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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. H. Burke

Deeper drilling, resulting in greater circulating distance and pressure, has directed attention to the advantages of the study of properties and control of rotary muds, which until recently have not had much consideration. One fundamental property of muds is viscosity, and viscosity is influenced by the quantity and character of colloidal material and can be controlled by chemical treatment. Colloidal Matter of Rotary Muds Two types of colloids are found in muds; the hydrophobic and the hydrophilic. Hydrophobic colloids do not associate intimately with water and are sensitive to small quantities of electrolytes. Hydrophilic colloids associate intimately with water, but are not so sensitive to electrolytes. The colloidal particles of rotary muds are derived from clay; In clay the particles may range in size from submicroscopic to macroscopic; a substance is a clay if the greater proportion of the particles are within the size limits prescribed for clay. The larger particles are inert and have no effect on the viscosity of normal hydrophobic colloidal muds. There are two theories accounting for the colloidal properties of clay-water suspensions: (1) the physical theory, that clay in water is a coarse colloidal suspension, and (2) Ashley's1 theory, that clay is a granular material with a colloidal gel surrounding the crystalline grains. The most important colloidal substances known to exist in clays besides the clay particles are: (1) colloidal silica, (2) colloidal alumina, (3) colloidal ferric hydroxide, (4) colloidal silicates, and (5) colloidal organic matter. Plasticity, a peculiar property of clay-water suspensions, is due to the colloidal particles. It is commonly (although not with strict accuracy) measured in terms of viscosity, and depends upon the amount and the state of flocculation of the colloidal matter present in the suspension. Fluidity in a rotary mud may be caused by a lack of colloidal clay particles or by deflocculated or flocculated clay particles, while viscosity in a

Jan 1, 1935

By Jei Y. Choi, P. G. Shewmon

Using a scratch smoothing technique, the magnitude and the ratio of the surface diffusion coefficients (D,) in two orthogonal directions have been measured on copper for over 100 different surface orientations. Anisotropy was found for all surface orientations except those lying near the (100) and (111); however, these anisotropies were rarely greater than 2.0. The direction of maximum D, appears to coincide with the direction of step edges on any given surface, and if no such steps exist, no anisotropy is found. Thus the jump frequency along a step edge is shown to be faster than the frequency of a jump over the step. The values of Ds and AH for the (100) and the (111) orientations agree quite well with those obtained earlier by the grain boundary grooving technique. It is proven that the directions of maximum and minimum D, (the principal axes) for any surface orientation are known if the perfectly ordered plane corresponding to the given surface orientation possesses a plane of mirror symmetry. Thus the principal axes of D, for orientations lying along the sides of the unit stereo-graphic triangle are always known independent of the extent of thermal disorder or impurity adsorption. The merits and shortcomings of King and Mullins' recently published equations relating Ds to the rate of scratch smoothing are discussed. 1N an earlier paper the authors have reported the variation of the surface diffusion coefficient (Ds) with surface orientation on copper.' In that study Ds was determined from the rate of growth of grain boundary grooves on symmetric bicrystals. This gave values of Ds from 850° to 1070°C in a given direction on each of the six surfaces. It was found that the activation energy for surface diffusion was essentially the same for all six surfaces. The theory developed to explain these data assumed that the free energy of any given type of surface site depends only on the number of nearest neighbors the atom has. This same theory predicted that on any given surface Ds should be independent of direction. The primary aim of this study was to check the validity of this prediction for a wide range of surface orientations on copper. The growth of grain boundary grooves is ideal for studying Ds in a given direction on a given surface over a range of temperatures, because the same specimen can be repolished and used again. However, there is considerable work involved in growing a symmetric bicrystal, and for a survey of Ds in two or more directions on many surface orientations, the technique would be arduous. A better technique appeared to be the scratch method used primarily by Mykura. 2 If a scratch is placed in a surface whose surface tension is independent of orientation, the surface will smooth out in time under the influence of surface tension. To determine D, from this flattening, Blakely and Mykura2 used an approximate solution which was assumed to describe the rate of flattening. Recently King and Mullins3 (hereinafter K and M) have given a more exact analysis of the flattening of an isolated scratch. A second aim of this paper was to check the validity of this newer analysis and compare the values of Ds determined thereby with the values obtained from grain boundary grooving techniques. EXPERIMENTAL PROCEDURE In an effort to work with a particular predetermined surface orientation, light orthogonal scratches

Jan 1, 1963

By S. Skowronski

The melting of cathode copper, ususally containing 95.98+ per cent. • Cu, would appear to be a simple matter. Owing to the well known affinity of copper for sulfur, however, so much sulfur is absorbed by the copper during the operation that a long and expensive refining process is required to remove it, and the final product is inferior in purity and lower in electrical conductivity than the original cathode copper. The furnace operation, as now conducted, includes the following stages: 1. Charging the cathodes into the furnace. 2. Melting the cathodes. 3. Oxidizing period—saturating the copper with cuprous sub-oxide and bringing the metal to the condition known as "set copper;'' this is now done by blowing air into the molten bath of metal. 4. Reduction period, otherwise known as "poling," whereby the oxygen previously added is removed by covering the molten bath completely with coke or charcoal and introducing large poles of green wood; this reduces the cuprous sub-oxide, bringing the copper to the "tough pitch" stage ready for casting. 5. Casting Period. Many experiments have been made to obviate the long periods of oxidation and subsequent reduction, with no success. While the copper first cast will be good, as indicated by the set surface of the bars, it is impossible to hold it to the "tough pitch" condition, and long before the whole charge has been poured the copper will become "overpoled," entailing numerous difficulties. Sulfur has always been blamed by the furnace men as the reason why this refining process is necessary, yet the literature on the subject does not sufficiently emphasize how small a proportion of sulfur will ruin copper for practical purposes. The sulfur absorbed by copper during the melting period comes from two sources: (1) the sulfate left on the cathode sheets in the tank houses; (2) the fuel. The percentage of sulfates on the cathodes is variable, and depends on the care taken in washing the cathodes after removing

Jan 1, 1919

By P. E. Demmler

Phosphorus combines with copper in various proportions, forming true alloys, some of which are of commercial importance. These materials find wide application as deoxidizers and as a means of introducing phosphorus into other alloys, as in phosphor-bronze. Phosphor-coppers containing 10 and 15 per cent. of phosphorus are the commercial grades that are most generally offered. Each has certain advantages when used in making other alloys. The 10 per cent, grade of phosphor-copper has an advantage over the 15 per cent. in that it has a much lower melting point and can be prepared by certain methods with a much lower loss in phosphorus. The 15 per cent. grade has the advantage of lower freight rates per unit of phosphorus and, by the method to be described, a uniform product can be prepared with practically no loss of phosphorus. Alloys of copper and phosphorus containing any desired percentage of phosphorus lower than 15 per cent. can be prepared by melting together the requisite amounts of copper and 15 per cent. phosphor-copper. Processes for making phosphor-copper may be divided into two classes as follows: (1) Those depending on the smelting of phosphate rock or superphosphate of calcium with copper or copper-bearing materials, and coal or other carbonaceous material; (2) those depending on the direct combination of metallic copper and elemental phosphorus. A number of formulas for preparing phosphor-copper according to the first method have been published. The Metal Industry' gives the following: Superphosphate of calcium, 60 lb.; granulated copper, 30 1b.; finely powdered coal, 10 1b. Similar formulas are given by Brannt2 and others, and detail variations are covered by patents, such as those of L. A. Jeffs3 and H. A. Webster.4 Among the objections to this method of producing phosphor-copper are the large amounts of raw material and resulting slag to be handled, and the difficulty of getting a satisfactory fusion. S. Skowronski5 found that at 1300' C. (2372' F.) it was impossible to get a good fusion

Jan 1, 1921

By Leland Van Wert

IN 1888, Howard,1 working at the Watertown Arsenal on the tensile properties of ferrous materials at various temperatures, noted the curious fact that the stress-strain diagrams of low-carbon steels tested within a certain temperature range (200° to 350° C.) departed more or less from the normal regularity of such diagrams as secured by testing at either above or below these temperatures. This same jagged appearance of similar diagrams for steels has been observed by at least one other investigator, and de Forest2 has reported similar irregularities in the tensile testing of some nonferrous alloys. Recently again, this anomaly in diagram contour has been shown in a most striking fashion, apparently because of its accentuation by the method of testing employed, by Dr. Albert Sauveur.3 He described (for nonaustenitic steels) two quite distinct types of torsional stress-time diagrams: (1) those with a regular and smooth outline, derived normally by testing at temperatures above 300° C., or below 200° C. (as, for example, Figs. 4a or e); and (2) those presenting a decided "stepped" appearance, which are invariably produced when twisting is done within the 200° to 300° C. range (examples, Figs. 5a and b). The torsion test brings out so much more sharply (and convincingly) the irregularities occurring at 200° and 300° C. than does the tensile test that they can no longer be considered as resulting from simply idiosyncratic or accidental and inconsequential causes. Clearly, from the temperatures involved, the "stepped" type of diagram, or more accurately, the peculiar manner of response to torsional stress which manifests itself in the diagram, is an aspect of the "blue-heat" phenomenon. One's curiosity if, nothing else, prompts an inquiry as to the nature and significance of these "steps." What do they mean? What causes them? To these questions there are no completely satisfactory answers. The following experimental observations are offered as suggestions towards the solution of the problem.

Jan 1, 1931

By R. W. Coughlin, W. U. Ault

Experiments in laboratory and mine have clearly demonstrated the usefulness of radioactivity detection for directly measuring the potassium content of potash ore as mined. This paper presents the results of these tests and documents the design of a system for automatically grading and sorting potash ore on the basis of radiation detection. It is shown how the experimental results in the subject mine lead directly to the design of this kind of an automatic control system. The system is capable of grading the ore with an accuracy of approximately ±2% K20 content or better. Due to the usual stratification of the ore body, mining potash seldom presents an extreme problem of gangue separation. Nevertheless, it is frequently necessary to transport within a potash mine and even hoist to the surface considerable quantities of halite and other valueless materials. Up to recent times it has been customary to recognize and route these materials by simple visual and manual techniques. However, the work reported here clearly demonstrates that it is now practical and economical to improve upon these techniques by continuous measurement1 of the naturally occurring radioactive isotope, potassium-40. It was the purpose of the work reported here to investigate this technique and assess its applicability. LOCALE OF EXPERIMENTS The work described here was carried out in a potash mine in Carlsbad, N.M. At the working face of this mine the potash ore is freed by blasting; it is then transported a short distance by shuttle car to a moving-belt system which conveys it to the main shaft where it is hoisted to the surface. Quantities of gangue which are also produced in the mining operation are disposed of in mined-out sections of the mine where possible. Otherwise, this material which contains only a small percentage of potassium (as K2O) must also be transported by the conveyor-belt system to the main shaft and then hoisted to the surface and discarded. With this situation, any measuring device for automatic control purposes must be capable of clearly distinguishing between gangue containing insignificant amounts of K2O and ore containing larger percentages of the same mineral. The conveyor-belt system transports the material from the mine face to a rotary crusher and then to temporary storage pits at the main shaft. This is shown in Fig. 1. Upon leaving the conveyor belt the material enters either one of the two storage pits according to the position of a manually operated gate. It was decided that all experiments should be carried out at the conveyor belt between the crusher and gate with a view to the possibility of providing a signal which could operate the gate automatically. THEORETICAL BASIS AND LABORATORY EXPERIMENTS In principle it is possible to grade potassium-bearing ore on the basis of radioactivity. Natural potassium contains 0.012% K40, which is radioactive with a half-life of 1.3 x 10' years. Although about 89% of the K40 disintegrates to Ca40 by beta decay, the other 11% changes to Ar40 by electron capture and the emission of gamma rays. Unlike the ß-rays which are readily absorbed in the first few millimeters of ore surrounding the disintegrating nucleus, the y-ray photons will escape from an ore sample several inches in size. A detector rigidly mounted under a conveyor belt loaded with potash ore will intercept some constant fraction of all the photons emitted from the ore within its field of view. Under these

Jan 1, 1968

By Carl H. Unruh, D. L. Katz

Experimental data are presented for hydrate formation conditions for gas mixtures of carbon dioxide and methane. Equilibrium constants for carbon dioxide, defined as the mole fraction of carbon dioxide in the gas phase (dry basis) divided by the mole fraction of carhon dioxitle in the hydrate (dry basis)... were calculated usine the equilibrium constants for methane developed in an earlier paper. INTRODUCTION A series of papers have been written on gas hydrates, giving temperatures and pressures at which hydrates would form.2. 3, 4. 5, 6. 9. 12, 13, 15 Vapor-solid equilibrium constants have been developed for methane, ethane, propane and iso-butane' by which it is possible to compute for a specific gas mixture the temperature and pressure at which hydrates will form. Carbon dioxide is present in many natural gases in concentrations usually from 0.1 to 2.0 per cent. It also forms a gas hydrate with water and presumably enters the solid solution when present with a natural gas which is forming a hydrate. The equilibrium constant giving the ratio of the concentration of carbon dioxide in the gas phase to the concentration in the solid phase is required for including the effect of the carbon dioxide when computing the conditions for hydrate formation. Direct determination of the concentration of carbon dioxide in solid hydrate requires a difficult separation to be made. Therefore, this research resorted to the measurement of the temperature and pressure at which specific mixtures of methane and carbon diox- ide would form hydrates. From the equilibrium constants previously mentioned for methane, it is possible to compute the equilibrium constant for carbon dioxide, without measurement of the composition of the solid phase. Fig. 1 shows the conditions at which methane and carbon dioxide form hydrates. The methane curve FG extents to some high pressure while the carbon dioxide curve AB intersects the vapor-liquid water-liquid carbon dioxide

Jan 1, 1949

By Carl H. Unruh, D. L. Katz

Experimental data are presented for hydrate formation conditions for gas mixtures of carbon dioxide and methane. Equilibrium constants for carbon dioxide, defined as the mole fraction of carbon dioxide in the gas phase (dry basis) divided by the mole fraction of carhon dioxitle in the hydrate (dry basis)... were calculated usine the equilibrium constants for methane developed in an earlier paper. INTRODUCTION A series of papers have been written on gas hydrates, giving temperatures and pressures at which hydrates would form.2. 3, 4. 5, 6. 9. 12, 13, 15 Vapor-solid equilibrium constants have been developed for methane, ethane, propane and iso-butane' by which it is possible to compute for a specific gas mixture the temperature and pressure at which hydrates will form. Carbon dioxide is present in many natural gases in concentrations usually from 0.1 to 2.0 per cent. It also forms a gas hydrate with water and presumably enters the solid solution when present with a natural gas which is forming a hydrate. The equilibrium constant giving the ratio of the concentration of carbon dioxide in the gas phase to the concentration in the solid phase is required for including the effect of the carbon dioxide when computing the conditions for hydrate formation. Direct determination of the concentration of carbon dioxide in solid hydrate requires a difficult separation to be made. Therefore, this research resorted to the measurement of the temperature and pressure at which specific mixtures of methane and carbon diox- ide would form hydrates. From the equilibrium constants previously mentioned for methane, it is possible to compute the equilibrium constant for carbon dioxide, without measurement of the composition of the solid phase. Fig. 1 shows the conditions at which methane and carbon dioxide form hydrates. The methane curve FG extents to some high pressure while the carbon dioxide curve AB intersects the vapor-liquid water-liquid carbon dioxide

Jan 1, 1949

By F. C. Pittman, D. W. Harriman, J. C. St. John

This paper mentions briefly the history of hydraulic jetting as applied to perforating and fracture initiation. It points out the advantages of hydraulic perforation and undercutting as an aid for creating a fracture at the point desired rather than depending upon the weakest point in the formation for breakdown. It describes early experimental work with jet nozzles in search of better nozzle materials. The effect of splash-back damage and its subsequent influence on jet body and tool design during this work is discussed. A series of cutting-rate curves for jets cutting steel and steel-cement-formation combinations is presented to show the effect of hydrostatic head and the point of diminishing returns with respect to cutting time. There is a series of photographs showing various types of rock formation in which perforation and undercutting tests were made. These stones were drilled and the casing cemented in place as in an actual well. The casing was perforated and circularly cut as if preparing for a fracturing job. The conclusion reached in the paper is that hydraulic jetting with sand-laden fluid can be used for perforating and undercutting casing, cement and formation rock for the intended purpose of inducing the formation to fracture at a desired point. INTRODUCTION Hydraulic jetting as a means of cleaning a formation during acidizing has been used for many years. The acid-jet gun was used to clean formation and for drilling cement from casing with acid. This tool was dropped to a seating ring installed on the tubing and could be retrieved by reverse circulation or wire line. In this process, the fluids were directed against the formation to clean and penetrate beyond the mud-damaged area. After the development of the hydraulic fracturing process, interest in jetting the formation with abrasive-laden fluid was renewed. The cutting action of abrasive fluid on pumping equipment, which is a well known problem, has been utilized to perforate and undercut casing, tubing and formation. In this process, surface areas are provided in the formation on which the frac- turing pressures may work to produce a fracture at the location desired. EQUIPMENT The tools used consist of bodies containing two, three or four jets in a single horizontal plane equally spaced around the circumference. The body is threaded to the end of a string of tubing and run into the well. In addition, an expendable tool is available that may be left in the hole after perforating and produced through until necessary to remove the tubing. The bottom of each tool is equipped with a ball-type back-pressure valve. The ball can be reversed to the surface and recovered. This allows reverse circulation so that loose sand which accumulated below the tool while jetting may be removed before the fracturing job. The present jetting tools are of such length that, when screwed together, the jets fall on 12-in. spacing. ANALYSIS OF THE PROBLEM Early work with nozzles indicated that hardened steel was not a suitable material for jets and that more durable material would be required. Ceramics were tried and found to be superior to steel but still too shortlived for most applications. Tungsten carbide, which was tried and found to be the best material available, is now being used for jet nozzles. Analysis of the problems presented by this process indicated that the following information was needed. 1. The effect of submergence on a jet stream and the effect of submergence on the cutting rate of a jet stream. 2. The cutting rate and depth of a jet stream in steel. 3. The cutting rate in various formations and point of diminishing returns. 4. Size of hole or slot cut in a pipe by a given jet. 5. Fluids and sands used. 6. The flow of various weight fluids through the jet nozzle and the discharge coefficients. 7. The type cut formed in the formation by the jet stream. 8. The stretch and contraction of tubing due to temperature and pressure. The cutting effect of a jet stream on a target in the atmosphere is rapid and spectacular as most of the

By Reynold Q. Shotts

CHEMICAL methods, based on the relative rates of oxidation of fusain, bright coal, and dull coal by nitric acid, have been devised to determine these coal components.1-4 Results obtained by oxidation methods for fusain have been checked against results obtained from microscopic methods5, 6on duplicate samples of the same coals, but to the author's knowledge this has not been done for bright and dull coal components. For this reason it is not certain that the two methods of analysis identify essentially the same chemical or physical units. It would be highly desirable to see results of the application of both methods to duplicate samples, but in the absence of any such data the author has attacked the problem indirectly. From the U. S. Bureau of Mines samples were obtained of three Alabama coals which the USBM had analyzed optically and reported on over the past 30 years. These samples were subjected to analyses by oxidation rate methods. Results of this work, and comparisons with the USBM analyses, have been published." This was the first indirect approach to the problem. The present report attempts a second indirect approach by way of internal validation. By nitric oxidation samples of two whole coals were carefully analyzed for fusain, bright coal, and dull coal. One coal was analyzed in duplicate. Duplicate portions of each of the coals were divided into three density fractions by means of heavy liquids. A duplicate portion of one of the coals was divided by sieving into three size fractions. Each fraction was analyzed by oxidation and its percentage composition calculated in terms of fusain, bright coal, and dull coal. Because the weight percent of each fraction was known, a material balance calculation for the whole coal was also made. The resulting reconstituted analysis of the whole coal could be compared to that determined by direct analysis. In addition, specific reaction rate constants were determined for each component and for each whole coal or fraction. Arbitrary reactivity indexes were calculated by dividing by 100 the sum of the products of the percent of each component in the coal and its specific reaction rate constant. The resulting figure was an average reactivity index for each coal or fraction. Weighting the reactivity indexes for each fraction by the percent of the fraction in the coal gave a reactivity index for each whole coal which could be compared to that calculated directly from the whole coal analysis. If oxidation analyses really delineate definite physical entities within the coal, or even definite groups of similar entities, reconstituted analyses calculated from fraction analyses should check closely those made of the whole coal. It probably is true that optical methods identify and describe a greater variety of components than do chemical methods and that variations are wide in the appearance and quantity of those components identified optically. Chemical methods based upon differences in oxidation reaction rates would of necessity be less discriminating, as between similar components, than would optical methods. The procedures followed for oxidizing the samples, analyzing the residues, plotting and calculating the percentage of each component, and calculating its specific reaction rate constant have been fully described.'-' In brief the method originally proposed by Fuchs et al.1 for the determination of fusain consists of the oxidation of small samples of coal in boiling 8N nitric acid in a condenser-fitted flask. After boiling for periods of 1/2 to 4 hr, the unoxidized residue is filtered and washed. The washed residue is treated with normal sodium hydroxide, diluted, and allowed to stand for several hours. The resulting brown liquor is removed, and the filtered residue dried, weighed, ignited, and weighed again. The ash-free residue is expressed as a percent of original dry, ash-free coal. The percent residue is plotted against time, and the extrapolation of this line to zero time gives the percentage of dry ash-free fusain present in the original sample. The shape of the resulting time plots has been explained' by the assumption that they are the result of two different types of reaction, the first part representing a first order reaction with rate a func-

Jan 1, 1956

` LAWRENCE ADDICKS, New York, N. Y.-We have really two competitive processes for the production of electrolytic zinc. In the process used at Great Falls, the ore is roasted and the calcines leached, leaving a residue which has to be smelted; in the other method, the ore is burned, the zinc and lead fumed off, and the condensed fumes are leached. I do not think that we can yet come to any decision as to which is the better way to attack the problem. Of course if we roast first and then leach, various substances remain in the calcines which may consume sulphuric acid; whereas if we do the burning first, we obtain simply the zinc and lead oxides, with considerable sulphate, in the fume, and there is no shortage of acid. It also depends partly on the complexity of the ore. The one that Mr. Hall is treating and the ore they are treating at Great Falls are not quite alike, but I think they are sufficiently similar to make a comparison of the two methods, working in competition, on different parts of the country, very interesting. C. E. SCHWARTZ, Miami, Okla.-Mr. Hall states that the Joplin conditions are not suitable for the manufacture of electrolytic zinc. When we speak of Joplin ore in general, we consider, of course, a 60-per cent: concentrate with comparatively low iron, but if a low-grade concentrate could be made from tailings and so-called chats, then the problem would be quite different. A Joplin ore is comparatively simple to treat electrolytically, and I believe the electrolytic process would open a field for the treatment of such ores as would not be ordinarily smeltable; that is,

Jan 1, 1918

By Richard H. Olson

"Rarely in our technological society does the discovery of a new class of inorganic materials result in such a wide scientific interest and kaleidoscopic development of applications as has happened with the zeolite molecular sieves." That opening sentence in a landmark volume on zeolite molecular sieves by D. W. Breck (1974), is, if anything, an understatement. Zeolites were recognized as a new group of minerals in the 1750s, but it was not until 1930 that the first analysis of the crystal structure of a zeolite mineral was made. In the late 1940s research workers at Union Carbide Corp. began a program of zeolite synthesis and study which has resulted in one of the major research achievements of all time. Naturally, with the vast research and development efforts devoted to the synthetic molecular sieves, Union Carbide became concerned in the mid-1950s about its position should minable deposits of natural analogues be discovered. Zeolite minerals have diverse origins, and even a brief discussion of these is beyond the scope of this paper. The early work on zeolites was confined to igneous rock occurrences (e.g., amygdules and veins) which were formed by "space-filling;" these crystals tend to be euhedral, thereby rendering them appealing to both mineralogists and collectors. During the first year or so of Union Carbide's exploration (which began in mid-1957) attention was devoted solely to such igneous, occurrences. A landmark paper by Bramlette and Posnjak (1933) heralded the potential significance of the occurrence of zeolite minerals as alteration products of vitric ash and similar materials. In the summer of 1958, full attention was directed by Union Carbide to the search for deposits of this type in the western United States. Since then, such exploration has been continuous by both commercial firms and private parties. The future economic potential for natural zeolite deposits seems to be restricted to those of the "open-and-closed system" types as described by Sheppard (this chapter). Therefore, this and the following discussions will concentrate upon these types; the other types of zeolites in sedimentary rocks (e.g., deep-sea sediments, burial metamorphic, and hydrothermal) will be, for the most part, ignored. Despite the relative cheapness of natural zeolite deposits as compared with the cost of synthetic molecular sieves, there has been minimal development of zeolite mining in the US over the past 25 years or so. Mumpton (this chapter) discusses the present commercial utilization of natural zeolites and their future potential in detail, but perhaps the following will serve as useful background. In the early days of synthetic molecular sieve research and production, the efforts were concentrated largely upon such high-value applications as physical separation of components in a stream (based upon molecular size and geometry) and in catalysis. Due to a number of reasons (some of which are difficult for an outsider to understand), natural zeolite ores (beneficiated or not) have not made substantial inroads upon the use of the higher-priced synthetic molecular sieves for the foregoing applications, but this is not to say that such a condition will exist forever. Furthermore, in view of the many other uses which are now known, or which loom in the future, the competitive position of the natural zeolites vs. the more expensive

Jan 1, 1983

By H. S. Cannon, F. N. Rhines

IT. H. Hausner( Sylvunia Electric Products Inc., Bay-side, N. Y.)—The results reported by the authors are interesting because they contribute some information on the principles of sintering and also because of a certain practical value for the manufacture of powder . metallurgical parts in production. Pressed powder compacts are frequently sintered in a boat in several layers so that the lower layers are actually sintered under the weight of the upper layers and, therefore, are frequently deformed. The authors gave information on this deformation process by determining the effect of the load on the density. The experimental setup of the authors, however, has a disadvantage—that the sintering occurred in a cylindrical container so that the deformation was stopped in the direction of the diameter. The authors should have rather called this a study of hot-pressing than of sintering. I want to call the attention of the authors and others interested in sintering under load to the experimental work described by Dawihl and Rix.' These authors sintered cylindrical compacts under a lengthwise ten-sional load of 0 to 25 g and found that the shrinkage in length and diameter changes considerably with the load, but that the volume shrinkage is affected very little by the load. H. S. Cannon (authors' reply)—We wish to thank Dr. Hausner for calling attention to the experimental work of Dawihl and Rix. The fact that they found volume shrinkage little affected by varying tensional loads during sintering seems to support the contention that the forces due to loading are equivalent to and additive to the forces which cause densification. This contention is the basis of our comparison of sintering and creep.

Jan 1, 1952

By Stanley L. Lopata, Eric B. Kula

The problem of preferred orientation has been considered in quantitative phase analysis by X-ray diffraction techniques. The average intensity of a diffraction peak can be obtained by integration over the whole pole figure, or by random rotation of the specimen in the X-ray beam, or by a combination of both. For rod or wire, where the pole figure shows rotational symmetry, the intensity is measured along a radius of the pole figure. Where no symmetry is present, rotational symmetry is imparted by rapid rotation of the sheet around its surface normal during measurement. These methods are applied to the determination of aus-tenite in an Fe-31 pct Ni rod and Fe-28 pct Ni sheet. X-RAY diffraction techniques are frequently used for quantitatively determining the relative amounts of two or more phases present in a structure.1,2 Briefly, the method requires a measurement of the intensity of a Bragg reflection for each phase. The method is based on the principle that the intensity of a Bragg reflection, IA, is directly proportional to the volume fraction of the given phase present, CA: T KRACA/2µ [1] where K is a constant independent of the diffracting phase, RA can be calculated and depends on the Bragg angle ? and the particular reflection measured, and µ is the linear absorption coefficient of the mixture.' For a mixture of two phases A and B, IA = RAcA [2] IA/IB=RAcA/Rbcb and CA+ CB = 1 [3] This allows the volume fraction of a phase to be calculated directly from the measured integrated intensities of the two phases present. This method is frequently used for quantitatively determining retained austenite in steels, but can be used for the quantitative determination of in titanium alloys, as well as phases in other alloy systems. The intensities are generally measured by diffracting only from planes whose normals are perpendicular to the specimen surface, with the implicit assumption being made that this intensity is typical of reflections from planes whose normals lie at other angles to the surface. If the specimen contains a texture or preferred orientation of the crys- tallographic planes by virtue of previous mechanical working, however, this measured intensity is correct only if the intensity level fortuitously is one times random. Examination of pole figures for actual rolled sheet shows that the intensity level at the center of the figure is seldom at the random level, and can very easily differ by a factor of five or more, leading to a commensurate error in the calculated amount of the phases. Textures have been commonly found in materials which are cold-rolled or recrystallized after cold rolling. This problem is becoming of greater importance since structural materials in use today, such as the high-strength stainless steels, frequently are further strengthened by cold rolling, and hence contain textures. Although high-strength carbon-containing alloy steels generally do not contain textures, some of the newer thermomechani-cal treatments will impart a texture even in these cases. In the case of hexagonal metals, such as titanium, probably every wrought sample will show some anisotropy. Since the standard X-ray techniques are inapplicable in all these cases, there is a clear need for some method of taking this anisotropy into account. The specific problem is to obtain the integrated intensity of a Bragg reflection for each phase, averaged over all orientations of the sample with respect to the X-ray beam. This can be done either by purely mechanical means or by a mathematical averaging. Mechanically, a small spherical speci-

Jan 1, 1965

By O. A. E. Jackson

In all three principal dunite dikes, minute disseminated grains of pyrrhotite are to be seen in the fresh rock in amounts less than 1 pct. Traces of nickel have been reported from many such specimens. Nickeliferous pyrrhotite is the principal nickel-bearing mineral, although olivine contains very minor amounts of nickel in solid solution, substituting for magnesium and iron. Such occurences are of no economic significance. Nickel analyses of possible economic significance (up to 3 pct Ni) have been returned from samples taken near the margins of the two large western dunite dikes. These samples were from schistose zones along and within the dike walls. The mineralized shear zones, up to 30 ft wide, strike N 30 W and dip from 65" to 90" west. They consist of layers of hard, fresh, green-gray dunite, mineralized with finely disseminated pyrrhotite. These layers alternate with layers of soft, black, oxidized schistose dunite up to 1 ft wide, well mineralized with pyrrhotite and tabular-fractured pentlandite in crystals up to 1/4-in. diam. Sulfides identified in polished sections were chiefly pyrrhotite and pentlandite, with much smaller amounts of chalcopyrite. There are two varieties of pyrrhotite. One develops a fine polish and conforms to published descriptions. The other is slightly darker and browner, does not polish as well, and displays flamelike growth or intergrowth structure when etched with nitric acid fumes. Pyrrhotite and pentlandite crystallized contemporaneously in the form of veins in the olivine and as fillings of the interstices of euhedral olivine crystals. Chalcopyrite replaces the other sulfides. The most striking feature of the deposits is their occurrence in intimately fractured and schistose zones in the dunite where faulting has been localized along the contacts of the sediments and the dunite dikes. Though far too little detailed work has been done to be certain, there appears to be a higher concentration of sulfides in the shear zones along the margins of dike apophyses, sediment reentrants, and strike and dip irregularities. Much more study would be required in order to submit a plausible theory of formation of the nickel deposits, supported by laboratory and field evidence. Results of the present study, especially localization of the metals by fracturing, certainly indicate that the nickel concentrations were brought about by precipitation of nickel sulfides from fluids that used the fractures as a means of ingress. Studies of nickel sulfide deposits throughout the world have demonstrated that such sulfides were deposited at considerable depths and at temperatures of several hundred degrees. This would rule out the possibility of groundwater as the transporting medium. The two possible sources of hot nickel-bearing fluids are quartz diorite and gabbro. The first possibility is that large volumes of fluids, expelled from the quartz diorite magma during its crystallization, obtained a supply of nickel by altering the nickeliferous olivine of the dunites. The likelihood of this process is lessened by the recognition that, although the dunites show some alteration to serpentine, talc, and trem-olite, they are for the most part remarkably fresh outside the schistose zones. The worldwide association of nickel with basic rocks, together with the presence of pyrrhotite in thin films on joint planes of the gabbro on Jumbro Mountain, favors the gabbro source. The writer extends thanks to C. Phillips Purdy, Jr., project chief of American Metal Climax Inc., for giving him the opportunity to study these deposits. He is also indebted to the officers of American Metal Climax Inc. and Discovery Mines Inc. for permission to publish this article.

Jan 1, 1961

By Henry Drinker

The Institute has lost a valued member by the death of Eckley B. Coxe, Jr. He bore the name of one who was largely instrumental in founding the Institute, and to whose support and guidance as active member, Vice-President, and President, the Institute owes. much. Eckley B. Coxe, Jr., was the nephew of the late Eckley B. Coxe. He held a large interest in the coal estates owned and developed by his family, and he was thus naturally led to take a continuing interest in mining matters, and for years and up to the time of his death was a full member of the Institute. He died at his residence, Drifton, Pa., on Sept. 20 last, aged 44. He was a member of the class of '93 of the University of Pennsylvania,. of which great institution he was a devoted alumnus. His educational and charitable activities were numerous, but his chief life-work and interest was in archeological investigation and research in Egypt, carried on through the Museum of the University of Pennsylvania of which Museum he was President. The discoveries made by the various expeditions financed and directed by him, and the notable publications issued by his direction and at his expense, chronicling the results, are among the most important researches ever made of buried Egypt. Mr. Coxe was a member of the International Historical Society and of many educational and charitable organizations. By his will, among other bequests, he left $500,000 to the Museum of the University of Pennsylvania and $100,000 to the University, the income of the latter fund to be applied to increasing the salaries of the professors of the Institution. He also left $100,000 to the Children's Hospital of Philadelphia, of which he was a manager, and in addition thereto $10,000 of which the income is to be applied in providing Christmas presents for .the child patients, and in providing an annual dinner for the patients and attendants of the hospital. He bequeathed $50,000 to Leonard Hall, an associate mission of the Episcopal Church, at South Bethlehem, Pa., $25,000 to the Epileptic Hospital and Colony Farm (Philadelphia) ; $50,000 to the Philadelphia Orthopaedic Hospital and Infirmary for Nervous Diseases; $15,000 to the United Charities of Hazleton, Pa., the income to be applied to the salaries of nurses; and $25,000 to the Mining and Mechanical Institute of the Anthracite Coal Region of Pennsylvania, founded by his uncle, Eckley B. Coxe, and of which Eckley B. Coxe, Jr., was an active trustee up to the time of his death. This Institute is known as one of the best preparatory schools for technical education in Pennsylvania, and is mainly devoted to extending an opportunity for education by day and night schools to the boys and young men of the Anthracite Region. Its principal is an alumnus of Lehigh University; it has an able local Board of Trustees, and an Advisory Board consisting of the Provost of the University of Pennsylvania, the President of Lafayette College, and the President of Lehigh University, all three of which institutions have established prize scholarships in the institute. Mr. Coxe carne of a distinguished ancestry, the record of which is fully given in the biographical notice of his uncle, Eckley B. Coxe, by Dr. R. W. Raymond, in Vol. XXV of the Transactions.`

Jan 12, 1916

By I. N. Knap

Discussion of the paper of HOWARD R. HUGHES, presented at the Now York meeting, February, 1915, and printed in Bulletin No. 99, March, 1915, pp. 629 to 635. I. N. KNAPP, Ardmore, Pa.-The claims made in the paper for the Sharp & Hughes cone bit are modest. I have used it with satisfactory results. It is a wonder for eating through hard, brittle rock; it will drill through iron pyrites that the fish-tail bit cannot enter. Soft ground is apt to contain concretions that are much harder than the containing ground. ?We have at times in drilling with a fish-tail bit thought the hole was partly in such hard material and partly in soft, thus making a difficult place to drill past in the ordinary way. By changing to a Sharp & Hughes cone bit such obstructions were easily overcome. This cone bit has greatly widened the range of work that may now be profitably accomplished by the hydraulic rotary method of drilling. It is not, however, adapted to drill soft or sticky ground, the old fish-tail bit being better for such purposes. The fish-tail bit usually scrapes its way through the material drilled, but not always. I believe at times it cuts and chips in soft friable rock. That is, the bit seems to bite into the rock, and when sufficient torsion is put on the drill stem it breaks its hold and jumps around and chips the rock from the bottom of the hole, like a stone cutter's chisel, and then takes another hold. This condition occurs only in friable material when the bit is sharp and the feed properly controlled. The Sharp & Hughes cone bit is a most valuable -tool for the rotary driller.

Jan 5, 1915

By Jan D. Miller

Under the name given to this column, I almost feel obliged to write about some aspect of grinding, but I have decided instead to comment on the future of chemical processing. In recent years, I have seen a tremendous interest in extractive metallurgy develop among undergraduate and graduate students at the University of Utah. For example, of the 12 graduating seniors this year, over half seem to prefer extractive metallurgy to physical metallurgy. In particular, they seem to be most interested in hydrometallurgy, or chemical processing, obtaining industrial exposure to the phenomena they study via part-time employment at the Kennecott Research Center and the USBM Metallurgical Center in Salt Lake City. The stimulus has been generated by society itself. Many students are dedicated to the proposition that new technology can circumvent the destruction of our environment, a concept which provides considerable motivation. At the governmental level, the recent concern for the quality of our environment has created action in the area of chemical processing both through imposition of stringent air and water quality standards, and through increased funding for technological research in this area. The National Academy of Sciences (NAS) gave impetus to this movement when it pointed up the need for development and support of such disciplines as extractive metallurgy, particularly chemical processing, in a recent report on Mineral Science and Technology. The recommendations in the NAS report have prompted governmental action on many fronts, including the Bureau of Mines, and have also given rise to direct legislation in the form of two bills -H. R. 3492 and S. 635- presently before Congress to a mineral engineering education. The report recommends that chemical processing technology (more generally extractive metallurgy) be developed by both new engineering techniques and unconventional chemical techniques such as application of the chemistry of nonaqueous liquids to mineral systems.

Jan 1, 1971

By I. R. Dunlap, R. F. Burdyn, F. D. Patchen

The composition and properties of a new type of cementing mixture are discussed. In these compositions, API Class A or C cements are added to n stable water-in-oil emulsion instead of the crsual water. The cement disperses in the oil phase and remains out of contact with the water under normal conditions of mixing and storage. At higher temperatcrres, such as those encountered down-hole during placement, the emulsion breaks and cement hydration can then proceed. An extremely low filtration rate is obtained; the major part of the filtrate is oil. Thickening times of the mixture may be increased to meet the 18,000-ft casing cementing schedule by varying the amount of emzilsifier. As in conventional Portland cement mixtures, high-temperature strength retrogression can be overcome by addition of silica flour. Results of several field app1ication.r show that mixing presents no diffculty if emulsion blenders are used and the emulsion is prepared beforehand. INTRODUCTION Water-in-oil emulsions., in which oil is the continuous or external phase and in which water exists as discrete droplets, have for some time been used successfully in drilling muds to reduce filtration loss.1,2 Applied to cement slurries, the same results are obtained; i. e., the fluid-loss is greatly reduced. In addition, thickening times may be extended, lower densities and strengths obtained, and water-base borehole fluids more easily displaced without contamination of the cement. A low filtration rate is often a desirable property in oil well cements since loss of fluid increases placement difficulties and may also cause damage to water-sensitive producing formations.' In the casing cementing operation where the cement slurry is pumped into the narrow annulus between open hole and casing, rapid loss of fluid to a porous formation can cause the slurry to thicken and plug the annulus before the desired fill is obtained. Where a casing or a liner is cemented against a productive formation and the well completed through perforations, the fluid lost between the time the cement first contacts the formation and the time a set is obtained may invade the zone past the depth of the perforations. If the sand contains a material which will swell upon contact with cement filtrate, permanent damage may result. Previous methods for reducing the fluid-loss of cements have employed bentonite4 as an additive, usually with a lignosulfonate as a dispersant, or a derivative of some naturally occurring polymeric material such as cellulose ether." Oil emulsion cements have also been proposedv or fluid-loss reduction, but these have been of the oil-in-water type. Bentonite cements have been used most widely and have been successful in reducing incidence of premature setting of cement attributable to loss of water by filtration. It is the purpose of this paper to describe preparation and properties of a water-in-oil emulsion cement and to relate procedures followed and results obtained in several field applications. DESCRIPTION OF SYSTEM AND MECHANISMS A water-in-oil emulsion cement is prepared by adding an API Class A or C cement to a stable water-in-oil emulsion. Fig. 1 is a photomicrograph of this emulsion before addition of cement. Here the droplets are water and the surrounding medium is diesel oil. High emulsion stability is indicated by the small droplet size [1-5 microns], and by their uniformity.' To form a stable water-in-oil emulsion as illustrated, several conditions must be met. A predominantly hydrophobic emulsifier must be present in sufficient concentration to produce a strong interfacial film; initially, the phase volume ratio (the water-to-oil ratio) must be low;