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By Walter Rose

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 gereatest 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

By Warren J. Jackson, John L. P. Campbell

Automatic recording of the radioactivity of the earth's formations provides a log of relative intensities that, if properly interpreted, can be applied to oil-field engineering. Production, engineering, and geological departments regard the radioactivity log as a forward step in the securing of more conclusive information for successful well completions. Explanations of the technique, together with some of the problems to which radioactivity logging have been applied, are presented in this paper. Introduction Those responsible for the completion of new oil and gas wells, or with planning workover operations on old wells, have followed closely the development of radioactivity well logging because they are interested in reducing the number of unknowns that usually are present in such work. Many operators have made use of the log, or are acquainted with at least one of the applications, but it is unlikely that any one operator is familiar with all of the many applications that are possible. The purpose of this paper is to present a representative example of each of the many applications, wherever the information has been released by an operator, and to illustrate by hypothetical examples other applications, releases for which have not been given. In this way, it is hoped that a better understanding of the scope of this new engineering tool may be obtained. Although the literature contains many references that describe in detail the theory, development, and application of radioactivity well logging, a brief discussion of the technique may be helpful to those who are investigating the subject for the first time. All rocks contain radioactive material in varying concentrations. In general, shales contain relatively more radioactive material than sandstones or limestones. These radioactive materials disintegrate with time into other materials of lower atomic weight, and in that process of disintegration the rocks are emitting many rays, the most penetrating of which is the gamma ray. The intensity of emission of the gamma ray is proportional to the quantities of radioactive materials present. A higher rate of emission would be observed, therefore, opposite a shale than opposite a sandstone or limestone. Since measurable intensities of gamma rays are capable of penetrating as many as five concentric strings of casing, and as the gamma-ray intensity is relative to the formations, the measurements of variations in gamma-ray intensities offer a means of identifying cased-off formations in their proper stratigraphic sequence. The Gamma-ray Curve The measurement of gamma-ray intensities is accomplished by means of an ioniza-tion chamber that consists of a heavy cylinder, about 3 ft. long, that contains two insulated electrodes and is filled with an inert gas under high pressure. Under normal conditions no current will flow through the gas when an electrical potential is set up between the electrodes, but when

Jan 1, 1946

By T. H. Dunn, P. L. Menaul

This paper discusses the results of an investigation made to develop a method of combatting corrosion of subsurface oil-well equipment caused by brines containing hydrogen sulphide. Carbon monoxide, aldehydes, and certain cyanide compounds were found by laboratory tests to effectively inhibit corrosion of steel by sulphide brines. Experiments were made for one year in eight wells in West Texas fields using formaldehyde as an inhibitor. It was found that the inhibitor treatment successfully prevented the severe corrosion previously experienced in these wells, and effected important net savings in operating costs. Introduction Corrosion of oil-field equipment has long been a problem in areas producing sour crudes. These areas include the major fields of Arkansas, Western Kansas, West Texas and New Mexico. Corrosion in these fields is caused primarily by the chemical action of hydrogen sulphide in the presence of water and by electric currents entering the wells through flow lines. Hydrogen sulphide is noncorrosive to iron or steel in the absence of water but under the usual conditions prevailing in oil wells where more or less water is present, hydrogen sulphide is very corrosive. This type of corrosion occurs over the pH range below 9, which includes all natural oil-field brines. If air is present in addition to hydrogen sulphide and water, corrosion proceeds at an extremely rapid rate. It was reported several years ago that a string of oil-well tubing was literally dissolved within 50 days where an air lift was used on a well producing considerable water and hydrogen sulphide. Air is generally absent in wells producing sour crude. After hydrogen sulphide corrosion starts, it proceeds with increasing severity and its correction becomes progressively more difficult. This characteristic of sulphide corrosion has been attributed to the formation of galvanic couples between the iron and steel equipment on one hand and the products of corrosion on the other.' Severe corrosion of subsurface oil-well equipment leads to a multitude of troubles. In addition to destruction of costly equipment, producing sands often are damaged by flooding with water leaking through corroded casing; bad mechanical conditions may develop in a well due to obstructions caused by corroded equipment lost in the hole, or partly collapsed casing; pumping operations are interfered with, and severe emulsification problems may result from the homogenizing action of corroded balls and seats.% A typical case of severe corrosion caused by hydrogen sulphide was reported in Howard County, Texas, where it was necessary to pull tubing once a week to repair leaks after the tubing had been in use for only one year. On one well in this area a string of tubing was pulled 11 times in 8 months; 11 joints of tubing being replaced because of leaks. In Ector

Jan 1, 1946

By R. S. Dean

MANY studies have been made of the properties of steel produced by adding varying amounts of sponge iron to the charges used in steel-making furnaces.1-3 The results of these previous studies, however, have failed to disclose a reason for the belief of steelmakers that steel made in this way is definitely different from steel made entirely from scrap or iron melting stock. This paper deals chiefly with the structure of the sponge iron, of the wrought iron made by welding the sponge iron into blooms, and of the steel made by melting the forged and rolled blooms. It is believed that the structure of the final steel is inherited from the ore and that this inherited structure produces marked differences in the properties of the steel and explains the feeling of steelmakers which is based on their experience. Three kinds of sponge iron were used in this investigation: One made from a limonite ore reduced with natural gas, one made from a hematite ore reduced with natural gas, and one made from a magnetite ore reduced with charcoal. The sponge iron made by reduction with natural gas

Jan 1, 1935

By John L. P. Campbell, Warren J. Jackson

Automatic recording of the radioactivity of the earth's formations provides a log of relative intensities that, if properly interpreted, can be applied to oil-field engineering. Production, engineering, and geological departments regard the radioactivity log as a forward step in the securing of more conclusive information for successful well completions. Explanations of the technique, together with some of the problems to which radioactivity logging have been applied, are presented in this paper. Introduction Those responsible for the completion of new oil and gas wells, or with planning workover operations on old wells, have followed closely the development of radioactivity well logging because they are interested in reducing the number of unknowns that usually are present in such work. Many operators have made use of the log, or are acquainted with at least one of the applications, but it is unlikely that any one operator is familiar with all of the many applications that are possible. The purpose of this paper is to present a representative example of each of the many applications, wherever the information has been released by an operator, and to illustrate by hypothetical examples other applications, releases for which have not been given. In this way, it is hoped that a better understanding of the scope of this new engineering tool may be obtained. Although the literature contains many references that describe in detail the theory, development, and application of radioactivity well logging, a brief discussion of the technique may be helpful to those who are investigating the subject for the first time. All rocks contain radioactive material in varying concentrations. In general, shales contain relatively more radioactive material than sandstones or limestones. These radioactive materials disintegrate with time into other materials of lower atomic weight, and in that process of disintegration the rocks are emitting many rays, the most penetrating of which is the gamma ray. The intensity of emission of the gamma ray is proportional to the quantities of radioactive materials present. A higher rate of emission would be observed, therefore, opposite a shale than opposite a sandstone or limestone. Since measurable intensities of gamma rays are capable of penetrating as many as five concentric strings of casing, and as the gamma-ray intensity is relative to the formations, the measurements of variations in gamma-ray intensities offer a means of identifying cased-off formations in their proper stratigraphic sequence. The Gamma-ray Curve The measurement of gamma-ray intensities is accomplished by means of an ioniza-tion chamber that consists of a heavy cylinder, about 3 ft. long, that contains two insulated electrodes and is filled with an inert gas under high pressure. Under normal conditions no current will flow through the gas when an electrical potential is set up between the electrodes, but when

Jan 1, 1946

By W. J. West, W. W. Garvin, J. W. Sheldon

One of the most important problems of reservoir mechanics is the prediction of the behavior of a gas and oil producing reservoir for a variety of production programs. In the absence of a knowledge of the behavior of even idealized systems, it has been difficult, if not impossible, to determine which production program would yield maximum economic recovery. The problem was formulated mathematically many years ago, hilt a solution of the equations had never been obtained because of their extreme complexity. The solution of the problem became possible, however, with the advent of modern computing machines. This paper describes a digital method of solving the problem and discusses some of the results which have been obtained to date. The IBM Type 701 Electronic Data Processing Machines located at IBM's New York Scientific Computing Service were used successfully to perform the computations. The flow of gas and oil through a reservoir can be described mathematically by two second-order, nonlinear partial differential equations which must be solved simultaneously. All derivatives were replaced by finite differences to bring the equations into a form suitable for digital calculations. A number of finite ditference formulations were investigated and one form was found which resulted in stable, convergent solutions. This form was used to obtain .solutions for both radial and linear systems producing by solution gas drive. The results presented in this paper are: (a) saturation profile within the hypothetical reservoir vs. time, (b) pres.strre profile within the hypothetical reservoir vs. time. (c) gas-oil ratio vs. cumulative recovery, and (d) ultimate recovery. The saturation profile clearly shows the effect of critical gas saturation. The saturation near the well-bore drops quickly to the critical gas saturation and remains essentially at that value until the remainder of the reservoir also has dropped to the critical gas saturation. The pressure profile shows a smooth variation of pressure across the reservoir. The gas-oil ratio drops slightly during the early stage of production until the critical gas saturation is reached, rises rapidly from then on and eventually passes through a sharp maximum just before the economic limit of production is reached. For the radial example presented in this paper, the average oil .saturation of the reservoir at a time corresponding to the limit of economic production was 56.5 per cent and the ultimate recovery was 6.86 per cent. The difference between change in saturation and ultimate recovery is caused by .shrinkage of the oil phase. The solution time with the 701 Computer is sufficiently short to permit an economically feasible investigation of the effects of variation of the many parameters which describe an oil reservoir. In particular, the ultimate recovery for various systems can he determined as a function of rock and fluid properties, of well spacing. and of production rate. INTRODUCTION The effective planning for maximum economic depletion of oil reservoirs is one of the major problems confronting oil producers. The most important part of the planning is prediction of the response of the oil reservoir to a particular production program. The production program can be selected by imposing certain controls available to the operator. Some of these controls are: (a) well spacing, (b) production rate, (c) time

Jan 1, 1955

By Frederick N. Rhines

Because of the nature of the environments in which metals are handled, it is natural that gases should be suspected of intruding into metallurgical operations, there to produce effects both beneficial and detrimental. The problem of tracing and controlling such effects is often made difficult by the complexity of the conditions surrounding their occurrellce, even though the fundamental mechanisms invalved may be simple and of familiar type. Many gas-metal reactions are known to be implemented by Processes of diffusion. These form a homogeneous group of phenomena which become more readily understandable when viewed together, in that the knowledge gained from one serves to interpiet the next. It is the purpose of the present Paper to present, by means of examples drawn from practice, a brief survey of the ways in which gas-metal diffusion serves and obstructs the Purposes of the metal-fabricating industries. The selection of the cases described was made by consulting more than thirty-six practicing experts whose combined experience provided an extensive coverage of the field and who were in a position to supply examples of occurrences of present day interest. The response was generous and it is regrettable that space permits the description of only a limited number of typical examples with ' but brief mention of parallel cases. The Nature of Gas-metal Diffusion The term ugas-metal diffusion," although commonly used, is ambiguous in so far as it implies that a definite group of " substances may be identified as gases and may be expected to behave in a manner distinct from other substances in association with metals. "Gases" such as oxygen and hydrogen when diffusing through a liquid or solid metal are properly components of the liquid or solid solution; they behave as alloying elements and are not to be distinguished in their diffusion characteristics from other elements, except that each has an individual rate of diffusion. On the other hand, a number of metals in certain.temperature ranges are volatile to the extent that they may appear in the form of vapor in metallurgical operations. For the sake of greater definiteness, therefore, it will be convenient to regard as "gas-metal diffusion" any process in which the result depends upon one or more of the diffusing elements appearing, at some stage, in the gaseous state, or as a compound gas. NO element, gaseous or otherwise, can diffuse through a liquid or solid metal unless it is at least slightly soluble in that metal. The elements of low atomic number

Jan 1, 1944

By Will H. Coghill, P. H. Delano, G. D. Coe

Data concerning the actual net energy required for pulverizing coal are lacking from the literature on coal pulverization. Power data given in the literature concern gross power and frequently include the power expended on the air blast or product-conveyor system, as well as power lost through friction in the pulverizer itself. Consequently, such data supply no information regarding the net energy consumed in pulverizing or the relative grinding resistance of various coals. In the study of coal pulverizing much work has been done on what is known as " grindability-index numbers," but grind-ability tests have seldom considered the energy input (that is, the "cause" part of the system "cause and effect"). There are many records of the effect, but even these have questionable value because the "grindability" tests did not make a pull'erized product by a method comparabLe with- commercial pulverizers. In many of the tests, only a selected part of the coal was ground, and the remainder continued to be an unknown factor. Furthermore, none of the grindability tests provide the balanced circulating load common to all modern commercial pulverizing. In order to obtain better understanding of the fundamental principles of coal pulvcrizing, the Bureau of Mines is investigating the "cause" phase; that is, the net energy input or net power excluding friction between the moving parts of the machine. As a first step in the investigation,it was necessary to design and construct a laboratory machine in which no friction-loss corrections are involved, which could grind and finish a minus-¾-inch feed, which could be emptied rapidly and completely, which could operate with a continuous feed and finish in an air separator; and, most essential of all, which would be equipped with a measuring device for recording only that portion of the total power consumed in actual pulverizing, hereafter referred to as "net energy input" or "net horsepower-hours." The channel-roller pulverizer hereinafter described is believed to meet these requirements. History oF the Machine The, work started when Ralph W. smith, engineer, St. Genevieve Lime Co., St. Cenevieve, Mo., was appointed one of the consultants of the Bureau of Mines, United States Department of the Interior, in cooperation with the University of Alabama, to develop a machine for testing the abrasiveness of coal. Smith had already developed a machine for testing the abrasive-ness of dentifrices,1 and it was thought the same principles might be applied to coal, Smith's machine had a revolving disk with an annular channel in which the sample was placed. Riding in the channel was a small block or runner of selected soft metal held

Jan 1, 1942

By Robert Goodrich

THERE is a small area about Murray where bedded gold quartz veins occur in Prichard slate. The ore taken from the upper levels, during the early days, was free milling and was treated by stamp milling and amalgamation. There was likewise a considerable placer working. The report is current that tungsten (scheelite) was encountered, which interfered with the amalgamation in the stamp mills and which, in placering, collected in the riffles in the sluice boxes and. clogged them. Consequently, in the quartz mines, the scheelite, when encountered, was rejected, being thrown into the waste, sometimes inside the mine and at other times outside on the clump. The free surface ores became worked out and as the ore in depth became pyritic and rebellious to amalgamation the mines closed down. Last spring tungsten ore brought a high price, near $80 per unit, 60 per cent. W03 and up. This so stimulated the output of tungsten ore that old clumps were explored and waste stored in the mines was gone over. Tungsten was likewise mined from virgin ground. So the district produced quite heavily for a time. The condition now is different. The price is not so high, about $20 per unit W03, which makes profits questionable when mining in new ground. The accumulations from early clay mining have been exhausted and the output has greatly declined. The Golden Chest mine was the heaviest producer of tungsten. The months of June and July were spent at this mine studying the problem. Since the mine had produced both gold and tungsten, we looked forward to the problem of recovering both from what might be called a gold-tungsten ore. A study of the Golden Chest vein showed this not to be so there. While gold ore and tungsten ore come from the same vein, the tungsten ore is confined to a more or less disturbed or distorted portion

Jan 8, 1917

By W. A. Ver Wiebe

The year 1940 was singularly unmarked by sensational developments in Kansas. Routine operations were carried on in a systematic, orderly fashion and the efforts of oil producers were concentrated on extending known fields. In Kansas an arbitrary yardstick for wildcats has been set up. A well drilled mile or more from a known pool or well is now considered a wildcat. A "rank wildcat" is one that is drilled at least 2 miles from any known producer. During 1940, rank wildcats resulted in the completion of 116 test wells, among which 16 were successful in finding new oil pools and the remaining I00 were dry holes. The ratio of successful wells to dry holes, therefore, was approximately I:6. During the year, 1890 wells were completed in eastern and western Kansas. This figure is somewhat lower than that given in several trade journals, because it does not include wells that were deepened or wells that were recompleted in a different geological horizon. About three fourths of these (1423) were completed as commercial oil wells (I220 in western and 203 in eastern Kansas). The commercial gas wells completed number 58 of which 10 are in eastern Kansas and 48 in western Kansas. Of the remzining completions 147 are dry holes in eastern and 262 are dry holes in western Kansas. Based on daily potential capacity, the new discoveries of the year account for a cumulative initial production of 46,000 bbl. in eastern and 2,128,000 bbl. in western Kansas. The state of Kansas attained a new peak in production, with the total of 66,245,000 bbl. for the year 1940, the number of contributing wells being 20,779. Thus the increase over 1939, when about 58 million barrels was produced, is considerable. The previous peak occurred in 1937, when 70,761,000 bbl. was marketed. In another still earlier peak, in 1917, slightly more than 45,000,000 bbl. was produced and sold. The production of gas probably reached a new peak also during 1940, with its total of 85 1/2 billion cubic feet. Between the peak of the year 1908, when over 80 billion cubic feet was produced, and that of 1940, the production dropped to a low point of 16 billion cubic feet in the year 1921. The number of test wells drilled was larger than in 1939; that is, 1890 compared with 1458. The first peak was reached in 1904, when 2782 wells were drilled. The number dropped off rapidly, to 368 three years later, but rose to the second and highest peak in 1918, when 4671 test wells were completed. In the period between 1904 and 1912 more gas wells were completed than oil wells. Between the high peak of completions in 1918 and somewhat lower peak of 1937, the low point was reached during 1931, with the completion of only 470 test wells. In the number of new pools discovered, Kansas again ranks high among the states. The exact number depends somewhat upon the interpretation of a "new" area— whether it should be called a new pool or a long extension of an old pool. Unfortunately, the matter of securing the right kind of production allowable also enters into this question. Often the decision regarding a new pool cannot be made until other wells

Jan 1, 1941

By J. Chipman, N. J. Grant, R. Rocca

Desulphurization of liquid iron by reducing slags of the electric-furnace type was studied from 65 heats. Variations were made in basicity over a wide range and in FeO up to about 5 pct for their effects on desulphurization. The role of FeO in desulphurization from the blast furnace, to the electric furnace, to the oxidizing conditions of the open hearth is shown to fit a relatively simple pattern of behavior. THE mechanism which controls the desulphurization of molten iron by basic slags has been the object of several investigations. In particular, equilibrium determinations have been made both in the field of basic open-hearth slags, which have a high iron-oxide concentration, and in the field of blast-furnace slags which have a very low iron-oxide concentration. In both cases the desulphurization ratio has been found to increase with increasing basicity of the slags; however, the mechanism of desulphurization differs in the two cases. In basic open-hearth slags desulphurization occurs mainly as a partition of iron sulphide:&apos; FeS * (FeS) and the desulphurization ratio is approximately independent of iron-oxide concentration in the slag. In blast-furnace slags the concentration of iron oxide is very low as a result of the highly reducing conditions in which they are formed. The controlling reaction for desulphurization is then:2,3 FeS + (CaO) <=* (CaS) + (FeO) The slags of the reducing stage in the electric furnace have an iron-oxide concentration which is intermediate between blast-furnace and open-hearth slags. The study of the mechanism of desulphurization for these slags has been the object of this investigation. The importance of low (FeO) in the slag for desulphurization was first verified by Bardenheuer and Geller,& who found that high desulphurization ratios were obtained in highly reduced slags. It was recognized" hat iron oxide in the slag becomes a controlling factor in desulphurization only at FeO concentrations approximately under 5 pct. A recent investigation conducted by Buehl,7 upon the suggestion of one of the authors, confirmed this opinion from the results obtained from a heat conducted in a small arc furnace. In the present investigation, slags of very high basicity, such as often are encountered in the basic electric furnace, could not be studied, but equilibrium data have been obtained for slags in a wide basicity range. The iron-oxide concentration in these slags ranged from 0.08 to 15 pct and was controlled by the addition of silicon to the metal. Other constituents of the slags were mainly CaO, MgO, SiO2, A120,, and CaF,. The experimental technique was essentially the same as that of previous investigations.1 8-lo In an open magnesia-lined induction furnace, 65 lb of Armco ingot iron was melted. An atmosphere of hydrogen was maintained over the melt for 1 hr to bring the carbon content down to approximately 0.010 pct maximum. The bath then was exposed to air for 25 min to remove hydrogen. The electrodes were put in place, and the furnace was operated from this point on in an atmosphere of nitrogen. A synthetic slag was added to which additions of silicon and iron sulphide were made. A rate study conducted at the beginning of this investigation had

Jan 1, 1952

By P. P. Reichert, L. S. Gournay, N. T. Burdine

An investigation of equivalent pore entry radii in typical samples of petroleum reservoir rock and the pore volume associated with each value of pore entry radius has been made. Theoretical discussions together with experimental procedures for obtaining pore entry radii and the distribution of pore volume with pore entry radii are presented. Experimental results on a number of core samples, along with typical distribution curves, are shown. Data on the per cent of the pore volume filled by mercury at a pressure of 1500 psi are included. The results of re-runs of samples, made possible by regenerative apparatus, show the repeatability of the data and indicate the amount of physical change in the samples by mercury penetration. Theoretical equations for calculating permeability from pore size distribution data were derived and the results of such calculations are compared with measured gas permeability data. The effect of the shape, surface area, and weight of the sample on the pore size distribution of reservoir rocks was investigated experimentally. Mercury capillary pressure curves are compared with those obtained by the porous diaphragm method using pas to displace water. Standard core analysis techniques, in general, lead to quantities which are statistical averages of the varying properties of the samples under examination. Although such statistical information has real value in predicting the gross performance of porous bodies. it fails to provide fundamental information concerning the properties of the porous medium itself or any processes which may be occurring in it. For example, a gas permeability measurement on a core sample is an indirect way of determining an average pore radius for that particular sample. Since there are many combinations of pore radii that will give the same radius. and, hence, the same permeability, no information is obtained on the pore size distribution. Furthermore, similar values in permeability do not imply similarity in other properties of a porous medium. For instance, it is possible to have two core samples with identical permeability which would have different residual oil contents at the end of an air-oil drive, or even different amounts of interstitial water. It has been recognized for some time by the petroleum industry that a determination of pore size distribution for porous reservoir rocks offered promise of increased understanding of fundamental flow processes in the porous matrix. and therefore of petroleum res- ervoir performance in general. There have recently been published several methods for determination of pore size distribution in porous materials. A report is given here of the modifications in equipment and technique required to adapt one of these methods to measurements on petroleum reservoir core samples. Although only a few correlations or applications of the method are available for presentation at this time, the technique is brought to the attention of the industry so that the opinions and experience of others with this or similar techniques may be exchanged. It seems possible that the method will have wide application in the future. METHOD There are three general methods which may be employed to measure the pore size distribution in naturally occurring rock formations. One method1 is based on experimentally determined adsorption isotherms for calculating the surface area of the porous medium. Knowing the surface area and the pore volume, a rough estimate of the pore radius can be made. Since this method depends on the thickness and uniformity of the adsorbed layer, the validity of the results would be highly questionable. A second method utilizes capillary pressure data obtained by static dis-

Jan 1, 1950

By M. Semchyshen, G. A. Timmons

The predominant orientation in both straight-rolled and cross-rolled molybdenum is the {100} [110] texture. Upon complete recrystallization, this same texture predominates, but there is less spread about the ideal orientation. A secondary orientation about the [111] direction as the axis develops in cross-rolled sheet. Compression-rolled sheet exhibits random orientation in the plane of the sheet. Some mechanical properties were measured at varying angles to the rolling direction to determine the effect of preferred orientation on anisotropy in molybdenum sheet which had been straight, cross, or compression rolled. THE development of the arc-cast process has made available large ingots of molybdenum from which it is possible to roll sheet of considerable size. It is anticipated that such sheet will be further fabricated by spinning, drawing, stamping, or forming. Anisotropy of physical properties caused by the preferred orientation developed in the sheet during rolling may be expected to affect the behavior of the metal when subjected to these fabricating operations. To produce a sheet which will be most amenable to the fabrication of a given shape by a particular operation, consideration should be given to the directions and magnitudes of plastic deformations produced in the operation. When possible, the rolling schedule should be controlled to develop a texture which favors the required deformation. The existence of preferred orientations in rolled molybdenum sheet has been reported by Jeffries,&apos; Konobejewsky,&apos; Fujiwara," Goss,&apos; and Ransley and Rooksby." None of these investigators obtained sufficient X-ray data to permit the construction of pole figures; instead, they based their conclusions upon Debye-Scherrer patterns of a limited number of positions. Ransley and Rooksby devoted some attention to transcrystalline cleavage at 45" to the rolling direction, indicating that it is appreciable in polycrystalline material only when the crystals are in the ideally preferred condition, and that this condition is only approached if the metal has been rolled successively in two perpendicular directions. In a recent paper, Custers and Riemersmao introduced the first pole figures to describe the textures of straight-rolled and cross-rolled molybdenum sheet. To increase the knowledge concerning the generation and effects of preferred orientations in molybdenum sheet, an investigation was undertaken to determine the effects of variations in rolling schedule and annealing treatments on preferred orientation, and to correlate preferred orientations with some mechanical properties. The orientations of straight-rolled, cross-rolled, and compression-rolled sheet have been determined by X-ray analysis, both as-rolled and after recrystallization. Pole figures have been constructed to describe the textures produced by these various rolling procedures. Texture of Cast Molybdenum Ingots In the arc-cast process, molybdenum powder is pressed into a vertical column which is sintered to increase its strength as it proceeds downward into a water-cooled mold, where the metal is melted in an alternating-current arc established between the end of the formed powder electrode and the metal bath at the top of the growing ingot. Since the solid-liquid interface moves continuously upward in the mold, the crystal axes are not normal to the cold surface of the mold but have the curvature shown in Fig. la. X-ray analysis reveals that the cube axis is the fiber axis and that it is normal to the cold surface of the mold; that is, the [loo] direction is parallel to the longitudinal axis of the ingot. This substantiates recent work by

Jan 1, 1953

By C. H. Li, J. Washburn, E. R. Parker

Yield stress in single crystals of zinc was shown to be dependent on prior annealing temperature and rate of cooling after annealing. Rate of strain hardening beyond the yield was not sensitive to annealing procedure. A tentative mechanism for the effect was discussed. COMPARATIVE mechanical tests of metal single crystals generally show a large scatter of results. Many factors may contribute to this variation. The present investigation was undertaken to evaluate the influence of two factors not ordinarily considered of major importance—annealing temperature and cooling rate after annealing. Since plastic properties of crystals are thought to depend on the presence of lattice imperfections, it follows that a variation in properties should result from differences in the distribution and density of these imperfections. Furthermore, in the light of current theories of interaction between edge dislocations and lattice vacancies,&apos; it seems possible that annealing temperature and subsequent rate of cooling might play a part in this distribution. Analysis of the effect of these variables on plastic properties may lead to a better understanding of the annealed state. Single crystals of zinc which have been strained in simple shear undergo complete recovery of mechanical properties upon subsequent annealing. This behavior is useful because a single specimen can be used repeatedly, thus eliminating the uncontrollable variables introduced by the use of many crystals. The test section of the crystals used for these experiments was a cylinder 1/8 in. thick with a cross-sectional area of about 1/3 sq in. The specimens were acid-machined from spherical single crystals 1 in. in diameter in such a way that the slip plane (0001) was at right angles to the axis of the cylinder. In testing, a shear stress was applied along one of the slip directions, [2110] in the (0001) plane.&apos; All crystals, unless otherwise noted, were grown in a helium atmosphere from molten 99.99 pct pure Horse Head Special Zinc. Fig. 1 is a family of curves obtained from one crystal. Each curve was obtained by deforming the crystal to 10 pct strain at a rate of 3 pct per min, following an anneal of 1 hr at 260°C. The strain direction was reversed every other time so that no progressive change in shape of the specimen took place during the series of tests. Since the stress-strain curve was reproducible within a fairly narrow range under the same conditions of annealing, it was then possible to determine the effect of changes in annealing conditions. A crystal was tested repeatedly as previously described but the annealing temperature and rate of cooling preceding each test were varied (Fig. 2). Two cooling rates were used, approximately 30°C per min and 3°C per min. Annealing was conducted at three temperatures, 200°, 300°, and 400°C. For a given annealing time and rate of cooling the room temperature flow stress was higher the higher the annealing temperature. The increase in flow stress was small as the annealing temperature was increased from 200° to 300°C but rose rapidly when the annealing temperature was raised from 300" to 400°C. Faster cooling from the high temperature produced an even greater strengthening of the crystal. The curves were obtained in the order indicated by the numbers. The stress level associated with a certain annealing treatment was, within the limits of scatter, always the same regardless of the

Jan 1, 1954

By R. Schuhmann, E. J. Michal

Experimental measurements are reported for the oxygen pressures of iron-silicate slags in equilibrium with solid silica. CO2-CO mixtures were bubbled through the slags in silica crucibles to find equilibrium values of p co2/p co over the entire composition range of silica-saturated slags at 1250°, 1300°, and 1350°C. From the data, the activity vs. composition relationships were calculated for O, FeO, and Fe. SLAGS composed primarily of silica and iron oxides have particular practical importance in copper smelting,&apos; in acid steelmaking, and in accounting for the service behavior of silica refractories. These slags all contain both ferrous and ferric iron, so that, strictly speaking, they are ternary or three-component liquid solutions. For convenience, the components may be taken as the three oxides, FeO, Fe2O3, and SiO2. The constitution of the FeO-Fe,O,-SiO, system at slagmaking temperatures has been studied in a recent investigation described in a separate paper.&apos; This work showed the compositional ranges of iron-silicate melts at temperatures up to 1450°C and also the temperature-composition relationships for melts in equilibrium with various solid phases, including iron, wüstite, magnetite, and silica. Broadly speaking, the compositions of iron-silicate melts at a given temperature should be thought of as varying over a two-dimensional field. In the first place, the silica/total iron oxide relationship varies from maximum silica for silica-saturated melts to minimum silica for wüstite-saturated melts or, at higher temperatures, to zero silica for straight iron oxide melts. In copper smelting, for example, the converter slags approach the low silica limits while the reverberatory-furnace slags have intermediate silica contents, perhaps approaching silica saturation in some circumstances. Liquids formed in the pores of silica refractories presumably are close to silica saturation. The second type of composition variation is in the ferric/ferrous relationship, which depends on how oxidizing or how reducing the process conditions are. Relatively reducing slags, such as acid-steelmaking slags, are lower in ferric oxide and ap- proach saturation with metallic iron. Oxidized slags, such as copper-smelting slags, contain larger percentages of ferric oxides and approach or reach saturation with magnetite. Since these two kinds of compositional variations are closely related to two general properties of interest for all metallurgical slags, basicity, and oxidizing power, it is hoped that the thermodynamic study of iron-silicate slags eventually will throw further light on the significance and nature of these long-recognized but as yet poorly understood slag properties. Measurements of oxygen activity as a function of slag composition, using CO-CO2 gas mixture to fix oxygen activities, afford an experimentally convenient approach to the study of the thermodynamic properties of iron-silicate slags. In a preceding investigation,³ his approach was used in a systematic study of iron-silicate slags in equilibrium with solid iron. The present paper gives the results of a similar study of the iron-silicate slags in equilibrium with solid silica. The experimental work consisted in the determination of CO2: CO ratios in gas mixtures at equilibrium in the system: gas: liquid slag: silica Determinations were made at temperatures from 1250° to 1350°C for slags ranging in composition from iron saturation to magnetite saturation. Also, equilibrium CO,: CO ratios and slag compositions were determined for the univariant systems: gas: liquid slag: silica: iron gas: liquid slag: silica: magnetite Experimental Methods The experimental procedure was essentially the same as that used in the previous study of iron-silicate slags saturated with solid iron," but in order to work with the silica-saturated slags an all-silica crucible assembly was used. A liquid slag was prepared from pure prefused stock materials and brought to equilibrium with the silica crucible at the desired temperature. Then a mixture of CO2 and CO was continuously bubbled through the melt

Jan 1, 1953

By C. E. Lesher

Coal has been fighting a rear-guard action since the last World War. The battle against competitive fuels has been largely guerilla warfare with more sniping within the ranks than of organized opposition. Oil and natural gas are the fuels that over these twenty odd years have driven coal backward and out of many profitable markets. Now, somewhat timidly, the coal industry is trying a new weapon; namely, Research, or let us more properly say, Organized Research. Engineers have been designing this weapon for many years, supported by those interested in coal, including some coal producers. A part of this pioneer work has been Fundamental Research, the Ph.D. kind that is over the heads of most of us. Another part has been aimed at immediate objectives and realizable profits, the practical, man-in-the-street sort. That is Industrial Research. Enough has been accomplished to make a fair exhibit, but whether this new weapon will have sufficient fire power to rout the opposition, whether the industry will really go into production and use it, the next few years will tell. Need foR Coal Research To utter "Research" is to use the modern magic word; to conjure up the miraculous—rubber from weeds; radar; magnesium from sea water; yes, even gasoline from coal. Research is a very general term. It means something different to every man. What is the coal industry seeking with its research; or what should it seek? And, specifically, how is it going about the job; and is it taking the best way? There are many who say that Coal has been asleep at the switch, while Oil and Gas have been taking the energy business. In an organized way this is true. Large-scale, privatelyfinanced research is just started in the Pennsylvania anthracite industry, and it is still a dream for bituminous coal. What has been done so far collectively is purely defensive; as, for instance, to improve mechanical devices for burning coal so as to be able to recover markets for house-heating fuel long since abandoned to oil and gas. To appreciate just how seriously bituminous coal has slipped back in the national economy in the past 2 5 years, one has only to recall that, in the last war the Navy required for its operations all the high-grade, low-volatile coal that could be produced, and that anthracite was withdrawn from the middle and northwest markets to keep the eastern seaboard warm. All coal was "rationed" by zones, if not to individuals. Now the Navy, the Armed forces and the Merchant Marine are propelled by oil and gasoline. Gasoline and heating oil are rationed to individuals. Production of all coal in this country in 1918 reached the historic figure of 678,200,-000 tons, and in 1943, after 25 years, it is expected to reach a special wartime total of 660,000,000 tons. Meanwhile, production of crude oil this year may exceed 1 ,500,000,000 bbl., and like that of natural gas, reach four times the amount produced in 1918.

Jan 1, 1944

By Gregoire Gutzeit

The development reported in this paper was begun by the author a number of years ago, while he was a lecturer on complex chemistry and metallurgy at the University of Geneva, Switzerland, and in charge of that institution&apos;s research laboratory. Completion of the development and reduction to practice did not occur until last year at the Westport mill, laboratories and testing plant of the Dorr Company, where this method is now in general use for identifying and localizing the mineral constituents of both metallic and nonmetallic ores. It has proved to be a practical tool of the metallurgical staff at the Westport mill, devising unusual milling flowsheets for complex and refractory ore bodies. In a number of instances the findings have been successfully used as fundamental factors in the design and specification of complete metallurgical plants. Seven examples of the use of this method in solving practical milling problems are included in this paper. General Outline The microscopic study of an ore, at first only of scientific interest, has proved extremely useful both in practical geology and in ore dressing. The binocular magnifying lenses for rough observation of the products of an ore-dressing plant have been in use for a long time; but only within the last few years has a systematic microscopical examination of ore samples become a normal tool of any research laboratory dealing with ore-dressing problems. Such an investigation avoids considerable loss of time as well as empirical trials and useless experimentation. It will generally indicate the correct grinding and often will suggest the proper method of treatment. . The petrographic determination of transparent minerals in thin sections, or even in grains, has been perfected, and very accurate methods have been devised to meet any requirement, such as Feodorof&apos;s rotating stage on the petrographic microscope. Almost all transparent minerals can be positively identified by their optical properties; i.e., isotropism, anisotropism, color, pleochroism, refractory index, cleavage, crystal form, birefringence, and others. The identification of opaque minerals is a much more difficult problem and can be done only by using polished specimens. Unfortunately, most of the valuable metallic ores, and even some of the nonmetallic ones, are not transparent; therefore it has been necessary to develop a special technique for the determination of these minerals. Some optical properties—for instance, isotropism, anisotropism, color, cleavage, reflecting power-—are often adequate in roughly classifying the mineral. Only "reflecting power" is a measurable value, provided special photometric equipment (ocular photometer or Orcel&apos;s photoelectric cell) is available. The other optical properties mentioned are more or less relative,

Jan 1, 1943

By S. R. B. Cooke, Y. S. Kim, I. Iwasaki

lron oxides or the gangue minerals of iron ores can be made to float, depending upon the choice of collector. The selectivity of the separation is controlled by the accompanying chemical and operating conditions. In this report the findings on the general flotation characteristics of magnetite are summarized and the results are compared with those obtained for other iron oxides. Depending upon the choice of collector, either the iron oxides or the gangue minerals of iron ores can be made to float, the selectivity of the separation being controlled by the accompanying chemical and operating conditions. The mechanism by which a collector exerts preferential affinity for either group of minerals has been a subject of extended discussion. Previous investigations on the electrokinetic properties and flotation characteristics of hematite,&apos; goethite,2 and quartz3 have demonstrated the electrical nature of the interaction of the collector with these oxide surfaces; anionic collectors are effective on positively charged surfaces and cationic collectors on negatively charged surfaces. Thus, from the differences in the electrokinetic properties of the above-named oxides, a theoretical basis has been provided for their separation by some typical collectors. Examination of the results reported for hematite and goethite shows that their electrokinetic properties and flotation characteristics are remarkably similar. It is of considerable interest, therefore, to examine similar information for magnetite, another common iron oxide, in order to consolidate the flotation characteristics of the three principal minerals of oxide iron ores. Such information is practically significant in the up-grading of both natural and artificial mag- netite produced from taconite, and in the treatment of partially oxidized magnetite ores. Information on maghemite and lepidocrocite, polymorphs of hematite, and goethite, respectively, is also of some theoretical interest in ascertaining the effects of crystal structure and of hydration in the iron oxide group. This article reports the findings on the general flotation characttxistics of magnetite, and compares the results with those obtained for other iron oxides. Experimentally, tlhe surface properties of magnetite were investigated by electrophoresis, and by measurement of the aclsorption of some typical flotation collectors. Its flotation behavior was tested by contact angle measurements and by simple flotation tests using a modified Hallimond tube. The basic information thus gathered was shown to be directly applicable to the interpretation of the results of batch flotation tests made on an artificial mixture of magnetite and quartz. EXPERIMENTAL MATERIALS Magnetite: Magnetite concentrate from Port Henry, N. Y., was further purified by fine crushing and magnetic separaiion, and was used throughout this investigation. For flotation tests the 150/200 mesh fraction was iso1ated and was cleaned by leaching briefly with warn 0.1 N HC1 followed by repeated washing with demineralized water. The final sample analyzed 71.71 pct Fe, 22.37 pct Fe" and 0.47 pct insoluble, and was stored in demineralized water. For e1ectrophoresis and adsorption measurements, the —400 mesh fraction of the magnetite concentrate was ground dry in a pebble mill. The surface area of the ground sample, as determined by the gas permeability method, was 70,000 sq cm per g. Since artificial magnetite has been reported to possess somewhat different physical properties than those of natural magnetite, it also was briefly examined. Preliminary flotation tests on a sample of artificial magnelite, prepared by reducing Brazilian hematite in a C0/CO2 mixture and analyzing 71.94 pct Fe and 23.78 pct Fe&apos;&apos;, gave, however, nearly identical results with those using natural magnetite. It was concluded that artificial magnetite behaves similarly to natural magnetite. Samples which had been magnetically separated showed a tendency to cluster together due to residual

Jan 1, 1962

By Orville R. Lyons

CENTRIFUGAL force has been utilized for the dewatering of fine coal for over 50 years by means of machines commonly called centrifugal dryers. In any centrifuge the coal and water are subjected to a spinning action which usually inctedtocreases in intensity as the coal progresses through the machine. This spinning action, or the centrifugal force that it induces, tears water away from coal particles and produces a dewatered coal. The effectiveness of the dewatering action for any particular machine is governed by the size-consist of the coal and the centrifugal force imparted to the water on the coal. Four makes of centrifuge are currently being used to dewater fine bituminous coal in the United States. These include the vertical, basket-screen C.M.I. (Centrifugal and Mechanical Industries) Carpenter, Reineveld, and the horizontal solid-bowl Bird. The C.M.I. and Reineveld centrifuges are similar in construction and are variations of the Elmore centrifuge, varying principally in the slope of the basket, operating speed, size of perforations in the basket, and diameter of the basket. The same operating description suffices for both. These centrifuges are made up of two rotating elements, an outside conical screen frame and an inside solid cone which carries spiral pusher blades. The screen frame is supported by a hollow shaft, and the solid cone by a spindle shaft passing through the hollow shaft. Both the screen frame and the solid cone rotate at high speeds; the solid cone, with its scraping flights, rotating somewhat more slowly than the screen. The wet coal enters the machine at the top, falls on the cone, and is thrown against the screen by centrifugal force. The coal slides down the screen until it meets the upper end of the flights, where it is moved slowly along the flights until discharged at the bottom. The elfluent passes through the sieve basket or screen and discharges into a launder. The Carpenter centrifuge consists of a conical rotating element with a vertical axis, built up of three rows of perforated stainless-steel plates or stainless-steel wedge-wire or round-wire sections cut and rolled to conform to the surface of the cone. Wet material is delivered to a conical hopper inside the centrifuge casing and is distributed in a thin, even layer over the inner surface of the cone by a disk mounted on the rotor shaft. Impacting of the coal against the screen and the centrifugal force exerted as the material moves downwards creates a dewatering effect. The moisture is forced through the coal bed and then through the perforated plates of the basket, collecting in a circular trough built into the centrifuge. The effluent is conducted from the trough through the centrifuge casing by outlet pipes. The dewatered coal is discharged over the inside bottom edge of the rotor. The Bird centrifuge consists of a tank or truncated conical shell, which is revolved at the desired speed by means of a drive sheave. A screw conveyor rotates inside the cone or bowl at a slightly lower speed in the same direction of rotation. The feed entrance, in the center of the large end of the truncated cone, is high enough to allow formation of a pool of slurry. Adjustable effluent-discharge ports are located in the large end of the bowl so the level of the liquid can be regulated. The solids are moved forward by the screw conveyor as fast as deposited and carried above the level of the pool for an interval before leaving the bowl. In the past these four makes of centrifuge could be compared only by indirect means. The author published a rough comparison method in 1949&apos; but

Jan 1, 1952

By J. Geertsma

In order to obtain a better insight into the pressure-volume relationship of reservoir rocks a theory of pore and rock bulk volume variations is presented. The theory is independent of the shape of the pores but is restricted to isotropic porous media built up of continuous homogeneous matrix material. The main conclusion obtained from this theory is that only three elastic constants and three viscous constants are required for describing pore and rock bulk volume variations if the porosity is explicitly introduced into the treatment. In addition, reasonable approximations are introduced for various types of reservoir rock, e.g., sandstones, limestones, and shales, which lead to further simplifications of the basic formulas. In consequence there is then a further reduction in the number of deformation constants which have to be determined experimentally. It is shown how measurements of these remaining deformation constants can be performed most conveniently. Finally the application of the theory to reservoir studies is discussed and the translation of experimental results obtained in the laboratory into reservoir behavior is considered. INTRODUCTION The decline of fluid pressure in connection with the withdrawal of fluid from an underground reservoir gives rise to a change in volume of both reservoir fluids and reservoir rock. The volume variation of the reservoir rock results in a decrease of both the pore volume and the total volume of the fluid-filled formation. Whereas the variation in volume of the reservoir fluids with pressure is usually known from PVT analysis, that in the volume of the porous medium is rarely measured, as it is considered of minor importance in reservoir engineering. Nevertheless, certain experimental results&apos; suggest that in a number of cases the neglection of the variation in pore volume may introduce errors into material balance calculations of reservoirs producing above the bubble point. Only a few experimental results on the compressibility of porous rocks have been published. The compressibility of pure quartz and of calcite can be found in a paper by Adams and Williamson&apos;. Botset and Reed&apos; carried out some experiments on the compressibility of loose sands, while Carpenter and Spencer&apos; measured the compressibility of a number of consolidated sandstones, which data were supplemented by Hughes and Cooke5. Hall&apos; finally reported a number of experiments designed to study the influence of the porosity on the compressibility of oil-bearing formations, from which it appeared that, particularly in the low porosity range, the compressibility of the pore volume is important enough to be taken into account. Difficulties, however, arise in applying these experimental results to field cases. This is partly due to the fragmentary nature of the published data. Yet even if more complete data were available, the need for a theoretical background would be strongly felt. Such a background can be partially found in studies carried out by Biot,6,7 who published a theory of elastic deformations of porous materials and their influence on fluid displacement within the pores, by Lubinski8, who studied the stress distribution in an elastic porous medium neglecting pore compressibility, and by Gass-mann" who mathematically analysed the elasticity of packings of spheres. The contributions of Biot intro-duce a number of deformation constants which are impractical for reservoir rocks from an aspect of experi-mental determination. The theory developed by dass-mann is correct but difficult to read. It appeared, how-

Jan 1, 1958