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By S. E. Buckley, M. C. Leverett

THE production of oil is accomplished as a result of its displacement from the reservoir by either gas or water, and the amount of oil recovery is limited by the extent to which the displacing gas or water accumulates. This paper describes the mechanism by which the displacement is effected and the advantages of water over gas as a displacing agent. In the light of the results of experimental observations of the flow of mixtures of oil and/or gas and/or water through sands, certain conclusions are drawn relative to the changing character of the displacement as depletion proceeds, and on the effects of the properties of the fluids and of producing conditions on the ultimate oil recovery. INTRODUCTION Crude oil has no inherent ability to expel itself from the pores of the reservoir rocks in which it is found; rather, it must be forcibly ejected or displaced by the accumulation of other fluids. Accordingly, a knowledge of the mechanism by which one fluid is displaced by another is essential to an understanding of the fundamental process by which oil is recovered. The displacing fluids normally available are gas and water, either or both of which may exist originally associated with the oil in a potentially usable form or may be supplied to the reservoir from external sources. Gas is present in most oil reservoirs. If the quantity is relatively small, it may exist originally completely dissolved in the oil, but if the quantity exceeds that which may be held in solution by the oil at the prevailing pressure, the excess will be found in the free state. Most reservoir sands appear to contain some water,1 and in the majority of fields the oil is trapped in the structure and held over water. In certain conditions the entrapping water may advance into the oil zone and displace the oil therefrom. This paper describes in a qualitative manner some of the characteristics of the displacement of oil by either gas or water, with an attempt to elucidate somewhat the mechanism by which such displacement is effected. ROLE OF DISSOLVED GAS When the pressure on an oil containing dissolved gas is reduced to the saturation or bubble-point pressure, gas escapes from solution and expands, imparting to the oil-gas mixture a high degree of expansibility and causing it to flow in the direction of reduced pressure. This expansibility has frequently been attributed to the oil; closer analysis, however, reveals that as gas escapes from solution the oil phase actually contracts. Hence, it is the accumulation and expansion of the liberated gas that supplies the propelling force for the oil. It has been shown experimentally2-5 that within certain limits a sand containing oil, gas and water will permit the simultaneous flow of all three; the readiness with which they may flow depends upon the characteristics of the sand, of each of the fluids, and upon the relative amounts of the fluids in the sand. Thus, in the initial stages of production by the mechanism of dissolved gas drive, the liberated gas is present in the sand in low concentration and is unable to

Jan 1, 1941

By W. B. Greer, J. J. K. Daemen

Introduction The performance of seals in boreholes, shafts and tunnels is an important concern in mine safety, in the control of effluents from operating and abandoned mines and in the underground containment of hazardous wastes (Einarson and Abel, 1990; Mining Waste Study, 1988). Despite the clear need for effective seals, few documented test results are available concerning the performance of in situ seals. Some evidence indicates that horizontal or near-horizontal holes are especially difficult to seal properly (Kelsall et al., 1982). This research involved the installation, extensive hydraulic testing, removal and post-test examination of a 10-cm-long x 10-cm-diam cement grout seal in a near-horizontal borehole in limestone. The work was performed in an underground mine on Marble Peak in the Santa Catalina Mountains, AZ. A test hole was diamond cored in the recrystallized limestone of the Escabrosa formation. The hole is 33.24 m long, 10 cm in diam, and dips at 10.4°. The hole extends between two drifts and thus is accessible from both ends. Seal installation Surveys to assist in selecting the interval to seal consisted of core logging, video logging and constant-head injection tests using a straddle-packer unit. The location selected, 3 m from the lower end of the hole, had low hydraulic conductivity (3 x 10-10 to 3 x 10-9 cm/sec) and was free of significant fractures. The grout used, an expansive Class A cement, was provided by Dowell-Schlumberger, Tulsa, OK. A grout mass about 1.5 m in length was installed, with a dump bailer, above a temporary mechanical plug. Groundwater in the hole, if any, was minimal during placement. After 13 days of curing, the grout mass was partially drilled out from both ends, leaving a seal 10 cm long. Water distribution in rock mass The distribution of water and fluid pressure in the rock mass near the seal appears to be complex. The generally dry condition of the borehole and rock mass suggests that the rock mass near the seal was unsaturated prior to the injection tests of this research. The injection tests presumably created an expanding saturated zone around the seal. However, anomalously high fluid pressures, consistently recorded by one of two piezometers installed near the seal, suggest connection to a source of significant natural hydraulic head. Comparable head variations for closely spaced piezometers have been reported by others (Sowers, 1976). [ ] Seal testing The seal was tested for 3.5 years, using steady constant-head, tracer travel-time, dye-injection, head-buildup and transient constant-head tests. These tests are fully described in Greer and Daemen, 1991. In the head-buildup test, transient flow occurs through the seal (and rock mass) to a closed, water-filled interval of the borehole adjacent to the seal. The test consists of monitoring the rise in head in the closed interval until steady conditions are approached. The test may be analyzed in terms of a one dimensional analytical model to obtain the effective hydraulic conductivity (Ks) and specific storage (Sss) of the seal. Analysis in terms of an axisymmetric three-dimensional numerical model may yield properties of both the seal and rock mass.

Jan 1, 1993

By L. B. Schmitt, N. H. Polakowski

Square bars of cold-dvawn copper, mild steel and a 2024 aluminum alloy were forced through an adjulstable gap between two hardened steel rollers by pulling or pushing. The rollers were either free to rotate or were locked in position so that conditions comparable with drawing, rolling, ad containerless extrusion could be created at will. Push or pull forces as well as roll separatirg forces were measured. Forming efficiency and coefficients of friction were determined. For- slow-rate deformation the values ot µ wrere between 0.09 and 0.14. Possibilities for further investigation are indicated. THIS work was undertaken with the aim of a) determining the principal parameters of cold drawing under simplified conditions directly, without recourse to speculative assumptions and b) comparing drawing with rolling and extrusion from the viewpoint of forces involved and deformation efficiency. Data of type a) relating forces in axially-symmet-rical drawing to die geometry. drafting schedules, material properties and lubrication conditions are abundant. Their intrinsic value is. however. limited as long as the radial die forces are unknown. On the other hand. the difficulties associated with measurement of these forces are serious as witnessed by the extreme paucity of such information."" Comparative investigations of type b) were also remarkably few and they all employed ring-shaped dies through which round bars were either drawn or pushed.2-4 Only in one case were the applied and the die splitting forces measured simultaneously.2 In order to simplify the problem, deformation under approximately biaxial conditions was adopted in the present work;. This enables both the drawing (rolling, extruding) efforts and the separating forces to be measured with reasonable ease by conventional methods. Since drawing, extrusion, and rolling can be carried out under virtually identical conditions only in a roller die. an adjustable tool of this type was constructed. The circular die profile involved a difficulty with interpreting the drawing and extrusion data. This was obviated by arbitrarily defining the angle between a contact chord and the drawing plane as the -.equivalent" die semiangle. The simplification was considered permissible since the effect of die angle was not specifically investigated. An additional conlplication was caused by the square cross section of the processed bars. This shape was selected as a compromise between the desire to have as massive as possible specimens and the capacity of the roller die. The metal was only partially restrained from spreading laterally. the flow conditions being therefore intermediate between plane stress and plane strain. On the Huber-Mises yield criterion the constrained and uni-axial yield strengths differ by up to 16 pct but the actual error due to the ignorance of the constraint factor was presumably much smaller than the maximum. In spite of these reservations it was felt that the method employed and results obtained have some merit. With certain further refinements to be indicated later, this technique can yield data perhaps more useful for checking metal forming theories than other, mostly indirect, methods. EXPERIMENTAL Materials—The metals used together with their principal mechanical properties are listed in Table I.

Jan 1, 1961

By C. J. Rodgers

The present day success of gravel packs to prevent or retard the migration of unconsolidated sands into the well bore is due to: (I) the use of a saline or non-aqueous, nonsolids drill fluid, (2) proper preparation of the well bore prior to gravel packing, and (3) pressure placement of the gravel. The experience gained from the "pressure pack" method of gravel packing indicates that sand-free fluid production can be maintained for a length of time sufficient to make the operation economically attractive. Data pertaining to the first 15 wells so completed by Gulf indicate that for each dollar spent to effect the completion, there will be a return of more than $2.92. The pressure pack technique of gravel packing is essentially the placing of gravel in and adjacent to the producing formations. This is done with fluid pressure and by the use of a drill fluid that will permit partial or complete loss of returns to the formation during placement. This technique was first intentionally used by Gulf in May, 1950, and since that time has been applied in more than 90 wells. Other advantages claimed for this type of completion are that the pressure placement of the gravel has a scouring effect on the casing perforations, that additional drainage channels to the well bore are created, and that the possibility of shifting of the formations adjacent to the casing is minimized and possibly prevented. During the past few years, the use of gravel to prevent or retard the migration of unconsolidated sands into the well bore has met with a favorable degree of success. Numerous methods and techniques of "gravel packing" have been used, each having its own relative merits, and with varying results. M. L. Cashion1 in 1939 ably reviewed the history of gravel packing to that time. As stated in his paper, ". .. the idea of gravel packing wells is not new." During the period 1939 to 1949, very little if any progress or change in technique in this type of completion was made. However, it was noted in some cases that during the placement of gravel, if there was a loss of drill fluid to the formation, there was a corresponding loss of gravel to the formation. Also, it was noted that in those gravel-packed completions (opposite casing perforations) that "sanded up," there was found to be an absence of gravel in the annular space between the liner and casing, although gravel had previously been placed in this space and no gravel had been removed from the well at the surface. These findings resulted in the placement of gravel with fluid pressure and by the use of a drill fluid that would permit partial or complete loss of returns to the formation during placement. Pressure placement of gravel became an accepted practice in late 1949 and early 1950. Another fact brought to light that has contributed to the current success of gravel pack completions is that drilling fluids containing solids will to some extent cause plugging of the screening medium or blocking of the producing section. The removal of these solids by chemical action, mechanical action, or a combination of the

Jan 1, 1955

By S. E. Buckley, M. C. Leverett

The production of oil is accomplished as a result of its displacement from the reservoir by either gas or water, and the amount of oil recovery is limited by the extent to which the displacing gas or water accumulates. This paper describes the mechanism by which the displacement is effected and the advantages of water over gas as a displacing agent. In the light of the results of experimental observations of the flow of mixtures of oil and/or gas and/or water through sands, certain conclusions are drawn relative to the changing character of the displacement as depletion proceeds, and on the effects of the properties of the fluids and of producing conditions on the ultimate oil recovery. Introduction Crude oil has no inherent ability to expel itself from the pores of the reservoir rocks in which it is found; rather, it must be forcibly ejected or displaced by the accumulation of other fluids. Accordingly, a knowledge of the mechanism by which one fluid is displaced by another is essential to an understanding of the fundamental process by which oil is recovered. The displacing fluids normally available are gas and water, either or both of which may exist originally associated with the oil in a potentially usable form or may be supplied to the reservoir from external sources. Gas is present in most oil reservoirs. If the quantity is relatively small, it may exist originally completely dissolved in the oil, but if the quantity exceeds that which may be held in solution by the oil at the prevailing pressure, the excess will be found in the free state. Most reservoir sands appear to contain some water,l and in the majority of fields the oil is trapped in the structure and held over water. In certain conditions the entrapping water may advance into the oil zone and displace the oil therefrom. This paper describes in a qualitative manner some of the characteristics of the displacement of oil by either gas or water, with an attempt to elucidate somewhat the mechanism by which such displacement is effected. Role of Dissolved Gas When the pressure on an oil containing dissolved gas is reduced to the saturation or bubble-point pressure, gas escapes from solution and expands, imparting to the oil-gas mixture a high degree of expansibility and causing it to flow in the direction of reduced pressure. This expansibility has frequently been attributed to the oil; closer analysis, however, reveals that as gas escapes from solution the oil phase actually. contracts. Hence, it is the accumulation and expansion of the liberated gas that supplies the propelling force for the oil. It has been shown experimentally2-5 that within certain limits a sand containing oil, gas and water will permit the simultaneous flow of all three; the readiness with which they may flow depends upon the characteristics of the sand, of each of the fluids, and upon the relative amounts of the fluids in the sand. Thus, in the initial stages of production by the mechanism of dissolved gas drive, the liberated gas is present in the sand in low concentration and is unable to

Jan 1, 1942

By P. W. Bridgman

FLOW and fracture are admittedly complicated phenomena of which we are yet only partially masters. There is not even universal agreement as to the details of the language best adapted merely to describe the phenomena, to say nothing of any theory. Certain points of view, however, are widely held, and there are certain general expectations as to what sort of procedures will prove permissible. A complete description of any situation involving fracture would demand a complete history of all the variables in the control of the experimenter. The experimenter endeavors so to choose his independent variables that they are adequate to determine completely the situation in the sense that when an experiment is repeated on the same initial material and with the independent variables running through the same sequence, all the other measurable properties of the system will also run through the same course. It is, I think, the universal conviction that when we are dealing with phenomena of flow and fracture, the most important of the necessary variables are the external forces acting on the various parts of the body; when the force history repeats, with certain obvious restrictions such as that temperature must be constant and non- mechanical forces, such as magnetic field, must be small enough to be ineffective, then the history of all measurable properties will repeat; in particular the alteration of geometrical shape due to flow will run through the same course, and when fracture comes, the character of the fracture will be reproduced. Complete mastery of merely the descriptive aspects of flow and fracture would demand the ability to predict the entire course of flow and complete characterization of the final fracture for every possible combination of forces, varying in time in all possible ways, when applied to bodies of all possible shapes. This full situation is obviously of prohibitive complexity. The first stage in reduction to manage- able simplicity is to resolve the total situation into the sum of contributions made by small elements. Our thesis is that if each of the elements is adequately characterized, the behavior of the whole system is fixed. The element is usually taken of a simple geometrical shape, suggested by the mathematics best adapted to the particular situation. The forces acting across the faces of the elements are ultimately determined by the forces acting across the free faces of the whole system. The detailed process of finding the precise forces on the faces of all the elements in terms of the external forces involves the use of a special mathematical invention, the stress, a constructional quantity consisting of six components. The stress at any point in the body is determined by both the external force system and by the physical properties of the body at all points; quite different stresses prevail at the interior of bodies of the same shape under the same external forces in the elastic and plastic ranges. The forces on the faces of any element are, however, uniquely determined by the stress system at the element. Our fundamental thesis

Jan 1, 1944

By G. Abowitz, R. B. Gordon

The velocity of sound, mass density, and thermal expansion coefficient were measured in dilute lead, tin, zinc, bismuth, cadmium, indium, and potassium amalgams as a function of composition. Measurements in the Hg-TI system extended ovev the wider range of composition, 0 to 40 at. pct TI. The sonic velocity was measured as a function of temperature. The calculuted adiabatic compressibility in all cases was found to decrease much more rapidly than would be expected on the basis of a linear variation with composition. An interpretation of the results is given in terms of changes in the Debye characteris -tic temperature of mercury on alloying and a possible change in the bonding of mercury itself. If a liquid is considered as an isotropic elastic medium, the phase velocity of a longitudinal elastic wave traveling in the liquid is given by where K is the bulk modulus, G the shear modulus, and d the mass density. G can be neglected for liquids of ordinary viscosity, i.e., approximately 1CT2 poise, because the shear stress component is relaxed essentially at once. That is, for liquids of ordinary viscosity and at frequencies of the applied stress up to several hundred megacycles, the relaxation time of the shearing process is much shorter than the period of the applied stress. Eq. [I] then reduces to The adiabatic rather than the isothermal compressibility is measured at the megacycle frequencies used in ordinary ultrasonic velocity measurements. The sonic velocity and compressibility have been determined for many organic liquids and aqueous eletroltes,' and the results have been interpreted in terms of existing theories for these fluids. The velocity of sound and compressibility are important parameters in theories of the liquid state. For example, equations of state have been proposed relating the free volume of liquids to the acoustic velocity.3 Comparatively very little work has been done on the acoustic properties of liquid metals and alloys. leppa,' orddon, and several other investigators

Jan 1, 1963

By Kazuteru Tozawa, Robert G. Robins

"The stability of calcium arsenate is discussed in relation to the possible misuse of lime in the treatment of gold processing waste waters. Stability diagrams have been derived and experimental results cited to show that calcium arsenate has a higher solubility in neutral to alkaline solution than has previously been recognized and this solubility is further enhanced by the presence of carbon dioxide, bicarbonate or carbonate.IntroductionThe removal of arsenic from gold mine waste waters has been of interest for more than thirty years, but with the recent emphasis on clean water standards there has been renewed activity in relation to that problem. The processing of gold-bearing sulphides which contain arsenopyrite and other complex arsenic sulphides is well established. Initial roasting to oxidize the sulphides leaves the arsenic in the form of both arsenic and arsenic, in which forms it is soluble in the subsequent leaching stage. Further oxidation of the leach liquors is required before the well-established procedure of precipitating calcium arsenate with lime, which is carried out despite an immense lack of knowledge of the calcium-arsenic-water system.The solubility product and free energy of formation for Ca3(AsO4)2, which are to be found in recent and reliable sources of data, originate from the work of Chukhlansev, whose experimental determination of the concentration of calcium from the solubility of calcium arsenate in solutions of various pH yields the results plotted in Figure 1. This is the work which has resulted in a wide acceptance of the ""insolubility"" of calcium arsenate and the use of lime to stabilize arsenic in that form.Laguitton attempted to further elucidate the chemistry of the lime addition method for treating arsenical waste waters from gold processing operations. The low solubility product for Ca3(AsO4)2 was the basis for his examination of likely chemical equilibria in the system. Laguitton and other workers have not considered atmospheric carbon dioxide as an important component in this system."

Jan 1, 1982

By R. D. Pehlke, J. V. Gluck

A study was made of the effect of small additions of metallic solutes on the thermodynamic activity of zinc in dilute solution with molten bismuth in the range 450o to 650°C. The experimental measurements were made in a multielectrode galvanic cell using. a fused LiCl-KCl electrolyte. The activity of zinc in binary solution exhibited a strong positive deviation from Raoult's law and obeyed Henry 's law to at least 0.050 mole fraction. The ternary addition of lead, gallium, or indium increased the activity of zinc. Cadmium or tin additions slightly decreased the zinc activity. Copper, mercury, silver, or antimony caused moderate decreases, while gold strongly decreased the zinc activity. The results are expressed in terms of Wagner's interaction parameter ejZn and a second-order cross-interaction parameter. The interactions for copper, gold, silver, and antimony showed a linear dependence with reciprocal absolute temperature, while the other interactions were essentially independent of temperature over the experimental range. Since tin and antimony decreased the zinc activity, the hypothesis of a purely periodic variation with atomic number was rejected. A semiquantitative explanation was possible with a free-electron model when relative electronegativities were used to express changes in the electron/atom ratio caused by the solute addition. Random solution and quasi-chemical models correctly predicted the majority of the interactions for which binary data were available to apply them. A knowledge of the thermodynamic interactions in liquid (and solid) metallic solutions is of considerable theoretical and experimental interest in the formulation of quantitative thermodynamic relations for metallurgical processes. The approaches to defining the interactions may be either phenomenological (i.e., "What mathematical function adequately describes observed behavior and permits extrapolation to new situations?") or theoretical, such as a specific model

Jan 1, 1968

By Tweedy. D. H.

"The paper describes the rapid development of, and operational experience in the utilization of, pneumatic low-pressure pipeline hoisting systems to vertically convey raw coal and rock through shafts, supplementing shaft capacity-the greatest lift to date being 535 m.A typical installation has raised over 250,000 tonnes in less than one year from a depth of 413 m through a 350/ 400-mm pipeline at a rate of 85 tonnes per hour. Operational experience on seven systems has provided valuable data on performance and operating costs.The main advantages of the systems lie in the flexibility of the pipeline to occupy existing free space in shafts and underground roadways, the relatively low first cost, the short delivery and installation time, and the economical running cost.Conclusions are therefore reached on future applications for example, the use of boreholes in older mines where new production technology has outstripped shaft or slope capacity, inter-level hoisting to implement concentration on transport roads and perhaps full mine output from relatively small mines.IntroductionIt is seven years since the basic art and practice of the pneumatic hoisting of minerals was described. The technique was developed in Western Canada by Radmark Engineering and found favour in the United Kingdom with the National Coal Board. Engineering and commercial feasibility trails were conducted in collaboration with the Mining Department and Mining Research and Development Establishment of the N.C.B. There was also considerable involvement with the British Health and Safety Executive.During the last five years, rapid progress has been made in the installation of new systems in the United Kingdom, Hungary and other countries. The operational experience gained makes it possible to report ""in depth"" on these installations, which cover a wide range of different physical mining applications."

Jan 1, 1982

By G. C. Weatherly, L Beitelman, M Gray, M. W. Bates, R Hadden

"A program of evaluation of in-mould electromagnetic stirring on the product of a straight-mould, billet continuous casting machine has been carried out. The effects on macrostructure, surface and internal quality, chemistry segregation and mechanical properties on carbon, low-alloy and resulphurized, free-machining steel billets and rolled bars are discussed. Operational aspects as a result of in-mould stirring are highlightedIntroductionA development program on electromagnetic stirring (EMS) in the mould of a continuous caster was started by Ferrco Engineering Limited in 1979, with the first experimental device being developed and installed at Lake Ontario Steel Company. As a result of these initial trials, new designs of in-mould EMS systems have been developed and are currently being used in continuous casters in North America and Europe. The rapid progress which has been made is in large measure due to the fruitful cooperation which has existed between the various parties, including Ferrco, the EMS equipment manufacturer, several operating plants and the University of Toronto.A brief review of some of the basic ' principles of electromagnetic stirring action on solidifying metal, and the landmarks of this process development, will explain the philosophy of this cooperation.From casting practice, it is well known that an equiaxed dendritic structure provides better' material properties than a columnar dendritic structure. Homogeneity of the equiaxed structure leads to better control of material properties, such as strength and ductility. Therefore, many efforts are being made to obtain this structure in continuous casting.The extent of the equiaxed zone is determined to a large degree by convective flow in the liquid. Fluid flow can fragment dendrites in the columnar zone, which then act as nuclei for grains in the equiaxed zone farther down the sump. This process is referred to as dendrite or grain multiplication."

Jan 1, 1982

By J. Charles Miller

Natural carbon dioxide has recently been exploited in the United States in consequence of oil and gas developments in the Western States and the growing demand by transcontinental and transoceanic shippers for solid carbon dioxidc. The discovery by drilling of commercial deposits resulted in consideration of its geographic and geologic distribution and occurrence. Its wide distribution in nature is evidenced by its occurrence in the atmosphere, hydrosphere and lithosphere. The question of origin of carbon dioxide involves consideration of theories similar to those concerning natural hydrocarbons, although available evidence favors an inorganic rather than an organic source. Areas favorable to development of commercia1 production appear to be those in proximity to igneous rocks or in the vicinity of decadent volcanic activity, where, it has long been known, the gas is evolved either free or dissolved in the waters of fumaroles, geysers or mud pots. Structure contour maps are presented showing the Wagon Mound anticline in New Mexico and the Farnham anticline, Utah. A well drilled on the latter supplies gas to a 20-ton plant manufacturing solid carbon dioxide at Wellington, Utah, on the Denver and Rio Grande R.R., whence it is shipped to surrounding territory and to the West Coast. Before funds are invested in a plant for the manufacture of liquid or solid carbon dioxide, whether supplied by wells or springs, an effort to ascertain the volume of gas available is advisable. The use of present methods of estimation of gas reserves with modifications to account for the quantity absorbed by any water present in the producing formation is recommended. The Farnham anticline is used as an example and computations are made of the probable volume of gas originally present in the structure. No attempt was made to compute reserves in the Niland area, California, for the reason that in such areas it is believed the volume is indeterminate. Introduction Carbon dioxide, in liquid and solid form, has found a wide variety of uses other than its primary application in carbonating beverages. It is now used in more than 40 different ways, ranging from cooling or freezing to use in gas or liquid form for mechanical purposes, chemical industry, explosive, fire extinction, and tire manufacturing. Undoubtedly the chief supply of carbon dioxide is obtained from industrial plants or artificial sources and until recently natural deposits of the gas have received little consideration. Few will question the utility and perhaps dependability of artificial sources, which possess the advantage over

Jan 1, 1941

By Edward Saibel

The various theories that have been advanced to explain or predict the conditions under which a metal fractures may be divided into two categories: First, there are the macroscopic theories generally used in engineering practice. These are empirical in nature and limited in application. For example, the maximum normal stress criterion, which is quite satisfactory for a mild steel in simple tension at atmospheric pressure,' no longer suffices when this steel is pulled under hydrostatic pressure.2 In all of these empirical theories, the critical condition characteristic of the material and of the loading conditions must be obtained experimentally. Secondly, there are the theories based on interatomic forces,3'4 or on the energy required to form new surfaces.5,6 These have all dealt with the theoretical evaluation of the tensile stress necessary to bring about rupture in a purely brittle manner; that is, without plastic flow preceding fracture. All of these attempts have led to values of the tensile strength of crystals or of polycrystalline bodies that are 100 to 1000 times higher than observed values. On this account, it has been thought necessary by some investigators to conceive of a microcrack structure or distribution of flaws throughout the specimen such that the resulting stress concentrations provide the factor necessary to bring about agree- ment between calculation and experiment. It has been pointed out by several observers' that this point of view is highly unrealistic, in that the weakening effect of these flaws or microstructures must be very uniform from specimen to specimen, since the fracture stresses found for various specimens of the same material tested under similar conditions are so nearly constant. Furthermore, since calculations based on atomic forces or atomic energy are for purely brittle fracture, a condition probably never satisfied in tests, agreement is hardly to be expected. Thermodynamic Theory of Fürth In order to resolve this apparent discrepancy between the theoretical cohesive strengths and the observed fracture strengths, Fürth8 advanced a thermodynamic theory of the tensile strength of isotropic bodies based on work of Born relating to the melting of crystals. Assuming an isotropic material free from imperfections and flaws, behaving elastically up to the breaking point, and assuming a connection between rupture and the melting phenomenon, Fürth obtains an expression for the rupture stress a, in the form where Q is the melting energy per unit mass, p is the density, and is Poisson's ratio. Furth compares fracture stresses computed from Eq I with the fracture stresses of metals as given in the Landolt-Bernstein Tables (1927) and in the Hand-

Jan 1, 1947

By J. Charles Miller

Natural carbon dioxide has recently been exploited in the United States in consequence of oil and gas developments in the Western States and the growing demand by transcontinental and transoceanic shippers for solid carbon dioxidc. The discovery by drilling of commercial deposits resulted in consideration of its geographic and geologic distribution and occurrence. Its wide distribution in nature is evidenced by its occurrence in the atmosphere, hydrosphere and lithosphere. The question of origin of carbon dioxide involves consideration of theories similar to those concerning natural hydrocarbons, although available evidence favors an inorganic rather than an organic source. Areas favorable to development of commercia1 production appear to be those in proximity to igneous rocks or in the vicinity of decadent volcanic activity, where, it has long been known, the gas is evolved either free or dissolved in the waters of fumaroles, geysers or mud pots. Structure contour maps are presented showing the Wagon Mound anticline in New Mexico and the Farnham anticline, Utah. A well drilled on the latter supplies gas to a 20-ton plant manufacturing solid carbon dioxide at Wellington, Utah, on the Denver and Rio Grande R.R., whence it is shipped to surrounding territory and to the West Coast. Before funds are invested in a plant for the manufacture of liquid or solid carbon dioxide, whether supplied by wells or springs, an effort to ascertain the volume of gas available is advisable. The use of present methods of estimation of gas reserves with modifications to account for the quantity absorbed by any water present in the producing formation is recommended. The Farnham anticline is used as an example and computations are made of the probable volume of gas originally present in the structure. No attempt was made to compute reserves in the Niland area, California, for the reason that in such areas it is believed the volume is indeterminate. Introduction Carbon dioxide, in liquid and solid form, has found a wide variety of uses other than its primary application in carbonating beverages. It is now used in more than 40 different ways, ranging from cooling or freezing to use in gas or liquid form for mechanical purposes, chemical industry, explosive, fire extinction, and tire manufacturing. Undoubtedly the chief supply of carbon dioxide is obtained from industrial plants or artificial sources and until recently natural deposits of the gas have received little consideration. Few will question the utility and perhaps dependability of artificial sources, which possess the advantage over

Jan 1, 1941

By Edward Saibel

The various theories that have been advanced to explain or predict the conditions under which a metal fractures may be divided into two categories: First, there are the macroscopic theories generally used in engineering practice. These are empirical in nature and limited in application. For example, the maximum normal stress criterion, which is quite satisfactory for a mild steel in simple tension at atmospheric pressure,' no longer suffices when this steel is pulled under hydrostatic pressure.2 In all of these empirical theories, the critical condition characteristic of the material and of the loading conditions must be obtained experimentally. Secondly, there are the theories based on interatomic forces,3'4 or on the energy required to form new surfaces.5,6 These have all dealt with the theoretical evaluation of the tensile stress necessary to bring about rupture in a purely brittle manner; that is, without plastic flow preceding fracture. All of these attempts have led to values of the tensile strength of crystals or of polycrystalline bodies that are 100 to 1000 times higher than observed values. On this account, it has been thought necessary by some investigators to conceive of a microcrack structure or distribution of flaws throughout the specimen such that the resulting stress concentrations provide the factor necessary to bring about agree- ment between calculation and experiment. It has been pointed out by several observers' that this point of view is highly unrealistic, in that the weakening effect of these flaws or microstructures must be very uniform from specimen to specimen, since the fracture stresses found for various specimens of the same material tested under similar conditions are so nearly constant. Furthermore, since calculations based on atomic forces or atomic energy are for purely brittle fracture, a condition probably never satisfied in tests, agreement is hardly to be expected. Thermodynamic Theory of Fürth In order to resolve this apparent discrepancy between the theoretical cohesive strengths and the observed fracture strengths, Fürth8 advanced a thermodynamic theory of the tensile strength of isotropic bodies based on work of Born relating to the melting of crystals. Assuming an isotropic material free from imperfections and flaws, behaving elastically up to the breaking point, and assuming a connection between rupture and the melting phenomenon, Fürth obtains an expression for the rupture stress a, in the form where Q is the melting energy per unit mass, p is the density, and is Poisson's ratio. Furth compares fracture stresses computed from Eq I with the fracture stresses of metals as given in the Landolt-Bernstein Tables (1927) and in the Hand-

Jan 1, 1947

By C. S. Barrett, O. R. Trautz

PREVIOUS investigations have shown that lithium is body-centered cubic from near its melting point to the temperature of liquid air1,2,3 Nevertheless there was an incentive to search again for a transformation at low temperatures: C. Zener4,5 has remarked that the low value of the elastic modulus (11 - C12)/2 of body-centered cubic metals and alloys implies a rapid increase in free energy with decreasing temperature, which would favor the occurrence of a transformation; also the shear movement to which this modulus applies is one that can transform a body-centered cubic structure into a slightly distorted face-centered cubic structure. It was confirmed that lithium does not transform spontaneously at liquid nitrogen temperature, but it was found that a transformation can be induced at this temperature by cold working the metal,6 and at slightly lower temperatures a different transformation occurs spontaneously. Transformations were also found in solid solutions of magnesium in lithium. THE NATURE OF THE TRANSFORMATIONS Before presenting a detailed treatment of the technique used and the specific data obtained, it would be well to give a brief survey of the general characteristics of the transformations. A new crystal structure begins to form spontaneously in a specimen when it is cooled below a critical temperature. In lithium the structure appears to be close-packed hexagonal; in the Li-Mg alloys most of the diffraction lines (but not all) are near those for hexagonal lithium. The transformation proceeds as the temperature is lowered and soon stops if the temperature is held constant or raised. The course of the transformation on cooling is indicated by the curve at the lower left of Fig I. This curve is drawn in stepped fashion because the transformation goes by discrete steps with audible clicks. Because of the similarity to the decomposition of austenite into martensite in steels, it seems appropriate to designate the beginning of the spontaneous transformation on cooling as the Ms point. On heating to room temperature after the low temperature treatment only the usual BCC structure is found. On heating, the low temperature modification begins to disappear at a temperature which will be designated as Ac. The transformation on heating is halted when the rise in temperature is halted. The temperature must be raised 40 to 50°C above Ac before the reversion is complete-an interval which is sensitive to the rate of heating and to the time of holding at temperatures above Ac. This behavior on heating thus has similarities also to the formation of martensite in the cooling of steels.

Jan 1, 1948

By J. Larsen-Badse

The resistance to dry sliding abrasion us been measured for some hardened and tempered carbon steels. The wear resistance, defined as the reciprocal of the volume loss per unit sliding distance, is found to vary linearly with the hardness of the abraded surface. The data fit two lines, one, of high slope, for the pure metals and for the annealed steels and another, of smaller slope, for the hardened and tempered carbon steels. A relationship is developed showing the alwasion resistance to be proportional to the hardness of the material and to en, where n is the exponent of work hardening. The values of n and of the hardness FOR most materials a high resistance to abrasion is generally associated with a high value of indentation hardness. Brine11 even used the abrasion resistance as a measure of hardness in an attempt at expanding the hardness range covered by his indentation-hardness test.' When comparing different types of materials there is, however, only a very general relation between abrasion resistance and hardness. Sample brittleness seems to contribute to the deviation from a direct relationship. In general, increased brittle- are those relating to the heavily deformed abraded surface. However, for materials having n constant or varying m a regular manner over a wide range of strailts, the wear resistance will also be a linear function of the bulk hardness of the material. For tempered steels containing a dispersion of cementite in ferrite the increase in wear resistance due to the dispersion is found to be a linear function of the volume fraction of Fe3C and of the reciprocal of the mean free ferrite path. This indicates indirectly that the yielding of this material, when it is already heavily deformed, follows the Orowan criterion. ness leads to decreased abrasion resistance.' When comparing materials in the same group, e.g., the metals, the spread is less. Kruschov found that the abrasion resistance of pure metals and of annealed steels is directly proportional to the hardness of the metal. For hardened and tempered steels he obtained another linear relationship, one of smaller slope and intersecting the line for the pure metals at the location of the data for the annealed steels. He also found that the abrasion resistance of cold-worked metals is independent of the degree of cold working. This shows, as he concluded, that the process of abrasion work hardens the metal in the surface region to a very high degree.

Jan 1, 1967

By J. W. Hickman

Most of the electron diffraction studies of oxide films which form on metals and alloys have been carried out by oxidizing the specimens in an auxiliary furnace, cooling down to room temperature and then inserting the sample in the camera and taking a diffraction photograph. Prior to the investigations at the Westinghouse Research Laboratories, no systematic study of the oxidation of any metal or alloy had been made over a wide temperature range with photographs taken at elevated temperatures except the investigation of iron by Jackson and Quarrell.' In order to interpret the electron diffraction patterns of the oxides which may form on alloys, it seemed advisable to make a comprehensive study of the oxidation of the purest metals available in the bulk form. Thus far studies have been completed on iron,2 cobalt,~ nickel,= chromium,= copper,z tungsten,s molybdenum,3 beryllium,' uranium,' thorium,' titanium6 and zirconium6 while investigations are in progress on tantalum and columbium. The next step in the study is concerned with the investigation of the oxides which form on binary alloys. Some of the alloys consist of a single phase while others contain more than one phase. The identification of the oxides on the surface of a binary alloy may be more difficult than on the metals since oxides containing both metals as well as those of each metal separately may form. Furthermore, it is possible that solid solutions of the various oxides may occur. In these cases the electron diffraction method may not be able to identify the oxidation products unequivocally. Examples of solid solutions which may present difficulties are MOO* and WOp, Fe304 and FeO.CrnOa since the diffraction patterns are so similar. Since electron diffraction can determine only the structure of the oxide, the chemical composition must be inferred from the diffraction data based upon X ray diffraction investigations of specimens of known composition. It is possible in some cases to decide whether a given solid phase reaction can occur on the surface of an alloy by a study of available thermodynamic data. Table I lists the equations for the formation of most of the oxides from the elements together with values of loglo Kg for the several temperatures. AF"B = -RT In KR AF°R and KR are the free energy and equilibrium constant of the reaction. Calculations may be made using the the given in I 1 to determine whether a given solid phase reaction is possible thermodynamically. For example, a solid phase reaction should occur between aluminum and chromium oxide to form

Jan 1, 1949

By O. C. Ralston, F. Fraas

VIRTUALLY all commercial use of electrostatic separation has employed separators depending on differences of conductance of the broken, solid mixtures treated by them. The two main types of conductance separators have been: (1) Those in which the separating field is as near a static field between two charged electrodes as it is possible to maintain in the face of the usual leakage that takes place between electrodes with some 5 to 50 kv tension between them and spacing of 1/2 to 3 in.; (2) those in which a convective discharge of corona or spray type, but not a spark discharge, takes place between the carrier electrode and a charged electrode facing it, which is of very restricted area, such as a row of needle points or a small diameter wire parallel to the face of the carrier electrode. The present paper deals with this latter type. The principle is usable in separators where the carrier electrode, usually grounded, has the shape of a roller, a conveyor belt, a vibrating table, a sloping chute, or a nearly vertical plate. The innovation studied by us has been the use of the convective field for charging material on the carrier electrode and succeeded by a field between the carrier electrode and an electrode made of a true dielectric which cannot take on a charge by conduction but is charged by being in the radius of the corona discharge. The acquired charge is of the same sign as that of the corona but is not dischargable by contact with a good conductor. However, high-tension charge tends to leak off because of the ionization of the ambient air. The field between this electrode and the carrier electrode is as near static as it is possible to obtain. There are some differences in behavior of this electrode and that of the gas tube electrode used by Sutton, as will be discussed below. Both electrodes cause increased adhesion of nonconductive particles to the carrier roll. The particles are pinned there because they are convectively charged on their outer surfaces facing the corona electrode. The electrodes also cause increased rate of release of conductive particles tending to be pinned by corona charging but conveying the charge to the grounded carrier roll almost as rapidly as it is received by the particles. The sign of the potential on the corona-emitting electrode makes little difference in the separation. An electrode usually emits negative corona somewhat more easily than it emits positive corona, as electrons are then the fundamental particles emitted. With a positive electrode the flow of electrons involved in positive corona discharge is onto the electrode from the ambient gas. Theory In the separator illustrated in fig. 1, the nonioniz-ing electrode is a rotating, nonconductive dielectric cylinder designated as B. The ions emitted by the corona electrode, or wire F, charge both the particles on the carrier electrode, or roll A, and the surface of the dielectric electrode B. Whereas the space between roll A and wire F contains ions, the space between electrode B and roll A is a pure static field free of ions. The dielectric electrode has been described by Bullock.1 However, the corona electrode, which Bullock uses for the purpose of charging only the dielectric electrode, is adapted here to also charge the particles on the carrier roll. In operation the ionic field from the corona electrode is balanced with the static field from the dielectric electrode. The ionic field charges the particle so that it adheres to the roll. The static field intensifies the discharge of the corona charge by interfacial conduction and permits the release of the particle. The ionic and static fields therefore have opposing effects.2 The values of both fields are adjusted so that the poor conductor will adhere and the good conductor will be released.

Jan 1, 1951

By P. R. Jochens, D. D. Howat, R. B. Atmore

INTRODUCTION The Miller chlorination process has assumed a preeminent position in the refining of gold bullion, a position it has maintained for over half a century. In the early sixties considerable interest was aroused by the idea of producing a consistently high grade bullion at the mine smelthouses themselves. However, as the use of chlorine in industrial plants is associated with considerable hazards, oxygen was considered a natural alternative, apart from bing less expensive than chlorine. Partial refining at the mine smelthouses would considerably decrease the requirements made on Rand Refinery Limited as well as indicating the possibility of reducing final refining costs. An added factor would be the purer silver chloride obtainable, after prior removal of the base metals by oxygen injection, which would facilitate the production of high-purity silver. The free energies of formation of the oxides of the metals;- silver, copper, lead, zinc, iron and bismuth indicate that, with the exception of silver, these metals should be capable of removal as oxides by oxygen injection. Rose1 had shown that during injection of gold bullion, considerable loss of silver to the boraxsilver slag occurred and, furthermore, that copper removal was not efficient and oxide attack on the refractories was severe. Plant test work2 had confirmed the difficulty of copper removal, but had shown that zinc and lead were almost completely removed. The difficulty of copper removal by oxygen injection warranted further investigation. Also, the high decomposition pressure of silver oxide suggested that by suitable control of the slag composition it might be possible to reduce to very small proportions the silver carried into the slag as oxide. The oxidation of copper by oxygen injection and subsequent dissolution of the oxide in a slag may occur according to the following reactions; Reactions 4 and 5 were considered because of the relatively high solubility of oxygen in molten silver and silver alloys. Thermodynamic data indicate that there is little possibility of any reaction involving the formation of CuO occurring at temperatures above 1 000 °C. To ensure that the operative reactions 1 and 4 take place to the maximum extent, the following factors He significant. (a) an increase in the activity of the copper in the bullion, (b) an increase in the partial pressure of oxygen in the system, (c) an increase in the activity of the oxygen in solution in the metal, (d) a decrease in the activity of cuprous oxide in the slag. From practical considerations, the operative variable most easily susceptible to control is the composition of the slag. SOLUBILITY OF COPPER OXIDES IN BOROSILICATE SLAGS Very scanty information exists on systems containing copper oxides but the indications are that slags containing considerable amounts of boric oxide would possibly prove to be the best solvents for cuprous and cupric oxides. This is attributed to the fact that the activities of copper oxides are much lower in boric oxide slags than in slags in which silica is the main network former. The number of possible slags containing boric oxide was limited by consideration of liquidus temperature, viscosity, corrosive action on refractories, volatilization, and ultimately cost (for industrial application). Slags in the systems soda-boric oxide-silica and lime-boric oxide-silica were selected paying due attention to the above limitations. Additions of 5, 10 and 15 per cent cupric oxide were made to the finely ground, premelted slags. These mixtures were then reground and 2g quantities held in re crystallized alumina crucibles at temperatures of 1150°C and 1 250°C respectively for 30 minutes. The crucibles were removed from the furnace, rapidly cooled, cut in half longitudinally, and a thin section taken from one half was subjected to microscopic examination.