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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 B. S. Lement

No appreciable stabilization of the austenite-martensite reaction occurs in a 15 pct Cr-0.7 pct C steel unless some martensite is initially present. Stabilization is induced by interrupting the subcool below M,; however, disappearance of the stabilization effect as manifest by burst formation of martensite may occur on continued holding at the final subzero reaction temperature. The higher the temperature of intermediate cycling after the initial subcool, the more permanent is the stabilization effect at the final reaction temperature. Appreciable conditioning of retained austenite occurs on reheating to about 500°C. These phenomena are explainable on the basis of the reaction-path theory. A RECENT investigation' carried out by the authors has shown that isothermal transformation of austenite to martensite definitely takes place in a 15 pct Cr-0.7 pct C steel and that appreciable amounts of martensite can form in this fashion. Investigations2-" arried out on other steels and iron alloys make it seem probable that isothermal formation of martensite is a phenomenon of fairly general occurrence. The reaction-path theory of Cohen, Machlin, and Paranjpe5,7 explains isothermal transformation on the basis of thermal activation of strain embryos which generate martensite plates with a velocity approaching that of sound. On the other hand, the nucleation and growth theory of Fisher, Hollo-mon, and Turnbull8 egards isothermal transformation as due to growth of athermally formed martensite nuclei. The experimental evidence obtained thus far favors the reaction-path theory in that the martensite reaction seems to be nu-cleation-controlled rather than growth-controlled. Stabilization is another phenomenon of importance with respect to the austenite-martensite reaction. According to the reaction-path theory, stabilization is a result of relaxation of strain embryos. It is postulated that strain embryos are present at the austenitizing temperature in the form of dislocations or lattice imperfections in the austenite which vary in the extent to which the lattice is displaced along the strain reaction path leading to martensite. On quenching from the austenitizing temperature, athermal martensite starts to form as soon as the M. is reached, because the activation energy of the transformation which decreases with decreasing temperature is lowered to below the level of the highest energy strain embryos. Martensite plates are generated during the cooling below M, from embryos possessing energies above the activation energy corresponding to the temperature at which the cooling is stopped. The distribution of lower energy embryos is changed because of the elastic and plastic strains produced in the remaining austenite as a result of the transformation. This effectively increases the number of strain embryos at all levels of energy below the activation energy and tends to stimulate further martensite formation either iso-thermally or on subsequent cooling. However, if the temperature at which the cooling is stopped is high enough for relaxation of strain embryos to occur, some degree of stabilization against further transformation may be induced. Whether stabilization will be observed on subsequent cooling will depend on the extent of decrease of activation energy with temperature. If the activation energy decreases sharply with temperature, it is possible that transformation will appear to continue with decrease in temperature in spite of the loss of embryos by relaxation. However, with a more gradual decrease in activation energy, stabilization will be manifest by no further transformation on cooling over a measurable temperature range until the

Jan 1, 1954

By Patrick H. O’Neill

FUNDAMENTALLY a dredge designed for operating under arctic conditions and particularly when the temperature is below freezing is not greatly different than one for use in more moderate climates. Because of the accumulation of ice it is necessary to design suspension units to carry an increased weight when ice forms on the digging ladder or stacker. Winch room and house must be made with double walls and insulated. The dredge must be heated either by steam or by circulating warm air electrically heated. The stacker must be covered and heated to avoid having the drive units frozen tight. Actually the worst trouble that might develop in a stacker, because of cold weather, is the freezing of spilled material and ice accumulation on the head pulley and the underside of the belt. For this reason, stackers are completely enclosed and the pan kept open to get rid of any spilled material and to prevent overloading. Since the stacker is the most vulnerable place on a dredge in cold weather, heat is turned on there long before it is necessary any other place on the dredge. The principal points of interest in' connection with dredging, under subfreezing conditions, concern the preparation of the ground being dredged and the frozen ponds. In the interior of Alaska, and also in the Yukon territory of Canada, most of the gold bearing gravel deposits are permanently frozen and they are also covered by variable thicknesses of fine grained sediment, locally called muck. The better pay areas in this frozen ground have generally been worked by the earlier miners who sank shafts to bedrock in the frozen ground, then drifted in four directions and dug out the areas between the drifts as they re- treated toward the shaft. They thawed only the area they were excavating, doing so with steam from wood-fired boilers, and hoisted pay gravel to the surface for subsequent washing.

Jan 11, 1954

By J. L. Rodda

A large amount of time has been devoted to the microscopical study of the copper-zinc alloys, emphasis naturally being placed upon the commercially important alloys of the system. Suitable methods are available for microscopically recognizing the two phases richest in copper, but none appear to have been developed for the positive identification of the other phases. This is, however, accomplished, for the phases normally encountered, by an electrolytic method described in the following pages. Five phases of the copper-zinc diagram (Fig. I) are considered for the purpose of this paper: the solid solution of zinc in copper, alpha (a); the intermediate phases, beta (ß), gamma (?), and epsilon (e); and the solid solution of copper in zinc, eta (11). Beta prime is not considered a separate

Jan 1, 1937

By B. R. Hollebone

The chemical action of molten anhydrous pyridinium chloride (pyridine hydrochloride) on oxy salts and ores of some Group IV and V metals are discussed-in particular zirconium, hafnium, niobium (columbium) , and tantalum. Laboratory-scale experiments are described whose results suggest that this reaction might provide a practicable means of converting ores of these metals to the anhydrous metal chlorides. Experimental results are given which provide some insight into the nature of the reactions and some of the compounds which could be present at intermediate stages. The treatment of ores of the more refractory metals is difficult and expensive and often demands the use of gaseous chlorine, hydrogen fluoride, or other reagents which are, if nothing else, expensive and dangerous to use. This situation is, of course, due to the strong metal-oxygen affinity resulting from the high charge and the small size of the metal ion which combine to produce such high lattice energy in the metal oxide as to defeat standard reduction methods. Thus, the characteristic of these metals which leads to one of their most important properties—corrosion resistance—is the main hurdle in obtaining the metal. Many common methods' for treating ores of zirconium and niobium (columbium), for example, proceed as directly as possible to the preparation of anhydrous halides. These halides are purified by now standard processes of solvent extraction, fractional distillation, and so on. This paper reports on preliminary stages in the development of a method of treating these ores—particularly of niobium—so as to prepare the anhydrous, volatile halides by the use of chemical reagents which are much more easily handled than those used at present. CHEMICAL PRINCIPLES The solvent action of aminium halides has been referred to periodically in the literature over several decades. The chemistry of pyridinium chloride has been discussed particularly by Audreith2 and Starke.3 However, since this is not familiar chemistry in its nonaqueous setting, it is perhaps well to point out some general metallurgical principles and applications. One can use, as point of departure, the fact that HC1 dissolved in pyridine is an acid very much the same as aqueous HC1. It thus gives essentially all the reactions of the HC1 with which we are familiar. However, when the ratio of HC1:pyridine reaches 1:l (a ratio far higher than is possible with H2O) the solution becomes solid C5F5NHC1, pyridinium chloride.* Inter- estingly, the acidic properties of HC1 persist in this medium, although they are manifest only in the molten state of the compound. Some typical reactions of divalent metal compounds which we have carried out in our laboratories are the following: 2PyHCl + Zn — (ZnCl2) + H2 + 2Py 2PyHCl + MnO — (MnCl2) + H2O + 2Py 2PyHCl + CuS — (CuCl2) + H2S + 2Py 2PyHCl + CaCO3 — (CaCl2) + H2O + CO2 + 2Py In these equations, the parentheses indicate a solvated compound which in water would be predominantly a hydra ted cation but which in molten PyHCl will more likely be a complex chloro-anion of the type MC14-. Some important physical properties of pyridinium chloride (PyHCl) are given in Table I. One sees from the data in Table I that at the temperature of molten pyridinium chloride both water and pyridine will boil away. Thus the system will be kept anhydrous. For this reason the reaction 2NbCl5 + 5H2O— Nb2O5 + 10HC1 has no counterpart in molten PyHCl. Instead, the chloride is made even more stable by the formation of a hexachloro complex: Nb2O5 + 12PyHC1 — 2PyHNbC16 + 5H2O + 10Py One interesting property of these complexes is their thermal instability which for the case of niobium can be illustrated as PyHNbCl6 — PyHCl + NbCl5 With a view to possible use of this chemistry in ore treatment, we have attempted to dissolve Pyrochlore (essentially FeO - Nb2O5) and recover the NbC15 from it.

Jan 1, 1968

Edward K. Landis, Philadelphia, Pa.: In studying Mr. Thackray's paper it seemed that a critical comparison of the results from different methods therein reported would he of interest. For this purpose Table I. was constructed by grouping all determinations made by the same method, and the probable errors were calculated. In this table all chemists titrating with permanganate (A1, E, F, G and 0 of Mr. Thackray's paper) are classed under "Emmerton;" those titrating with nitric acid (C, J, S and Y) under " Handy; " those re Probable error of result: a, ±0.0008996; b, ±0.000694; c, ±0.00107; d, ±0.00115; e, ±0.000674; f, ±0.000473; g, ±0.003675; h, ±20.0007959; i,0.000.5098; k, ±0.0008303. Probable error of single determination: a, ±0.001989; b, ±0.001547; c, ±0.00214; d, ±0.0023;e, ±0.00116;f, ±0.000818;g, ±0.0019;h, ±0.00224; i, 40.00143; k, ±0.00234. The formula for calculating the probable error is 0.6745, where N (N— 1)' S is the sum of the squares of the differences from the mean and N is the number of determinations.

Jan 1, 1897

By A. Rosenzweig, M. M. Karnowsky

The generalized binary diagram of the Au-Sn-Pb system is presented. The chief characteristic is the pseudobinary between lead and AuSn. On the high-gold side of the pseudobinary, four reaction isotherms were found at 363°, 274°, 225°, and 204°C. On the low-gold side of the pseudobinary, three reaction isotherms at 277°, 205°, and 176°C were found. A vertical section from the eutectic solder composition to gold was developed from the isothermal sections generated. METALLURGICAL problems arising from the intentional or accidental formation of Au-Sn-Pb alloys in soldering applications have indicated a need for information on the phase equilibria in this ternary system. The literature indicates that a complete diagram presenting this information has not been prepared. Even the recent excellent work by prince' entitled "The Au-Pb-Sn Ternary System" actually extends only to the AuSn or 50 at. pct Au range. There are more events in the 50 to 100 at. pct Au than in the less than 50 at. pct range. This article by Prince furnished much guidance in preparing this report. Initial efforts with the isopleth from the eutectic solder composition 61.9 wt pct Sn-38.1 wt pct Pb and 0 to 90 wt pct Au indicated that extensions of the work to the whole of the diagram (even if in less detail) were necessary to understand this system. In undertaking the construction of such a diagram, this study used differential thermal analyses (DTA) and metallography with verification and identification of phases by electron microprobe analyses. EXPERIMENTAL PROCEDURE The procedure began with the development of a cell which would be unreactive with lead, tin, and gold, retain its strength to 1100°C, exclude oxygen, and also furnish a suitable well for insertion and protection of a thermocouple to monitor temperature changes in the material. Such a cell would make it possible to reuse the sample should a repetition of determination be desired. Fig. 1 is a photograph of two such quartz cells as finally developed. The specimens have been run many times. The cell is made up of an inner sample bucket and an outer capsule with a thermocouple well which the sample surrounds. The DTA unit was an assembly devised from available instrumentation. The sample holder was a 3-in.-long cylinder of nickel, 2 1/2 in. in diam, fitted securely in a vertical tube furnace. Two holes 7/8 in. in diam were symmetrically located to receive the quartz cells. A dummy cell with nickel powder was used as the reference. The absolute temperature was recorded with a Pt/Pt 10-pct Rh thermocouple with an automatic Kaye ice bath compensator. (Calibration indicated the compensator to be accurate to better than ±0.5° over the 100° to 1000°C range.) The absolute temperature was measured in the sample and recorded on an L&N mul-tirange recorder with a full-scale display of 1 mv and automatic ranging of 99 mv. The differential signal between the sample temperature and the reference temperature was amplified with an L&N microvolt amplifier and recorded on an L&N Speedomax G recorder. Since two charts were obtained, the chart speeds were equalized and each event was noted on the differential chart, and the temperature at that time was obtained from the temperature record.

Jan 1, 1969

By John B. Myers

Vermiculite is the commercial name used to describe a micaceous mineral that expands appreciably when heated. This process, called exfoliation, results in a light weight material. The light weight material is also called vermiculite, or more exactly, expanded vermiculite. Practically all uses of vermiculite are for the expanded material. Composition and Properties Vermiculite, in its natural state, has the characteristic micaceous habit and a perfect basal cleavage and readily splits into thin laminae, which are soft, pliable, and inelastic. The monoclinic crystal faces are often marked by triangular lines at 60° and 120°. The hardness varies from 1.5 to 2 or more, depending on the composition. The specific gravity varies from 2.2 to 2.7; specific heat 0.2; fusion temperature 2,000° to 2,500°F; luster pearly to greasy; color amber, bronze, brown, dark green, and black. Feel is like talc and sometimes soapy when wet. When heated quickly at elevated temperatures, vermiculite exfoliates by expanding at right angles to the cleavage into long wormlike pieces (the name vermiculite is from the Latin vermiculari, to breed worms). This important characteristic of expansion is believed to be a mechanical separation of the layers when the contained water is converted to steam. The increase in bulk volume of commercially prepared material is 8 to 12 times, but individual flakes may expand as much as 30 times. There is no expansion parallel to the cleavage. Vermiculite may also be expanded by several chemical processes such as soaking in hydrogen peroxide, weak acids and other electrolytes. The color changes during expansion. Heat-treated material changes to a light golden bronze or cream color depending on composition. The conditions of heating affect color. Heating in an oxidizing atmosphere produces reddish colors and heating in a reducing atmosphere produces dull gray colors. The iron is generally not oxidized during chemical expansion. Vermiculite is hydrated magnesium-aluminum silicate. Although there has been much research on the chemical and structural composition, there is not yet complete agreement on the exact formula and composition. This is to be expected since vermiculite is not a mineral of fixed composition and different workers have examined different varieties. It has been proposed that vermiculite is not a single species but a family of related minerals. This has also resulted in many names for the particular vermiculite found in a certain deposit. All of this difficulty arises from the very nature of its crystal chemistry. Unlike most minerals, certain crystal structure properties and the chemical composition can be changed by the ordinary forces of nature or in the laboratory. This would suggest that vermiculite be thought of more as a variable mineral rather than a group of related species. It was stated on page 261 of this volume in the chapter on Clay Minerals by H. H. Murray of the Georgia Clay Co., that vermiculite is an equidimensional, expandable clay mineral. Gruner (ref. 14, Chap. 12) showed that the structure consists of a layer made up of two silica tetrahedral sheets with a central magnesium, iron octahedral sheet separated by two layers of water molecules and adsorbed magnesium and calcium ions. Mathieson and Walker,2a in a recent publication, agree that vermiculite must be regarded as a true clay mineral. The characteristic properties of the mineral, such as high cation ex-

Jan 1, 1960

By B. S. Butler

AN understanding of mineralizing solutions and how they carry and deposit metals is of prime importance to students of ore deposits. Lindgren states: "The whole problem surely is very complicated. One difficulty is that we know so little about the stability field of ore minerals."1 Lindgren further states: It is believed that they [the solutions] were in small part oxidized to sulphates, for instance, but in large part they were composed of hydrogen sulphide, alkaline sulphides and various halogen compounds. Doubtless, however, free carbon dioxide was present. Becker's view of the double sulphides as important constituents of the solutions probably holds good. In the fourth edition of Mineral Deposits2 Lindgren had changed his views somewhat: From the work of Day, Allen, Shepard, and others, it would seem probable that many of the volcanic gases are acid when given off but are in unstable equilibrium, and could not have preserved this acid character after having been long in contact with the surrounding rocks. It is believed that they were in small part oxidized to sulphates, for instance, but in larger part they were composed of hydrogen sulphides, alkaline sulphide, and various halogen compounds. Doubtless, however, free carbon dioxide was present. Becker's view of double alkaline sulphides as important constituents of the solution probably holds good. The writer wonders if progress would not result from an attack on the problem in steps, the steps to contribute to the attack on the whole. The initial step would deal with the simpler bodies of supposed magmatic (hydrothermal) origin, that is, those composed essentially of silicates, oxides, sulfates, and sulfides. The following discussion attempts to develop one step of a method that was proposed on a more comprehensive scale in 1929 by the writer and W. S. Burbank.3 The accompanying partial table (Table I) of the electromotive series is from a table distributed by Merck & Co. Inc., manufacturing chemists, prepared in turn from Fundamental Chemistry.& The electromotive arrangement brings together elements that in hypogene ore deposits occur: 1) in oxygen combination only; 2) in combination with sulfur as well as with oxygen; and 3) as sulfides, arsenides etc., and as native metals, see Table 11. The writer clearly recognizes that he is not qualified to discuss the formation of ore deposits as a chemical problem, but he feel that some of the relations that are met by the geologist can well be stated with the hope that the chemical explanation will be forthcoming. By consideration of a group including mainly the elements oxygen, hydrogen, sulfur and iron, complications are avoided, especially with elements of the lower electromotive group. The results can only contribute to the solution of the problem, not to the completion of it. The pH and Eh of the solutions and also temperature probably determine what minerals form. The mineral groups that contain elements high in the electromotive series are alumino-silicates, titanites, simple silicates, spinels, oxides, carbonates and sulfates, in all of which the elements are combined with oxygen. These groups are also recognized as the general order of temperature at which the minerals start to form, see Table 11. At low temperature are sulfides, arsenides, antimonides, sulfo-salts, and native metals, in all of which the elements are characteristically not combined with oxygen. The intermediate temperature group contains elements that form both oxygen compounds and sulfur compounds.

Jan 1, 1957

By L. W. Bahney

FREQUENTLY in using a thermo-electric pyrometer for measuring the temperature of a furnace, a hole is drilled at the back or side of the furnace, through which is introduced the tube containing the thermo-couple. At times the couple is left almost where it drops, for the reason that it soon becomes too hot to be handled easily, and the space at the back or side of the furnace may be so small and uncomfortably hot that an easy and accurate adjustment is nearly impossible. In order to overcome this clumsy and unscientific method of using the thermo-electric pyrometer, I designed an adjustable stand, to hold the clay or quartz tube unclosing the platinum and plati-num-rhodium leads that constitute the couple of the Le Chatelier thermo-electric pyrometer. This stand also allows an easy and rapid adjustment of position to varying heights and angles, as may be desired for special reading. This stand is illustrated in Fig. 1. The couple in the tube might be of better service if the tube were held a little higher above the charge in a roasting-dish, changing the height and angle if desired. The stand, made of 1.5-in, water-pipe and mounted on casters, is heavy enough so it cannot be tipped over easily. It is adjusted to any position, and has a universal clamp which holds the clay or quartz protecting-tube. To avoid disturbing the wires of the couple at the cold junction each time the tube is moved, the cooling-bottle sets in a wire basket so placed that it moves forward or back with the couple. To overcome the necessity of leveling and adjusting a galvanometer at each furnace, a switch-board is used to connect

Jan 1, 1910

By B. Fernow

The question of preserving the forests in this country is an impor tant one, not only to trades using wood but to the whole nation, and though agitated for many years has not received that general consid eration which its broad bearing demands. Those who are interested in and working for reform in the treat ment of American forests are looking to the government for help, suggesting the creation of a commission to study the conditions of forests at home and abroad, and hope that a sound system of manag ing the woodlands will be thereby inaugurated. This reform will cost time and money, all the more because the government can bring to bear upon private owners hardly any power but that of good example and encouragement. There is, however, another aspect of the question to which I wish to draw your attention, namely; the more economical use of the valuable material which our forests offer, a more careful and ex haustive utilization of its constituents in all cases where wood or its products are applied. The wasteful consumption of wood in the United States is in every way so enormous as to justify the statement that by merely adopting an economical husbandry in this particular the destruction of forests might be delayed for many years, while the neglect of this imperatively needed and immediately practicable reform deprives legislative remedies of much of their value. In this regard I wish to draw the attention of metallurgists, especially those who are in terested in the manufacture of charcoal iron, to a more economical and profitable use of wood in iron manufacture. For thousands of years of human history wood was the main, nay, the only material used for fuel. Mineral coal came into use only in the fourteenth century, and it is only recently that it has largely displaced its less carbonaceous predecessor as fuel. The art of concentrating carbon in the form of charcoal for easier transportation and readier use in distant places was, according to Pliny, known to the ancients long before Christ., and was practiced in all countries, especially in connection with the iron-manufacture.

Jan 1, 1879

By R. A. L. Black

13.8-1. Introduction. Table 13.8-1 shows that production from the African continent is an important part of total world mineral production. In three of the major particular resources listed, diamonds, gold, and cobalt, African production accounts for considerably more than half the world output. Overall, South Africa including South West Africa plays a dominant role in the mineral economy of Africa, other than in petroleum production. Table 13.81 also shows that much of the production is won by surface mining methods. In addition to the minerals listed in Table 13.8-1, Africa is a main world source for the following minerals: [Beryl 33% of total world production Columbium-tantalum 50%" " 1' Platinum group metals 20% l' " 11 Corundum 55%" " " 11 Vermiculite 30% (' " (6 Uranium oxide 15 0/, of free world production] South Africa and Rhodesia together account for nearly all of this production, except for columbium (niobium) of which Nigeria is the main producer. Thus the importance of southern Africa as a major mineral province can readily be appreciated. The consequences of serious political or military conflict between white-dominated southern Africa and the rest of the continent would be grave indeed, particularly for the West whose financial and economic interest in Africa as a whole is very large. The development of mineral resources in Africa involves the same basic elements as are involved anywhere else in the world: exploration, drilling and sampling, metallurgical assessment, and economic evaluation before, if it is justified, a prospect is brought to the productive stage. The same range of factors controls the economic viability of a project in Africa as elsewhere, of which the most important are:

Jan 1, 1968

By Barry K. McMahon

The fundamental problem in rock mechanics is accounting for the discontinuous and anisotropic nature of the jointed rock mass. It is this problem that makes rock mechanics distinct from the mechanics of steel, glass, or concrete. Existing mathematical models explain much of the behavior of rock cores in the laboratory but, in civil engineering at least, the rocks that matter are the ones that are already broken. On the other hand, the basically descriptive methods now used in engineering geology do not lend themselves easily to mathematical analysis. A set of indices of geological properties related to the strength and deformation characteristics of jointed rock is needed. Like the index properties used in soil mechanics these will probably not have precise mathematical meaning, but once correlations are established with large scale tests they can form a basis for the transfer of test results, obtained in one area under one set of conditions, to the prediction of rock behavior in another area under another set of conditions. Indices of rock properties are even more important in rock mechanics than in soil mechanics as the cost of testing is much higher. To be useful, these indices must be easily and quickly measured and give reproducible results when measurements are made by different people. In this paper the word "joint" means all naturally occurring rock fractures with less than 3 in. of clay or other soft coating material. EXISTING INDICES OF ROCK PROPERTIES A comprehensive review of indices of rock properties for intact rock is given by Deere and Miller.' They provide charts ". . . for estimating the strength or modulus properties for intact rock from the numerical indices obtained by either the Schmidt hammer, the Shore Scleroscope,

Jan 1, 1968

By D. D. Dunlop, J. R. Welker

The growing interest in the use of CO, in crude oil recovery increases the need for data on the effect of CO, on hydrocarbon physical properties. Data are presented on the solubility of CO, in various dead oils, the swelling changes in CO2-oil solutions and the effect of CO, on dead oil viscosity. This latter property shows the most pronounced effect, with viscosity reductions up to 98 per cent of the uncarbonated viscosities. An empirical method of estimating the viscosity of carbonated oils is presented. The apparatus and procedures used are described in sufficient detail to allow others to make similar studies. INTRODUCTION The effect of dissolved carbon dioxide on the swelling and viscosity reduction of specific hydrocarbon oils has been observed and recorded by a number of investigators.'- me object of this paper is to offer a means of predicting these effects for crude oils free from natural gas, using the dead state viscosity and gravity of the crude oils. The CO, solubility and swelling of numerous crude oils were determined in a visual cell at various pressure levels. The viscosity of the oils carbonated to various pressure levels was then determined by measuring the pressure drop across a capillary tube. From these data, the physical properties were correlated empirically. The resulting correlations allow the prediction of CO, solubility, swelling and viscosity reduction if the dead state gravity and viscosity of the oils are known. SOLUBILITY AND SWELLING MEASUREMENT EQUIPMENT AND PROCEDURE A high pressure visual cell was installed in a constant temperature cabinet. A test gauge was attached at the top of the cell for pressure measurement, and a line was run through the cabinet wall to a wet test meter which was used for volumetric measurement of the gas. The first step in making a test run was to put the oil in the cell up to a level about half to two-thirds of the total volume. This required about 50 to 65 ml of oil. carbon dioxide was then bubbled up through the oil for a time during which the pressure of CO2 in the cell was kept above 800 psia. Saturation of the oil with CO2 at this pressure and ambient temperature was confirmed by slowly bleeding CO2 through a valve to the atmosphere. If the oil was completely saturated with CO2, bubbles of gas would form in the oil at the first small decrease in pressure. If the oil was under-saturated, no bubbles formed until the pressure was decreased to the saturation pressure existing in the oil. If this saturation pressure was lower than that desired, more CO2 was bubbled through the oil until the desired level was reached. After saturation at ambient temperature was completed, the cabinet temperature was adjusted to the desired level and the cell was allowed to reach temperature equilibrium. After temperature equilibrium was reached, the pressure was again decreased slightly, and the oil again checked for full CO2 saturation at the cell pressure. The pressure now had changed because of the difference in solubility of the CO, in the oil at higher temperatures and the expansion of CO2 as the temperature increased. The outlet tube from the cell was then connected to the wet test meter and the CO2 was allowed to flow slowly out of the cell and through the wet test meter at ambient temperature and pressure. The water in the wet test meter had previously been saturated with CO2 at ambient temperature and pressure by allowing CO2 to flow continuously through it lor a period of several hours. The gas flow was stopped at several pressures during the run and the cell was allowed to come to equilibrium; this made possible the measurement of solubility and swelling data at the intermediate pressures. The volume of the oil in the cell was recorded at each of the equilibrium pressures in order to obtain swelling data. DATA AND RESULTS The solubility of CO2 in the oil was calculated by the relationship V — V, where R. = solubility of CO, in crude oil, cubic feet of CO, measured at 60F and 1.0 atm/ bbl of dead state oil at the temperature under which solubility was measured, V, = volume of gas released from the cell between the saturation pressure and zero pressure, corrected to 60F and 1.0 atm, cu ft, V, = volume of CO: contained in the gas space above the oil, corrected to 60F and 1.0 atm, cu ft, and V, = volume of the dead oil in the cell in bbl at the temperature of the run. The volumetric data of Sage and Lacey' were used to calculate V., from the volume of CO2 at high pressures. The swelling factor was calculated as where V, is the volume of the C0,-

By C. O. Brawner

Introduction The procedures used to design slopes in rock have only been developed over the past 10 years. Therefore, continued review and assessment of field experience by the publication of case studies is necessary to determine the accuracy of the theory and the application of the design techniques being used. Where failures have occurred, mine management should insist that the slides be 'back analyzed' to determine the shear strength parameters at failure. These values should be used for any pit design as they reflect site conditions more accurately than any other procedure. The previous papers have dealt with the basic concepts and factors that influence stability. To illustrate the application of these concepts in the study of practical stability problems, six ease studies have been selected for review. The examples include failure of tailings dams due to an earthquake, failure and redesign of a slope in overburden, review of failures of rock slopes, calculation of the amount of seepage into a pit and influence of the groundwater on stability, and the design of slopes for a proposed 2,500 ft. deep open pit mine. All but the first example are drawn from the authors personal experience. EXAMPLE 1 Failure of Tailings Dams Due to an Earthquake On March 28. 1965 a serious earthquake occurred in Chile with the epicenter located near the town of La Liqua, about 80 miles north of Santiago. The earthquake had a rating of 7 to 7.25 on the Richter scale. A record of the acceleration was taken at Santiago where a maximum horizontal acceleration of 0.18 g. was recorded. Many small mines are located in this region. Each of the mines provided impoundment storage for tailings with one to three dykes. As a result of the earthquake, most of the dams failed. The most serious failure involved two dams at El Cobre where more than 2,700,000 cu. yd. of tailings flowed into the valley, travelled over 7 miles in a few minutes, destroyed part of the town of El Cobre and killed more than 200 people. The Chilean government commissioned an investigation into the failures. A summary of the findings was published by Dobry and Alvare7 in 1967 (1). The location of the earthquake and the tailings dams which were investigated is shown

Jan 1, 1971

By D. McLean

For many pu@oses uniform strength is desired over a long temperature range, coupled to a band of softness at the hot end for easy shaping. Various types of material fulfill such a requirement to different degrees, depending on the regularity of their atomic structure. In long-chain polymers and vitreous glasses the irregular structure leads to a steep temperature dependence of deformation resistance and the temperature band between the hard and brittle condition and the soft condition is only about 100 C. In crystals and especially metals the atomically regular structure leads to a much smaller sensitivity over a wide temperature band, thus approaching the ideal behavim. The reason for this insensitivity is that the regular crystalline structure deforms by the movement of dislocations and the elastic interactions of dislocations in- PLASTICS, GLASSES, AND CRYSTALS The ease or otherwise of deformation varies with temperature much more in some substances than in others. This is an important matter when service over a wide temperature range is needed, especially volve energies of several hundred electron volts compared with which the energy of thermal agitation is insignificant. However, temperature affects a metal's defmmation resistance through its influence on the annealing, m coarsening, of the three-dimensional dislocation network. This coarsening is a phenomenon very similar to grain growth and ideas about grain growth can be applied to it. Taking into account also the temperature dependence of the glide resistance from alloying additions, a reasonable account can be given of the overall effect of temperature on deformation strength and of stress and grain size on deformation rake. Special structures me described. some arising from these ideas and as yet untried, which may benefit metals and polymers but not ni-treous glasses. when in addition a degree of softness suitable for shaping is required at some stage. It would be nice if one could write on this subject in as much detail about plastics, glasses, and so forth, as about metals, but there has been far more study of this matter in metals than in other substances, which is one reason why most of this paper concerns metals. However, in Fig. 1 there are shown the deformation strengths of several nonmetallic substances as a function of temperature. In many tests the attempt at deformation caused breakage and the graph lines are then drawn dashed. Long-chain plastics, a glass, and a crystalline substance are included in Fig. 1. The notable feature of all of them is the sensitivity of the

Jan 1, 1969

By S. L. Payne, J. P. Morris, R. L. Kipp, G. R. Zellars

The activities of iron and nickel in liquid Fe-Ni alloys were determined by measuring the vapor pressures of iron and nickel above the alloys and comparing with the vapor pressures of the pure metals. Nickel was found to deviate negatively from Raoult's law over the entire composition range. Iron behaves ideally down to 0.7 mole fraction but shows negative deviations at lower concentrations. At 1600°C the activity coefficients at infinite dilution are 0.40 for iron and 0.66 for nickel. 1 HE formulation of the conditions of chemical equilibrium between liquid metals and gases or slags is an important application of thermodynamics to pro- cess metallurgy. Usually the metal and slag phases are solutions of several components; and for accurate calculations, it is often necessary to use the activities of the components in place of their concentrations. Data concerning activities, however, are quite meager. The evaluation of the activities of iron and nickel, presented in this paper, is part of a project to determine activities in iron alloys at elevated temperatures.

Jan 1, 1960

Experimentation which measures differences in pressure across the interfaces of immiscible fluids in the interstitial spaces of porous media may be termed "capillary pressure experimentation". In the literature of petroleum technology since 1941 there have appeared twelve papers popularizing capillary pressure concepts and developing applications of these concepts for the solution of problems of practical reservoir engineering importance, such as the determination of connate water, fluid distribution. in transition zones, reservoir rock textural properties, and oil recovery from petroleum reservoirs.' Although a review of the literature would be justified at this time in order to reconcile the conflicting viewpoints which are contained in the cited papers, the object of this note will be of more limited scope. It is believed that the recent paper of Muskat alls sufficient attention to many of the uncertainties which arise upon examination of the published literature. such that until satisfactory counter-proposals can be made it will serve our purpose only to mention some other like uncertainties. This will emphasize further the need confronting petroleum technologists to re. consider and reformulate the application possibilities of capillary pressure experimentation. In particular, I sug- gest that we examine the thesis that capillary pressure experimentation as above defined can lead to measurements reflecting the recovery of oil from petroleum reservoirs, as was proposed first" by Amyx and Yuster" and was first reduced to practice by the experimentation of Welge. In fact. I shall deal exclusively with the Welge papers since it is the principle one on this subject which has appeared to date. I shall attempt to show that the possibility of describing oil recovery features in terms of capillary pressure phenomena has not been established entirely. The Welge paper was a pioneering effort to evaluate this recovery application possibility. P. P. Reichertz' comments on the Welge paper state that non-wetting phase discontinuities are developed occasionally in the Welge experiment, and restate Muskat's argument that discontinuous fluid elements (partially saturating the interstices of porous media which are elsewhere saturated with some other immiscible phase or phases) are not subject to the requirements of hydrostatic equilibrium. It is the purpose of my comment to show that it is unnecessary to make Reichertz' postulation regarding non-wetting phase discontinuities (however valid) when it is desired to criticize welge's theoretical treatment of his problem. It can be shown that Welge's method of measuring values for ''capillary pressure" is invalid in many instances of application, such that his reported curves of capillary pressure Versus fluid saturation often have no physical meaning, even throughout the interval of fluid saturation where it might be otherwise suspected that no phase discontinuities occur. By considering established principles of capillary pressure experimentation it can be shown that the pressure difference experimentally observed between wetting and non-wetting fluid Phases which are contained in external reservoirs will reflect on the capillary pressure difference at the interfaces of contact between these phases only when the following conditions are satisfied: (a) There shall be a balance between the opposing forces of gravity and capillarity, as obtains under conditions of hydrostatic equilibrium when the positions of the interfaces of contact become fixed in pore spaces of certain geometry (b) The wetting and non-wetting fluids within the interstitial spaces shall everywhere be continuous with the external wetting phase reservoir and the external non-wetting phase reservoir, respectively. It will become apparent immediately that in any instance when a greater pressure is recorded in the external wetting phase reservoir than in the external non-wetting phase reservoir, one may establish either that static equilibrium has not been attained or that discontinuities in one or more of the fluids have been developed. This is because the pressure otherwiee is always ereatest in the non-wetting phase at each static interstitial interface of contact with the wetting phase. such that the externally measured pressure in the non-wetting phase likewise must be greatest if the above conditions are to be satisfied.

Jan 1, 1949

Experimentation which measures differences in pressure across the interfaces of immiscible fluids in the interstitial spaces of porous media may be termed "capillary pressure experimentation". In the literature of petroleum technology since 1941 there have appeared twelve papers popularizing capillary pressure concepts and developing applications of these concepts for the solution of problems of practical reservoir engineering importance, such as the determination of connate water, fluid distribution. in transition zones, reservoir rock textural properties, and oil recovery from petroleum reservoirs.' Although a review of the literature would be justified at this time in order to reconcile the conflicting viewpoints which are contained in the cited papers, the object of this note will be of more limited scope. It is believed that the recent paper of Muskat alls sufficient attention to many of the uncertainties which arise upon examination of the published literature. such that until satisfactory counter-proposals can be made it will serve our purpose only to mention some other like uncertainties. This will emphasize further the need confronting petroleum technologists to re. consider and reformulate the application possibilities of capillary pressure experimentation. In particular, I sug- gest that we examine the thesis that capillary pressure experimentation as above defined can lead to measurements reflecting the recovery of oil from petroleum reservoirs, as was proposed first" by Amyx and Yuster" and was first reduced to practice by the experimentation of Welge. In fact. I shall deal exclusively with the Welge papers since it is the principle one on this subject which has appeared to date. I shall attempt to show that the possibility of describing oil recovery features in terms of capillary pressure phenomena has not been established entirely. The Welge paper was a pioneering effort to evaluate this recovery application possibility. P. P. Reichertz' comments on the Welge paper state that non-wetting phase discontinuities are developed occasionally in the Welge experiment, and restate Muskat's argument that discontinuous fluid elements (partially saturating the interstices of porous media which are elsewhere saturated with some other immiscible phase or phases) are not subject to the requirements of hydrostatic equilibrium. It is the purpose of my comment to show that it is unnecessary to make Reichertz' postulation regarding non-wetting phase discontinuities (however valid) when it is desired to criticize welge's theoretical treatment of his problem. It can be shown that Welge's method of measuring values for ''capillary pressure" is invalid in many instances of application, such that his reported curves of capillary pressure Versus fluid saturation often have no physical meaning, even throughout the interval of fluid saturation where it might be otherwise suspected that no phase discontinuities occur. By considering established principles of capillary pressure experimentation it can be shown that the pressure difference experimentally observed between wetting and non-wetting fluid Phases which are contained in external reservoirs will reflect on the capillary pressure difference at the interfaces of contact between these phases only when the following conditions are satisfied: (a) There shall be a balance between the opposing forces of gravity and capillarity, as obtains under conditions of hydrostatic equilibrium when the positions of the interfaces of contact become fixed in pore spaces of certain geometry (b) The wetting and non-wetting fluids within the interstitial spaces shall everywhere be continuous with the external wetting phase reservoir and the external non-wetting phase reservoir, respectively. It will become apparent immediately that in any instance when a greater pressure is recorded in the external wetting phase reservoir than in the external non-wetting phase reservoir, one may establish either that static equilibrium has not been attained or that discontinuities in one or more of the fluids have been developed. This is because the pressure otherwiee is always ereatest in the non-wetting phase at each static interstitial interface of contact with the wetting phase. such that the externally measured pressure in the non-wetting phase likewise must be greatest if the above conditions are to be satisfied.

Jan 1, 1949

Meeting of Oct. 23, 1914.-It was voted to take no action concerning the proposed amendments to Article VIII, Sections 2 and 3, but that they be sent to the membership, as provided by the Constitution, together with a statement of the arguments for and against the proposed changes. It was voted that the following proposed amendment, which had been unanimously approved at the annual meeting of the Institute on Feb. 18, 1914, be sent to the membership as provided by the Constitution, together with the approval of the Board of Directors of this change: Article III, Section 1, paragraph 3, sentences 2 and 3: substitute the following: "Any Member, Junior Member or Associate in arrears for two years shall be dropped from the rolls unless the time for payment is extended by the Directors. A Member so dropped may be reinstated by the Directors on paying the arrears of clues and other indebtedness with which he was charged on the books of the Institute it the time he was dropped. A Member or Associate thus reinstated shall receive the Transactions for the back year for which he pays." It was unanimously voted to extend the sincere thanks of the institute to Samuel A. Taylor, Chairman, and to each member of the several Committees of the Pittsburgh meeting, for the enjoyable and successful meeting which they brought about.

Jan 12, 1914