Search Documents

By F. Lynwood Garrison

The future of the Witwatersrand depends upon the possibility of mining and milling profitably the large tonnage of relatively low-grade gold ores known to exist in that area. The problem must be solved if the existence of the gold-mining industry in South Africa is to be saved and continue. To show that this disaster may be avoided, or at least postponed for another decade or longer, the following official statement is of interest: "There is a fairly large area of possible orebody on the East Rand of whose value and depth from the surface we have some though not very accurate knowledge. There is a far larger area south of the Central Rand which probably carries much payable ore, but at depths that at present appear too great to mine. Finally, there is a narrow strip of country over 100 miles in length stretching south from the Rand to Klerksdorp and beyond, which may contain large ore-bodies. The Witwatersrand rocks outcrop over portions of this ground and in places conglomerates occur in it that carry small bodies of payable ore. There is reason to believe that conglomerates of the Witwatersrand system exist over all this strip, though they are for the most part covered by later sediments. It seems probable also that there are large blocks of payable reef in this belt, at any rate in the area that lies close to the present western limit of the developed mines. The structure in this neighborhood is however very complicated and to prove the orebodies will be both difficult and costly." Ores in the Witwatersrand It should be explained in this connection that the conglomerates mentioned here were originally old gravel beds now consolidated into bedded sedimentary rocks, very hard because strongly cemented with secondary silica. The gold exists in this cement and is rarely found in the pebbles composing the rock or bed called locally reef. It is important to realize that these gold deposits are beds; not veins as generally understood by mining engineers and geologists. In addition to these low-grade ore reserves we have also to consider the ore left behind in the old stopes of the upper levels near the surface,

Jan 1, 1931

By Willis H. Carrier

Particular interest in the ventilation of deep mines, especially those in South Africa, has been created by a very complete system of cooling of the world's deepest mine, the Turf shaft of the Robinson Deep in Johannesburg. The writer visited this mine in January, 1936, and again in 1937. During these visits and subsequently, a considerable part of the theory involved in rock cooling in tunnels was developed and this has been checked by practical observations of the rates of rock cooling made within mines. The purpose of this paper is to set forth the method of attack of the mine problem. The cooling or air conditioning of mines by the use of mechanical refrigeration was not wholly newl-5 when the Robinson Deep installation was made. The first mine to be cooled was the Morro Velho mine, in Brazil. The first installation in this mine was put into operation in December 1920, the refrigerant being ammonia.5 The surface cooling gave considerable benefit but it proved inadequate as greater depths were reached, therefore in 1929 two centrifugal refrigerating machines were installed at the 6000-ft. level. These were used in conjunction with the surface cooling system to furnish additional cooling at the lower levels. This later installation used Carrene as a refrigerant. This nonflammable refrigerant, having a boiling point of 104" at sea level, insured reasonable safety, since all parts of the machine operated at subatmospheric pressure. Very favorable reports have been received on the effectiveness of this installation, but no recent data are available. An interesting feature of that plant is that the condenser water is cooled by spraying it into the exhaust air from the mine at the base of the ventilation upcast, which permits the water to be cooled within a few degrees of the wet-bulb temperature of the air entering the upcast, and the only water that has to be supplied for condensing purposes is that lost by evaporation, or about 0.5 per cent of the volume circulating through the condenser. This plan affords an ideal means for the removal of the heat load from the refrigerating system, and of course also from the mine itself. In many mines, however, especially those in South Africa, there is no

Jan 1, 1940

By Willis H. Carrier

Particular interest in the ventilation of deep mines, especially those in South Africa, has been created by a very complete system of cooling of the world's deepest mine, the Turf shaft of the Robinson Deep in Johannesburg. The writer visited this mine in January, 1936, and again in 1937. During these visits and subsequently, a considerable part of the theory involved in rock cooling in tunnels was developed and this has been checked by practical observations of the rates of rock cooling made within mines. The purpose of this paper is to set forth the method of attack of the mine problem. The cooling or air conditioning of mines by the use of mechanical refrigeration was not wholly newl-5 when the Robinson Deep installation was made. The first mine to be cooled was the Morro Velho mine, in Brazil. The first installation in this mine was put into operation in December 1920, the refrigerant being ammonia.5 The surface cooling gave considerable benefit but it proved inadequate as greater depths were reached, therefore in 1929 two centrifugal refrigerating machines were installed at the 6000-ft. level. These were used in conjunction with the surface cooling system to furnish additional cooling at the lower levels. This later installation used Carrene as a refrigerant. This nonflammable refrigerant, having a boiling point of 104" at sea level, insured reasonable safety, since all parts of the machine operated at subatmospheric pressure. Very favorable reports have been received on the effectiveness of this installation, but no recent data are available. An interesting feature of that plant is that the condenser water is cooled by spraying it into the exhaust air from the mine at the base of the ventilation upcast, which permits the water to be cooled within a few degrees of the wet-bulb temperature of the air entering the upcast, and the only water that has to be supplied for condensing purposes is that lost by evaporation, or about 0.5 per cent of the volume circulating through the condenser. This plan affords an ideal means for the removal of the heat load from the refrigerating system, and of course also from the mine itself. In many mines, however, especially those in South Africa, there is no

Jan 1, 1940

By Arthur C. Simmons

In common with all other producing areas of the United States, Pennsylvania enjoyed increased activity and prosperity during 1937 (Table I). Prices of crude oil were better than for any year since 1930, and the Bradford average was $2.599, compared with an average price of $2.60 in 1930. Production and drilling activities were increased over 1936, although drilling for oil represented almost entirely a program of secondary development in both the water-flood areas and the air-gas repressuring areas. Bradford Oil Field The Bradford oil field continued to produce the major portion of Pennsylvania oil; however, no changes occurred in oil-production methods during 1937. Practically all of the production in the Bradford field is by water-flooding and the total number of oil and water wells completed within the area increased from 3205 in 1936 to 4112 in 1937; an increase of approximately one-third over 1936 completions. The percentage of water wells is approximately one-half of the total completions, although any specific five-spot development will have a proportion of 55 to 60 per cent water wells and 40 to 45 per cent oil wells. Offsetti~ig and boundary oil wells probably will result in a division or percentage of 50 per cent oil and 50 per cent water wells. The quoted figures for well completions include the entire Bradford field, approximately 12 per cent of which is in Cattaraugus County, New York. It is possible to make a segregation of production, but it is not possible to segregate well completions. Production in the Pennsylvania end of the Bradford field in 1937 totaled 15,076,000 bbl., or a daily average of 41,300 bbl. compared with a daily average of 37,000 hbl. in 1936.

Jan 1, 1938

By R. A. Flinn, John T. Norton

A CONSIDERABLE number of experiments in recent years have definitely established the fact that the internal friction or mechanical hysteresis of a metal under cyclic stress is a property that is highly "structure sensitive." Because of this fact, it has been suggested that an observation of this property, which often is referred to as "damping. capacity," might be a useful indicator of structural. changes taking place when a metal or alloy is subjected to any of a number of metallurgical treatments. Damping capacity is of interest to both engineer and metallurgist, but from a rather different point of view, and the information that each desires from such observations is of a different nature. The metallurgist is in search of various external indications of changes taking place in the interior of a metal; changes which are in themselves not directly observable. Even if the observed phenomenon cannot be explained in fundamental terms, it may be empirically related to certain characteristics of the material and prove of real value in research. Internal friction os mechanical hysteresis occupies such a position, and, although it is nor well understood in terms of basic metallic theory, an observation of itt changes can serve in a very useful capacity. Of course, there is nothing new in the measurement of damping, but the use of this property in metallurgical research constitutes a vast field, which has received all too little attention: The present work is essentially of an exploratory nature in this field and is an attempt to evaluate the process as a research tool. The phenomenon of age-hardening was chosen as a typical example of a structural change and one method of measuring damping was examined in considerable detail.

Jan 1, 1938

By J. W. Spretnak, G. W. King

THE crystallography and morphology of 0-Al,Fe precipitates in an A1 + 0.5 wt pct Fe alloy have been studied by transmission electron microscopy. The alloy was cast in cylindrical ingots, 15 cm in diameter and 60 cm in length, and cooled slowly. The measured composition was 0.527 wt pct Fe, 0.001 wt pct Mg, and 0.003 wt pct Cu. Spectrographic analysis revealed no additional trace impurities. Thin slices were cut from the ingot and reduced by more than 95 pct by rolling to a thickness of 0.1 mm with no intermediate annealing treatments. These thin sheets were then vacuum-annealed for 1 hr at 612°C and air-cooled in their capsules. Thin foils for examination in the electron microscope were prepared by electropolishing. The precipitate is found in the form of oval platelets on the (110) planes of the matrix. The major axes of the platelets are parallel to the (110) directions of the matrix, and vary in length from 1/2 to 2 p. The thickness is about 1/10 p. Examples of platelets, both in the plane of the foil and normal to the foil, are shown in Figs. l(a) and l(b), respectively. lack' found that ?-A13Fe (more correctly All13Fe4) belongs to the monoclinic system. Using Black's structural data and simultaneous electron-diffraction patterns from the matrix and precipitates, the habit planes and directions were determined to be: (00l)? || (110)Al [100]? || [001]Al The orthogonal crystallographic axes of the precipitates are accurately in the habit plane, while the measured coincidences of the directions are only within 10 deg. The major axis of the platelet is parallel to [010] in the 0. This orientation corresponds to the direction of nearest registry of the lattices.

Jan 1, 1964

By C. T. Eddy

The refining of native copper in the reverberatory furnace, as practiced in the Lake Superior district of Michigan, is very similar to the reverberatory melting and refining of cathodes, but the presence of arsenic in some of the copper concentrates renders the operation somewhat more difficult. Though the copper occurs as the native metal, which is often excep tionally pure—purer, in fact, than after it has undergone refining—its intimate association with the gangue minerals necessitates the cumbersome reverberatory treatment. The gangue consists chiefly of complex silicates of calcium, magnesium, iron, aluminum and sodium, but in certain ore deposits other minerals are often found, among them the native copper arsenides—mohawkite, whitneyite, algodonite and the like. These latter minerals, when present, because of their relatively high specific gravity (7.5 to 8.5), find their way into the concentrates through the gravity concentration processes employed in the recovery of the copper. When such concentrates are melted, the silicates are removed as slag, but, because of the great affinity of molten copper for arsenic, the arsenides dissolve more or less completely in the copper bath. Because of the stability of the resulting melt, the arsenic is tenaciously held in solution. The influence of arsenic on the properties of copper, especially on its electrical conductivity, is generally recognized. For certain uses it is beneficial, and in many instances its presence in limited amounts is not objectionable, but if the metal is to be used for electrical purposes, the almost complete removal of the arsenic is of prime importance. Considerable research has been done on the subject of the influence of arsenic on the electrical conductivity of copperll but the conclusions presented in the literature dealing with the problem show some disagreement. The methods now in use for the removal of arsenic have not

Jan 1, 1931

By J. L. Brimhall

Slip-line formation during bending has been studied on neutron-irradiated molybdenum single crystals. For equivalent strains, the slip lines are coarse and distinct in the irradiated molybdenum and not resolvable in the unirradiated molybdenum. The slip lines have been directly correlated with dislocation channels present in the irradiated and deformed thin foils. The heterogeneous distribution of the dislocations during deformation in the irradiated material results from dislocation interaction with the dejects produced during irradiation. Impurities , in the form of' carbides, affected the dislocation channeling Principally by acting as dislocation sources. ALTHOUGH the mechanical behavior of irradiated materials has been studied extensively, the precise mechanism of irradiation hardening has not been established. Some information on the microstructural species responsible for hardening of irradiated materials has been derived from direct and indirect observations. The direct observation of the structure of deformed irradiated metals, particularly by transmission electron microscopy, is a relatively new and unexplored area. Slip-line studies in fcc metals have been restricted primarily to copper.1-3 Very coarse slip lines, representing slip on many closely spaced planes, have been observed in deformed, irradiated copper. Coarse slip lines have also been observed in irradiated aluminum.4 Clear channels in irradiated copper caused by dislocation motion through the defect structure have been seen by transmission electron microscopy and correlated with slip lines.5-6 To date, little work has been reported on the irradiated bcc metals. Eyre described the slip lines around hardness indentations on irradiated iron and found them to be more distinct than lines in unirradiated material.' Mastel et al.' have observed channels in deformed irradiated molybdenum similar to those reported in copper. As part of a program concerned with the effect of neutron irradiation on metals, the slip-line

Jan 1, 1965

By J. M. Davey

Lead-zinc sulphide ores at Mount Isa are currently treated at the rate of 180,000 long tons per 28 day period in the No. 2 Concentrator of Mount Isa Mines Limited. Prior to June 1966 lead-zinc ore was treated in part of the No. 1 Concentrator up to a rate of 70,000 long tons per period. Since 1955, two major changes in ore type being processed have occurred. Because of these changes, problems arising from treatment of the ore have altered and during the period several major changes in practice have been advocated and experimentally tested. Most of these flow sheets were developed with a view to overcoming one major problem in the ore. These were invariably abandoned as the Mount Isa lead-zinc ore contains a number of equally major problems all of which must be overcome in the treatment process. MINERALOGY The orebodies are situated in the Mount Isa Shale Group which is Proterozoic in age (Carpentarian System). The sediments consist dominantly of fine grained dolomitic, quartzo-feldspathic shales and siltstones. Specifically, the Mount Isa orebodies lie in the Urquhart shale formation which is characterised by sediments of high albite and orthoclase content denoting a large volcanic component. The Urquhart shales are approximately 3,500 feet thick and extend at least north and south of Mount Isa for 20 miles in each direction. In the area of the silver-lead-zinc orebodies the Urquhart shales are highly pyritic and have a relatively high carbon content. The

Jan 1, 1970

By R. A. Pasternak, B. Evans

A dynamic technique for the determination of solubilities of gases in metals has been explored, using the N-Nb system as a test case. An initially clean sample, maintained at constant high temperature, is exposed to the gas at low pressure: the rate of sorp-tion and the corresponding change in sample resistance are measured continuously. A pronounced decrease in the slope of the resistance concentration curve is observed at the terminal solubility. The rate of gas uptake by the sample was determined in an ultrahigh-vacuum flow system equipped with a servo-control which maintains constant pressure in the sample chamber; the system and the technique have been described in detail elsewhere. 1,2 The sample was held at constant temperature during sorption by maintaining approximately constant power input into it; this results in constant temperature, since the emissivity of a metal is independent of moderate concentrations of dissolved gas. The simple electrical circuit used both for heating and for resistance measurement is shown in Fig. 1. The power input into the filament is where R is the filament resistance, RL is an adjustable resistance in series with the filament, and VT is the constant dc potential of the power source. If RL is set equal to R at the beginning of an absorption run, the power input becomes insensitive to subsequent resistance changes; for example, an increase of 20 pct in sample resistance is accompanied by a decrease in power input of less than 0.8 pct; i.e., the

Jan 1, 1967

By William M. Boorstein, Robert D. Pehlke

The rates of solution (of hydrogen in liquid pure iron and in several liquid binary iron alloys were meas-ured using a constant volume technique. The rates of absorption and desorption were found to be equal un-der all experimental conditions. increasing concen-trations of S, Si, or Te decrease the rate of hydrogen uptake but additions of Al, B, Cr, Cu, or Ni have no measurable effect up to concentrations normally en-countered in steelmaking practice. No relation ship was found between the effect of an alloying element on the equilibrium solubility of hydrogen in liquid iron and its effect on the solution rate constant. Mathe-rnatical analysis of the data indicates that under the present experimental conditions the rate of reaction of hydrogen with liquid iron is controlled by transport of gas solute atoms in the metal phase. Comparison of the present resuts with data on nitrogen taken un der similar conditions establishes that the hydrody-nurnic conditions which exist near the surface of a metal bath are best approximated mathematically by a surface renewal model for the case of rapid in-ductive stirring and by a boundary layer model for more quiescent melts. HYDROGEN has long been recognized as being a detrimental constituent in steel. If dissolved in the molten metal in excess of its solid solubility, hydro-gen can be evolved during solidification and cause bleeding or porosity in ingots and castings. In the solid metal, lesser amounts play a definite role in causing other defects such as hairline cracks, blisters, and embrittlement. For significant refinements to be made in metallurgical procedures designed to control or eliminate hydrogen from liquid iron or steel dur-ing processing, available equilibrium solubility data must be supplemented with reliable fundamental in-formation pertaining to the kinetic factors involved in the transfer of hydrogen to or from the metal. The scarcity of such information in the literature prompted the present investigation. PREVIOUS RESEARCH Whereas much of the existing data on the solution kinetics of gases such as nitrogen were obtained during the course of thermodynamic investigations, the solu-tion rate of hydrogen has been found too rapid to be accurately determined by conventional solubility meas-urement techniques. Consequently, little work on hy-drogen solution kinetics has been reported in the lit-erature. Carney, Chipman, and crant1 attempted to study the rate of solution and evolution of hydrogen from liquid iron by employing a newly devised sampling method. Although no significant quantitative data could be obtained, it was observed that the rate of solution was approximately equal to the rate of evolution of hy-drogen from the melt. Karnaukov and Morozov2 stud-ied the rate of absorption and Knuppel and Oeters3 the rate of desorption of hydrogen from molten iron by measuring pressure changes with time in a constant volume system. Karnaukov and Morozov determined the hydrogen pressures over their inductively stirred melts with the aid of a McLeod gage and therefore, were forced to work at pressures not in excess of 40 mm of Hg. Their experimental data conformed to a mathematical correlation based on diffusion control: and the rate coefficients calculated on this basis were shown to be independent of the initial absorption pres-sure. These authors reported the solution rate of hy-drogen to be eight-to-ten times higher than they had found for nitrogen in a previous study. They also re-ported that under identical conditions, hydrogen dis-solves somewhat more slowly in iron-columbium alloys than in pure iron. Knuppel and Oeters found that the desorption of hydrogen from pure iron at 1600°C was controlled in all cases investigated by diffusion in the metal bath as long as bubble formation was sup-pressed. This was substantiated by Levin, Kurochkin, and umrikhin4 who studied the kinetics of hydrogen evolution from liquid (technical) iron while applying a vacuum. Salter5 measured the rate of hydrogen ab-sorbed by iron buttons, arc-melted by direct current, as a function of hydrogen partial pressure in a hy-drogen-argon atmosphere. A carrier gas technique was used for analysis of the hydrogen absorbed. The initial rate of absorption was found to increase di-rectly with the square root of the partial pressure of hydrogen. EXPERIMENTAL METHOD Because of the rapid uptake and evolution of hydro-gen by iron-base melts, a constant volume technique was devised in order to obtain meaningful kinetic data over the entire course of the solution process. Apparatus. A schematic view of the experimental apparatus is given in Fig. 1. The hydrogen-liquid iron reaction system consisted of a gas storage bulb con-nected to a meltcontaining reaction chamber through a normally-closed solenoid valve. The gas storage bulb, an inverted 250 ml round-bottomed Pyrex flask was joined to the inlet port of the solenoid valve by a glass-to-metal seal. A more detailed illustration of the reaction chamber is shown in Fig. 2. The design of the Vycor reaction bulb was essentially that de-scribed by Weinstein and Elliott6 with the exception of a shorter, larger diameter gas inlet for this kinetic study. In position, the reaction bulb was closely by an eight-turn coil of water-cooled copper tubing which, when energized by a 400-kc oscillator, provided the inductive heating source. The walls of the bulb were maintained relatively cool by circulating cold water along their outer surface, thus preventing

Jan 1, 1970

By L. C. Michels, O. G. Ricketts

The disorientations between s?nall grains, whose growth has been arrested at an early stage of recrys-tallization, and the deformed matrix in cold-rolled aluminum single crystals were determined using transmission Kikuchi line and electron diffraction patterns. The orientations of the recrystallized grains were found to be random, and the disorientations of these grains with the matrix weve found to be intermediate to large. This leads to the conclusion that the observed vecrystallization began in small areas of large disorientation present in the cold-worked structure. heavily cold-worked thin sections of aluminunz single crystals and of polycrystalline aluminum and nickel were produced directly by a mechanical technique. The specinlens thus prepared were heated with the electron beam to bring about vecrystallization during observation in the electron microscope. Motion pictures taken du.ring heating and the electvon, microg.raphs taken both before and aftev heating allowed the recrystallization process to be traced to its ovigin. Re cvystallized grains originated in very s,mall regions of the cold-worked structure and developed through rapid migration of high-angle boundaries. The boundaries either were present as such in the matrix or were formed out of dense dislocation networks. SIGNIFICANT advances have been made in recent years in the study of nucleation of recrystallization using the technique of transmission electron microscopy of thin metal foils. Bollman1 in a study of heavily rolled polycrystalline nickel found support for the Cahn-Cottrell2,3 theory of nucleation. According to this theory nuclei form by the initially slow growth of subgrains formed through polygonization. During this initial period of slow growth (the incubation period) the migrating boundary of the subgrain increases its disorientation with the cold-worked matrix and thereby increases its mobility to become a rapidly migrating high-angle boundary. Bailey4,5 investigated the annealing behavior of several metals deformed both in tension and by rolling and concluded that recrystallization took place through the migration of high-angle boundaries. With low deformations these boundaries were present in the metal before deformation. With high deformation it was not possible to tell whether the boundaries were pieces of the original grain boundaries or were produced either during deformation or by polygonization during ameal- ing. Direct observation during heating of metal foils indicated that subgrains form by polygonization and grow at an uneven rate. The grain size obtained decreased with decreasing foil thickness indicating that the foil surface resists boundary motion. Votava,6 in heating stage experiments on rolled copper, observed nuclei to appear suddenly and grow in jumps of differing magnitude. However, he found no special dislocation configurations where the nuclei appeared. Fujita,7 as a result of a study of subgrain growth in heavily worked aluminum, concluded that the boundary of a recrystallized grain initially forms from the boundary of a group of subgrains. This occurred by a process of deposition of vacancies and dislocations in the group boundary as the boundaries within the group disappear. HU8,9 directly observed a similar process in heating stage experiments on 70 pct rolled Si-Fe single crystals. The growth of subgrains appeared to proceed by a coalescence mechanism. The observed fading away of the boundary between two subgrains was explained by the moving out of dislocations from the disappearing boundary into the connecting or intersecting boundaries around the subgrains. The subgrain size and degree of disorientation with the surrounding structure were thus increased. With the increase in disorientation occurred a corresponding increase in boundary mobility, which eventually allowed the boundary to migrate rapidly. This process was observed to occur within "microbands" consisting of parallel narrow segments disoriented by a few degrees present in the as-rolled structure. The conclusion of Rzepski and Montuelle10 that growth is preceded by the coalescence of blocks through disappearance of their common boundaries supports this view. In contrast to Hu's coalescence model for nucleation were the conclusions of Walter and ~och.""~ Working with the same material as Hu, of the same orientation and rolled to the same reduction, they concluded that nucleation occurred by the Cahn-Cottrell mechanism. They observed, in agreement with Hu, that recrystallization began in the "microband" regions which they referred to as "transition" bands. Bartuska13 studied subgrain growth in heavily rolled nickel using a beam heating method in the electron microscope. He concluded that nuclei for recrystallization form from the largest most perfect subgrains present in the cold-worked structure by rapid intermittent migration of parts of subboundaries. In rare instances he observed subgrain growth by coalescence. EXPERIMENTAL PROCEDURE The materials used in this study were 99.999 pct A1 supplied by A.I.A.G. Metals, Inc., and 99.999 pct Ni supplied by Johnson and Matthey and Co., Ltd. The Hitachi HU-11 electron microscope, with uniaxial

Jan 1, 1968

By Anton Sawatzky, Erich Vogt

By means of mathematical solutions to the appropriate diffusion equations, we describe the kinetics of the thermal diffusion of hydrogen in Zircaloy-2 for the various temperatures and concentrations encountered in a heavy water moderated reactor. When the hydrogen concentration is below terminal solid solubility only the a Phase is present. Redistributions are then described in terms of the characteristic functions of the difhsion equation. For higher concentrations both the a and 6 phases are present. We assume the two phases to be always in equilibrium. For moderately small hydrogen concentrations exact solutions of the two-phase equation approach the the approximate solutions derived by Sawatzky and for all concentrations the exact solutions exhibit the qualitative features of his result: the two-phase concentration increases with time, everywhere; in the absence of a hydrogen current at the hot end of the sample an a-phase region always exists there; the interface of the a + 6 , a-phase boundary moves toward the cold md of the sample and the hydrogen concentration is discontinuous at the interface. Simultaneous solulions of the a and a + 6 hydrogen distributims and of the concomitant interface motion are obtained and compared to the observations of Sawatzky and Markowitz. The kinetics of the hydrogen diffusion process are shown to lead to m apparent heat of transport of the a phase which is lower than the actual value (even for samples with long anneals) thus resolving at least partially the disparity between experimental measurements of this quantity. A number of recent papers1"4 have reported measurements on the diffusion and redistribution of hydrogen in Zircaloy-2 under temperature and concentration gradients. These studies were instigated by problems arising from increasing use of Zircaloy-2 as a fuel element cladding material in pressurized-water power-reactors. The Zircaloy-2 picks up hydrogen during the operation of the reactor: the consequent precipitation of zirconium hydride in the Zircaloy-2 has pronounced effects on its mechanical properties. The Purpose of the present Paper is to describe the kinetics of the thermal diffusion of hydrogen in Zircaloy-2 for the various hydrogen concentrations and temperatures likely to be encountered in reactors. When the hydrogen in the Zircaloy-2 is entirely in the solid solution phase (a phase), the differential equation for thermal diffusion is well known and the redistribution can be described by standard mathematical methods some of which are given in Section 11 below. The treatment of the a + 6 (hydride) region differs from the earlier treatment of sawatzky3 by taking into account several modifications of the two-phase diffusion equations as suggested to us by Markowitz4 and Kidson.5 Even with the modifications the results obtained in our more complete treatment are substantially the same as those found by Sawatzky. As we show, the difference between the results of sawatzky3 and kIarkowitz4 is largely due to the difference in the geometry of their experiments. In the next section we derive the modified two-phase equation for arbitrary geometry. The exact solution of this equation is given in Section III for linear and cylindrical geometry. It is shown that Sawatzky's approximate solution is quite accurate for almost all the temperatures and hydrogen concentrations which are actually encountered. In Sawatzky's approximate theory the hydrogen concentration everywhere in the two-phase region increases continuously. As his paper pointed out, this result, together with hydrogen conservation, implies that in a sample with no hydrogen current flowing into the hot end a two-phase region is always accompanied by a single-phase region at the hot end of the sample. The net hydrogen gain in the two-phase region is supplied by the decrease of hydrogen in the single-phase region and by the movement of the (a, a + 6) boundary toward the cold end of the sample. Hydrogen conservation at the (a, a + 6) boundary leads to a discontinuity in the concentration and its derivative there. In Section IV it is shown how these qualitative features of the thermal diffusion kinetics arise from the simultaneous solution of the a-phase differential equation and a + 6 phase equation. Methods derived by us previously for the solution of the redistribution in both phases and the accompanying motion of the boundary are used to obtain approximate solutions valid for large times. The solutions account well for the observed redistributions of Sawatzky and Markowitz. It is shown how the continuing motion of the (a, a + 6) boundary leads to measured values of the heat of transport lower than the actual value, even for specimens with relatively long anneals.

Jan 1, 1963

By R. A. Thomas, R. L. Solbod

The importance of transverse diffusion on the finger development in a miscible-phase displacement at an adverse mobility ratio of tbree was studied in a porous plate 1/4-in. thick, 3-in. wide and 18-in. long. Fast displacement rates (29 ft/D) and slow rates (1.6 ft/D) were used to determine the effect of residence time on the geometry of the fingers. The shape of the fingers was observed directly by use of the X-ray technique. At fast rates numerous narrow fingers were observed, but at slow rates a single somewhat bulging finger was produced. The amount of material moved transversely by diffusion across the plate was sufficient to modify the finger geometry in the slow-rate run because of the long residence time. These results are in contradiction to some of the postulates in the literature. The composition of the effluent stream, however, was not affected by the flow rate. This result is not inconsistent with the observed change in the shape of the finger in a short model, but it seems likely that a short model does not offer adequate and proper scaling of the reservoir. The model used was probably a valid one for studying the effect of transverse diffusion on the finger geometry, but a longer model would be needed for proper scaling of the effect of the change in the finger shape on the efficiency of displacement as measured by the composition of the effluent stream. INTRODUCTION Fingering can be defined as the uneven advance of the injected phase as it moves into a porous medium displacing the resident phase from the pore spaces of the rock. The use of this term is usually restticted to the situation in which the displacing phase is less viscous or more mobile than the fluid being displaced. Under these conditions, not only are fingers formed, but the length and width of the fingers grow with distance traveled in the porous medium. This subject has become one of great interest to the oil industry because of the present trend toward the use of various forms of miscible-phase displacement to increase oil recovery. Since in nearly all of the known modifications of the miscible-phase displacements an unfavorable mobility ratio exists (the displacing phase has a lower viscosity than that of the crude oil), the conditions are proper for fingering to develop. An appreciable amount of fingering appears to be a severe handicap to these processes for it increases the volume of agent required for the process to be a success, and such an increase puts a severe strain on the economics of the proposed processes. In some cases, such as for a mobility ratio of 200 unfavorable, it has already been demonstrated that the proposed process would not be economic if the fingering in the field were to be of the same magnitude as that observed in the laboratory. A number of aspects of fingering have been studied and reported in the literature. While the phenomenon of fingering cannot be regarded as a completely understood subject, considerable information exists on the effect of the path length and the mobility ratio on the growth of fingers. Less-complete data are available on the effect of the diameter of the flow path on the character and amount of the fingering, and even less agreement in results exists on the effect of rate of flow on the nature of fingering. This paper deals with one aspect of this latter subject. OBJECTIVE The objective of this study was narrowed down to one rather specific feature of the behavior of fingers in miscible-phase displacement in porous media. The variable studied was the effect of rate of flow on the nature and the development of fingers. It should be made clear at this point that, while rate was the apparent variable, the real variable was residence time; that is, at low rates the fluids are present at a given spot in the porous medium for a longer time interval than at fast rates. The purpose of the study, therefore, was to determine the changes which occur in the fingering and the possible benefits which might accrue from a longer residence time during that period when fingers are

By A. L. Barnes

Residual oil in watered-out reservoirs is a tremendous reserve which has been unrecoverable by established production methods. A study of the new recovery methods indicated that the forward combustion urocess might- recover oil from such reservoirs; however, no thermal recovery operating experience in a watered-out system was available. The Delaware-Childers pilot thermal test was undertaken to test the feasibility of thermal recovery in this watered-out reservoir. The pilot test consisted of a 2.22-acre, inverted five-spot in the 600-ft deep Bartlesville sand. The reservoir in the pilot area had a porosity of 20.6 per cent, a permeability of 118 md and an average sand thickness of 45 ft. The reservoir contains a 33' API, 6-cp oil. Combustion was started Nov. 22, 1960. The initial air injection capacity was 750 Mscf/D, but it was eventually increased to 2,000 Mscf/D. The test was surrounded by an active water flood; therefore, water production was initially high, but decreased as the heat wave moved toward the producing wells. Oil-bank arrival at an individual well was indicated by a drop in GOR and WOR, and an increase in oil production. Combustion-front arrival was evident at three of the pilot producers, and they were plugged. Cumulative oil production from pilot area wells war over 12,000 bbl. Operational difficulties were negligible and only conventional equipment was necessary. The combustion efficiency of this test averaged over 80 per cent. Results from coring showed that the leading edge of the combustion front tended to be wedge-shaped but a nearly complete sweep of the reservoir was eventually obtained. An isopach map based on evidence from 10 core holes and the existing wells showed that 126 acre-ft had been swept by the heat wave. Using this swept volume, an air requirement of 15.7 MMscf/acre-ft was calculated. It was calculated that 275 ,STB/acre-ft was consumed bv the heat wave. INTRODUCTION There is a large amount of oil remaining in reservoirs that have been water flooded. A study of ways to recover this oil showed that the forward combustion process might be applicable. Results from a number of forward combustion tests have been reported in the literature, but none of these tests were conducted in a watered-out system. The Delaware-Childers pilot thermal test was initiated in 1960 to define the operating characteristics of underground combustion in this watered-out Bartlesville sand reservoir, The purpose of this paper is to present the pilot test results in detail. FORWARD COMBUSTION PROCESS The forward combustion process consists of initiating combustion in the formation surrounding an injection well and driving this heat wave through the formation toward offset producing wells. As the combustion front progresses through the reservoir, oil and formation water are vaporized, driven forward in the gaseous phase, and recon-densed in the cooler part of the formation. These distilled liquids, water of combustion and gaseous combustion products, form a bank or three-phase region ahead of the burning front. This bank pushes mobile reservoir fluids toward the production wells. The rate of movement of the combustion front is controlled by the rate at which the nondistill able residue which serves as process fuel can be completely burned off the sand. The production performance from a heat wave conducted in a watered-out oil reservoir will differ from one conducted in a dissolved gas-depleted reservoir because of the difference in fluid saturations. The primary depleted reservoir contains connate water saturation, relatively high oil saturation and some gas saturation. The watered-out reservoir contains a highly mobile water saturation, residual oil saturation and little gas saturation. As the combustion front moves forward in either type of depleted reservoir, it drives the distillable oil, the water in place and the water of combustion ahead, and burns the nondistillable portion of the oil. The heat-wave process in a watered-out reservoir differs from the process in a

Jan 1, 1966

By Alton B. Cook, G. B. Spencer, F. P. Bobrowski

In estimating production gas/oil ratios and oil recoveries from reservoirs containing highly volatile oils it is highly important to include condensate that may be recovered from the gas produced from the reservoir. The volume of the hydrocarbon liquid condensed from the production of the solution gas that has been liberated. in some reservoirs may equal or even exceed the volume of recoverable stock-tank oil as estimated by present methods. The usual procedure1, 2, 3 in estimating future reservoir performance includes use of relative permeability data of the reservoir rock to gas and oil and includes material-balance calculations utilizing data on the volume of the reservoir fluids, oil and gas production and reservoir pressure decline, and data on the physical properties of the initial reservoir fluids. The inaccuracy in the procedure results from the false assumption that all of the free or liberated gas that enters the well bore of reservoirs containing highly volatile oils remains in the gaseous phase as it is produced. This paper presents a method for estimating future reservoir performance and oil recoveries based on special labora. tory analyses of reservoir-oil samples and recognition of the additional volume of hydrocarbon liquid that will be recovered at various stages of depletion from a solution.gas.drive reservoir. The method also includes calculations of the volume and composition of the hydrocarbon liquids that can be recovered by processing the produced gas in a natural-gasoline plant. The development of the method resulted from a study of laboratory analyses of reservoir samples and of field data obtained from two reservoirs containing oil of the highly velatile type. Relatively high pressures and temperatures prevail in oil reservoirs discovered at the greater depths of present-day drilling. The contained fluids may have high saturation -Dressures and large volumes of gas in solution. The oils and gases under these conditions may be almost identical in compositions and densities.4,5 Also, engineers have noted that, for a number of oil reservoirs and especially the deeper reservoirs, the API gravity of the stock-tank oil increaees as the production gas/oil ratios increase. They attributed this increase in API gravity of the stock-tank oil to the formation of condensate as the liberated gas in the reservoir is being produced. SOURCE OF DATA FOR CALCULATIONS Subsurface oil samples and well-test data were obtained from the E. Constantin-Lambert Well No. 1 in the Elk City Field, Okla., to demonstrate the need for and a method of calculating future reservoir performance when consideration is given to the recoverable hydrocarbon liquid from the production of solution gas that has been or will be liberated in a reservoir. The Lambert well is located in C, SW 1/4, SW 1/4, Set- 18, T-l0-N, R-20-W, Washita County, Okla. At the time of completion it was on the east edge of the development and Was producing from conglomerate through 30 perforations in the 5 1/2-in. casing at a depth of 9,859 to 9,864 ft. The well Was completed on July 9, 1949, and subsurface oil samples were obtained July 29 and August 1, 1949. Production gas/oil ratio data were obtained during the operation in series of two Separators at high and low-pressures of 314 and 44 psia, respectively, and at an average temperature of approximately 60°F. The flowing bottom-hole pressure at the time of sampling was 3,934 psis. The static bottom-hole pressure was not obtained at the time of sampling, as the well could not be shut in long enough for testing because gas produced from the well was used for fuel at an offset drilling well. However, the initial reservoir pressure was calculated to be 4,364 psia from knowledge of pressure gradients in other wells in the field and the depth of the casing perforations in the Lambert NO. 1 well.

Jan 1, 1951

By K. T. Aust

The relative interfacial energies of symmetrical tilt boundaries in silver of greater than 99.999 pct purity were measured as a function of orientation difference 0 between 9° and 36° about <001>. The results are in good agreement with the dislocation model of the grain boundary. The energy vs H curve may be represented by the Shockley and Read equation in the form Eoe (0.55—In 8). READ&apos; has indicated that an ideal experimental method of testing the predictions of the dislocation theory of the grain boundary would be to measure the interfacial energies of symmetrical tilt boundaries between face-centered-cubic grains that have a common <001> axis, as a function of orientation difference 0. The misfit H should be defined by a rotation of each grain through an angle of H/2 away from the boundary. Such boundaries might be expected, from geometrical considerations, to be made up of a series of edge dislocations, at least for small values of 0. Energy vs H relationships for tin&apos; and lead:&apos; were previously obtained for an asymmetrical tilt boundary separating two grains in which generally only one grain was rotated about a <001> specimen axis through an angle of H away from the boundary, the other grain remaining fixed. It is possible, however, that the boundary atoms in tin and lead may have attained a symmetrical position, in relation to the orientations of the grains on either side of the boundary, during equilibrium annealing. The two sets of measurements on silicon ferrite&apos; were somewhat better suited for comparison with theory, since the boundaries were symmetrical tilt boundaries in which the axis of relative rotation was <110> in the first series and <l00> in the second; but this alloy has a body-centered-cubic structure. Although the grain boundaries in silver" were symmetrically tilted, the axis of relative rotation was not a simple crystallographic direction, and it varied from boundary to boundary. Although the above measurements were in good agreement with the Shockley and Read equation,"&apos;: it appeared desirable to carry out experiments under the ideal conditions specified by Read.&apos; Consequently, the relative energies of symmetrical tilt boundaries in silver between grains that have a common <001> axis were measured. The technique of equilibrating grain boundaries in oriented tricrystals was used rather than the less satisfactory thermal groove method previously employed for silver bicrystals." Experimental Details and Observations The solidification and seeding techniques, described previouslyh for growing tricrystals of controlled orientations, were used to prepare tricrystal specimens from silver of greater than 99.999 pct purity. The silver was obtained from American Platinum Works, Newark, N. J., in the form of poly crystalline rods 10 cm long and 7 mm in diam. These rods were then cold worked by rolling or drawing them into suitably shaped blanks. Single crystal seeds and tricrystals were grown in a high purity graphite boat by means of a movable furnace with globar heating elements. The graphite boat was enclosed in a Vycor tube, which was first evacuated to about l00/u Hg and then filled with a static argon atmosphere. The maximum temperature outside the Vycor tube was 1250°C. A typical tricrystal specimen of silver is shown in Fig. 1. Grains B and C were grown from seed crystals with a <001> specimen axis or longitudinal direction parallel to the direction of growth and with another <001> direction perpendicular to the surface. Each of the two seed crystals was rotated 18" about the <001> specimen axis but in opposite directions away from the boundary. A symmetrical tilt boundary, therefore, separated grains B and C with an orientation difference 8 of 36" about <001>. Grain A in Fig. 1 was grown from the middle seed with a <110> direction parallel to the specimen axis and with a <001> direction inclined at 45&apos; to the surface of the specimen. The interfaces sepa-

Jan 1, 1957

By F. P. Bobrowski, G. B. Spencer, Alton B. Cook

In estimating production gas/oil ratios and oil recoveries from reservoirs containing highly volatile oils it is highly important to include condensate that may be recovered from the gas produced from the reservoir. The volume of the hydrocarbon liquid condensed from the production of the solution gas that has been liberated. in some reservoirs may equal or even exceed the volume of recoverable stock-tank oil as estimated by present methods. The usual procedure1, 2, 3 in estimating future reservoir performance includes use of relative permeability data of the reservoir rock to gas and oil and includes material-balance calculations utilizing data on the volume of the reservoir fluids, oil and gas production and reservoir pressure decline, and data on the physical properties of the initial reservoir fluids. The inaccuracy in the procedure results from the false assumption that all of the free or liberated gas that enters the well bore of reservoirs containing highly volatile oils remains in the gaseous phase as it is produced. This paper presents a method for estimating future reservoir performance and oil recoveries based on special labora. tory analyses of reservoir-oil samples and recognition of the additional volume of hydrocarbon liquid that will be recovered at various stages of depletion from a solution.gas.drive reservoir. The method also includes calculations of the volume and composition of the hydrocarbon liquids that can be recovered by processing the produced gas in a natural-gasoline plant. The development of the method resulted from a study of laboratory analyses of reservoir samples and of field data obtained from two reservoirs containing oil of the highly velatile type. Relatively high pressures and temperatures prevail in oil reservoirs discovered at the greater depths of present-day drilling. The contained fluids may have high saturation -Dressures and large volumes of gas in solution. The oils and gases under these conditions may be almost identical in compositions and densities.4,5 Also, engineers have noted that, for a number of oil reservoirs and especially the deeper reservoirs, the API gravity of the stock-tank oil increaees as the production gas/oil ratios increase. They attributed this increase in API gravity of the stock-tank oil to the formation of condensate as the liberated gas in the reservoir is being produced. SOURCE OF DATA FOR CALCULATIONS Subsurface oil samples and well-test data were obtained from the E. Constantin-Lambert Well No. 1 in the Elk City Field, Okla., to demonstrate the need for and a method of calculating future reservoir performance when consideration is given to the recoverable hydrocarbon liquid from the production of solution gas that has been or will be liberated in a reservoir. The Lambert well is located in C, SW 1/4, SW 1/4, Set- 18, T-l0-N, R-20-W, Washita County, Okla. At the time of completion it was on the east edge of the development and Was producing from conglomerate through 30 perforations in the 5 1/2-in. casing at a depth of 9,859 to 9,864 ft. The well Was completed on July 9, 1949, and subsurface oil samples were obtained July 29 and August 1, 1949. Production gas/oil ratio data were obtained during the operation in series of two Separators at high and low-pressures of 314 and 44 psia, respectively, and at an average temperature of approximately 60°F. The flowing bottom-hole pressure at the time of sampling was 3,934 psis. The static bottom-hole pressure was not obtained at the time of sampling, as the well could not be shut in long enough for testing because gas produced from the well was used for fuel at an offset drilling well. However, the initial reservoir pressure was calculated to be 4,364 psia from knowledge of pressure gradients in other wells in the field and the depth of the casing perforations in the Lambert NO. 1 well.

Jan 1, 1951

By R. E. Cook

This paper presents results of a study to determine to what extent errors in estimated free gas saturation affect the results of static pressure calculations from build-up curves in two-phase systems. Use is made of the method of pressure build-up curve analysis developed by Miller, Dyes and Hutchinson1 , with modifications for two-phase flow advanced by Perrine2. Cornhined fluid compressibility of gas-oil mixtures is included, with special attention given to the discontinuity that occurs in fluid compressibility at the saturation pressure and its effect on static pressure calculations from build-up curves. The sensitivity of static pressure calculations to errors in gas saturation is considered over wide ranges of formation and fluid properties and reservoir pressure conditions. It is concluded from this study that for analyses of two-phase pressure build-up curves (I) the use of under-saturated crude compressibility data, even when producing GOR&apos;s are at or near solution values, will result in very significant negative errors in calculated static pressrrre, and (2) except for large values of buildup curve .slope and/or very low crude gravities, rather large errors in calculated gas saturation can he tolerated without .significant effect on calculated static pressures. The conc1usions arc qualified as referring only to the effects of gas saturation and excludc possible errors in the nuumerous other factors that enter into the ancllysis of pressure build-up curves. INTRODUCTION As part of the analysis of basic data for several major Eocene reservoirs in the Bolivar Coastal field (Western Venezuela), it was necessary to analyze a large number of pressure build-up curves for oil permeability and static reservoir pressure. From performance data it became apparent that gravity segregation is very active in these reservoirs. As a result of this performance it was recognized that the free gas saturation within the oil leg of the reservoirs would be small but would be subject to certain errors in calculation due to the inaccuracy of relative permeability data in the low gas saturation region. Since all of the various methods of build-up curve analysis were originally derived for sin- gle-phase, constant compressibility systems, and since the presence of a small but rather indeterminate gas saturation would greatly affect the reservoir fluid compressibility, a study was undertaken to investigate the effect of gas saturation on the results of two-phase pressure build-up analyses. TWO-PHASE BUILD-UP CURVE ANALYSIS The method of analysis used in this investigation is basically that originally developed by Miller, Dyes and Hutchinson1, with modifications for two-phase flow advanced by Perrine2. Miller, et al, showed that the original equation for single-phase permeability away from the well bore, held for two-phase flow except that the calculated permeability is the effective permeability to oil away from the wellbore. This finding was acknowledged by Per-rine, who also presented the equation for effective gas permeability* as Since Eqs. 1 and 2 contain no terms influenced by fluid compressibility, no distinct problem should develop in calculating permeability from two-phase build-up curves. In regard to the calculation of static reservoir pressure from build-up curves in single-phase systems, the modified Miller, et al, method as presented by Perrine is briefly as follows. 1. From build-up curve data, PVT data for the reservoir fluid and the well spacing and sand thickness, calculate the climensionless shut-in time corresponding to the highest value of actual shut-in time (t, hrs) on the straight-line portion of a semi-log build-up curve. Dimenrsionless shut-in time is related to actual shut-in time by the relation, t- 0.000264 kt 2. From a graph of dimension less shut-in time vs dimensionless pressure difference (Fig. 1 1 ) find the value of dimensionless pressure difference corresponding to the value of 7 calculated under (1) above. Dimen-

By G. F. Sager, B. J. Nelson

Magnesium alloy forgings offer higher and more uniform mechanical properties than heat treated magnesium alloy castings and are used principally for light weight parts that may be stressed in fatigue or subject to impact loads, or where space limitations do not permit the use of the necessarily bulkier magnesium alloy castings. Compositions and Properties of Magnesium Forging Alloys The nominal compositions and properties of the principal commercial magnesium forging alloys are given in Table 1. The two that are most commonly used are AMC58S and AM65S. The former has the highest strength and is, therefore, employed for heavy duty applications. However, the forging of this alloy and of AMC57S ordinarily requires the use of slow speed hydraulic presses. The forging alloy AM65S combines good, although somewhat lower, mechanical properties with excellent forging characteristics. This alloy can be forged on hammers, upsetters, rolls, and mechanical presses, as well as on hydraulic presses. These characteristics make it particularly useful for many applications. Manganese Segregation in AM65S The alloy AM65S contains 5 pct tin, 3 1/2 pct aluminum, and a small amount of manganese, the manganese being added to insure satisfactory resistance to corrosion. Some manganese segregation was occasionally encountered in this alloy. In many applications, such segregation is of no particular consequence, but when forgings are acid dipped prior to the application of various chemical coatings, the segregated particles of manganese constituent may stand in relief. The resultant surface roughening may impair appearance and is undesirable in forgings employed in the textile industry, where very smooth surfaces are essential to avoid the catching and breaking of fine threads. An effort was therefore made to determine the cause of manganese segregation in this alloy and find a method for its elimination. Radiographic examination of a series of cast ingot sections and extruded samples of the AM65S type having manganese contents ranging from zero to about 0.7 pct revealed no appreciable manganese segregation when the manganese was less than about 0.4 pct. A small amount was observed with a manganese content of 0.46 pct and considerable with manganese contents of 0.6 pct or higher. Attempts to eliminate the manganese segregation by variations in the melting and casting conditions were unsuccessful and it soon became apparent that the trouble was attributable to the fact that the manganese contents that caused segregation were in excess of the amounts that would remain in solution at temperatures encountered in the melting and/or casting operations prior to the complete solidification of the ingots. A knowledge of the amounts of manganese that would be soluble in molten alloys of the AM65S type at various temperatures was obviously desirable. The liquid solubilities of manganese in binary Mg-Mn alloys and in Mg-Al-Mn and Mg-Zn-Mn alloys have been determined by Tiner and others,* but no data on the solubility of manganese in molten magnesium alloys containing tin and aluminum are given in the literature. For this reason, an investigation to determine the solubility of manganese in a magnesium alloy containing 5 pct tin and 3.5 pct aluminum (AM65S type) was undertaken.

Jan 1, 1950