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By A. Gatti, R. L. Fullman

A very fine dispersion of aluminum oxide is produced by internal oxidation of solid-solution alloy of 0.14 pet A1 in Ag. The particle size of the aluminum oxide is approximntely 50 to 100A in radius. The yield strength of the alloy is increased markedly by internal oxidation. A further increase in strength is produced by cold working the internally oxidized alloy. Recrystallization is retarded by the finely dispessed aluminum oxide particles, so that the strength increase resulting from cold work is retained on annealing at temperatures 14 to about 700°C. MANY workers'-3 in the past have studied various aspects of the internal oxidation of aluminum-silver alloys. This paper is an extension of these studies with emphasis placed on the effect of time and temperature of annealing on the strength of these alloys after oxidation and subsequent cold working. Two general conditions are necessary to internally oxidize an alloy. First, oxygen must diffuse through the base material more rapidly than does the addition; otherwise oxidation will take place as a surface layer. Secondly, the affinity of oxygen for the addition must be greater than for the base material. After internal oxidation of certain alloys takes place, a marked increase in hardness accompanied by higher yield stress and improved creep properties is noted, presumably as a result of the highly dispersed oxide within the base material. Meijering and Druyvesteyn1 also noted that the internally oxidized portion of a partly oxidized alloy failed to recrys-tallize under annealing conditions that led to coinplete recrystallization of the unoxidized part. EXPERIMENTAL-METHODS AND PROCEDURES Few alloys can be made to contain a second phase that is extremely stable at high temperatures. Silver plus aluminum in solid solution was chosen for these internal oxidation studies because of the high rate of oxygen diffusion through silver and the very stable nature of aluminum oxide. Two alloys were vacuum cast. The nominal compositions were: Alloy A—1 pct Al, balance Ag; Alloy B—0.1 pct Al, balance Ag. Chemical analysis, which does not distinguish between aluminum and aluminum oxide, showed the conlposition to be: Alloy A—1.6 pct Al, and Alloy B—0.14 pct Al. The ingots were machined for surface cleaning, swaged and drawn to 0.020-in. diam wire. A sample 20 ft long of the 0.020-in. dianl wire of each composition was annealed 24 hr at 800°C in pure dry hydrogen. Each wire was then cut into two equal pieces. Photomicrographs of the 0.14 pct A1 alloy are shown in Fig. 1, the annealed 0.020-in. wire at the left and the oxidized wire to the right. The oxidation treatment for the first set of data was 1000 hr at 800°C in air. After this treatment the 1 pct A1 proved to be brittle. It is assumed that high alunlinum oxide concentration at the grain boundaries was responsible. The 0.14 pct Al wire remained ductile and all further data were derived using this alloy. One-half of this wire, about 5 ft, plus 5 ft of as-homogenized wire, was then drawn cold to 0.005 in. diam. All tensile tests were conducted with an Instron Engineering Corp. tensile-testing machine, Model TT-B. Unless otherwise indicated, the tests were made at room temperature with a strain rate of 0.1 per min. All metallographic samples were etched with an aqueous solution of 2 pct each of CrO3 and H2SO4 . EXPERIMENTAL RESULTS AND DISCUSSION PARTICLE SIZE DETERMINATION A study was made of the particle size of the aluminum oxide produced in the samples of Ag + 0.14 pct Al, oxidized 1000 hr at 800°C. A cross section of the as-oxidized wire was mounted in bakelite, polished, and etched with an aqueous solution of 2 pct each of CrO3 and H2SO4. The specimen was then thoroughly cleaned by stripping successive coatings made by applying 10 pct nitrocellulose in amyl acetate. The final replica of the cross section was made by applying 2 pct nitrocellulose in amyl acetate. The replica was stripped, transferred to a copper screen, shadow cast with chromium at 10 deg and photographs taken using a Phillips Metallix electron microscope at an accelerating potential of 100 kv. A photograph of an etched sample of the as-oxidized material is shown in Fig. 2. We believe the pits in the photograph are places were A12O3 inclusions were sitting in the matrix. By inspection, it appears that the volume fraction ob-

Jan 1, 1960

By W. E. D. Jr. Stokes

THE application of aviation to mining and petroleum operations, on the basis of economy and attainment, has become a demonstrated fact. According to Dominion Government records, 30. Canadian companies engaged in air transportation with northland mining camps, carried 13,000 tons of freight in 1935, and in 1936 carried 16,000 tons. In addition, many mining companies used planes to transport prospectors with canoes, outboard motors, gasoline drums and supplies to remote locations, and one company maintained a plane to take radium-bearing ore from its mine on Great Bear Lake nearly 1000 miles south to the rail-way at Waterways, Alberta. Heavy pieces of mining machinery weighing 2 tons are being carried by Ford trimotor planes over the Andes, at an altitude of not less than 15,000 feet. At Bulolo, New Guinea, 17,500 tons of disassembled gold-dredging equipment has been flown over inaccessible terrain, while supplies and building materials for a, community of 1000 whites have been transported by airplane. A 3 1/2-ton shaft was carried on one notable trip, while at another time an automobile, 2 tons of rice and a large safe went over the mountains in one plane. Fig. 1 shows an electric generator that was carried by plane to Bulolo.

Jan 1, 1937

By C. E. Mills

STUDIES of ground movement and subsidence resulting from mining operations cover a broad field. It is also a very important consideration and one that eventually affects nearly every mining operation of any extent. The damage to surface buildings, removal of mine surface plants and replacements of main hoisting shafts must reach an astounding expenditure were these cost figures available over a period of years. Were the subject one of mathematical formula and dependent only on the angle of draw of the walls or country rocks, the problem would be relatively simple. Consideration must be given to depth and extent of workings; structural conditions of the orebodies and enclosing country rock; physical properties of these same rocks, including schistosity, bedding, jointing, slips, dikes, faults, and other structural weaknesses. The method of mining, extent of openings, supporting pillars, and amount of moisture or water underground are other pertinent factors. With such a large number of variable factors, it is apparent that the subject of subsidence is one that must be based largely on experience and results at other mines where conditions are somewhat comparable. In presenting this paper, it is the intent to describe the progressive results of past ground movements at the United Verde, to bring out physical conditions largely responsible for this movement, but to refrain from theorizing on the ultimate extent of subsidence resulting from future mining operations.

Jan 1, 1934

By C. H. Mathewson

COPPER and the copper-base solid solutions readily form twin crystals when plastically deformed at a suitably elevated temperature or annealed after cold deformation. In fact, no feature of the microstructure of these materials is more prominent or characteristic than these straight-sided bands or simple lines of division which sometimes come from groups of thin polysynthetic lamellae, penetrating part way or wholly through the parent grain substance, but often divide the grain into a few or perhaps only two crystallographically related parts. Nearly always the bands as seen in the usual microscopic examination of a specimen come into vivid contrast with the adjacent crystalline material owing to the inherent difference in orientation. Bands which under special conditions of orientation cannot be seen with vertically incident light are often visible under oblique illumination and, when this fails, contrasting effects usually may be obtained by using polarized light. There is no longer any doubt that these synthetic banded structures obtained in the ordinary course of working and annealing are due to twinning of the spinel type which was observed long ago in a number of metals crystallizing in the isometric system.1 It has been customary in metallurgical literature to designate these synthetic twins, which grow into prominence during an annealing process, as "annealing twins" without regard to the actual mode of their formation, which is, indeed, obscure and with scant recognition of the fact that prior deformation is essential, no twins having been observed in metal of known unstrained history. This is questionable; especially in view of. the fact that in a number of metals and minerals, reorientation into the twin configuration is known to occur as a result of a simple shearing mechanism along the recognized twinning planes and the

Jan 1, 1930

By L. L. Wyman

The exact nature of the changes that take place in the iron-nickel alloys, giving rise to the interesting and useful expansion alloys in the Invar range, has yet to be fully understood. Similarly, the ternary iron-nickel-cobalt alloys, which also possess such commercially useful expansion characteristics,1,2 are concerned with transformations that appear to be identical with those found in the parent iron-nickel alloys. The investigations on iron-nickel alloys in the range 26 to 29 per cent Ni have been reported by several authors3-9 wherein it is shown that there are factors other than temperature, such as stress and grain size, which play an important part in determining the temperature at which the low-temperature transformation takes place. It will be shown in this paper that the ternary iron-nickcl-cobalt alloys having nickel contents comparable to the alloys mentioned above behave in a parallel manner. The alloys in the range of 26 to 31 per cent Ni and 16 to 21 per cent Co have a coefficient of expansion of about 4.0 X 10-6 per degree Centigrade, and the alloys in this range of composition find considerable application in making glass-to-metal seals, because these expansion properties so well match commercial glasses. The behavior of these alloys is not a simple matter, for it has been observed in alloys of 28.5 per cent Ni and 18.5 Co that severe working ran cause the appearance of a second phase having a needlelike structure similar to the martensite structure in carhon steels. Fig. 1 shows the change brought about in an alloy of this composition when a strip of this material was cut with tin shears. This second phase has been identified as the body-centered cubic alpha phase, and it is the purpose of this paper to describe the results of some of the preliminary investigations in the study of the changes involved in these alloys. Materials The past work on these alloys has concerned itself primarily with materials made by the usual casting procedure and involving the use

Jan 1, 1939

By Richard Thomas Newcomb

Chapters 5a, 5b, and 6 discuss the long- run supply of minerals and the characteristics of reserve search and production peculiar to extractive industries. It is now necessary to complete the picture by examining supply and demand in commodity markets to show how mineral prices are determined and how both price and production trends might be predicted over long periods of time. These practical interests can be served best by reviewing first some of the characteristics of the short-run static market models familiar to all readers of elementary economic texts, and then extending the theory to models of a more dynamic nature. It is important at the outset to note that economic theory provides a wide variety of economic models based on varying assumptions concerning the behavior of economic agents, the properties of the goods, the time period considered, and so on. Each variety of model offers certain analytical advantages and suffers certain shortcomings. The art of the applied economist or practioner lies in knowing enough both about the technology and practice of his problem and about theory to select the appropriate models for his analysis. In our approach it will be useful first to consider the role of markets for minerals and mineral products in relation to the efficient determination of what and how goods are produced in the whole economy, i.e., a general system of markets, before getting down to the task of analyzing supply and demand conditions in specific markets. The former study is called general equilibrium analysis, while the latter is called partial. By equilibrium is meant a state of the sys- tem under study in which supply equals demand in each market, and the prices which equilibrate the quantities offered and asked are called equilibrium prices. The tendency of prices to return toward equilibrium values if temporarily displaced, or to converge to new equilibrium values if important new conditions for supply or for demand are placed, defines "stable" equilibrium systems. The short-run describes a period in which adjustments to fixed capital are not made, although variable factors such as labor or materials can be adjusted. The long-run envisions a period in which fixed capital and other such constraints can be adjusted. Thus, it may take a sharp increase in price to bring out additional supply of a factor in the short-run with existing plant, while new capacity might permit additional quantities in the long-run without an increase in supply price.

Jan 1, 1976

By B. H. Caudle, L. H. Silberberg

Reservoir depletion by natural water drive is typified by the movement of water from an aquifer into the adjacent oil-bearing formation. Prior studies of this type 01 water movement have generally neglected the resistance to flow in the aquifer and its effect on the movement of water into the oil bearing zone. A method for designing and operating scaled models of such reservoir systems is presented. Experimental data on a model of an edge-water-drive reservoir are shown and discussed. INTRODUCTION Most petroleum reservoirs derive at least a part of their productive capacity from water influx. This water may be injected from the surface or it may come from an aquifer adjacent to the oil zone. In either case, the reservoir engineer must be able to estimate the advance of the water as a function of either the elapsed time or the fluid produced. This paper describes a type of fluid flow model which includes the effect of viscous and gravitational forces in the reservoir and the surrounding aquifer. Natural water influx can be divided into three general (but widely overlapping) categories according to the direction of flow in the aquifer. These are shown schematically in Fig. 1. Fig. l(a) illustrates an edge-water-drive mechanism. In this case, water advances updip along the stratum but the movement of water is essentially horizontal and very little of the oil is actually underlain by water. The bottom-water drive (Fig. l(b)) is characterized by a thick aquifer underlying the oil zone. The water movement is generally vertical in the aquifer. The third category is illustrated in l(c). Referred to as the "thin oil column", this type of oil accumulation consists of oil over water in a relatively thin stratum. Fluid movement is horizontal in both the oil and water zones, except close to the producing well. One characteristic which all three of these types have in common is that part of the water flow takes place in the water invaded region of the oil reservoir while the remainder of the water flow occurs in the aquifer. The resistance to the flow of water usually will not be the same in these two regions. This occurs because the porous rock normally contains only water in the aquifer, while the water-invaded region always contains microscopic globules of bypassed oil (residual oil) which interfere with the flow of water through the rock. The production history of any type of a water-drive system is a function of two phenomena — where the water goes, and how it displaces the oil in the area invaded by the water. It is usually impractical to study these two phenomena at the same time. In most cases one type of analysis is used to predict the gross movement of water in the reservoir, while a different type of analysis is employed to determine the amount of oil to be recovered from the gross volume contacted by the water. The portion of the oil reservoir which is invaded by water is mainly a function of the resistances to fluid flow in the several parts of the flow system. This gross water influx in the three types of natural water drive typically results in water cusping to the production wells either from the side or from below (water coning). In 1747, Muskat described a greatly simplified mathematical model for predicting the area invaded by water in a bottom-water-drive reservoir.1 This model used the Laplace equation and suitable boundary conditions to describe the isopotentials and streamlines in the flow system. The use of this model assumes that (1) the reservoir rock is homogeneous in nature, (2) the oil and water mobilities are equal, (3) there is no oil flowing in the water invaded region, and (4) external forces — such as gravity — do not affect the flow. This method has been used for both natural water drives and water injection projects. In this, as in most models, the method of images is used to reduce the size of the model necessary to describe the reservoir. The assumption of equal viscosities and permea-

Jan 1, 1966

By M. S. Seltzer

High temperature steady-state creep rates have been determined jor lead sulfide single crystals whose defect concentrations were fixed by equilibration under controlled sulfur pressure. The activation energy of creep, Qc , for undoped lead sulfide, is a function 01 composilion, decreasing from 2.9 to 2.2 ev as the carrier concentration increases from 9 x 1016 to 8 1018 electrons cm-3 for lead excess crystals, and increasing from 1.7 to 2.3 ev as the concentration of holes increases from 4 x 1017 to 1 x 1018 cm-3 in sulfur excess material. For five different composilions, Qc for undoped and bismuth-doped crystals has been found to be equal to Qpb + Qs, the self-diffusion activation energies for lead and sulfur in PbS. It is well-established1 that high-temperature steady-state creep of pure metals is a diffusion-controlled process, where the activation energy of creep is equal, within experimental error, to the activation energy of self-diffusion. The relationship between the activation energy for steady-state creep and those for self-diffusion in binary compounds is more complicated, however, because two different diffusing species must be considered, and becayse the activation energies may be influenced by compositional variations and by foreign atom additions.2-4 In some cases experimentally determined creep activation energies are correlated with those for self-diffusion of the slower-moving species, but such agreement is by no means universal. Interpretation of experimental results is difficult because few investigations include measurements of creep rates and self-diffusion coefficients of both diffusing species on single crystals of similar composition and foreign atom concentration. The objective of this investigation, therefore, is to determine the influence of stoichiometric defects and foreign atoms on steady-state creep and self-diffusion for a well-characterized binary compound. Lead sulfide, a compound semiconductor which crystallizes in the NaC1-type structure, and whose homogeneity range includes compositions on either side of the 1:l atom ratio, was chosen for study in this investigation. The pressure-temperature-composition relations for PbS are available,5,3 and deviations from stoichiometry may be monitored by electrical measurements.7 Single-crystal specimens are available to allow observation of effects due to bulk phenomena without interference from grain-boundary effects. These crystals have been employed to determine steady-state creep rates under compressive stress for "pure" and bismuth-doped PbS as a function of sulfur pressure and temperature as well as crystal orientation and applied stress in order to establish the relationships between defect concentrations and creep rates. EXPERIMENTAL PROCEDURES Crystal Growth. Lead sulfide crystals, prepared by the Bridgman method, are grown in evacuated quartz crucibles, filled with almost equal atomic proportions of high-purity (99.999 pct) lead and sulfur, and heated to a temperature above the melting point of PbS (about 1127°C) so that the lead and sulfur react to form molten PbS. The crucible and melt are dropped through the hot zone of the crystal-growing furnace at the rate of 1 cm per hr. The maximum melting point of PbS is slightly on the lead-rich side of the 50:50 composition; hence crystals grown from a near stoichiometric melt are usually n-type semiconductors containing excess lead atoms. Typically the lead excess concentration in solid solution with the PbS is 3 x 1018 atoms cm-3. Crystals containing either 1/20 or 1/2 mole pct Bi2S3 were prepared by addition of the foreign atoms prior to crystal synthesis. Preparation of Specimens of Controlled Stoichiom-etry. Since it is difficult to grow crystals of desired composition, the process of crystal growth and control of stoichiometry are separated into two distinct operations. Equilibration of as-grown PbS to a desired composition is most easily accomplished by first annealing the n-type crystals under high sulfur pressure (about 1 atm) at temperatures above 700°C. This process serves to put excess lead precipitates into solution, yielding 0 -type crystals upon quenching to room temperature. Inter diffusion occurs readily in crystals so treated, and the methods described by Bloem may then be employed to obtain crystals of controlled stoi-chiometry. For the creep measurements made in this study, this involves heating crystals in mixtures of H2 and H2S The equilibrium constant for H2S is given by: Thus the sulfur partial pressure is obtained from knowledge of the H2/H2S ratio and Kh2S for the temperature in question. Fig. 1 shows the p-T-x diagram for PbS. It can be seen that, within the stability limits for single-phase lead sulfide, desired compositions may be obtained by equilibrating under a specified sulfur pressure and temperature. Characterization of Crystals. The principal methods for evaluating PbS crystals include measurement of electrical properties and mass-spectrographic analysis. The measured electrical parameters include Hall coefficient, conductivity type, and electrical resistivity Bloem7 has shown that there is a 1:l relation between the defect concentration and carrier concentration obtained. Hence, if the contribution to the carrier con-

Jan 1, 1968

By C. Dirksen

This study investigates whether oxygen consumption during segregated forward combustion may be affected by natural convection. Linear theory indicates that thermal instability occurs in a horizontal porous medium when the modified Rayleigh number N 'Ra exceeds a critical value of about 40. Most experimental results, including those described here, indicate this value to be about an order of magnitude smaller. N ', is derived from "differential similarity" and the proper time scale factor is also obtained. The critical value of N'ra for a horizontal, water-saturated porous medium at atmospheric pressure subjected to a uertical temperature gradient was found to be about 3.0. The ambiguity in the value of N'R, arising when fluid properties cannot be assumed constant is indicated. Natural convection was observed for oblique systems below N 'Ra , while simultaneous horizontal flow did not affect N Racrit. The expected range of values for the various parameters pertaining to segregated forward combustion is indicated and the corresponding values of N 'Ra calculated. Only under very favorable conditions, such as high permeability, high pressure and low top temperature, can the critical value of N 'R, be exceeded. Thickness of the convection layer should not become too large, since the time required to obtain significant mixing is proportional to the square of the thickness. For an oblique combustion frant the conditions for significant mixing may be less strenuous. LNTRODUCTION Laboratory1,2 and field314 experiments have shown that a markedly upgraded oil can be produced by in situ forward combustion. Under certain conditions injected air may move through a high permeability, gas-saturated channel over the oil-saturated layer, while combustion takes place, exclusively, at the horizontal interface (Fig. 1). Such a channel may be a natural gas cap, or it may result from a forward combustion process in which injected air and combustion gases fingered through the top of the formation, causing a premature breakthrough at the production well. In this particular case of segregated forward combustion, the air stream moves parallel to the combustion front. Molecular diffusion and transverse mechanical dispersion will be insufficient to cause all the oxygen in the air stream to reach the combustion front. When the oxygen in the air stream is not completely consumed in the combustion process, it will reach the production well and create a serious fire hazard. In addition, the reduced efficiency may make the process economically unprofitable while also serious corrosion problems may be experienced in the production we11.3 This undesirable situation should, therefore, be prevented. However, in a situation as depicted in Fig. 1, an unstable temperature gradient exists in the gas phase. The combustion is taking place at the lower boundary at a nearly constant temperature that may be anywhere from 600 to 1,200F, depending on the conditions. The upper boundary of the gas phase is overlying, impermeable rock; its temperature might be around 100F, but may increase to 300F or higher due to conduction and convection as the combustion process continues. This represents a steep temperature gradient and it is conceivable that under those conditions free or natural convection will take place in the gas

Jan 1, 1967

By N. A. D. Parlee

The diffusion rate of hydrogen in liquid iron has been measured by a gas-liquid metal diffusion cell technique. The diffusion cell was formed by immersing an alumina tube containing hydrogen gas at 1 atm in a bath of stagnant liquid iron. The change in the composition of the melt in the cell was determined by measuring the rate of absorption of the gas in the cell. The appropriate solution to Fick's second law was used to examine the data and calculate diffusivi-ties. The absorption of hydrogen in stagnant pure liquid iron has been found to be diffusion-controlled. The results show that the chemical diffusion coefficient, D, of hydrogen in pure iron in the range of 1547" to 1726°C can be represented by the following Arrhenius relation: D(sq cnz per sec) = 3.2 x X exp(- 3300 i 1800/RT) where the uncertainty in the activation energy corresponds to the YO pct confidence level. Oxygen in the melt (above 0.015 pct 2) increased the apparent rate of absorption of hydrogen. The importance of diffusion data on liquid metals for predicting the rates of certain metallurgical processes has been recognized for a long time. Moreover, these data are much needed to test and develop theory for diffusion in liquid metals. Despite this practical and theoretical interest, however, relatively little reliable information about diffusion in liquid metals is available in the literature. This is particularly true for gas components such as hydrogen, oxygen, and nitrogen in liquid metals, where almost no data on chemical diffusion coefficients are to be found. This is probably due to a multitude of experimental difficulties particularly associated with high-temperature melts. In an effort to fill this gap in information, a research program was undertaken to study the diffusivities and rates of solution of gases in liquid metals. This paper presents the results of a study of the diffusion of hydrogen in liquid iron. EXPERIMENTAL METHOD Two methods for the study of the kinetics of dissolution of gases in liquid metals are being employed in this laboratory. Both involve the measurement of the volume of gas absorbed by the melt as a function of time and as such both avoid the uncertainties involved in chemical analyses of quenched samples for relatively small amounts of gas. In the first method, the gas dissolves in an inductively stirred melt and, in the absence of a slow surface reaction, the results are often interpreted in terms of mass transport across a liquid "boundary layer" between the homogeneous gas phase and well-stirred part of the melt. Other interpretations of the results of such experiments have also been described in the literature.1'5 In the second method a gas-liquid metal diffusion cell is used.' The gas dissolves in a cylindrical column of stagnant liquid metal and, in the absence of a slow surface reaction, the results are interpreted in terms of a non-steady-state diffusion solution to Fick's second law. The weakness of the first method is that while it gives information on the mechanism of absorption by stirred melts it yields an overall rate constant which even in the simplest cases depends on the nature and the thickness of the "mass transport layer" or "boundary layer". It yields no values of diffusion coefficients. The second method was used in this research because in many cases it is possible to determine the diffusion coefficient of the gas component in the liquid metal. In this research it has been utilized to measure diffusion coefficients of hydrogen in liquid iron. The apparatus used was essentially the same as that described by Mizikar, Grace, and par lee but certain modifications have been introduced to meet the elevated temperatures and special conditions of this research. Fig. 1 is a schematic drawing of the apparatus and Table I gives the identification of various parts in this figure. The diffusion cell, shown in detail in Fig. 2, was formed by immersing an impervious alumina tube (hereafter called absorption tube) in a bath of pure liquid iron contained in an alumina crucible. Two types of tubes were used, Morganite triangle RR and McDanel AP35. The crucible was contained in a vertical impervious alumina combustion tube (32 mm ID by 914 mm long) which was closed at both ends by water-cooled brass heads employing O-ring compression seals, Fig. 1. A protection tube enclosing a Pt, 5 pct Rh-Pt, 20 pct Rh thermocouple was introduced through the lower end of the combustion tube

Jan 1, 1968

By A. G. Spillette, R. L. Nielsen

The purpose of this paper is to further the understanding of reservoir response to hot-water injection by desuribing a two-dimensional, mathematical model of the process. Key assumptions are that no gas phase is present, and that the injected fluid reaches thermal equilibrium instantaneously with the reservoir fluids and sand. The resulting system of three partial differential equations is solved simultaneously through the use of a "leap-frog" application of standard alternating direction implicit methods for the solution of the mass-balance equations and the method of characteristics for solution of the energy-balance equation. The utility of the mathematical model is demonstrated by comparing numerical and analytic temperature distributions for hot-water bank injection and by comparing calculated with observed field behavior. Additional calculations show that hot waterfioding can recover significantly more oil than cold waterflooding, and that a hot-water bank recovers, with less energy input, nearly as much oil us continuous injection. Introduction Consistent field success with hot fluid injection processes requires good reservoir description and a thorough understanding of recovery mechanisms. The latter is fostered by a combination of well designed experimental studies and physically sound mathematical modeling. The purpose of this paper is to further the understanding of reservoir response to hot-water injection by describing a two-dimensional mathematical technique, indicating its validity, and demonstrating its utility for studying the effects of reservoir and operating parameters. Published experimental studies of hot fluid injection processes are few." Even if extensive data were available, two considerations discourage exclusive reliance on laboratory or field work. First, because of the severity of scaling requirements," laboratory results must be interpreted with care. Second, because of the one-shot nature of field experiments — injectivity/productivity tests and pilot floods—results seldom are available over the desired range of operating conditions. These factors emphasize the need for devoting attention to mathematical modeling to complement laboratory and field work. Through the use of mathematical models, scaling uncertainties can be bridged and response can be predicted for unique combinations of reservoir and operating conditions. Numerous mathematical models developed during recent years enable us to calculate temperature distributions, thermal efficiency (or conversely, fraction of heat lost), and oil recovery behavior for hot fluid injection. Ramey" and Spillette' recently have provided reviews of these methods. Most models have concentrated on predicting temperature distributions and thermal efficiency; few have been directed at predicting oil recovery.'."1° Although these techniques are useful for estimating effects of reservoir parameters and operating conditions on process performance, results are limited by the assumptions made and by the methods of coupling independently solved fluid-flow and energy-balance equations. A computer-based method is presented for predicting total reservoir response to hot-water injection that obviates most simplifying assumptions. The model simulates fluid flow and heat transfer in two dimensions within a vertical cross-section spanning the oil sand and adjacent unproductive strata. Known numerical procedures are used to solve the governing partial differential equations. The mathematical model handles the effects of reservoir heterogeneity, gravity, capillarity, relative permeability and temperature-dependent fluid properties. In addition, a wide range of operating conditions can be modeled, including hot-water followed by cold-water injection. Mathematical Description of Hot-Water Injection Key assumptions in the mathematical model for hot-water injection are that (1) no gas phase is present and (2) the injected fluid reaches thermal equilibrium instantaneously with the reservoir fluids and sand. Relative permeability and capillary pressure are assumed independent of temperature. Darcy's law for multiphase fluid flow relates the velocities of the oil and water phases to the phase pressure gradients by the following relations:

Jan 1, 1969

By A. H. Cottrel

SINCE metallurgy exists to provide strong, tough, engineering materials it must inevitably be perpetually concerned with the problem of brittle-ness. The steel-making industry was created because chemically unrefined iron is brittle. The steel-working and alloy-steel industries exist partly because hardness and ductility are mutually exclusive qualities in structurally unrefined steel. Yet, in spite of these immense industries, the brittle failure of steel ships hulls, bridges, pressure vessels, and pipelines, is still a contemporary problem. In fact, brittleness is a normal property of most solids, including metals and alloys, at low temperatures. Only face-centred cubic metals are commonly ductile at the lowest temperatures, and even here exceptions are known.'," Expensive are-melting processes. under inert gases or vacuum, have been developed to overcome brittleness in titanium, zirconium, columbium. and molybdenum. Polycrystal-line zinc, magnesium, and uranium have little ductility at room temperature. Beryllium, chromium, and tungsten have even less; similarly for antimony, bismuth, germanium, silicon, intermetallic compounds, and metallic carbides, nitrides, silicides, and borides. Oxides and other ceramics would be ideal creep-resistant materials but for their extreme brittleness when cold, and great efforts have been made to overcome this problem by mixing ceramics with metals. In fact, the traditional use of the name metallurgy for what is really the science of engineering materials is a recognition that most non-metallic solids have so far been precluded, by their extreme brittleness, from use as major structural materials in mechanical engineering. Most of what we know about brittleness in metals has come from studies of structural steel, and it is this material that shall mainly be considered. The things we have learned from it have a wider application, at least to other body-centred cubic transition metals, although the extent to which similar ideas can be applied to hexagonal metals and other materials is not yet clear. Fracture and Plastic Deformation The theoretical breaking strength of an ideal solid, about E/10 where E is Young's modulus, has been approached reasonably closely in experiments on fibres. But large specimens break at much lower stresses. For example, brittle cracks in large structural steel assemblies have been observed to spread catastrophically at speeds of 6000 ft per sec under stresses of about 10,000 psi, i.e. about E/3000. There are two sources of weakness; stress concentrations, and chemical agents in grain boundaries or on crack faces that lower the surface energy y of the material. Although we shall deal mainly only with the first of these, much of the discussion is also applicable to the second when different values of y are used. Griffith's well-known formula p = [ 2Ey/p(1 - v2)c]1/2 [1] gives the smallest tensile stress p able to propagate an atomically sharp surface crack of length c or interior crack of length 2c through a thick plate (compared with c) of elastically isotropic material of

Jan 1, 1959

By Henry M. Howe

Jan 1, 1908

By Louis A. Panek

This report deals with the combined friction and suspension effects in the reinforcement of horizontally bedded mine roof by bolting. Other reports have treated these two effects separately. Friction effect refers to the reduction of bending in a laminated roof due to the clamping action of tensioned bolts. If the beds tend to have unequal deflections, the bolts oppose this tendency, thus creating a suspension effect, which consists of a transfer of part of the weight of weaker or thinner beds to the flexurally more rigid beds within the bolted unit. The combined effects of friction and suspension on the bending of the beds, whether an increase or a decrease, are difficult to generalize because they depend on the bedding sequence and the bolt pre-tension. Some analysis of the bedding sequence usually is required to determine the critical bed within a set of bolted beds. However, if the suspension effect is substantial and if the bolts are pre-tensioned, then the greatest bending stress is likely to occur in the thickest bed. Findings are based partly on theory and partly on tests of mine-roof models in a centrifuge, which were found to verify the theory. Mathematical formulas are obtained for the change in maximum roof bending stress and for the change of roof deflection due to the combined friction and suspension effects. The maximum bending stress is needed for designing a roof-bolting system and the deflection for evaluating its effectiveness.

Jan 1, 1962

By Ali M. Ghazi, Ronald J. Goble, Lowell S. Whiteside

"Geerite (Cu1.6S) is a rhombohedral copper sulphide which occurs naturally in epitactic replacement of sphalerite; cell dimensions closely approximate those of the host sphalerite.Geerite-type structures can be produced by leaching digenite (Cu1.8S) in ferric sulphate solutions. X -ray diffract ion and electron microprobe studies indicate that eight metastable geeritetype structures can be produced, depending upon the concentration of f erric sulphate solution used and the duration of the each. Although compositions cluster on or near values observed for natural phases, optical properties indicate that we are dealing with polymorphs of these phases. Leaching of chalcocite (CU2Sj in dilute f erric sulphate solutions produces similar results. In contrast, leaching of chalcocite in more concentrated solutions seems to produce true analogues of natural minerals.During froth flotation, sphalerite is activated with a monolayer of floatable copper sulphide with the composition, CuS, of the mineral covellite. However, covellite is not significantly more floatable than sphalerite, and has an incompatible structure because of the presence of covalently-bonded atoms of sulphur. Leaching ofdigenite was used to produce a polymorph of covellite with a geerite-type structure, compatible with that of sphalerite. This polymorph has a flotational behaviour similar to copper-activated sphalerite, suggesting that the monolayer has a geerite-type CuS structure. IntroductionIn an ideal close-packed sulphide structure the distance between sulphur layers, D, is equal to 2R 2/3, where R is the radius of the sulphur atoms. In sulphides with covalently-bonded sulphur layers, such as covellite (Fig. I), D will be an average of the number of covalentl y-bonded and close-packed sulphur layers, weighted as to the relative number of each type of layer. Both D and R are spacings which are readily identifiable structurally and on X-ray diffraction patterns. Goblel has shown that for copper-iron sulphides with metal-to-sulphur ratios between 0 and 2 and copper-to-total metal ratio s between 113 and I there are strong correlations between composition and measured D and R distances (Fig. 2). D can be represented by a single empirical equation relating interlayer spacing to composition; R must be represented by three equations relating the radius of sulphur atoms to composition. One of these equations (R, in Fig. 2) represents ideal close-packed behaviour, the other two represent sulphur radii greater than (R1) or less than (Rh) the ideal."

Jan 1, 1988

By V. L. Elliott, C. L. Meyette

The conditioning of semifinished steel products such as billets, blooms, and slabs to remove surface defects before further processing to finished products is a necessary accompaniment to steel mill rolling operations. A knowledge of the kinds of defects which occur and of the conditions in melting, teeming, and rolling that may lead to their occurrence is favorable to the production of quality products. Surface defects may be classed as either of mechanical origin such as those that occur in the heating and rolling operations and include breaks, tears, guide marks, mechanical laps and the like, or they may have been in the ingot before heating and rolling. Examples of the latter are ingot cracks, blow-holes, scabs, and inclusions which lead to the numerous known types of seams and surface flaws. Most of the common types of surface defects and methods for their identification by visual examination or by the aid of macro-etch tests are well known. The conditions which caused their formation are also appreciably understood and this knowledge has been instrumental in the establishment of methods for metallurgical control. There are, however, defects of doubtful origin. In any endeavor to trace the causes for their occurrence, the question of first concern is: I. Whether they were formed in the rolling procedure. 2. Whether they existed in the ingot prior to rolling. In the case of semifinished products which are rerolled to finished products there is also the question of whether they were formed in the primary or in the secondary rolling. In metallurgical laboratories where numerous or routine examinations of the quality of rolled products are made over the course of time, there will doubtless be many puzzling cases of defect origin. Microscopic examination of the defects may, however, reveal a characterizing condition that can be used to classify them broadly with respect to their origin. Such a condition has been observed and, after detailed investigation, is described here with the thought that it may offer a usable and relatively simple solution to a bothersome problem. Basis For Classifying In this discussion the term "mechanical type defects" will be used to designate those that have occurred as a result of the rolling operations such as in rolling from the ingot to billets, blooms, or slabs or in rerolling to finished products. The term "steel type defects" will be used to designate those that were present in the ingot prior to primary rolling or that were in the semifinished product prior to secondary rolling to finished product. The basis for distinguishing between the two types of defects lies in the relative degree of subscale formation surrounding them. Subscale is defined1 as a zone of

Jan 1, 1949

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May 1, 2006

By Walter Harvey Weed

Introductory.............449 Summary oF Types............452 I. The Virgilina Type...........452 The Virgilina mines...........452 Location.............452 History.............453 The rocks of the district..........453 The veins.............454 Notes on the mines.... 458 The Holloway. 458; Yancey and Durgy. 465 ; Copper World. 467 ; Frazier. 467 ; Thomas. 467 ; Anaconda. 468; Blue Wing. 468; High Hill. 472; Dorothy.......474 II. The Gold Hill Type...........474 The Gold Hill mine...........475 Location.............475 History............• 475 Surface improvements.......... 476 The rocks............478 Vein.phenomena...........478 Character of the ore..........481 Origin of the ore...........481 Notes on the mine.workings.........482 Other occurrences of ore-deposits of the Gold Hill type.. .. 483 III. The Ducktown Type..........484 The Ducktown mines...........485 Other examples of the Ducktown type....... 494 Alabama mines...........494 North Carolina examples : Ore Knob.......496 Virginia examples..........497 IV. The Catoctin Type.. ......... 498 General characteristics,......... 498 The Linden district...........499 General distribution of the Catoctin type.......503 Introductory. In the early history of this country the existence of copper in the Appalachian region was well known. but no mining mas attempted until the discovery of the Ducktown deposits in

Jan 1, 1901

By George R. St. Pierre, John Chipman

METALLURGISTS have been studying the chem-ical behavior of sulfur in steelmaking for many years in order to have a better control of the sulfur content of finished steel. During the refining period in the open hearth, molten steel is separated from a gas phase by molten slag. Chemical reactions occur principally at the slag-metal interface and at the slag-gas interface. A need for physical-chemical investigations of reactions between sulfur-bearing gases and steelmaking slags was recognized some time ago.'.' From the early work, it can be qualitatively concluded that increased sulfur content and low partial pressure of oxygen in the gas phase favor the passage of sulfur from gas to slag. Using radioactive sulfur S Koch and Fink' have demonstrated the rapid rate of exchange of sulfur between gas and slag in an open hearth furnace. Gurry and Darken and Darken and Shields (as reported by Derge and Marshall') have equilibrated lime-iron oxide slags with SO—O2 gas mixtures. The major conclusion from the reported results is that sulfur content increases with increasing lime content in lime-iron oxide slags equilibrated with a gas of high oxygen pressure (10-2). The data were interpreted as indicating the presence of SO, and S,O, ions. Richardson and Fincham' have conducted the most extensive experimental study of sulfur equilibria between gas and slag. Their results confirmed many of the conclusions drawn from calculations of Richardson" and Withers. Richardson and Fincham's data fitted very well into the sulfur scheme represented by the reactions 1/2 s2 (g) + (0) melt - 1/202(g)+ (S) melt [II 1/2 S, (g) + 3/2 O (g) + (0) melt - (SO,) melt. [2] At oxygen pressures greater than 10 to 10 they found that reaction Eq. 2 was predominant while reaction Eq. 1 was controlling at oxygen pressures less than 10." to 10.". The slag compositions and gas mixtures used in their investigations were different from those used in the present study. Wherever possible, comparison has been made between their results and these, and agreement is excellent. It is evident that the distribution of sulfur between slag and gas depends upon the oxygen pressure of the gas. In FeO slags, a change in oxygen pressure produces a change in ferric oxide content, and a knowledge of this equilibrium is a prerequisite to studies of sulfur distribution. The data are found in the work of Darken and Gurry" on the FeO system and the more recent experiments of Gurry and Darken" and of Larson and Chipman" on FeO slags containing lime and silica. The effect of oxygen pressure on the ratio Fe /(Fe" + Fe ), the so-called j-ratio, reported by these investigators will be used in interpreting the results which follow. Experimental Method The purpose of the experimental program was to determine the equilibrium sulfur content in slags exposed to gases of known oxygen and sulfur pres- sures. The slag compositions selected for study were from the lime-silica-iron oxide system. Additions of magnesia were made to some of the slags. Apparatus—The apparatus used by Larson and Chipman was modified slightly to accommodate the addition of SO2 to the gas mixtures. As in their work, slag samples of 0.5 to 2.0 g were held at temperature (lcc) in platinum crucibles under a steady stream of gas, 100 to 200 ml per min, for several hours and then rapidly lowered to the bottom of the furnace where they were quenched in mercury. Preparation and Analysis of Gas Mixtures—Mixtures of SO,-CO were prepared from Virginia Smelting Co. Extra Dry liquid SO, and Pure Co. CO,. After removing traces of water vapor with an-hydrone, the CO, was passed over graphite at 1200°C, at which temperature the conversion to

Jan 1, 1957

By Vernon R. Miller

The Bureau of Mines developed and evaluated a detector-sorting device to separate the copper-bearing portion from the barren portion of native copper ores. Small-scale sorting tests were run on minus 1-inch plus 1/2-inch size materials from the following Michigan samples: Winona, Kingston, and Centennial ores, and "poor" rock from the Champion mine dump. Results showed that 60 to 85 pct of the copper was recovered in 9 to 19 wt-pct of the sorted fraction. About 90 pct of the copper recovered was obtained in the first pass through the sorter. For the Kingston and Centennial ores, combinations of sorter concentrates and fines generated during crushing, resulted in recoveries of 93 and 94 pct, respectively, of the total copper in the samples. The combined products constituted about 66 wt-pct of the total sample and allowed the balance to be discarded with only a 6 to 7 pct copper loss.

Jan 1, 1974