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By W. M. Gray

The determination of the state of stress existing at a point in any solid body requires the determination of the six components of the stress tensor relative to a convenient set of axes. One general method of doing this in rock is to make strain or deformation measurements associated with local relief of stress in a number of boreholes penetrating a limited volume in the vicinity of the point at which the stress is to be determined. The stress is assumed to be constant throughout this volume. Leeman1 has described a number of the instruments that have been developed for making deformation or strain measurements in boreholes. Panek2 has described the application of statistical methods to the determination of the average components of ground stress from sets of measurements made in boreholes by means of deformation meters of the type developed by the U.S. Bureau of Mines. In this paper attention is given initially to the strain cell developed for use on the flattened ends of boreholes by the Council for Scientific and Industrial Research (CSIR) , South Africa. The equations required for evaluating the average components of ground stress from measurements made by means of the CSIR strain cell are derived. These equations are similar in form to those applying to measurements made by the borehole deformation meter developed by the U.S. Bureau of Mines. The results of an investigation of the properties of the equations are described. These results are important in the practical use of both the instruments mentioned above and any instrument based on similar principles.

Jan 1, 1968

By Joseph Hyde Pratt, Douglas B. Sterrett, CHAPEL HILL

I. DESCRIPTION. MONAZITE is one of the minerals which, for a long time, was considered rather rare in its occurrence, but, upon a commercial demand arising for it, prospectors and engineers soon located large deposits of it in the Carolinas and Brazil, and the supply has always been able to meet the demand. During 1908 further sources of supply of monazite have been discovered and developed in Idaho. North and South Carolina, however, are the only States that have thus far put any monazite on the market. Monazite is essentially an anhydrous phosphate of the rare-earth metals, cerium, lanthanum, and didymium (Ce, La, Di)PO;. There is nearly always present a varying but small percentage of thoria, ThO2, and silicic acid, SiO, which are very probably united in the form of a thorium silicate, ThSiO4 Some monazites contain but a fraction of a per cent. of thoria, while others have been recorded that showed the presence of from 18 to 32 per cent. ; but the majority contain from 3 to 9 per cent. of this oxide. It is the presence of the thorium oxide that gives the monazite its commercial value. The analysis occasionally shows also the presence of other constituents, as the yttrium and erbium oxides, zirconia, alumina, magnesia, lime, iron oxides, manganese oxide, and titanium oxide. Monazite is light-yellow, honey-yellow, reddish-, brownish-, or greenish-yellow in color, with a resinous to vitreous luster, and is translucent to subtransparent. It is brittle, with a conchoidal to uneven fracture, and is from 5 to 5.5 in hardness, and from 4.64 to 5.3 in specific gravity. It crystallizes in the monoclinic system, and some crystals have been observed that were 6 in. in length. The more perfect crystals are, however,

Jun 1, 1909

By D. W. McGlashan, K. N. Mcleod

IN the use of free bubbles with precise temperature control and continuous pH measurement, the contact angle apparatus differs from all previous equipment. Experimental procedures differ sharply from the captive bubble method1,2 of introducing the gaseous phase in the three-phase system. When freed from the tube and captured by a solid surface, a bubble more closely conforms to the spherical ideal set up by the usual mathematical analysis of surface free energy or surface tensional relationships of the forces involved. The assembled equipment, Fig. 1, departs from the usual contact angle apparatus in providing: 1) water circulation for fixing temperature, 2) instruments to measure and record pH during testing, and 3) a system for producing and using free bubbles. The apparatus allows testing over a broad range of closely controlled conditions, and the use of free bubbles gives contact angles independent of operator manipulation, which was unavoidable in the older captive bubble method. A bubble released below the specimen rises through the liquid and contacts the mineral. If the mineral is gas-avid the bubble adheres, developing a finite contact angle. Reaction cells (1), 2x33/8x5 3/16 in. ID, are of pyrex glass 5 mm thick. To prevent optical distortion, the sides are optical flats and are planed parallel to within five wave lengths of light over the entire surface. Special cement is required to withstand chemical attack and thermal shock. The cell is placed in a thermal jacket (2) made of welded aluminum. A water seal for the optical ports is made by using O-rings tightened against the flats of the cell by fine-threaded and adjustable ports, Fig. 2. In-flow water is discharged downward from a manifold located near the bottom of the cell jacket. Water overflows the weirs at each end of the cell jacket, discharging from both sides to a collecting manifold (24). A hose (26) leads the overflow water to the thermal-conditioner well (4), which is recessed to accommodate a reaction cell and two beakers (150 ml). Both the thermal jacket and the thermal-conditioner well are insulated to minimize the effects of temperature differentials. Water, discharging from the thermal-conditioner well, returns to a thermostat bath and pump (3), from which it is pumped to the thermal jacket. The thermostat bath permits temperatures to be adjusted from 1" or 2°C to 80°C and will maintain the selected temperature within 0.2ºC. An electrode support (22) groups the four electrodes (8) so that they fit conveniently into the reaction cell, Fig. 2. This assembly holds the glass electrode, the calomel electrode, the temperature-

Jan 1, 1957

By Edward Keller

Jan 1, 1906

By Donald C. Barton

The theory of gravitation is based on Newton's law that any two bodies exert a mutual attraction which is proportional to the product of their masses and inversely proportional to the square of the distance between them; i. e., A = KMRm2 (1) where K is a constant, M and m are the respective masses of the two bodies, and R the distance between them. In the earth's gravitational system, the earth is one of the bodies; the other may be any body within or without the earth. In theoretical discussions and calculations,in regard to gravity, that other body usually is taken as a unit of mass: in the C:. C:. S. system, a body of one gram in mass. Gravity and Level Surfaces Gravity is defined in geophysics as the force of attraction exerted by the earth, towards itself, on a body of unit mass. The intensity of gravity is usually expressed in dynes of force or in centimeters of acceleration In geophysical work in America, most commonly it is expressed in dynes (per gram) with the "per gram" understood and not directly expressed. In geophysical work in Europe, most commonly it is expressed in centimeters per second per second (cm. /sec.2) and less commonly lrierely as centimeter-gram-second units (c. g. s). At sea level, the intensity of gravity amounts very nearly to 980 dynes. The vertical is the direction along which the attraction of gravity is exerted at any point. In most cases, it is very nearly, but not quite, perpendicular to the earth's surface. The path that would be taken by a body falling freely through space toward the earth is vertical at each point and may be spoken of also as ('the vertical," or as the line of the vertical, or as a line of force of gravity. At the earth's surface it comrrlonly is very nearly, but not quite, a straight line.

Jan 1, 1929

By R. S. Craig, W. E. Wallace, G. S. Kamath

The destruction of long-range order in Mg-Cd, has previously been thought to occur as a second order process. In the present work a variety of X-ray diffraction techniques are employed to show that in this case and in Mg-Cd alloys containing frorn 20 to 33 1/3 at. pct Mg the process more nearly resembles an ordinary first order phase transformation. It is found that the ordered alloy, which occurs as a single phase at lgw temperatures, transforms with increasing temperature into a Cd-enriched disordered (P) phase and an Mg-enriched ordered (a) phase. The interval over which these two phases coexist under apparently equilibrium conditiovs extends from 25" to 87°C content. At 33 1/3 at. pct Mg the two-phase region has disappeared. Measurement of the long range order parameter, s, for the ordered phase in MgCd, (from superlattice line intensities) shows that it disorders only very slightly before it is transformed into the p form. Kinetic experiments reveal that when the a phase is formed frorn the p phase by suitably quenching so as to suppress phase segregation, the transformation is essentially complete and the a phase has acquired its equilibrium value of S in less than 1 min. In an earlier investigation carried out in this Laboratory1 the rate of disordering of the MgCd3 superlattice was determined over an extensive range of temperature. The process was found to be first order and the rate constant, k, was established. At the lowest temperatures studied k was found to increase exponentially with temperature. At higher temperatures, however, it passed through a maximum and for the 100 deg interval below the point at which the superlattice was destroyed k was observed to decrease with increasing temperature. The various theoretical treatments1-3 of order-disorder phenomena lead to a negative temperature coefficient for k near the superlattice critical temperature but this region for MgCdB seemed unusually wide. Detailed analysis of the point indicated' that either the long-range order parameter, S, for MgCda varied with temperature in an anomalous way or the disordering in this instance is more complex than in the cases which have been treated theoretically. The original objective in the present work was simply to determine S vs temperature for MgCda to ascertain whether the disordering was in conformity with theoretical expectations.2° In an early stage of the work it was noted, however, that under equilibrium conditions ordered (a) and disordered (0) phases coexist in MgCd, over a considerable range of temperature. Since on thermo- dynamic grounds the coexisting phases must differ in composition, the investigation was enlarged to permit the compositions of the two phases in MgCd3 to be determined and to establish the extent of the two phase regions for alloys containing from 20 to 33 1/3 at. pct Cd.

Jan 1, 1963

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 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 T. L. Loucks, E. T. Guerrero

Pressure drop characteristics in a system composed of two adjacent concentric regions of different permeability were studied. The differential equations for continuity of mass flow in the two regions were solved using the Laplace transformation and the necessary boundary conditions to give the pressure distribution in the composite reservoir, the resulting equation for pressure drop at the inner boundary was evaluated for a variety of composite reservoirs and compared with the results for a uniform reservoir. From this study it was found that under certain conditions the permeability in both zones, as well as the size of the inner zone, can be determined from the pressure drop curve. INTRODUCTION The theory for the pressure distribution and pressure build-up behavior of a well producing a single, slightly compressible fluid from infinite and finite homogeneous reservoirs was presented by Hornerl and Miller, Dyes and Hutchinson.2 Extensions on this original work to provide improved and extended interpretations and better agreement between theory and observed results have been made by Matthews, et a1,3 van Everdingen,4 Gladfelter, et al5 Stegemeierand Matthews,6 Hurst and Guerrero,7 and Perrine.8 More recently Lefkovits, et al,9 studied pressure build-up behavior in bounded reservoirs composed of stratified layers. Houpeurtl0 has suggested various approaches to the general problem of variable permeability and porosity but presented no analytic solutions for particular permeability variations. Albert, Jaisson and Marionll studied the finite composite reservoir and presented numerical solutions to the unsteady-state case and an analytical solution valid only for large times. They also studied the so-called pseudo-steady state for several examples of radial permeability variations. Very similar examples have been treated in the unsteady state with application to pressure build-up by Loucks in an unpublished manuscript. More recently Hurst12 has presented the complete point-sink solution (valid for all times) for the infinite composite reservoir. He applied these solutions to interference between oil fields along with an even more elegant application of his explicit solution to the material-balance equation including water influx. Mortada 13 approaches the same application by avoiding the point-source limitation but gives the solution for the aquifer region which is valid only for large times. Hopkinson, Natanson and Temple14 have treated both the finite and infinite composite reservoir obtaining the pressure distribution for the inner zone valid for large times. This paper presents a theoretical study of the pressure distribution in an infinite composite reservoir composed of two adjacent concentric regions of different permeability. The object was to determine the manner in which pressure drop at the inner boundary of a composite reservoir depends upon time, the permeability of each zone and the size of the inner zone. Expressions for the pressure distribution in both zones are developed which take into account the radius of the sink and are valid for small times as well as large times. It was felt that an understanding of the pressure drop behavior in various composite reservoirs would be of assistance in the interpretation of some pressure build-up curves which do not behave according to the theory derived for uniform systems. Often the region surrounding the wellbore is either more permeable or less permeable than the reservoir because of the various drilling and completion practices. The effects of reduced permeability due to drilling-fluid invasion and of increased permeability due to fracturing or acidizing need to be more carefully defined. Therefore, an equation for the pressure drop in a composite reservoir was developed, and the effects of both the permeability in each zone and the size of the inner zone were studied. STATEMENT AND SOLUTION OF PROBLEM BOUNDARY CONDITIONS AND ASSUMPTIONS The physical system studied was a composite

By J. V. Vogel

Jan 1, 1969

By A. R. Kaufman, P. Gordon

THE large-scale manufacture and use of uranium in conjunction with the atomic energy development during the war led to a need for knowing the equilibrium diagrams of uranium with various other metals. The alloys of uranium with aluminum and with iron were among the first that were studied for this purpose. Much of the work was done in the manner of a survey since it was necessary to determine the important features of the phase diagrams rather than to obtain completely detailed results. For this reason no attempt was made to locate exactly such features as liquidus lines, solid solubility limits and compound and eutectic compositions. It is believed, however, that there are no great inaccuracies in the diagrams reported here and that no important points were overlooked. Earlier work on alloys of uranium with aluminum and iron is almost nonexistent and in each case is considered to have been of little value by M. Hansen. It is interesting to note, however, that the compound UAl3 was first reported in 1902 by L. Guillet. Experimental Procedure Materials: The uranium used for making most of the aluminum alloys was obtained from material prepared by Metal Hydrides, Inc., and melted in vacuum at M.I.T. Because of the lack of an adequate supply of metal, it was necessary to use material from several different batches and hence it is impossible to state an exact analysis. However, a few results indicated about 0.01 to 0.03 pct iron and probably about 0.03 to 0.05 pct carbon. Toward the end of the work a small amount of metal was obtained from Brown University and from Iowa State College and this was used in determining the transformations in pure metal and in some dilute alloys. All of the aluminum used in this investigation came from a supply of high purity metal (greater than 99.9 pct aluminum) which was obtained through the courtesy of Dr. Mehl of the Carnegie Institute of Technology. The uranium used for making the alloys with iron was produced by the bomb reduction process which has been described by J. Chipman.² This metal, after vacuum melting, contained about 99.9 pct uranium by weight with carbon and iron as the chief impurities. Electrolytic iron containing about 0.012 pct carbon, 0.020 pct nickel and 0.009 pct copper was used in making the melts. Melting Equipment: The melting of the alloys went through a stage of development which culminated in the use of beryllia or beryllia-lined crucibles and in the use of high frequency heating in either vacuum or in an atmosphere of argon. It was found that uranium at a few hundred degrees above its melting point would pick up aluminum and to a lesser extent silicon from an alundum thimble while aluminum above 1000°C would extract silicon from the impure alundum. No reaction of either metal with beryllia was noted at temperatures as high as 1800°C. The distillation of aluminum from the aluminum-rich alloys was quite troublesome at temperatures above about 1300°C and was only partially avoided by the use of argon instead of vacuum. Melting in resistance furnaces,

Jan 1, 1951

By R. D. Carnahan, J. E. White

A study of dispersion strengthening in TD-Nickel (nickel plus 2 vol pct Tho2) was conducted employing microstrain techniques at ambient room temperature. It was found that optimum strength was due primarily to the incorporation of stored energy developed by a variety of thermal-mechanical treatments. The relatively low strength of the recrys-tallized condition implies that the dispersed particles themselves offer only token resistance to deformation. The development of resistance to large-scale recovery or recrystallization at temperatures near the melting point requires a more extensive sequence of strain-anneal cycles than does the development of optimum strength. A micro-Bauschinger effect was observed which appears to be related to the lattice resistance to the movement of free dislocations. The effect was nearly identical to that in pure nickel indicating that the presence of the dispersed phase and considerably increased dislocation density (stored energy) only alters the number or effectiveness of barriers. THE early stages of deformation of engineering materials can be conveniently studied by utilizing strain-gage techniques which permit resolution of strains less than 5 X 10-7 in. per in. for testing in four-point bending (Carnahan and white1). The present investigation, part of a continuing study on the very early stages of deformation, was designed to reveal the true role of a dispersed phase in promoting high strength in a commercially available dispersion-strengthened alloy. Although this technique has been used for some time to study microdeformation in pure metals and alloys, it has just recently received attention as a means of investigating dispersion strengthening. Studying the very early stages of deformation in alloys which depend upon a finely dispersed inert phase for strength may prove to be a very important method for a better understanding of these materials. It is essential to obtain considerable clarification of actual dislocation movement and the kinds of deformation barriers which exist before optimum properties can be designed into this type of material with any degree of confidence. Considerable research on a variety of dispersion-strengthened materials has resulted in two different schools of thought regarding the strengthening mechanism. One faction2-4 favors the idea that the particles themselves resist the motion of dislocations. The criterion for yielding is the fracture of the dispersed second-phase particles due to an array of piled-up dislocations. Other invesfigators5-a have shown that particles are effective primarily by allowing a greater buildup of stored energy or dislocation density through thermal-mechanical treatments in the composite than the pure matrix material. The particles themselves, then, are not exclusive obstacles, but the complex network of particles, dislocation tangles, subboundaries, and grain boundaries are strength determining. The development of such a complex dislocation network in SAP has been studied recently in some detail by Goodrich and Ansell. The ability of dispersion-strengthened alloys to resist softening or recrystallization is also of considerable importance; however, the criteria for maximum stability may not necessarily be those for maximum strength. In this study, in addition to the evaluation of the microstrain properties of TD-Nickel, it is felt that considerable clarification of the true dependence of strength and stability on the dispersed phase is shown. I) MATERIAL AND PROCEDURE TD-Nickel is a dispersion-strengthened alloy developed by the E. I. DuPont de Nemours Co., which contains 2 vol pct thoria (Tho2) in a pure-nickel matrix. The average ThO2 particle size is approximately 0.1 p and the interparticle spacing is less than 1 u. The material was supplied by DuPont in two conditions: hot-extruded bar stock, and stress-relieved cold-rolled sheet 0.025 in. in thickness. The bar was extruded at 2200°F from a cold-pressed and sintered billet. The sheet stock was prepared from the extruded material by a process involving ten or more 50-pct cold reductions by rolling with intermediate anneals at 1800° to 2000°F. Test specimens used in this study were prepared in the form of rectangular parallelepipeds measuring 0.375 by 1.375 in. in thicknesses ranging from 0.025 to 0.040 in. Samples prepared from sheet and extruded stock were mechanically polished before heat treatment and were handled with extreme

Jan 1, 1964

By Thomas T., Read

THE decades immediately before and after the end of the nineteenth century (1890-1910) were a period of increased activity in mineral industry education. One reason for ,this, undoubtedly, was the rapid increase in mineral production in the decade 1880-1890; pig iron and copper production tripled; coal, lead, and zinc output more than doubled. Most of the other mineral substances followed the same general trend. Aluminum production began in 1886; petroleum output, which in 1888 was less than it was in 1882, almost doubled in the next three years. Gold alone showed no appreciable change until its discovery at Cripple Creek in 1891, followed by the Klondike in 1896, brought to boiling a public interest in minerals that had been simmering for some years previously. The first cyanide plant in the United States was erected at Bodie in 1893, and the first chlorination plant at Cripple Creek* the next year. Silver- lead smelting had already greatly developed, and the metallurgy of copper was almost transformed. The hearth area and smelting capacity of copper reverberatory furnaces more than quadrupled between 1878 and 1894; matte converters were first erected at Butte in 1884. Copper production of the United States in 1899 was 30 times that of 1872. While it was the increased technology used in mineral production that really made the field attractive for educated young men, undoubtedly they did not realize that, and were impressed mainly by the quantitative increase in output. Another factor was the increased general interest in engineering education; three times as many men took engineering degrees in the United States in 1890 as in 1880; 1893 showed almost a 56 per cent increase over 1890. Industry had come to recognize that technical training was worth while. The mineral industry lagged somewhat at first; the total number of mining degrees

Jan 1, 1941

By M. E. Tyrrell, Alan H. Goode

The application of a simple, two-dimensional computer technique for evaluating rock burst potential in cut-and-fill stopes was investigated. The principal purpose of the study was to compare the effectiveness of high-modulus fill and destressing as aids in the control of rock bursts. Two conclusions that are probably of general applicability are drawn. First, high-modulus fill is ineffective as a means of increasing the mine stiffness and acts to control rock bursts only if it supports enough load to reduce substantially the stresses on the unmined vein material. Second, destressing is most effective if it is performed when the vein material is near the point of failure.

Jan 1, 1975

By W. A. Klikoff, I. Fatt

The concept of fractional wet wattability is examined. Fractional water wettability of a reservoir rock is defined as the fraction of the internal surface urea that is in contact with water. Capillary pressure and relalive permeability of unconsolidated sand are shown to be functions of fractional wettability. INTRODUCTION The petroleum industry has long recognized that wettability of reservoir rock has an important effect on multiphase flow of oil, water and gas through reservoirs. As early as 1928 the American Petroleum Institute sponsored a study of wettability as part of API Project 27 at the U. of Michigan.' Despite 30 years of research, there is still little exact knowledge of the wettability of reservoir rocks. There are two parts to the wettability problem. After agreeing to a uniform nomenclature in regard to wettability,' the first question to be answered is, "What is the in situ wettability of a given reservoir rock?" If this can he answered the next question is, "What part does wettability play in determining the characteristics of multiphase fluid flow through the rock?" This paper represents an oblique attack on the problem of wettability. No attempt is made here to answer the basic question of wettability in situ. instead the consequences of the concept of fractional wettability are examined. Multiphase flow in sandpacks is shown to he highly influenced by fractional wettability. Jennings' has given 3 definition of wettability and the other terms used in discussing wettability. These terms must be applied to the physical situation existing In reservoir rock. A survey of the pertinent literature from 1928 to 1956 indicates that the concept of a contact angle was applied to reservoir rock in the same way it would be applied to a flat, homogeneous surface. Attempts were made to state quantitatively the wettability of a reservoir rock in terms of a contact angle which was presumably constant at all points on the very rough and heterogeneous interior surface of a porous rock. Calhoun, et al,3-6 prepared synthetic consolidated and un-consolidated porous media in which they claimed there was a known uniform contact angle. They then showed the effects on the capillary pressure and relative permeability characteristics of varying this angle. The API Project 47 at the U. of Texas' and others' have made extensive studies of an indirect approach to the contact angle through the use of heat of wetting data. Even if successful. however, this approach also states the wettability of porous rock in terms of a contact angle which is uniform over the entirc surface. If the angle varies from one part to another on the internal surface, there is no way of determining from the measurements the area distribution of contact angles. In 1956 Brown and Fatt5 suggested that the concept of a contact angle, as applied to reservoir rock, be abandoned. This suggestion was made because it is known that the internal surface of most reservoir rocks is composed of many different minerals, cach with a different surface chemistry and a different capacity to adsorh surface active materials from reservoir fluids. Furthermore, the operation of a contact angle in determining the form of a fluid-fluid interface is difficult to picture in the very complex geometry of a pore. Brown and Fatt proposed that the wettability of reservoir rock be stated in terms of the fractional internal surface area that is in contact with water or oil. All surfaces on which there is water are called water-wet; surfaces on which there is oil are called oil-wet. The fractional water wettability is then stated as a number which represents the fraction of the internal surface that is in contact with water. A symmetrical statement can be made for the fractional oil wettability. The concept of a fractional wettability as previously stated has in its favor the recognition of the heterogeneous mineral composition of most reservoir rocks. Another point in its favor is that fractional wettability can be measured quantitatively with relative ease. Hol-brook and Bernard10 se a simple dye adsorption test to obtain fractional wettability of reservoir rocks. Amott11 uses a combination of imbibition and displacement to arrive at a wettability index of reservoir rocks which seems related to fractional wettability in the range 0.25 to 0.75 fractional water wettability. Jennings" has shown the changes in relative permeability that take place when a porous material is changed from unity to zero fractional water wettability. He also shows that reservoir rocks in their natural state, but at room temperature and atmospheric pressure, have relative permeability characteristics which would indi-

A comprehensive, systematically structured mineral evaluation system is a prime requirement for objectively assessing mineral supply impacts on the economy. The Minerals Availability System developed by the US Bureau of Mines is a step in the right direction-a well-organized unraveling of the mineral supply network, structured in format to allow quick retrieval for rapid listing, supply analysis, and other uses.

Jan 9, 1977

By R. Schuhmann

Available thermodynamic data applicable to copper smelting systems are collected and tabulated, and the important gaps are pointed out. A few examples are given of estimations which can be made from the available data. An experimental research program is proposed to supply the thermodynamic data that appear most essential to better quantitative understanding of the chemistry of copper smelting. The proposed program is designed also to shed specific light on the practical problems of slag losses and magnetite behavior. OPPER smelting, from flotation concentrates to V-/ blister copper, is conspicuous among the large scale chemical processes which are conducted with only relatively incomplete knowledge of the physical chemistry involved. For example, no common metallurgy text explains adequately why copper enters the matte phase while iron enters only to the extent that sulphur is left over after satisfying the copper. Explaining this important phenomenon as a manifestation of the greater affinity of sulphur for copper than for iron is unsound because the affinities of copper and iron for sulphur are about the same at smelting temperatures. As will be shown, other affinities are really decisive in the relatively clear-cut separation of copper in the matte. In contrast, thermodynamic studies have contributed much to our understanding of copper refining, zinc oxide reduction, magnesium production, steelmaking, etc. For each of these processes, the important reactions are clearly recognized, and fair to good quantitative values of the free-energy changes and equilibrium constants are available. Such data have proved to be of constantly increasing practical value in process development and improvement. Work in other fields has furnished much thermodynamic data applicable to copper smelting systems. In fact, several promising starts have been made in applying such data to specific smelting problems. Kelleyl made an appraisal of the possibilities of recovering elementary sulphur from low grade matte. His calculations and compilations of thermodynamic data have represented the starting point for much of the work in this field, including the present survey. Huang and Hayward2 nd Aksoy3 used thermodynamic methods in the study of copper losses in reverberatory slags. Peretti4 used thermodynamic data in explaining the chemistry of converting. The recent publications of Darken and Gurry"." and of Darken,' dealing with the iron-oxygen and iron-silicon-oxygen systems, respectively, present equilibrium data that are applicable to copper smelting systems. Also additional data were reported recently on the affinity of sulphur for copper, manganese, and iron8 and on the sulphur pressures of iron-sulphur melts." The survey presented in this paper was made as the basis for planning an experimental program on the thermodynamics of copper smelting. Few researches on the chemistry of copper smelting have been reported in recent years, so that a reappraisal and coordination of old and new data are essential if further work is to take the directions of maximum value. The experimental program is now in progress, and the plan of attack is outlined at the end of this paper. Progressive Oxidation and Desulphurization of Copper-bearing Liquid Phases: The chemical activities of sulphur and oxygen are two of the most important thermodynamic yardsticks to be applied to copper smelting processes. Virtually the entire smelting and refining sequence involves a series of systems characterized by decreasing sulphur activity and increasing oxygen activity. In this section, therefore, an attempt is made to define and explain these activities in terms of equilibrium partial pressures of SO2, s2, and O,. Also, estimates of these quantities are presented, the estimates being based largely on calculations presented in a later section of this paper. The sequence of steps from raw flotation concentrate to fully oxidized copper ready for poling involves progressive and controlled oxidation. Iron is oxidized and enters the slag. Sulphur is oxidized and leaves in the gas. Table I summarizes several important features of this oxidation and desulphurization sequence, starting at the beginning of the matte blow in the converter. The top line gives in order the principal smelting and refining stages up to fully oxidized copper, plus the additional step, not used commercially, of oxidizing all the way to Cu,O. In the second line are shown the principal copper-bearing liquid phases which characterize the process. Through most of the sequence the copper

Jan 1, 1951

By Scott Tzcrner

WITHIN recent years people have begun to realize the importance and significance of the mining and allied industries. The leading part the engineer plays in civilization is becoming recognized. However accurate quantitative knowledge of the industrial importance of mining is still seldom possessed except by those close to this business. It is true that there are a few who go to the extreme and represent the whole progress of civilization as a reflection of man's gradual mastery of mineral utilization, but on the whole, the magnitude of the-industry is underestimated. In this paper I shall call attention briefly to the importance of mining in the United States, in Canada, and in the world. Ordinarily, the annual primary mineral production of the United States is about $5,500,000,000. The average for the last 5 years has been a little over that, but last year, sadly enough, it was less than 31/4 billion. Just now, we are on the decline, and have been for the last two years. In Canada, the 5-year average was about $268,000,000, and last year it was 227 million. Due in part to gold mines (in 1930, for the first time, Canada's gold production exceeded that of the United States), the Canadian average is holding up better than ours. Average world mineral production over the last -5 years has been estimated at about $12,000,000;000 whereas in 1931 it was less than than 8 billion.

Jan 1, 1932

By A. P. Anderson, J. H. Jensen, W. E. Breckoff

Bromine is the intermediate member of the halogen family of elements between iodine, a solid, and chlorine, a gas. The name is derived from the Greek "bromos," meaning stench. Bromine is the only nonmetallic element that is liquid at room temperatures with a melting point of -7.2° C and a boiling point of 58.78º C. Reddish brown in color, it dissolves easily in water to yield a red solution. Bromine volatilizes at ordinary temperatures to a red vapor that is very irritating to the eyes, nose, and throat. Density of the liquid is 3.12 and gas weighs 7.59 gpl at standard conditions. As the element is highly active, it exists in nature only as bromide compounds. Bromine was discovered by Antoine Jerome Balard in seawater bitterns in 1826 and first prepared in quantity in 1860. Distribution Bromine is widely distributed in nature and compounds occur in solution in natural brines, in seawater, saline lakes, oil and gas well brines, and in evaporite chloride minerals. The concentration of bromine salts ranges from 60-65 ppm in seawater to several thousand ppm in oil well brines and saline lakes. The distribution of bromine in marine evaporite minerals and in the solutions from which they crystallized was determined many years ago by H. E. Boeke (1908). Theoretical aspects regarding the geochemistry of bromine have been published in numerous papers (Raup and Mite, 1969). Bromine occurs in solid solution in carnallite and sylvite associated in potash deposits; in halite in salt beds; salt in oil shales; and in trona deposits. Its presence is useful as a guide in geochemical exploration. The analysis of small amounts of bromides in the presence of large amounts of chlorides is discussed by W. Schwerdtner (1963). Manganese, iron, and iodine may interfere with the determination. Other analytical methods are discussed at length in the literature (Stenger and Atchison, 1964). Sources and Reserves The sources and reserves of bromine, given in Table 1, appear ample to meet present and foreseeable requirements in all producing countries. With the occurrence of bromine salts in seawater and other brines, the potential for bromine production is worldwide. It has been estimated that 99% of all commercially recoverable bromine is in the ocean. However, actual subterranean brines having a higher bromine content than seawater will continue to be the preferred sources of bromine for the foreseeable future. [ ]

Jan 1, 1983

By M. W. BERNEWITZ

IT is 27 years since I last visited Broken Hill, New South Wales, one of the world's greatest lead-silver-zinc districts. Then, the flota¬tion of ores was in its infancy. The Minerals Separation process had its birth as a practicability in the Central Mill, which is still operating and yielding high recoveries. The average Australian knows that Broken Hill is an important mining center in a "corner" of New South Wales, but he does not know what a factor it is in the lead, silver, and zinc production of the world. Nor does he realize that among the ramifications arising from metal production at Broken Hill are the great lead smelter at Port Pirie, South Australia, 254 miles southeast; the electrolytic zinc works at Risdon, and the limestone mine at Davenport, Tasmania; the acid works at Cockle Creek, New

Jan 1, 1935