenance of satisfactory boundary conditions for the attainment of the steady-state condition. Type B specimens differed from type A in having a weight of about 300 g supported on the copper disk by 15 to 20 short quartz rods. This change was made when it was observed that the copper disk was being bowed upward by the difference in the pressures acting on its two surfaces. Since the grain-boundary cracking which occurred in the bowed specimens could be attributed largely to the accompanying creep,3 it was desirable to minimize this effect. The counterweight was effective in significantly decreasing both bowing of the disk and cracking at grain boundaries. Type C specimens differed considerably from the others in that the low-zinc atmosphere at one sur-

Jan 1, 1959

By Y. A. Rocher, J. E. Dorn, L. A. Shepard

Creep activation energies for single aluminum crystals favorably oriented for shear by (010) [101] glide were detemined over the temperature range from 78" to 900°K. Observations of slip bands on the specimen surface were made in conjunction with the investigation. From 78" to 780°K, the activation energies obtained in this imestigation agreed closely with those previously found for creep by (111) [101] slip. Between 78" and 140°K, the activation energy was identified with the Peierls process, while between 260°and 780°K the activation energy was close to that for cross-slip. The coarse wavy slip bands nominally parallel to the (010) plane observed above 260°K were attributed to fine cross-slip. From 800" to 900°K, unusually high apparent activation energies ranging from 28,000 to 54,000 cal per mole were obtained. These apparent activation energies were attributed to re crystallization. AS illustrated in Fig. 1, a recent investigation1 has shown that creep of aluminum single crystals by the (111) [i01] mechanism is controlled by three unique processes, each of which is characterized by a single activation energy which is independent of the applied stress and the creep strain. A comparison of the observed activation energies with theoretically calculated values permits a fairly clear identification of the three operative creep processes. Below 450°K, where the activation energy for creep is 3,400 cal per mole, the deformation is controlled by the Peierls process, the activation energy for creep agreeing well with that calculated by seeger2 for the energy required to nucleate the motion of a dislocation loop against the atomic forces of the lattice. Between 590° and 750°K, the observed activation energy for creep of about 28,000 cal per mole agrees well with the energy necessary to induce cross-slip. Seeger and schoeck3 estimate that the activation energy is about 24,000 cal per mole whereas Friedel4 recently calculated this activation energy to be 28,000 cal per mole. Above 800°K the activation energy of 35,500 cal per mole that was observed for creep agrees well with that estimated for self-diffusion in aluminum.= In this range the operative rate-controlling slip process has been clearly identified as that arising from the climb of edge dislocations. The objective of this investigation is to ascertain whether a single crystal of aluminum favorably oriented for simple shear in the [loll direction on the (010) plane might exhibit uniquely different activation energies for creep from those obtained previously for (111) [101] slip. Whereas the exis- tence of such unique activation energies would constitute incontrover table evidence for new mechanisms of slip, the absence of any new activation energies might suggest that slip of aluminum is confined to the (111) [loll mechanism. Several factors prompted the selection of the (010) [101] orientation for study. First, there are more reported observations of (010) [loll slip than of any other nonoctahe-dral mechanism.8-10Secondly, Chalmers and Martius1l have concluded from considerations of the energies of dislocations that (010) slip is the second most favored mechanism in face-centered-cubic metals. Finally, favorable orientations for simple shear by the (010) [loll mechanism provide the least favored orientation for slip by the (111) [101] mechanism. EXPE-RIMENTAL PRO-CEDURE The high-purity aluminum stock, specimen preparation, shear fixture, extensometry, and experimental technique used in this investigation were the same as those previously reported.' Single-crystal spheres grown from the melt of 99.995 pct pure Al* were _ *The high-purity aluminum used in this investigation was graciously given by the Aluminum Company of America. oriented, carefully machined into dumbbell-shaped shear specimens, annealed, and chemically polished. The finished specimen had a central reduced section 0.190 in. wide and 0.590 in. in diam and 1/4-in. grip sections at both sides, 0.690 in. in diameter. The specimen was oriented in the stainless steel grips of the shear fixture with the (010) plane perpendicular to the dumbbell axis and the [loll direction parallel to the stress axis within 2 deg. Creep activation energies were calculated in the previously described manner1 from determinations of the instantaneous change in shear strain rate produced by an abrupt 15 to 20 deg increase or decrease in test temperature. If is the instantaneous strain rate at strain y and temperature T1, and ?2 the instantaneous rate at y and T2,

Jan 1, 1960

By A. R. Orban, R. B. Engdahl, J. D. Hummell

The initial phase of a research program on smoke abatement from Bessemer converters is described. In work sponsored by the American Iron and Steel Institute, a 300-lb experimental Bessemer converter was assembled to simulate blowing conditions in a commercial vessel. Measurements of smoke and dust were also made in the field on a 30-ton commercial vessel. During normal blows the dust loading from the laboratory converter averaged 0.51 lb per 1000 lb of exhaust gas. This was similar to the exhaust-gas loading of a commercial vessel. The addition of hydrogen to the blast gas of the laboratory converter caused a decided decrease in smoke density. Smoke was also reduced markedly when methane or ammonia was added instead of hydrogen. The research is continuing on a bench-scale investigation of the mechanism of smoke formation in the converter process. DURING the past 2 years, on behalf of the American Iron and Steel Institute, Battelle has been conducting a research program on the control of emissions from pneumatic steelmaking processes. The objective of the research program is to discover a practical method for reducing to an unobjectionable level the emission of smoke and dust from Bessemer converters. PRELIMINARY INVESTIGATION Although conceivably some new collecting technique may be devised which would be economically practicable for cleaning Bessemer gases, no such system based on presently known principles seems feasible because of the extremely large volume of high-temperature gases involved. Hence, the research is being directed toward prevention of smoke formation at the source. A thorough review was first made of former work to determine the present status of the cleaning of converter gases. No published work was found on work done in the United States on collecting smoke or on preventing its formation in the bottom-blown, acid-Bessemer converter. In Europe, however, a number of investigations have been made on the basic-Bessemer converter. Kosmider, Neuhaus, and Kratzenstein1 conducted tests on a 20-ton converter to obtain characteristic data for dust removal and the utilization of waste heat. They concluded that because of the submicron size of the dust, special equipment would be necessary to clean the exhaust gases. Dehne2 conducted a large number of smoke-abatement experiments at Duisburg-Huckingen in a 36-ton Thomas converter discharging into a stack. A number of wet-scrubbing and dry collectors were tried unsuccessfully. A waste-heat boiler and electrostatic collector with necessary gas precleaners was felt to be the best solution for this particular plant. Meldau and Laufhutte3 determined that the particle size was all below 1 µ in the waste gas of a bottom-blown converter. Sel'kin and zadalya4 describe the use of oxygen-water mixtures injected into a molten bath in refining open-hearth steel. They claim that with use of oxygen-water mixtures the amount of dust formed was reduced between 33.3 and 20 pct of its previous level, and emission of brown smoke almost ceased. Pepperhoff and passov5 attempted unsuccessfully to find some correlation between the optical absorption of the smoke, the flame emission, and the composition of the metal in a Thomas converter in order to determine automatically the metallurgical state in the melt. In a recent U. S. Patent (NO. 2,831,762)' issued to two Austrian inventors, Kemmetmuller and Rinesch, the inventors claim a process for treating the exhaust gases from a converter. By their method the inventors claim that the exhaust gases from the converter are cooled immediately after leaving the converter to a degree that oxidation of the metal vapors and metal particles to form Fe2O3 is inhibited in the presence of surplus oxygen. Gledhill, Carnall, and sargent7 report on cleaning the gases from oxygen lancing of pig iron in the ladle. They claim the Pease-Anthony Venturi scrubber removed 99.5 + pct of the smoke, thereby reducing the concentration to 0.1 to 0.2 grain per cu ft, which resulted in a colorless stack gas after the evaporation of water. Fischer and wahlster8 developed a small basic converter and compared the metallurgical behavior of the blow with that of a large converter. Later work by Kosmider, Neuhaus, and Hardt9 on the use of steam for reduction of smoke from an oxygen-enriched converter confirmed that the cooling effect of steam is detrimental to production. From review of all of the published information on the subject, it was concluded that a practical solution to the smoke-elimination problem had not been found. Accordingly, it was deemed desirable to investigate the feasibility of preventing the initial formation of smoke in the converter.

Jan 1, 1961

By G. Baralis, P. Gondi, I. Tangerini, G. Scandola

The precipitation behavior of Zn-0.5 pct A1 alloy single crystals was studied by means of electrical resistivity measurements and by optical and electron microscopy. The single crystals for the resistivity measurements were prepared by an original method in - 100-p -thick sheets. The order of the precipitation kinetics ranged between 1 and 1.5. The dislocations play a relevant role in the first-order kinetics. Precipitation always occurs both on dispersed particles and on dislocations. Statistical examinations have shown that the first-order kinetics can have two different activation energies; i.e., the precipitation can have dz;fferent mechanisnrs which could not be identified, however, in the course of the research. During the tnetallographic exanzination of the precipitation structures a specific process of dislocation decoration was obsereed. The main purpose of this work was to study the contribution of dislocations to the precipitation. A number of authors have observed precipitation on dislocations and reference might be made to several monographs on the ubject.'' The possibility that dislocations also accelerate precipitation has been considered by Turn-bull3 and Fischer et al.4 The studies described in the present paper were carried out on zinc, chosen as a base metal owing to the ease with which dislocations can be introduced into it and because of the absence of excess vacancies after quenching in conditions where phenomena of accelerated precipitation still occur. Aluminum was preferred as alloying element because of the accelerated precipitation phenomena that resulted in a preliminary reearch. EXPERIMENTAL METHODS The observations refer to a Zn-0.5 pct A1 alloy. The zinc was 99.995 pct pure; a typical spectroscopical analysis is given in Table I. As a rule the alloy was subjected to homogenization, quenching, or slow cooling and annealing. Homogenization was carried out by heating at 390" to 410°C for 24 hr. From the homogenization temperature, some specimens were quenched and some slowly cooled at a rate of 2°C per sec. At this rate no precipitate was detectable under the optical microscope just after cooling. Quenching was carried out simply by dropping the specimens into water, aqueous ethylene glycol solution at -30" c, or liquid-nitrogen baths placed close to the homogenization oven. Vaseline oil baths were used with a thermal stabilization of 10-20 for both the aging treatments and the measurements; aging was generally carried out at 90" or 130°C. To avoid oxidation phenomena during heating, the vaseline oil baths had to be frequently renewed. The precipitation kinetics were studied by means of electrical resistivity measurements, using ans potentiometric method (reproducibility ± 5 x 10 5 v, that is 0.5 pct of the total voltage decreases on the specimens during precipitation). First, various types of specimens were tested, i.e., polycrystals, single crystals grown in capillary quartz tubes, and thin single-crystal sheets prepared by means of an original method requiring no container except for the natural oxide. Even if fully annealed, the polycrystals and the capillary grown single crystals showed resistivity in -creases, most probably due to dislocations introduced in the course of the measurements. Similar resistivity increases in pure zinc were noticed by another author. Only the single-crystal sheets showed no resistivity change; thus they were chosen for the subsequent tests. As already mentioned, these single crystals were obtained by using, as a container, the natural oxide on the zinc surface; the oxide strength is sufficient to maintain the original shape during melting with sheets up to 500 p thick. An initial zone melting and subsequent zone leveling, which led also to formation of the single crystals, were thus carried out on rolled sheets of the required thicknesses (- 100 p) and shape, lying on a flat silica surface. The resistivities were first evaluated by measurements at the liquid-nitrogen temperature. This method gave poor reproducibility, however, and this was attributed to the thermal cycles which had to be operated. To avoid cycles and handling, it was therefore decided to make measurements directly in the annealing oil baths; this required thermal stabilization at ilo-' "C. In this way only the resistance changes were measured. Specimens of pure zinc and of completely annealed alloy were always examined as controls together with those under consideration; only those measurement runs were taken into account where the reference samples showed no resistance increases. Again, the main inconvenience was due to oxidation and this was avoided by renewing the oil baths; even so data reproducibility was poor and the observations were therefore carried out on a large number (many hundreds) of specimens so as to provide indications of statistical value. For the transmission observations under the elec-

Jan 1, 1969