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By Thomas C. Wilder

ALTHOUGH there is an abundance of thermodynamic information available in the literature today, no experimental data on the standard molar properties of formation of zinc oxide have ever been reported for the temperature range 419.5" to 908°C. This is the temperature range for which zinc metal is a liquid. so that the formation reaction is: Data have been reported for Reaction [I] where zinc is a solid or a gas. Maier. Parks, and nderson' measured the electromotive force of the cell: in order to obtain the free energy of the reaction: over a limited temperature range. With the known properties of H2O, those of ZnO were calculated. These workers found that t;j of ZnO is -75,930 ± 150 cal per gfw and Mtf is-83,000 300 cal per gfw at 25°C. akolkin made similar measurements to obtain ilF7 and AH; of -75,870 and -82,540 cal per dw respectively at the same temperature. Truesdale and arirlg and Kitchener and 1gnatowicz4 measured the equilibrium of the reactions: respectively, in order to determine Ff of ZnO from the known values of CO, CO2, and H/X The thermodynamic properties of ZnO, presumably taken from the above investigations, are tabulated by Kubaschewski and vans' and Wicks and Block" The latter reference also gives values for the range where zinc is a liquid. These numbers are probably acquired from the known extremities of the range plus Cp data of the components. In the present work the electromotive force of the cell: was measured in order to calculate the properties of ZnO from the well known values of NiO for the temperature range where zinc is a liquid. In Cell [B] the cathode reaction is: and at the anode: The overall reaction is: for which the free energy change is: where is the electromotive force in volts of cell [B] after correction for the Pt-Ta thermocouple. The standard molar free energy of formation of NiO is very well known as a function of temperature. Kiukkola and agner's data are used in most tabulations. The error is probably less than I00 cal per gfw, The latter authors were the first to use solid mixed oxide electrolytes in galvanic cells. Their work with NiO and other oxides was performed with cells similar to Cell [B] using a variety of reference electrodes of fixed oxygen potential. There may be a small composition range for which either NiO, ZnO or both exist. If nonstoichiometry does exist for these oxides, then the properties described herein are those for the metal saturated compositions. The simple cell design was the same as described elsewheres except that the molten metal electrode was about 125 g of pure zinc including a small (0.25 to 0.50 g) amount of ZnO. The mixture of pure nickel and NiO powders making up the reference electrode was contained in a tube of the ZrOl + CaO electrolyte which was immersed in the molten zinc. A platinum contact was made to the reference electrode; tantalum to the zinc. A refractory cement plug was necessary at the open end of the electrolyte tube in order to prevent zinc vapor from contaminating the reference electrode. Experimental details such as the vessel containing the cell, furnace, temperature control and measurement, and electromotive force determinations of the cell have all been outlined previously. The temperature was varied randomly in the range between the freezing and boiling points of zinc. After each temperature change, time was allowed for the drift at the new temperature to be less than +;"c whereupon a series of three cell readings was taken at least 10

Jan 1, 1970

By Blake M. Loring, Robert A. Colton

MeltiXg procedures for most metals and alloys usually include some provision for the control of oxygen, since this element frequently has some undesirable effect on the properties of the metal or alloy concerned. In the melting of the various bronzes, this is especially true, since oxygen can be introduced into the melt in a number of ways, most of which are difficult to control. In making bronzes from virgin materials, oxygen is usually present in the commercial grades of copper used; electrolytic fire-refined copper ingots usually contain from 0.02 to 0.05 per cent oxygen. When ingot metal or scrap bronze is used in the charge, oxides are almost always present to some degree. Under certain melting conditions and in certain types of melting equipment the atmosphere over the metal may be highly oxidizing. This, of course, may be desirable in the melting practice used, but is certain to introduce appreciable amounts of oxygen into the melt, and that may not be entirely desirable. From the foundry viewpoint oxygen may have several harmful effects on bronzes. The formation of excessive amounts of oxides may produce drossy metal, which, in turn, means dirty castings and a potentially high rejection rate. It is claimed, too, that oxides in the metal may combine with hydrogen to form steam and thereby produce porosity in certain of the bronzes. The presence of certain refractory oxides, such as SnOz, may be undesirable from the viewpoint of making machining difficult, or as possible stress-raisers in the metal matrix. It is often said that excessive oxide present in the liquid metal makes the metal run sluggishly. Since it appears impractical to try to control the amount of oxygen introduced into the metal beyond taking the economical limit of precaution about charging dirty scrap, it would seem' that control of the oxygen content of the liquid metal offers the most promising approach to this problem. This might be done by using slags, or covers, or by the use of some element or compound added to the melt to remove oxygen preferentially. Most aspects of this problem have been considered and considerable work has been done along these lines. A reconsideration of the problem is indicated, however, by the controversial nature of the evidence at hand, especially on the possibility of using a chemical deoxidizer to control the oxygen content of bronzes. Choice of Deoxidizer The choice of the chemical agent selected as a deoxidizer would naturally depend first on the alloy in which it is to ~he used: in this particular case the alloy is Navy gun metal. In Table. I are listed a group of elements that might be considered as deoxidizers for bronze, with some of their properties that should be considered in

Jan 1, 1946

By Blake M. Loring, Robert A. Colton

MeltiXg procedures for most metals and alloys usually include some provision for the control of oxygen, since this element frequently has some undesirable effect on the properties of the metal or alloy concerned. In the melting of the various bronzes, this is especially true, since oxygen can be introduced into the melt in a number of ways, most of which are difficult to control. In making bronzes from virgin materials, oxygen is usually present in the commercial grades of copper used; electrolytic fire-refined copper ingots usually contain from 0.02 to 0.05 per cent oxygen. When ingot metal or scrap bronze is used in the charge, oxides are almost always present to some degree. Under certain melting conditions and in certain types of melting equipment the atmosphere over the metal may be highly oxidizing. This, of course, may be desirable in the melting practice used, but is certain to introduce appreciable amounts of oxygen into the melt, and that may not be entirely desirable. From the foundry viewpoint oxygen may have several harmful effects on bronzes. The formation of excessive amounts of oxides may produce drossy metal, which, in turn, means dirty castings and a potentially high rejection rate. It is claimed, too, that oxides in the metal may combine with hydrogen to form steam and thereby produce porosity in certain of the bronzes. The presence of certain refractory oxides, such as SnOz, may be undesirable from the viewpoint of making machining difficult, or as possible stress-raisers in the metal matrix. It is often said that excessive oxide present in the liquid metal makes the metal run sluggishly. Since it appears impractical to try to control the amount of oxygen introduced into the metal beyond taking the economical limit of precaution about charging dirty scrap, it would seem' that control of the oxygen content of the liquid metal offers the most promising approach to this problem. This might be done by using slags, or covers, or by the use of some element or compound added to the melt to remove oxygen preferentially. Most aspects of this problem have been considered and considerable work has been done along these lines. A reconsideration of the problem is indicated, however, by the controversial nature of the evidence at hand, especially on the possibility of using a chemical deoxidizer to control the oxygen content of bronzes. Choice of Deoxidizer The choice of the chemical agent selected as a deoxidizer would naturally depend first on the alloy in which it is to ~he used: in this particular case the alloy is Navy gun metal. In Table. I are listed a group of elements that might be considered as deoxidizers for bronze, with some of their properties that should be considered in

Jan 1, 1946

By Thomas T., Read

DESIRABLE as it is to summarize what has been set forth in preceding chapters, the task can only be approached with great hesitation. What follows represents the personal views of the author at the moment of writing, reserving the privilege to change them on more mature reflection or in the light of further evidence. With that reservation they may be stated somewhat as follows. Education for the mineral industries falls into two categories; general education and technical vocational, using the word vocational not in its usual sense but to signify preparation for specific activities, in which sense a law school is a vocational school. Even at the beginning, as indicated in the first chapter, mineral industry education was partly general and, partly technical and that relationship still persists, because technical education requires a firm basis of general education. Our general American system is to provide free public' general education through the twelfth grade, or completion of high-school work, though there are already many technical vocational high schools, and even in a community where nearly all the young people are preparing for entrance to college there will be some who wish to qualify for employment at the end of the high-school course, or even on completing junior high. Our educational system, therefore, has not only to provide education for those who intend to proceed beyond the twelfth grade but also for those who, for a variety of reasons, may wish or be forced to cease full-time education at any level between the first and twelfth grades. This study has been chiefly concerned with the problem of what kind and how much technical education to provide for those who have completed the twelfth grade and who wish to make their living in the mineral industries. The obvious fact that the mineral industries employ all sorts of trained persons,

Jan 1, 1941

By W. O. Philbrook, H. E. Burner, F. S. Manning

The equation of continuity for the hydrogen reduction of hematite in a fixed bed of closely-sized particles is solved assuming a flat velocity profile, negligible temperature gradients, md negligible axial diffusion. A kinetic expression from the literature is used which assumes the reduction process is controlled at the oxide-metal interface. The integral fractional conversion is computed, and the importance of particle diameter, flow mte, temperature, bulk axial diffusion, and inter- and intra-particle mass trarnsfer is predicted. Comparison with experimental data suggests one or more additional undefined variable(s) is significant. Equipment modifications are suggested for fidture experimentcll work. WITH the increasing desire to "design" the ore feed of a blast furnace, it has become necessary to define more quantitatively the process variables and to evaluate the extent of their control upon the reduction process. The bulk of the work reported in the literature has centered about the reduction of single particles; however, the blast furnace process more closely resembles reduction of a fixed bed than that of single particles. To simplify this analysis, the isothermal reduction by hydrogen of a natural hematite in a fixed bed of closely-sized particles is examined. With appropriate modifications in the kinetic and flow rate expressions, the approach employed should be extensible to mixtures of carbon monoxide, hydrogen, and inert nitrogen, and to adi-abatic conditions, thus approaching the blast furnace process more closely. The fixed bed variables which are investigated in this study are particle diameter, flow rate, temperature, and bulk axial diffusion, as well as inter-and intra-particle mass transfer. Of particular interest is the effect of particle size upon fractional conversion for a bed operating under constant pressure drop. The constant pressure drop concept bears a close resemblance to the blast furnace process, where regions of larger particles may provide a greater permeability to divert most of the reducing gas flow from the regions of smaller ore particles. Under such conditions one would expect qualitatively that, for sufficiently small particle sizes where the flow rate is small and the total surface area is large, the reduction rate would be limited by the gas flow rate. Initially the gas entering the bed reacts very rapidly and the composition approaches the equilibrium conversion value a short distance from the reactor inlet. This concentration "wave-front" then moves up the bed as the flow of reducing gas is continued, leaving in its wake an ever increasing layer of reduced particles. Providing that the reducing gas leaves the bed at equilibrium concentrations, conversion is expected to increase with an increase in flow rate, and hence with an increase in particle diemater. Conversely, for sufficiently large particles the flow rate will be high but the surface area available for reaction will limit the reduction rate. Since the total surface area decreases with an increase in particle size, conversion, in this case, is expected to decrease as the particle diameter is increased. It is clear then that between these two extremes an optimum particle diameter must exist. THEORETICAL DEVELOPMENT Above the temperature where wiistite is stable (about 560°C) the reduction of hematite proceeds through the series Fe2O3/Fe3O4/FeO/Fe. On the basis of microstructural studies and earlier work, Edström1 has postulated a mechanism for the reduction of an ideal hematite lattice: 1) Iron phase formation at the boundary between wiistite, iron, and gas (for sufficiently porous iron). 2) Diffusion of iron across a wustite layer. 3) Phase boundary reaction of Fe3O4 to FeO. 4) Diffusion across a dense magnetite layer. 5) Phase-boundary reaction of Fe2O3 to Fe3O4. According to the mechanism postulated, gaseous reaction product has to be removed only at the boundaries between wüstite and iron or gas, the only possible exception being enveloped Fe3O4 specks. On this basis McKewan2,3 has proposed that one may consider the hematite reduction process as a simple two-phase system of oxide/metal. If, for FeO and Fe3O4 layers of negligible thickness, the hypothesis is made that the rate of formation of a

Jan 1, 1963

By H. J. Ramey

As fluids move through a wellbore, there is transfer of heat between fluids and the earth due to the diflerence between fluid and geothermal temperatures. This type of heat transmission is involved in drilling and in all producing operations. In certain cases, quantitative knowledge of wellbore heat transmission is very important. This paper presents an approximate solution to the wellbore heat-transmission problem involved in injection of hot or cold fluids. The solution permits estimation of the temperature of fluids, tubing and casing as a function of depth and time. The result is expressed in simple algebraic form suitable for slide-rule calculation. The solution assumes that heat transfer in the wellbore is steady-state, while heat transfer to the earth will be unsteady radial conduction. Allowance is made for heat resistances in the wellbore. The method used may be applied to derivation of other heat problems such as flow through multiple strings in a wellbore. Comparisons of computed and field results are presented to establish the usefulness of the solution. INTRODUCTION During the past few years, considerable interest has been generated in hot-fluid-injection oil-recovery methods. These methods depend upon application of heat to a reservoir by means of a heat-transfer medium heated at the surface. Clearly, heat losses between the surface and the injection interval could be extremely important to this process. Not quite so obvious is the fact that every injection and production operation is accompanied by transmission of heal between wellbore fluids and the earth. Previously, the interpretation of temperature logs',' has been the main purpose of wellbore heat studies. The only papers dealing specifically with long-time injection operations are those of Moss and White3 and Lesem, et al.' The purpose of the present study is to investigate wellbore heat transmission to provide engineering methods useful in both production and injection operations, and basic techniques useful in all wellbore heat-transmission problems. The approach is similar to that of Moss and White:' DEVELOPMENT The transient heat-transmission problem under consideration is as follows. Let us consider the injection of a fluid down the tubing in a well which is cased to the top of the injection interval. Assuming fluid is injected at known rates and surface temperatures, determine the temperature of the injected fluid as a function of depth anti time. Consideration of the heat transferred from the injected fluid to the formation leads to the following equations. For liquid, Eqs. 1, 1A and 2 are developed in the Appendix. These equations were developed under the assumption that physical and thermal properties of the earth and wellbore fluids do not vary with temperature, that heat will transfer radially in the earth and that heat transmission in the wellbore is rapid compared to heat flow in the formation and. thus, can be represented by steady-state solutions. Special cases of this development have been presented by Nowakl and Moss and White.3 Both references are recommended for excellent background material. Nowak' presents very useful information concerning the effect of a shut-in period on subsequent temperatures. Since one purpose of this paper is to present methods which may be used to derive approximate solutions for heat-transmission problems associated to those specifically considered here, a brief discussion of associated heat problems is also presented in the Appendix. Analysis of the derivation presented in the Appendix will indicate that many terms can be re-defined to modify the solution for application to other problems. Before Eqs. 1, 1A and 2 can be used, it is necessary to consider the significance of the over-all heat-transfer coefficient U and the time function f(t). Thorough discussions of the concept of the over-all heat-transfer coefficient may be found in many references on heat transmission. See McAdams5 or Jakob," for example. Briefly, the over-all coefficient U considers the net- resistance to heat flow offered by fluid inside the tubing, the tubing wall, fluids or solids in the annulus, and the casing wall. The effect of radiant heat transfer from the tubing to the casing and resistance to heat flow caused by scale or wax on the tubing or casing may also be included in the over-all coefficient. According to McAdams, on page 136 of Ref. 5>

By H. J. Ramey

Conventional calculation of total system isothermal compressibility for a system containing a free gas phase involves, among other things, evaluation of the change of oil and gas formation volume factors and the gas in solution with pressure. Preferably, this information should be obtained from laboratory measurements made with particular oils and gases. Often, experimental measurements are not available. In this case, it is necessary to obtain pressure-volume-temperature relationships from general correlations such as those of Standing' for California oils. In order to speed estimates of compressibility, generalized plots have been prepared of the change of both oil formation volume factors and gas in solution, with pressure from Standing's correlations. A generalized plot for estimating the change in the two-phase (oil and gas) formation volume factor with pressure is also presented. Usually, the effect of gas dissolved in reservoir water upon the total system compressibility is neglected for gas saturated systems, due to the low solubility of gas in water. Results of this study indicate that the increase in total system compressibility caused by solution of gas in water is often as large as the compressibility of wafer, and can be magnitudes larger for low pressure systems. Generalized results for estimating the change of gas in solution in water with pressure are presented in tabular and graphical form. INTRODUCTION During the past decade, pressure build-up and drawdown techniques have gained an important place in reservoir engineering. Build-up and drawdown analyses are only two special applications of the broad field of transient fluid-flow theory. All solutions of transient fluid-flow problems contain a parameter called the total system isothermal compressibility. This property of fluids and porous rock is a measure of the change in volume of the fluid content of porous rock with a change in pressure, and it may vary considerably with pressure. Evaluation of total system isothermal compressibility is not difficult, but it is tedious and time-consuming. Often compressibilities are estimated roughly, or transient flow methods are neglected completely. The benefits of using accurate system compressibility in properly-executed build-up or drawdown analyses are: 1. Better planning of pressure build-ups may be achieved to avoid unnecessary loss of revenue due to excessively long shut-in periods, or to shut-in periods too short to yield useable data. 2. Better and more reliable estimates of static formation pressures for reserves estimates and rate performance estimates. 3. Reliable information for evaluation of well completion effectiveness, and planning and interpretation of well stimulation efforts. The purpose of this paper is to clarify the nature of the total system isothermal compressibility, and to present useful methods for estimation of compressibility, particularly for systems containing a gas phase. DEVELOPMENT Numerous publications have presented solutions to transient single-phase flow of slightly compressible fluids, stressing pressure build-up applications. In transient flow, a compressibility* term arises to permit volume content of fluids in porous rock to change as pressure changes. The basic nature of the compressibility term is usually taken for granted. Problems arise in practical applications of transient fluid theory because most published works consider only one flowing fluid—in an ideal porous system containing only one fluid. In 1956, Perrine2 presented an intuitive extension of single-phase flow pressure build-up methods to multiphase flow conditions. Later, Martin- established conditions under which Perrine's multiphase build-up method had a theoretical foundation. Perrine has shown that improper use of single-phase build-up analysis in certain multiphase flow situations can lead to gross errors in estimated static formation pressure, permeability and well condition. It is likely that, much pressure build-up data for oil wells should be analyzed on the basis of multiphase flow. For both single-phase and multiphase build-up analysis, the isothermal compressibility term in dimensionless time groups often should be interpreted as the total system compressibility. All real reservoirs contain one or more compressible fluid phases. In addition, rock compressibility can contribute in an important way to the total system compressibility. The proper total system compressibility expression may contain terms for compressibility of oil, gas, water, reservoir rock and terms for the change of solubility of gas in liquid phases.

Jan 1, 1965

By Hsun Hu, R. S. Cline

The formation of annealing textures during the course of recrystallization in 2 pct Al-Fe crystals rolled in the (111) [112], (112) [111], and (112) [Till orientations has hem studied in detail. When the rolling texture is composed of both (111) [121] and (001)[110] components, the annealing texture consists of mainly (110) [001] and (113) [332] components. As the (001) [110] component diminishes from the surface to the interior of the rolled crystal, the relative concentration of the (113) [332] component in the annealing texture decreases accordingly, whereas that of the (110)[001] component increases with the (111)[112] component in the rolling texture. Such dependence of the annealing texture on the composition of the rolling texture is in accmdance with the oriented growth mechanism. Grain-growth characteristics during recrystallization, hence the annealing texture, can he considerablv different in (112) [111]-type crystals depending sensitively on the initial orientation of the crystal. In a previous publication,' the formation of rolling textures in 2 pct A1-Fe single crystals with initial orientations of approximately (1ll)[112], (112)[111], and (112)[111] was studied in detail. The deformation texture of these crystals consisted of either a single (111)[112] or a combination of (111)[112] and (001)[110] components in various concentrations. For the (lll)[112] crystal, the deformation texture was a single (lll)[112] up to 70 pct rolling reduction, but it became (lll)[112] plus (001)[110] after -90 pct reduction. For the (112)[113.]-type crystals, the relative concentration of the (111)[ 112] and (001)[110] components varied with the depth below the surface of the crystal, as well as with the amount of deformation. These series of specimens, having deformation textures with a range of concentration of the (111)[112] and (001)[110] components, could therefore be used for a thorough investigation of the effect of deformation-texture components on the formation of annealing textures. In a study of rolling and annealing textures in Si-Fe crystals, Dunn and Koh3 noted that the addition of a (001)[110] component to the (111)[112]-type deformation texture had practically no effect on the recrystallization texture.* According to the ori- ented growth mechanism for the formation of annealing textures, nuclei related to the deformation texture by approximately 30-deg rotation around a common [110] axis have the highest rate of growth and the resulting annealing textures generally have such an orientation relationship with respect to the deformation textures.314 It was reasoned by Dunn and Koh3 that if the oriented growth mechanism operated the recrystallization texture developed from a deformation texture containing both (111)[112] and (001)[110] components should be strongly centered around (113)[332], because (113)[332] is approximately midway between the (111)[112] and (001)[110], and is related to both of these two orientations by [110] rotations of 25 to 30 deg. Hence, nuclei of (113)[332] orientation should have a high rate of growth in the deformed matrix. However, their results were not in accord with this prediction. It was felt by the writers that a detailed study was needed to clarify the effect of deformation-texture components on annealing-texture formation. For this reason, the present investigation was conducted. EXPERIMENTAL PROCEDURE Specimens used for the present investigation were taken from the crystals rolled previously for deformation-texture studies.' In order to follow the progress of annealing-texture formation during the course of recrystallization, a single specimen was taken from each rolled crystal and its textural changes examined after successive anneals until recrystallization was complete. The specimen was carefully cut from the rolled strip with a jeweler's saw. Prior to annealing, the sawed edges were etched to remove distorted metal, while both faces of the specimen were protected from the etching solution by acid-proof plastic tape. After annealing, the specimen was etched from the "bottom" face only (the reference or "top" face of the specimen was protected by plastic tape) to one half of its original thickness, so that the texture at the surface and at the central section of the strip could be determined by the reflection technique. The

Jan 1, 1965

By D. R. Wieland, A. N. Barron, A. R. Hendrickson

A definite relationship has been found between the reactivity of flowing hydrochloric acid and its shear rate in a carbonate fracture. Both flow velocity and fracture width affect the acid reaction rate. Laboratory studies were conducted on acid reactivity at different flow velocities through horizontal-linear fractures, using 15 per cent hydrochloric acid at 80' F and approximately 1,100 psi. Fracture width varied from 0.02 to 0.20 in. These data provide a new basis from which the spending time and penetration of the acid can be estimated. Equations were derived expressing the relationship between injection rate, fracture width, acid concentration, time and fracture height, for linear and radial fracture systems. Because the penetration of the acid before spending is closely related to the extent of productivity increase resulting from an acidizing treatment, these data provide a valuable insight into some of the controlling factors that must be taken into consideration during treatment preplanning. INTRODUCTION Acidizing of carbonate reservoirs to improve production characteristics has been widely practiced since 1932. Originally, it was assumed that the acid uniformly penetrated natural formation pores and flow channels, enlarging them and thereby increasing their flow capacity. Little consideration was given to the reaction rate of the acid, or how far it would penetrate away from the wellbore into the formation, before spending. It has been shown recently' that, unless fractures are present in the rock, very little penetration is attained before spending, and the benefits of the acidizing treatment are largely confined to the immediate vicinity of the well-bore. Therefore, acid treatments may be classified into two categories: (1) matrix acidizing, in which the acid flows through multiple: formation pores; and (2) fracture acidizing, in which the bulk of the acid travels through fractures in the rock, whether natural or induced. When acidizing treatments are conducted at pressures of sufficient magnitude to open and extend such fractures, it is often desirable to inject a propping agent to hold the fracture open after the treating pressure has been released, thus providing a highly conductive flow channel through the rock. In some cases where acid attack produces surface irregularities, the resulting flow passages can be sufficient to provide high conductivity without use of a propping agent. During injection, the acid dissolves the carbonate rock with which it comes in contact until it is spent. Deeper penetration of the spent acid into the formation produces no appreciable benefit (if no propping agent is used) because the unetched fracture faces will rejoin when treating pressures are released and the fracture will "heal", with negligible resultant conductivity. The spending time of the acid thus becomes important in determining how far from the wellbore the improved-conductivity zone extends. The spending time of acid after injection into carbonate rock depends on the rate at which the acid reacts with the rock. This in turn is controlled by a number of factors, as previously reported. 2-4 These include temperature, pressure, acid concentration, rock composition, injection rate and the area-volume relationship between the acid solution volume and the surface area of the formation flow channels through which it penetrates. Thus, in matrix acidizing, where an extremely large area is exposed to the acid, spending is rapid. In contrast, spending time is prolonged in open fractures, where the area-volume ratio is much lower. Thus, greatest penetration of the acid before spending will be achieved in acid-fracturing treatments where fractures are held open by hydraulic pressure. Perkins and Kern5 have presented equations for fracture-width determinations which, for hard formations such as limestone or dolomite, indicate that high injection rates and viscous fluids are required to create wide fractures. Increasing the injection rate will, in itself, produce faster reaction rates. Because this type of reaction can be considered to be first-order diffusion-controlled, '-' the rate of movement of fluid past the rock surface affects the thickness of the diffusion layer, in turn affecting the reaction rate. Staudt, et al,10 report the results of tests in which a rotating marble cylinder was immersed in acid, and the weight loss at different speeds determined. Such test conditions, however, are not truly indicative of the situation in a formation during an acid-fracturing treatment. This paper reports reaction-rate data obtained under

Jan 1, 1954

By R. A. Morse, P. M. Bridges, L. E. Wilsey, Howard N. Hall, P. L. Terwilliger

Theoretical and experimental investigations of a constant pressure gravity drainage system are reported. Experimental data are presented to show that recovery to gas breakthrough by gravity drainage is inversely proportional to rate. The gravity drainage reference rate, which is numerically equal to the so-called "maximum theoretical rate of gravity drainage" is shown to have no particular significance from a recovery standpoint. Before this rate can be used as a basis of comparison for recoveries, it is necessary that the relative permeability and capillary pressure characteristics and displacing fluid viscosities be identical for the systems compared. A method is presented by which accurate prediction of the performance of a gravity drainage system can be made. Close agreement between experimental and calculated drainage performance shows that steady state relative permeability and static capillary pressure data can be used to describe fluid displacement behavior. The very wide range of liquid recoveries before gas breakthrough which result from production rate variation alone demonstrates the importance of this factor in planning depletion of a gravity drainage reservoir. Calculated results are presented which show that little additional recovery can be expected from a high pressure gravity drainage system between the times of gas breakthrough and attainment of such high gas/liquid ratios as to make further pressure maintenance impractical. INTRODUCTION It bas been recognized for some time that gravity forces play an important part in the recovery of oil from some types of reservoirs. Field experience has shown that under certain conditions, gravity drainage can result in very high oil recov- eries. Qualitative reasoning has led most engineers to the general conclusions that: (1) Where gravity drainage is important, the reservoir pressure should be maintained by gas injection at the crest of the structure to prevent shrinkage of the oil in place and to keep a low viscosity so the oil can drain at the fastest possible rate. (2) Recovery by gravity drainage is rate sensitive. A survey of the literature indicates that while considerable work has been done on the effects of gravity in oil production problems, no satisfactory method of calculating the performance of gravity drainage reservoirs has been reported.1,2,3,4,5 In the absence of any proven method of calculating reservoir performance, the level at which pressure should be maintained and the rate of production for most efficient operation has been open to debate. The limits and general character of the recovery us rate relationships are apparent from the following: As rates of production approach zero, oil will drain by virtue of its own weight fast enough that the saturation distribution is always approximately the same as the original static capillary distribution. That is, at the gas-oil contact the liquid saturation goes from 100 per cent to a value of perhaps 10 to 30 per cent in a very short distance, so that as production continues. a relatively sharp gas-oil contact moves down-structure, leaving a very low residual oil saturation in the originally oil saturated zone. At very high rates of production, the oil that drains by virtue of its own weight is negligible and recovery will approach that of a horizontal gas drive, leaving a much higher residual oil saturation. At intermediate rates of production. recovery should be between these extreme*. Despite the lack of quantitative methods, tentative agreement had been reached on the question of optimum producing rate. It has been generally concluded that rather sharp decrease in recovery would occur at rates of production above the "maximum rate of gravity drainage" and hence this rate should not be exceeded. The "maximum rate of gravity drainage" is defined as the rate of production from a 100 per cent

Jan 1, 1951

By L. E. Wilsey, R. A. Morse, P. L. Terwilliger, Howard N. Hall, P. M. Bridges

Theoretical and experimental investigations of a constant pressure gravity drainage system are reported. Experimental data are presented to show that recovery to gas breakthrough by gravity drainage is inversely proportional to rate. The gravity drainage reference rate, which is numerically equal to the so-called "maximum theoretical rate of gravity drainage" is shown to have no particular significance from a recovery standpoint. Before this rate can be used as a basis of comparison for recoveries, it is necessary that the relative permeability and capillary pressure characteristics and displacing fluid viscosities be identical for the systems compared. A method is presented by which accurate prediction of the performance of a gravity drainage system can be made. Close agreement between experimental and calculated drainage performance shows that steady state relative permeability and static capillary pressure data can be used to describe fluid displacement behavior. The very wide range of liquid recoveries before gas breakthrough which result from production rate variation alone demonstrates the importance of this factor in planning depletion of a gravity drainage reservoir. Calculated results are presented which show that little additional recovery can be expected from a high pressure gravity drainage system between the times of gas breakthrough and attainment of such high gas/liquid ratios as to make further pressure maintenance impractical. INTRODUCTION It bas been recognized for some time that gravity forces play an important part in the recovery of oil from some types of reservoirs. Field experience has shown that under certain conditions, gravity drainage can result in very high oil recov- eries. Qualitative reasoning has led most engineers to the general conclusions that: (1) Where gravity drainage is important, the reservoir pressure should be maintained by gas injection at the crest of the structure to prevent shrinkage of the oil in place and to keep a low viscosity so the oil can drain at the fastest possible rate. (2) Recovery by gravity drainage is rate sensitive. A survey of the literature indicates that while considerable work has been done on the effects of gravity in oil production problems, no satisfactory method of calculating the performance of gravity drainage reservoirs has been reported.1,2,3,4,5 In the absence of any proven method of calculating reservoir performance, the level at which pressure should be maintained and the rate of production for most efficient operation has been open to debate. The limits and general character of the recovery us rate relationships are apparent from the following: As rates of production approach zero, oil will drain by virtue of its own weight fast enough that the saturation distribution is always approximately the same as the original static capillary distribution. That is, at the gas-oil contact the liquid saturation goes from 100 per cent to a value of perhaps 10 to 30 per cent in a very short distance, so that as production continues. a relatively sharp gas-oil contact moves down-structure, leaving a very low residual oil saturation in the originally oil saturated zone. At very high rates of production, the oil that drains by virtue of its own weight is negligible and recovery will approach that of a horizontal gas drive, leaving a much higher residual oil saturation. At intermediate rates of production. recovery should be between these extreme*. Despite the lack of quantitative methods, tentative agreement had been reached on the question of optimum producing rate. It has been generally concluded that rather sharp decrease in recovery would occur at rates of production above the "maximum rate of gravity drainage" and hence this rate should not be exceeded. The "maximum rate of gravity drainage" is defined as the rate of production from a 100 per cent

Jan 1, 1951

By S. S. Clarke

Late in 1942, the increasing demand for zinc, coupled with the growing shortage of miners and the knowledge that some abandoned mines would have to be reopened for prospecting and development, led to considerable thought as to the possibilities of further mechanization in order to conserve man power. The ore bodies, locally termed "sheet ground," are an important ore bed in some mines and are in the lower part of Boone formation of the Mississippian Series. Some mines contain interbedded layers of nearly pure galena and sphalerite in horizontal sheets ranging in thickness from a thin seam to several inches and is persistent over large areas. This type of ore body offered the best opportunity for study and experiments. The use of Jumbo drill carriers was advanced but some doubt was expressed as to the adaptability of Jumbos as then in use to mine headings as compared to post and arm mounting (Fig I). Another consideration was the introduction of truck haulage when several mines were trackless. A drill frame, built to carry 2 4-in. drifters, was mounted on a truck chassis. This design proved a failure as it was not rigid and the resiliency of the tires and springs allowed too much play. Long screw jacks were then used to hold the truck firmly in place, but placing the jacks and securing the truck required more effort and time than setting up post drills, so the truck carrier was abandoned. The use of a bull dozer underground had been under consideration for some time to be used in "brunoing" the broken dirt from behind pillars and other inaccessable places so the slusher drags could load without double dragging the dirt. A dozer with hydraulic blade lift was purchased and R. I. Tuthill, Superintendent of Section 30 Mines, suggested that a long drill arm be substituted for the blade, and the drills mounted on the cross member. The hydraulic lift would permit drilling holes at any required spacing. The "cat" was very mobile and answered the problem of a trackless mine. The initial tests showed that the "cat" would make a good carrier, but the hydraulic controls were not positive enough to keep the drills in alignment while drilling. The next step was to build a small hoist. This hoist was attached to the power take-off on the "cat" and by means of sheaves and a double line of 3/8-in. hoist cable, a positive control for raising and lowering the boom was obtained. To avoid serious injuries to the drillers should the cable break, a safety chain was fastened to the drill boom and hooked into a slot in the back of the "cat" frame. A different power unit was obtained for the "cat," as a state law prohibited the use of internal combustion engines in mines. A custom machine shop had just placed on the market a small hoist powered by a Model A Ford engine that had been very ingeniously converted to a slide valve engine using compressed air. To use this unit on a "cat," our master mechanic de-

Jan 1, 1949

By J. E. Worthington, W. H. Spence, I. T. Kiff

Gold was discovered at the Haile mine in Lancaster County, South Carolina, in 1827 or 1828, and since that time the mine has been worked intermittently by both open-pit and underground methods until its forced closure in 1942 by World War II. Production figures are incomplete, especially for the early years, but the total gold produced is estimated to have been greater than 200,000 oz. Thus, the Haile mine has been the most productive gold mine in the eastern United States. The upper, residually enriched ores were relatively rich, but the bulk of the production has come from the mining of lower grade ores. General Geology The Haile mine is located in late Precambrian or early Paleozoic rocks of the Carolina slate belt at the edge of the Atlantic Coastal Plain [(Fig. 1)]. The metamorphic grade is lower greenschist facies and the rocks have been folded into a sequence of northeast-trending isoclinal folds. The gold is associated with siliceous, pyritic, and kaolinized felsic pyroclastic and tuffaceous rocks in an interbedded volcanic and volcanoclastic sequence of felsic to mafic tuffaceous rocks and argillaceous sediments [(Fig. 2)]. The ore bodies occur in two northeast trending zones approximately 500 m apart; each zone is 30-70 m wide and 600 m or more in length, with possible extensions to the east beneath the Coastal Plain sediments. Mineralogy. Gold in the Haile mine is always associated with siliceous and/or pyritic ores. The gold occurs in at least three states: As native gold as originally deposited; as residual gold derived from the breakdown of pyrite; and as gold included in pyrite. Major associated minerals in addition to quartz and pyrite are kaolinite, sericite, and iron oxides. Minor molybdenite, arsenopyrite, pyrrhotite, copper sulfides, sphalerite, rutile, and topaz are also present. Petrology. The gold-bearing ore zones vary from highly siliceous rocks to pyritic massive sulfide lenses. This variation is most easily seen today along strike from the Haile pit to the Red Hill pit. Ore grade material still exposed in the wall of the Haile pit consists of a highly siliceous and very thinly bedded rock containing minor pyrite. Along strike, the character of the mineralization changes to pyritic massive sulfide lenses occurring interbedded with siliceous horizons at the Red Hill pit. The siliceous rocks vary from the thinly-bedded material as just described from the Haile pit to silicified fragmental-appearing rocks to totally recrystallized cherty rocks lacking any recognizable primary features. Scattered, apparently at random, throughout the very thinly-bedded and very fine-grained ore face of the Haile pit are seemingly anomalous silica-rich clasts or concretions up to 5 cm in diameter which will be discussed later in this paper. Alteration. One of the most striking features of the Haile deposit is the alteration mineral assemblage which is intimately associated with the siliceous and pyritic ores. This altered material has been intersected in drill core at depths greatly exceeding the modern weathering profile and is, therefore, of hydrothermal origin rather than from supergene processes. This "sericite," actually a fine-grained mixture of sericite, kaolinite, and quartz, can be shown to stratigraphically underlie the gold- quartz-pyrite zone, and is well exposed in the open pit just southeast of the Haile and Bumalo pits. Relict textures indicate that this highly altered material was originally a felsic ash flow. Other similar alteration zones have been found in outcrop and drill core underlying the remaining ore bodies. Thus each of the mineralized zones consists of two parts: A siliceous and/or pyritic gold-bearing ore zone which is stratigraphically underlain by a zone of high alumina minerals, in this case sericite and kaolinite along with variable amounts of quartz. A green chrome mica, presumably fuchsite, is present in trace amounts in the high alumina zone. Genesis An adequate model to explain the origin and distribution of the gold deposits in the Carolina slate belt is presently lacking. Worthington and Kiff1 suggested a volcanogenic origin for certain gold deposits in the North Carolina slate belt from the waning exhalations of felsic volcanic piles. They also pointed out that such an origin has similarities to many epithermal precious metal deposits located in more recent volcanic piles in the western United States. A further key to the understanding of the genesis of the gold mineralization at the Haile mine is the close association of the mineralization in siliceous and sulfidic horizons to the genetically related and stratigraphically underlying high alumina alteration. Such high-alumina alteration is common around felsic volcanic centers in the Carolina slate belt and the mineralogy as seen today consists of some combination of kaolinite, sericite, pyrophyllite, kyanite, andalusite or sillimanite depending on the local prevailing grade of metamorphism. Accompanying the high-alumina alteration are large quantities of pyrite and iron-oxide minerals as well as characteristic minor accessory minerals often including base metal sulfides, fluorine-bearing minerals (topaz, fluorite, apatite), titanium-bearing minerals (ilmenite, rutile),

Jan 1, 1981

By J. A. Coll, R. W. Cahn, A. Lawley

WHILE the creep properties of pure face-centered-cubic and close-packed-hexagonal metals have been thoroughly investigated and are well established, body-centered-cubic metals have been studied less extensively. Moreover, very few fundamental studies on the creep of solid solutions, irrespective of crystal structure, have been reported. The present study is concerned with the creep of a series of body-centered-cubic solid solutions. The present position concerning creep of pure metals is, briefly, as follows.1"3 Creep at first takes place at a steadily decreasing rate; this is the stage termed primary or transient creep. Except at the lowest temperatures this is succeeded by a stage of secondary or steady-state creep. At high temperatures and stresses, this may be succeeded by an accelerating stage, termed tertiary creep, with which we shall not here be concerned. There is no well-defined physical model at present for the transient stage; in general terms, transient creep is best regarded simply as a manifestation of work-harden ing. Steady-stage creep can certainly take place by several different mechanisms: the choice of dominant mechanism depends primarily on temperature. We shall here be concerned only with high-temperature steady-state creep, a term usually reserved for creep at absolute temperatures higher than 0.5 Tm, where T, is the melting point. In this range, the activation energy for creep is, for many metals, equal to the activation energy for self-diffusion, and this is generally interpreted in terms of a "climb mechanism.1-4 The creep rate is determined by the speed at which dislocations, impeded by obstacles the nature of which is disputed but which are probably established during transient creep, can climb by means of a diffusion process, until they are able to by-pass the obstacle. In solid solutions, the intrinsic resistance to the slip motion of dislocations may be much larger than in the solvent, to the extent that the motion of dislocations in the glide plane, rather than their escape by climb out of this plane, may become the rate-controlling factor. weertman5 has considered this possibility from a theoretical point of view, and concluded that some form of "viscous slip" is likely to be rate-controlling at comparatively low stresses. The resistance to slip may arise from "atmospheres" of impurities forming around dislocations; a high Peierls force in materials of high cohesion; or some structural peculiarity such as clustering or ordering of solute atoms.= We shall be concerned here with the case of ordering. The only published investigations concerned explicitly with the effect of order on creep refer to creep in ß-brass by Herman and Brown,7 and in Ni-Fe alloys, by Kornilov and panasyuk8 and by Suzuki and Yamamoto.9 Recently, Herman and Brown's paper has been supplemented by a determination of the tensile yield point of ß-brass as a function of temperature.10 Both studies showed a sharp drop in resistance to deformation of ß-brass over a range of a few degrees just above the critical temperature Tc at which order finally disappears. These observations are especially noteworthy, because in ß brass the degree of order diminishes steadzly to zero as the temperature approaches Tc. It is, therefore, the disappearance of the last traces of long-range order which has the largest effect on the resistance of the alloy to plastic deformation. In the Ni/Fe alloys of various compositions, resistance to creep at a given temperature and stress is maximum at the stoichiometric composition, both below Tc, (long-range order), and above T,. (short-range order).' Near Tc, the creep resistance of an ordered alloy is much higher than that of the same alloy in the disordered condition.9 The aim of the present investigation was to study the creep behavior in the neighborhood of Tc, of another system of ordering alloys. The iron-aluminum alloys were considered the most suitable. because: i) The order again diminishes steadily to zero as the temperature approaches Tc; there is no sudden drop in order at Tc, and it therefore is

Jan 1, 1961

By N. E. Truitt, D. G. Russell

The transient pressure behavior of a well which produces a single compressible fluid through a singte-plane wrticat fracture has been investigated mathematically. The fracture is assumed to possess infinite flow capacity, to be of limited mdial extent, and' to penetrate the producing formation completely in the vertical direction. Previous studies of vertically fractured wells have been concerned primarily with production rate performance or semisteady-state pressure behavior. This study was undertaken to ascertain the influence of vertical fractures on transient pressure tests such as pressure build-ups and flow tests. In a vertically fractured system, flow in the region nearest the fracture is practically linear, whereas farther away from the fracture essentially radial flow prevails. Thus, transient pressure analyses based on radial flow theory are somewhat inaccurate. As fracture penetration increases radially, kh values calcutated from pressure build-up and flow test curves become increasingly larger than true values. Failure to consider the effect of fracture penetration also introduces inaccuracies into the catculation of fracture length from the apparent skin factor and into the determination of average reservoir pressure. If the total length of the fracture is 20 per cent, or greater, of the drainage radius of the well, corrections must be made to pressure build-up and flow test results. Methods for correcting such results are discussed in this paper. For wells with prefracturing pressure build-up or flow test data, it is possible to estimate fracture length by comparison with postfracturing build-up or flow test results. In new wells or wells without prefracturing build-up or flow test data, fracture length must be estimated to correct the values obtained from analysis of pressure tests after fracturing. Fracturing efficiency calculations should be made whenever possible to provide an estimate of fracture length. Tables of the dimensionless pressure drop as a function of time and fracture penetration are included in this paper. Using these values should permit analysis of other types of transient pressure behavior in vertically fractured wells. INTRODUCTION Hydraulic fracturing has been used quite successfully for over a decade as a completion and stimulation technique in oil and gas wells completed in low-permeability reservoirs During this period a considerable amount of theory has evolved on the performance of hydraulically fractured reservoirs and on more efficient means of artificial fracturing. Although theory has been developed, no rigorous investigation has been made of pressure build-up and flow test behavior in such wells. Prats et al.1 first discussed the performance of vertically fractured reservoirs for the case of a compressible fluid. Their work was primarily concerned with production performance at constant flowing pressure. These authors also considered large-time (semisteady-state) constant production rate behavior for vertically fractured wells; however, transient pressure behavior at constant rate was not investigated. McGuire and Sikora10 and Dyes, Kemp, and Caudle2 employed an electrical analog to investigate the influence of artificial vertical fractures on well productivity and pressure build-up. They found that fractures which extend beyond 15 per cent of the drainage radius away from the well alter the position and slope of the straight-line portion of the build-up curve. They concluded that these effects must be considered both in the determination of the effective permeability of the formation and in any calculations of final build-up pressure. Although these authors did not undertake an exhaustive study of the influence of vertical fractures on pressure build-up performance, their limited results were quite interesting from the standpoint of the effects they demonstrated. In a more recent paper, Scott- reported the results of an investigation of the effect of vertical fractures on pressure behavior, which was conducted with a heat flow model. Scott's results appear to be consistent with those reported in Refs. 1 and 2. However, the effects of different fracture lengths on performance were not investigated. Pressure build-ups and transient flow tests are among the most diagnostic tools available to the reservoir engineer or production engineer. Since a very high percentage of present-day well completions incorporate the hydraulic fracturing technique, a definite need exists for information on the effect of fractures on transient pressure performance. For these reasons we have undertaken a rigorous study of pressure build-up and flow test behavior in vertically fractured reservoirs. The objectives of this study were (1) to obtain synthetic pressure build-up and flow test

Jan 1, 1965

By C. W. Beattie, R. L. Solter

ALUMINUM-KILLED, low carbon steel sheets are used extensively for severe deep drawing and other difficult forming operations. They usually, but not always, have a characteristic grain structure in which the grains are elongated both in the lengthwise and in the transverse direction. As described by Burns and McCabe,&apos; a typical grain in the plane of the sheet has its two axes in that plane from 1 Y2 to 4 times as long as the axis normal to the plane of the sheet. Rickett, Kalin, and MacKenzieZ have also reported on the recrystallization behavior of such steel. The contrast in grain structures of fully processed sheets of aluminum-killed and rimmed steel is illustrated by Figs. 1 and 2. The elongated grain structure of the aluminum-killed sheet is not developed on all heats or lots of this metal, and studies of the factors controlling and influencing its formation are reported in this paper. Jeffries and Archerb tate that unstrained grains are normally equiaxed, but exceptions are common. For example, if a metal containing a material mechanically obstructing grain growth is subjected to considerable working followed by thorough annealing, it may exhibit grains consistently elongated in the direction of working. Our experiments demonstrate that aluminum-killed, low carbon steel is such a metal, and that the substance mechanically obstructing grain growth is aluminum nitride. The effectiveness of aluminum nitride in inhibiting grain growth has been found to be influenced by the degree of cold reduction, the rate of heating in annealing, the thermal history of the sample before cold reduction, and the residual aluminum content. A correlation between grain shape and austenitic grain coarsening temperature also was indicated and additional experiments demonstrated that aluminum nitride is also the principal cause for the fine grain characteristic of aluminum-killed steels. Manufacture In conventional practice, aluminum-killed sheet steel is manufactured from a low carbon steel containing approximately 0.02 to 0.07 pct residual (HC1 soluble) Al. With the exception of certain samples containing greater or lesser amounts of aluminum, the steels used in these investigations were within the following composition range: C, 0.03 to 0.06 pct; Mn, 0.28 to 0.38; S, 0.017 to 0.032; Al, 0.03 to 0.06; P, <0.01; and Si, <0.01. Properly heated ingots are rolled to slabs about 4 in. thick. After surface conditioning, the slabs are reheated to about 2300°F and hot rolled continuouslv to strip about 1/10 in. thick. The strip rolling is completed at a temperature of 1550°F or higher, and the strip is coiled, usually at a temperature near the lower critical transformation. After cooling, the strip is pickled to remove oxide, cold reduced 40 to 70 pet to final thickness, then annealed to 1250° to 1350°F in 20 to 80 ton charges, the size of which results in slow heating and cooling rates. Effect of Cold Reduction According to Sachs and Van Horn,&apos; the deformations of the individual grains in rolling are similar to those of the total volume. Thus individual grains would elongate in rolling according to the amount of cold reduction imposed. This is true theoretically, but as cold reduction increases the individual grains tend to fragment, and measured grain elongations become less than theoretical. The amount of grain elongation may be described by a numerical rating based on grain counts made by the intercept method. Specimens are polished normal to the plane of the sheet, with the polished surface extending parallel to the rolling direction. After etching, grain intercepts are counted along a 50 mm line on a micrograph of suitable magnification. In random locations parallel to the plane of the sample 20 counts are made and 20 are made in the thickness direction of the sample the average count in the thickness direction divided by the average count parallel to the plane of the sample gives a numerical rating of the grain shape called grain elongation. For example, a grain elongation of 2.00 means that the average grain is twice as long as it is thick. The average of both counts may be converted to grains per sq mm by a nomograph relating intercept counts and grain count. By the same procedure the grain elongation in the plane of the sheet but transverse to the rolling direction may be determined, using transverse metallographic samples. A comparison of theoretical and measured grain elongation was obtained on an aluminum-killed

Jan 1, 1952

By John Brownson

Ge-Si N-N heterodiodes hare been built recently which show promise as high-speed logic devices. Low-resistivity germanium is deposited on silicon substrates held at temperatures above the germanium melting point and an alloyed heterojunction formed. The diodes are fabricated from this material using conventional mesa techniques. Over-all device qualify has been greatly improved by the use of epitaxial silicon substrates, that is, a subsirale consisting of a film of thin, high -resistivity silicon on a thicker Piece of low-resistirily silicon crystal. A semimpirical device design equation has been devised which predicts switching performance fairly well within the range of resistivitics and geometries employed. Switching times 01 0.9 ns and PIV &apos;s of —20 v are typical of the better 10-ma diodes. Switching times as low as 0.5 ns have been observed for 10-ma diodes and as low as 2.8 ns for 200-ma diodes. With further development it should be possible to improve switching speed by a factor of four. IN our laboratory, Ge-Si heterodiodes have been built recently which show promise as high-speed logic devices. The diodes have been built using a process reported in some detail in an earlier publication.&apos; The process in short involves alloying a thin film of low-resistivity germanium into a silicon substrate. the germanium having been transported and deposited by the well-known Theuerer halide reduction process.2 This process contrasts with that reported earlier by Oldham who used an essentially conventional direct epitaxial deposition technique.3 Oldham&apos;s process, unlike ours, requires cleavage of the silicon sample inside the reactor furnace the instant prior to deposition. Our process has the advantage of yielding large-area macro-scopically plane heterojunctions. Heterodiodes in general have several interesting properties. Without attempting to summarize the theory of heterojunctions.4 two of these properties which have direct relevance should be mentioned. First, N-.V and P-P heterojunction diodes rectify alternating current. Provided that either the band gap or the electron affinity of the two materials is different (which in general is the case), electronic barriers will exist in the junction band structure. When the device is sufficiently forward-biased, the barriers shift so as to permit current flow, and when it is reverse-biased. the barriers block current flow. Second, for N-N and P-P heterodiodes. the foward-conduction process involves majority carriers only. Consequently. when such a device is turned off. there is no minority-carrier storage and hence the diodes switch on and off quite rapidly. As we have reported earlier. N-P and N-N Ge-Si heterodiodes have been built in this laboratory. As one would predict from theory, the N-P heterodiodes were rather slow in turning off while the N-N&apos;s were quite fast. Similarly, the turn-off time of the N-P&apos;s increased rapidly with forward current while that of the N-N&apos;s was independent of forward current. Both N-N&apos;s and N-P&apos;s were moderately photosensitive. Photocurrents resulting from normal room illumination were as high as 1 µa at 1 v for small-area devices. The most disappointing parameter of the early N-N devices was reverse leakage.&apos; The reverse characteristic was invariably "soft" and leakage at only several volts reverse bias was intolerable. The reverse characteristic was greatly improved by using higher-resistivity silicon substrates. Leakage becomes large at voltages about one third of the avalanche voltage one would expect of a P-N homo-junction formed on silicon of the same resistivity. Thus leakage could be reduced to reasonable limits by using unconventionally high-resistivity silicon. Medium-power diodes formed on 30 ohm-cm substrates leaked typically 15 to 50 µa at 100 v reverse bias. The use of high-resistivity silicon substrate material, however, created a new problem. In order to have an acceptable forward-conductance characteristic. the area of the diodes had to be increased. With this increase in area, the capacitance increased. Switching time for N-N heterodiodes is essentially a linear function of capacitance. Thus when the resistivity was raised. so was the switching time. A SEMIEMPIRICAL HETERODIODE DESIGN EQUATION As a result of our experiments with a limited range of diode geometries and resistivities. a semi-

Jan 1, 1965

By W. J. McKenna

The International Smelting Co. concentrator at Tooele, Utah, first operated on a custom basis for the treatment of lead-zinc-iron ores on Nov. 1, 1924, with a capacity of 500 tons per day. On May 1, 1925, the capacity was increased to 1000 tons per day by the addition of another 500-ton section. The concentrator has since operated on the two-section basis, each treating 500 tons per day entirely by flotation. Laboratory and Test Mill In connection with the concentrator, a well-equipped laboratory and small continuous testing plant are maintained. The flotation equipment in the test plant is of both the Callow and Mineral Separations Sub-"A" types, so that actual concentrator conditions may be duplicated as closely as possible. Purchasing of Ore A new shipper usually sends to the plant a 25 to 50-lb. samplc, representative of the ore to be shipped. Batch flotation tests are made on this sample to determine its amenability to the concentrator treatment flowsheet and reagent combinations. The results of these tests, which are accurately correlated with those obtained at the concentrator, both as to grades of products and recoveries, determine the actual value of the ore as submitted in the ore purchasing department&apos;s treatment schedule. Hearty cooperation has existed at all times between the ore purchasing and operating departments in the selection of ores as conccntrator feed. Ores Treated The basic tonnages for mixtures on the two sections come from the Park City and Bingham mining districts. The Park City tonnages arc received by rail and consist of crude ores and gravity mill products. Those from the Bingham district arc received by rail and aerial tramway,

Jan 1, 1928

By Bruce Vandre

Jan 1, 1985