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By W. D. Von Gonten, R. L. Whiting

Regression analysis was used to correlate the physical properties of 478 sandstone and 90 carbonate core samples. Porosity, permeability, electrical formation resistivity factor, capillary pressure and the sonic velocity of the shear and compressional waves were measured. Prediction equations for porosity, permeability and electrical formation resistivity factor were found which should be useful in understanding the relationships between the physical properties of porous media in formation evaluation. INTRODUCTION The physical properties of porous media are important to the petroleum engineer and geologist. To evaluate fully the potential and behavior of a subsurface formation such as a petroleum reservoir, certain physical properties of the porous medium must be known. The problem of accurately determining physical properties of subsurface formations has not been solved because many determinations must be made by indirect measurements and because of the difficulties caused by complex pore structure and presence of clays in most naturally occurring porous media. Due to the difficulty in measuring some of the physical properties of porous media, it would be advantageous to be able to predict a certain physical property of a rock from other physical properties of the rock which could be measured more easily and more accurately. Since most potential reservoir rocks are heterogeneous, relationships between the physical properties are very complex and thus far no satisfactory correlations based on theory or laboratory models have been developed. It appears that empirical relationships obtained by measuring the physical properties of a large number of samples of naturally occurring porous media and applying regression analysis to develop equations for one physical property in terms of other rock properties is the best approach. REVIEW LITERATURE The three physical properties used as dependent variables for correlating purposes were porosity, permeability and formation factor. Since formation factor is more difficult to determine, a brief review of the literature is provided on this property. The first work on determining formation factors was published by Archie1 in 1942. He defined this property of a porous medium as F - Ro/Rw......(1) where Ro is the resistivity of the porous medium when completely saturated with a brine of resistivity Rw. Archie found the best correlation between formation factor and porosity was the following equation, where is the porosity fraction and m is the constant characteristic of the rock. The value of m was 1.3 for unconsolidated sand packs, and ranged from 1.8 to 2.0 for consolidated sandstones. In 1950 Patnode and Wyllie2 and De Witte3 observed that the formation factor as determined by Eq. 1 was valid only when the porous medium contained no conductive solids such as clay or shale. When conductive solids are present the formation factor is also dependent on the resistivity of the saturating fluid. Therefore, in samples containing conductive solids the formation factor decreased as the resistivity of the saturating fluid increased. Because of this. the measured formation factor was called the apparent formation factor and was designated Fa. Patnode and Wyllie proposed the following equation,

By H. C. H. Darley

Particles of montmorillonite-type clays consist of plate-like clay crystals stacked face to face. Under certain conditions in a suspension, these particles disperse to individual platelets with the formation of diffuse double layers round each platelet. This action has a profound influence on the rheo-logical and other properties of the suspension. This paper describes a test for degree of dispersion and uses this test to correlate changes in dispersion with changes in viscosity and gel strength. The test is of practical value in determining and controlling dispersion in drilling muds. INTRODUCTION It has long been recognized that the hydration and dispersion of clays, particularly those of the montmoril-loilite type, strongly influences the rheological and other properties of drilling muds, but little has been done to measure either of these phenomena under conditions that exist in drilling muds. The hydration of clays as such has been extensively studied by those interested in clay mineralogy, but in drilling muds it is to be expected that dispersion is at least as important a factor as hydration because of the much higher water-to-clay ratios and the very high degree of mechanical agitation. The term dispersion as generally applied to colloidal systems means the subdivision of large particles to small. Particles of montmorillonitic clays, however, consist of plate-like particles stacked face to face. Dispersion of these aggregates to individual platelets may be expected to have an unusually large influence on the properties of the suspension because of the shape factor, the enormous increase in specific surface, and the pronounced surface phenomena exhibited by the crystal surfaces. It is this form of dispersion that is particularly considered in this paper, -and the term degree of dispersion is used to imply the number of platelets per particle. The term aggregation is used to denote the opposite of dispersion, the association of individual platelets face to face to form stacks. It is important, as Garrison' has pointed out, to distinguish between the deflocculation-flocculation phenomenon and the dispersion-aggregation phenomenon. Flocculation of clay suspensions is characterized by the formation of voluminous sediments that are stable under quite high centrifugal fields. This indicates an edge to plate association of particles to form an open network type of structure, which obviously will have quite a different influence on the properties of the suspension than aggregation of the platelets face to face. The work described in this paper was primarily concerned with developing a test for degree of dispersion in clay suspensions and by means of this test to follow changes of dispersion brought about by addition of electrolytes and to show the influence of dispersion on the rheological properties. The Clay-Volume Test This test is based on the assumption that the greater the number of particles per unit weight of clay in a suspension the greater will be the volume of sediment when it is flocculated under standard conditions and centrifuged. After considerable experimentation the following procedure was established: 1 cc of the test mud vigorously shaken with 100 cc of 1-N NaCl in an ASTM oil centrifuge tube and centrifuged for five minutes in an International No. 2 centrifuge at 2,000 rpm. When drilling fluids of different solids content are being compared, the clay volume is expressed in cc per gram of clay solids, but generally changes in dispersion in a given mud are being compared and it is more convenient to report as cc of sediment. The test is strictly a comparative test, so that it is not necessary to adhere to the conditions specified above, e.g., with field muds a stronger flocculant such as Al2(SO4)3 may be preferable to NaCl.

Jan 1, 1958

By O. E. Palasvirta

Close examination of most so-called n.eu processes in mineral dressing reveals that they were conceived and developed a long time ago. High-intensity magnetic separation is no exception. Although its application in iron ore beneficiation seems new, in Germany the process has been commercially successful for almost two decades. High-intensity separators have long been standard equipment in the glass sand industry; they have also been used in concentrating some of the more unusual para-magnetic minerals. The basic features of an induced-rotor, high-intensity magnetic separator were described by Desire Korda in Paris in 1905,' and many patents have since been issued for improvements on the original design. Fig. 1 shows the basic design of an induced-rotor separator. Several U. S. manufacturers have been supplying induced-rotor separators for many years, but these are all devices of relatively low capacity, not suitable for treating such low-cost commodities as iron ore. On the other hand, two German manufacturers are offering induced-rotor separators of high capacity, both proven in the field. The present investigation was prompted by the apparent success of the German installations and by the discovery of iron ores on this continent which may be amenable to high-intensity separation. The objective was to gain better insight into the underlying principles of separation in a high-intensity field and to use this knowledge in selecting or designing an optimum separator. THEORETICAL CONSIDERATIONS he well known low-intensity magnetic separators are. without exception, of the the magnet type with more or less similar field shapes. It is therefore permissible to speak of their comparative strengths in terms of field intensity alone. However, proper understanding of the high-intensity magnetic separation process requires somewhat deeper analysis of the relationship between the magnetic field and the attractive force. Contrary to a widely held belief, a magnetic field of parallel lines of flux exerts no attractive force on a magnetically susceptible particle, but merely aligns its poles parallel to the lines of flux. On the other hand, a non-uniform field attracts a magnetically susceptible particle in the direction of the converging lines of flux. Thus the force of magnetic attraction varies as the product of the field intensity and the field gradient: dH ds As the induced-rotor magnetic separator is primarily intended for separating feebly magnetic materials, it is important that maximum attraction be attained. For the designer, then, the relationship between the magnetic field and the attractive force has the following implications: 1) Insofar as possible, the separation gap must be saturated with flux. 2) The rotor surface must be shaped to insure maximum convergence of lines of flux toward the rotor. 3) The primary pole face (opposite the rotor, on the other side of the separation gap) must be shaped so that the lines of flux do not diverge from it at any location in the effective separation zone. The actual attractive force of the rotor, and its critical speed, can be calculated as shown by Runo-linna, provided that the true flux density, the field gradient, and the magnetic susceptibility of the mineral can be measured with sufficient accuracy. The irregular shape of the rotor surface makes flux measurements difficult, but it can be done if a suitable gaussmeter is available (see Fig. 2). Calculations by the author, and comparisons with the centrifugal force exerted by the rotor, indicate that the force pinning a hematite particle to the rotor is of the same order of magnitude as the force holding a

Jan 1, 1960

The performance of a two-horizon depletion-type reservoir produced through combination wells is analyzed. By introducing some simplifying approximations, it has been possible to obtain formulas which are easy to handle. Only ordinary differential equations are used, and the development of the analysis can be followed without difficulty by the non-specialist. A rigorous analysis has been made of this problem. It has been found that the approximations introduced in the simplified analysis are fully justified and that errors seldom will be more than 2 per cent. The report shows the effect of the rate of withdrawal upon the relative depletion of the two horizons. Numerical examples are given. INTRODUCTION In its simplest form an oil reservoir consists of a continuous, homogeneous body of porous and permeable rock, enclosed at the top and the bottom by impermeable material. The flow of fluid through such a reservoir has been the subject of numerous papers, and the mathematical analysis of well performance, pressure build-up, etc., has reached a high degree of refinement. One of the basic assump tions introduced into these analyses is the homogeneity of the reservoir. In non-homogeneous reservoirs, these computations still can be carried out satisfactorily, provided small irregularities in the physical properties of the rock are distributed in a random fashion. The flow equations are derived as solutions of the continuity equation, and their solutions are dependent upon the assumption of many constant factors in the reservoir: permeability to oil, compressibility of the reservoir fluid, viscosity saturation, etc. When these axe assumed to be constant, the continuity equation can be solved rigorously. When these assumptions do not hold and corrections are introduced, it becomes very difficult and often impossible to solve analytically. The present analysis is concerned with production from a two-layer depletion-type reservoir in which the layers have different permeabilities. Instead of using the continuity equation, results were derived from some simple physical ideas. In a single-layer reservoir in which the oil is at a pressure above the bubble point, the rate of production often has been assumed to be directly proportional to the pressure drawdown. In the simplified analysis it has also been assumed that the drop in average reservoir pressure is directly proportional with the cumulative withdrawal. These considerations in the past have been the basis of the analysis of reservoir performance and have been applied to a variety of problems, often with marked success. In the problem under investigation these relationships are shown to be compatible with the equation of continuity, but the approach has the advantage of leading to ordinary differential equations in which changes in constants can be introduced without making the analytical solution impossible. It has the additional advantage that it can be understood more readily by the large group of engineers who are not reservoir specialists. For that reason, detailed steps in the mathematical developments have been shown in full. SCOPE OF ANALYSIS The analysis in this paper has been applied to a two-layer depletion-type reservoir in which both horizons are produced simultaneously in the same well. Because of the difference in permeability, it is obvious that the depletion of the two zones will proceed at different rates. For various problems it may be of interest to know the degree of depletion of the two zones at any arbitrary time and to in-

By T. R. Ingraham

The thermal decomposition of cupric sulfate and of cupric oxysulfate has been examined by deter-mining the equilibrium gas pressure generated over each pure compound. The equilibrium data have been used to calculate the thermodynamic properties of both compounds, and the results have been combined with previously published data to establish a predominance-volume diagram for the Cu-S-O system over the normal range of roasting temperature and gas composition used in the treatment of copper minerals. Copper oxysulfate recrystal-lizes at 1100°K with an apparently irreversible en-dothermic heat requirement of 2.9 * 0.3 kcal per mole. WHEN mixed sulfide minerals containing copper are roasted, either of two procedures may be followed, depending on the nature of the other metals. In the first procedure, the roasting is controlled to produce a maximum amount of water-soluble copper sulfate which may be removed selectively from the water-insoluble compounds of the other metals. In the second, control is directed toward the production of water-soluble sulfates of the other metals and an insoluble salt of copper. Effective control of either of these processes would be enhanced by knowledge of the thermal stability of cupric sulfate and of cupric oxysulfate. In this paper, established data for the thermal stability of cuprous and cupric sulfide and of cuprous and cupric oxide will be combined with new data for the therma1 stability of cupric sulfate and cupric oxysulfate, to designate the volumes of stability of the significant compounds in the Cu-S-O system in the temperature range 750° to 950°K. EXPERIMENTAL Materials, Apparatus, and Procedure. The copper source material used in all experiments was Fisher Certified Reagent Grade "anhydrous" cupric sulfate, for which the following analysis was supplied by the manufacturer: chloride, 0.002 pct; alkalies and earths, 0.2 pct; insoluble, 0.002 pct; iron, 0.020 pct. Cupric oxysulfate was prepared from the normal sulfate by two procedures. In the first, equimolar quantities of cupric oxide (prepared by decomposition of the sulfate) and cupric sulfate were ground together and heated under vacuum in a sealed silica vessel at 800°C. This procedure was subject to failure because of explosion of the silica vessels due to the pressure of the final traces of water released from the sulfate on the initiation of its decomposition. The second procedure involved roasting the cupric sulfate, with frequent rabbling, in a muffle furnace at 725°C for a period of 48 hr. This produced an excellent product, which was confirmed as copper oxysulfate by X-ray and chemical analyses. The experimental technique used was that of measuring the total pressure exerted by the sulfur trioxide, sulfur dioxide, and oxygen produced by the following reactions: 2 CuS04 = cuo • CuSO4 + SO3 [1] cuo . CuSO4 = 2 cuo + SO3 [2] SO3= SO2 + 1/2 O2 [3] The apparatus used in the experiments has been described previously.1-3 Its main feature of a U-tube mercury manometer in which the mercury is protected from corrosion by enclosure in a flexible Pyrex bellows. Before beginning a run, the interior of the apparatus, including the bellows-manometer and all connecting tubing, was thoroughly washed with hydrochloric acid and distilled water to remove any

Jan 1, 1965

By B. F. Oliver

A levitation zone melter is described which has the necessary characteristics for processing metals of controlled purity. No crucible is required; control of the solidification variables is stable; the environment of the charge is chenzically controlled. Rotation of the solidifying interface and mixing in the liquid by the magnetohydrodynamic stirring produce an eight-fold increase in freezing velocity over former melting units with better resulting solute redistributions. The smooth appearance of processed specimens, resistivity ratios as a hnction of position, as well as a segregation curve, are presented as evidence of smooth continuous solute fransport over distances in excess of ten zone lengths. THE difficulties of the floating zone-purification of higher density metals in large quantities under conditions of lowered surface tension are well known and have hindered fundamental research programs for some time. The inordinate amount of time required to obtain a small reproducible yield of high-quality metal has excluded the use of such material for many important material research programs. However, with the use of controllable induction levitation forces' to accomplish stable liquid zones with nearly flat solidifying interfaces, and with good physical and chemical control of the processes involved, these difficulties can be overcome. A zone melter that is to be used for both high-purity and controlled composition work in metal systems must have the following three characteristics: 1) The process must avoid the use of containers. 2) Physical control of the solid-liquid interface and of the mixing within the liquid phase must be stable. 3) The chemical environment of the melt chamber must be controllable. A description of an apparatus that accomplishes these objectives follows.* APPARATUS One of the basic features that is necessary for good process control of large sections is that the charge, the coil, and the motion mechanisms be within the same chamber. This arrangement permits a close coupling between the work coil and the load, which then provides a good flexibility for adjustments of coil dimensions, for controlling the amount of levitation needed for stable operation at a given power level. An overall view of the melter is shown, with the melt-chamber door open, in Fig. 1. The radiation shields surrounding the single-turn induction coil are of water-cooled copper. The chamber is stainless steel, as are most of the components within the chamber. The control panel for the scanner is located at the immediate lower right of the melt chamber. This panel controls the operation of the scanner. The operations controlled are the interface rotation rate, the stretch-squeeze or diameter control, the up and down scanning speeds, and the induction power. All of the drive motors are constant-torque variable-speed motors. The scanning speeds are set with precision helipots and continuously observed with the voltmeter on the control panel and checked with a mechanical indicator within the melt chamber. The rotation rate is also set with a precision helipot. The up-scanning speeds are 2 to 300 in. per hr.

Jan 1, 1963

By John Riegle

To date. utility company underground storage of gas has generally been restricted to depleted dry gas fields. The Playa del Rey project is probably the first to successfully store gas in a partially depleted oil reservoir with the recovery of large volumes of pas at high rates as the main objective. Oil recovery has been a secondary consideration. Problems encountered unusual to those of storage in a dry gas zone were: (1) the removal and retardation of formation of emulsion. (2) the upstructure movement of fluid during withdrawal periods which formed fluid blocks, and (3) reservoir shrinkage resulting from encroachment of edgewater. The solution of these problems as outlined in the paper has resulted in increasing the withdrawal rate from the original design capacity of 4,000 Mcf per hour to the current 10.000 Mcf per hour. Additional increase is anticipated as the operations continue. Migration. reservoir performance. operational procedure and a historical record are included to make this a resume of the project from its war-time inception in 1942 to the first of 1952. INTRODUCTION The Playa del Rey underground gas storage project is probably the first project in which gas has been stored in a partially depleted oil reservoir, with the recovery of large volumes of gas at high rates as the main objective and the recovery of oil a secondary consideration. Problems unusual to those of storage in dry gas zones have made this a pioneer endeavor. The total storage capacity of approximately 1,500,000 Mcf of this reservoir is small in comparison with other underground gas storage projects. However. by study and experiment the deliverability into transmission lines. operating at pressures in excess of 150 lbs., has been nearly tripled in the past three years. to the current 10.000 Mcf per hour late, without the use of compression. It is anticipated this rate will gradually increase as additional fluid is removed from the formation. LOCATION AND HISTORY Playa del Key is located on Santa Monica Bay about two miles south of the beach commuity of Venice and 15 miles southwest of the renter of the City city Los Angeles. Fig. 1. The discovery well was completed at 6,194 ft in 1929. An upper zone at 3,905 ft was found on June 18. 1930. Townlot development was very rapid and by the end of 1930 there were 141 producing wells in the field. The Union Oil Co. completed a lower zone well south of the Townlot Field in May, 1931, which was believed to be an extension, until additional drilling of about 50 wells during 1934 and 1935 indicated this area to be a separate accumulation as shown on Fig. 2. The lower oil horizon, which is now the storage zone, had no original gas cap and is believed to be a continental detrital deposit of conglomerate that accumulated in valleys and depressions of a weathered schist high. which later subsided and was overlain by an impervious nodular shale. This type of formation has rapid variation of porosity. permeability and thickness due to lack of sorting action common to marine deposition. and the uneven surface of the original schist high. Production was limited on the upstructure sides by the pinching out of the conglomerate, and downstructure by edgewater. Unrestricted production, together with high permeabilities, led to large wastage of gas from this new area as facilities were not available for transport of gas to market. The decline was very rapid and by 1942 the portion of the new area south of Ballona Creek was nearly depleted. ACQUISITION OF PROPERTY The rapid increase in industrialization of Southern California during World war 11 forced upon the local gas com-

Jan 1, 1953

By R. G. Knickerbocker, W. E. Brown, G. J. Vahrenkamp, M. M. Fine

THE results of a research and development laboratory and pilot-plant mineral-dressing investigation by the Bureau of Mines of the complex copper-lead-cobalt-nickel ores of southeast Missouri are reported in this paper. This investigation, in cooperation with the National Lead Co., showed that separate concentrates of lead, copper, and cobalt-nickel could be made by fine grinding and flotation. An industrial plant built subsequently by the St. Louis Smelting and Refining Div. near Fredericktown, Madison County, Mo., produced such concentrates during the war years. Present commercial production at the mill is limited to lead and copper concentrates, but research to permit economic utilization of the cobalt and nickel values is continuing. The complex sulphide deposits near Frederick-town in Madison County, Mo., have an operating history that dates back to the years preceding the Civil War. Perhaps these operations can best be summarized in terms of output which are given by Tyler: "Previous to 1900, the Mine la Motte Co. shipped cobalt ore to Swansea and in 1903 produced 120,000 pounds of oxide in a Missouri plant. Another cobalt refinery erected in 1906 by the North America Lead Co. at Fredericktown, Mo., operated intermittently until 1910. In 1909 it produced 83,384 pounds of cobalt oxide, 328,403 pounds of nickel, 8,314 tons of nickel-cobalt concentrates, 600 tons of copper concentrates, and 1,353 tons of lead concentrates. This plant was purchased at a forced sale in 1915 by the Missouri Cobalt Co., which produced a certain amount of oxide in 1918 and in 1920 recovered 102,410 pounds of cobalt oxide and cobalt hydrate, valued at $262,810." According to Buehler,2 "The ore, which consists of a complex mixture of the sulphides of cobalt, nickel, copper, lead, and iron, occurs at the contact of the pre-Cambrian porphyry and the overlying Lamotte sandstone and Bonneterre dolomite." The source of most of the cobalt and nickel is siegenite, a member of the linnaetite series of minerals. Its composition is variable, and although the chemical formula may be given as (CoNi),S,, it usually contains both iron and copper. The siegenite is characterized in this instance by an intimate association with chalcopyrite, and to a lesser extent with iron sulphides. Galena, on the other hand, while dis- seminated throughout the ore, is not closely bound to other constituents. Gangue is composed essentially of dolomite and quartz. Petrographic examination showed that fair liberation of sulphides and gangue could be attained at — 100 mesh. Complete liberation of micronsize inclusions, particularly of sulphides in each other would not have been possible at —400 mesh. Beneficiation Studies Many samples of the southeast Missouri ore were tested, but most of the work was confined to five samples of churn drill cuttings weighing 15 tons. The samples were reportedly representative of five sections of the deposit and were tested individually and as a composite. Only the results of the tests on the composite, which contained 1.28 pct lead, 2.03 pct copper, 1.06 pct nickel, 0.87 pct cobalt, 3.57 pct iron, 15.4 pct lime, and 23.9 pct silica, are presented in this report. In view of the rather complex and intimate association in the mineralogical composition of the ore, flotation was the logical choice in the selection of a beneficiation process. Other mineral dressing unit operations were considered as an adjunct to flotation, but none were beneficial. Many tests were made on these samples to determine the flotation characteristics of the mineral siegenite. As a result of this work, it was noted the siegenite was intermediate in floatability between chalcopyrite and galena on one extreme and iron sulphides on the other. The difference in floatability between siegenite and the iron sulphides was not very great and, in general, the same reagents that depressed pyrite and marcasite would also, in slightly larger quantities, depress siegenite. This tendency for siegenite

Jan 1, 1952

By A. D. K. Laird, C. A. Johnson

Drag coefficients for a cylinder being towed through water at constant velocity and also at constant linear acceleration were measured. Drag coefficients for constant velocity towing showed reasonable agreement with previous results. The drag coefficients found for constant acceleration showed little correlation with either the magnitude of the acceleration or the value of the modulus AD/V2 and tended to be slightly lower than those for constant velocity. INTRODUCTION For the design of offshore structures, wave forces acting on immersed cylinders are of importance. Several investigations have been made of these forces and of how they can be predicted from wave theories. A paper by Crooke' summarizes much of the work already done. More recent research by the Wave Research Laboratory at the University of California, Berkeley, has added much to the body of data collected under ocean wave conditions, but has not found a reliable method of force prediction from basic theories of wave motion. The present investigation is part of a long-range program to collect data with which to test current and future theories and correlations. The immediate objective was to measure drag forces on a circular cylinder subjected to linear accelerations over the range of Reynolds numbers between l04 and 105 where the drag coefficient was a constant for constant velocities. In particular, the effect of constant acceleration from rest and from uniform motion was to be investigated. The effect of acceleration may be evaluated in terms of drag coefficients. A useful resistance coefficient, C, is defined by the equation for total drag force, D, exerted by the fluid on the cylinder. DT =CSp V2/2.........(1) The coefficient C may be plotted as a function of the parameter AD/V2. Here D is the diameter and S is the projected area of the cylinder. The acceleration and velocity are A and V. The mass density of the fluid is p. An alternate drag coefficient, C, corresponds to the total force of the fluid opposing the motion minus the virtual mass force. This drag coefficient, arising from the velocity of the fluid, may be compared with that for the same cylinder in uniform motion. The similarities and differences between this coefficient as calculated for accelerated and for steady motion are of interest in the inverse process of predicting drag forces on cylinders under arbitrary conditions. One serious difficulty in this method is the specification of the virtual mass which depends also on the flow picture about the cylinder.1 EXPERIMENTAL EQUIPMENT The experiment was performed in the combination wave and towing tank at the Engineering Field Station of the University of California. The tank is 200 ft long, 8 ft wide, and 6 ft deep. The tow carriage is externally propelled by a cable, and the velocity of the carriage is maintained essentially constant by means of an am-plidyne. For the purpose of the present investigation, the speed control of the amplidyne was modified by inserting a linear speed control rheostat, which was rotated at a constant speed by a small d-c motor equipped with a slip-clutch. Accelerations which were constant over a reasonable length of time were thus produced. The magnitude of the acceleration depended upon the speed of the d-c motor and the limiting speed of the carriage. Data were obtained for a range of accelerations of 2 to 10 ft/sec,2 and a range of velocities of 2 to 15 ft/sec. An accelerometer (Statham Type C-2-350) with a range of ±2g was attached to the carriage and connected to a Brush analyzer and penmotor. A continuous coil of wire with 10 turns/ft wound around a fixed wooden form extending for a distance of 40 ft along the length of the tank was connected by an electrical contact mounted on the carriage to a Brush analyzer and penmotor, to give the time-position history for each run. The test cylinder was machined from solid aluminum alloy, 17-ST. to a diameter of 1.250 in., and could be

Jan 1, 1957

By John E. Carr

A bewildering variety of continuous thickeners and clarifiers are used in mineral industries and other heavy industries. General topes arc: ? Conventional thickeners ? Thickeners with flocculating feedwells ? Solids contactors ? Tray thickeners ? Lamellas ? Conventional thickeners with Lamellas ? High flow, fluid bed thickeners These units must be adapted to varied applications. They must provide operating flexibility to meet process needs. Such factors multiply the decisions which must be made prior to the selection of a thickener. The seven types of thickeners listed above, with their variations, share design concepts which limit their application and which can be used to evaluate their performance. Some of these arc: ? Feed velocities must be limited and/or controlled. ? Natural or reagent flocculation is necessary. ? Horizontal settling area is the basis for capacity. ? Overflow velocities must be limited and. or controlled. ? A controlled underflow is necessary. Thickener selection is the application of these needs to the basic process concepts. The basic function of a thickener, in the minerals industry, is the separation of a thickener sludge containing fine solids from water. In addition to this primary separation function, others include: ? Separation of solids from water ? Separation of flocculated solids from slimes ? Storage of solids ? Control of percent solids ? Storage of water ? Process control by absorbing fluctuations in feed ? Process control by increase in head clue to the depth and percent solids of the thickened sludge. Most thickener designs, suitable to minerals applications, are based on the separation of minus 65-mesh, 2.7 specific gravity solids containing slimes. These designs are routinely adapted to coarse and or denser materials. Materials of lower specific gravity such as coal, wood, char, some chemical precipitates and organics act Hike slimes if a thickener is used. Perhaps the most conservative approach to sizing and application is the use of comparative data from similar plants or similar industries. Thickeners are-routinely used in a great number of industries from which there is good historical information available. In the minerals industry, thickeners are used in: clay sizing, coal refuse, heavy media, copper concentrates, copper tailings, gold flotation concentrates, and countercurrent decantation for cyanidization in gold and CCD in uranium. Concentrate and tailings thickeners are used in iron ore plants, and concentrate and tailings units in lead-zinc plants. In addition, there arc thickeners designed to handle lime mud; limestone concentrates and tailings; phosphoric acid; potash; and rutile concentrates. Thickeners are, in addition, widely used in gravel plants for water reclamation. This gives excellent data on clay settling in some cases. Thickeners are used extensively for slurries generated by flue dust from wet scrubbers. Thickeners in flue dust applications are operating with considerable variations, treating blast furnace dust. BOF flue dust, and wood char. Similar applications are met in the power industry with fly ash and SO2 scrubber systems. Even though field data is preferred, such data has limitations as listed: ? Flowsheets are seldom identical. ? Data is often incomplete or limited. ? Ores vary significantly. ? Operating needs are changing. For these reasons, mathematical and theoretical methods are needed for application of field data to a specific project. In addition, laboratory data for similar projects and, if possible, laboratory data on a representative sample should be used to specify the thickener. There is a great volume of thickener literature. The references for this paper, along with their references, and past AIME papers provide excellent background. Older literature can be reviewed in light of current methods. It is interesting to note that the requirements for higher flow rate designs, more extreme flocculation systems, etc., can be logically introduced by reading Gaudin's Sections on Flocculation and Thickening, which was written before field installations could illustrate all of his ideas. The problem, then, is to select hardware which will take into consideration the functions of flocculation, separation of the solids, water clarity, control of the underflow, and control of the overflow. Reliable operation and simple control are customary.

Jan 1, 1979

By J. G. Balkestein, J. W. R. Baerts

During an attempt to develop a method for accurate, rapid, continuous analysis of ash content of wal, the Dutch State Mines Laboratory found that the absorption coefficient for X-rays was related to ash content. This relationship was utilized in the development of an apparatus called CendreX, used to measure the absorption and in turn the ash content. The principle, procedure, accuracy, and applications of the CendreX automatic determination of ash in coal are discussed in detail. Until recent years coal preparation research was concentrated on the possibilities and efficiency of preparation equipment. Ever increasing demands for quality in coal, however, have caused researchers to become concerned with quality control. One of the characteristics strongly influencing quality (calorific value) and, consequently, the price of coal is ash content. Both customer and producer require that the ash content be controlled. To make this possible it is necessary for the producer to collect samples from the coal stream in the washery and to determine their ash content. On the strength of the results obtained the production process can then be adjusted, if required. Until recently incineration was the only method for determining ash content. When coal is incinerated with oxygen, it takes at least 15 min to determine the ash content. Even then some time may be lost in passing on the data. Therefore, this discontinuous and time-consuming method does not make a suitable starting point for checking, re-adjusting, or modifying the production process. Since it was not possible to accelerate incineration by mechanization and automation, another type of rapid continuous analysis had to be found. This would have to depend on some coal characteristic closely linked with ash content. At the Central Laboratory of Dutch State Mines, Dijkstra and Sieswerda found that the absorption coefficient for X-rays was suitable for this purpose. An apparatus based on the measurement of this characteristic was developed. Named CendreX,* this patented equip- *A Stamicarbon N. V. registered trademark. ment, used in combination with a sampler and conditioning apparatus, permits continuous determination of ash content with satisfactory exactness to within 3 min.t At the American Mining Congress meeting of May 1961, Log A. Updegraff, surveying aspects of continuous analyaia, reported on the CendreX appartus (Mining Congress Journal, August 1961). Since the first Condition for correct ash determination, whatever the method used, is always a sample taken in the right way, some practical aspects of sampling will be discussed first. SAMPLING In coal handling operations, each grain has its characteristic properties. In both the cross-sectional and longitudinal direction of the product stream the mixture of these grains is imperfectly blended. The elimination of the factor of segregation between the cross-sections from the direction of the stream is the principal aim of continuous analysis. Therefore, the samples to be analyzed are withdrawn in various places from the segregated product stream in such a way that they form a semi-continuous flow. In order to be truly representative of the product stream, the sample flow must fulfil two conditions: 1) The sample flow must be sufficiently large to insure that adventitious differences between the composition of the product stream and sample flow will be as small as possible. 2) All grains through the entire cross section of the product stream must have an equal chance to get into the sample flow. Since there is always a segregation through the cross section the sample flow will have a bias if the sampler collects only part of this section. In order to prevent the volume of the sample flow from becoming too large, the cross sections are taken discontinuously. However, this discontinuity gives rise to the adventitious differences that arise between the composition of product stream and the sample flow, and these differences become greater and are more deranging as the fluctuations follow each other more quickly. Moreover, the intervals between the morrnents of sampling mean a delay in the analysis. The aim will, therefore, be to collect small samples, or in other words thin cross-sectional increments, taken at sufficiently high frequencies. The following points should also be taken into account: 1) The smallest dimension of the openings in the sample collector must be equivalent to at least 3 d in

Jan 1, 1962

By Leonard H. Goldman, Harold E. Marr

The PGT uranium assay probe is a borehole tool developed by Princeton Gamma-Tech over the last several years. It has the ability to do an in-situ assay of uranium in the presence of any amount of disequilibrium. It has some advantages over coring including cost, speed of analysis, and accuracy. In this paper we would like to give a brief description of the measurement and then show some sample logs from South Texas. Uranium exploration and development is carried out primarily by gamma logging since uranium daughters are prolific emitters of gamma rays. The conventional gross gamma tool for uranium logging is limited in value because of the inability of this tool to distinguish uranium from its daughters and other naturally occurring radioisotopes, such as potassium and thorium. This problem becomes severe in cases of disequilibrium. Disequilibrium, in a geological context, is defined as the condition when the gamma radiations from the daughter products are being emitted in a location different from that of the parent uranium. In the decay chain of uranium almost all the gamma radiation emitted in the entire chain comes from the daughter product, bismuth-214. Bismuth-214 is separated from uranium by several long-lived isotopes that are chemically active and have different physical properties, often resulting in shifts in the location of bismuth- 214 relative to the parent uranium. In the United States orebodies exhibiting disequilibrium are a common occurrence and the use of a gross gamma log to delineate uranium orebodies can lead to errors. At present the solution to the disequilibrium problem is extensive coring followed by chemical analyses of the cores. There are several drawbacks in using this technique. First is the high cost of coring, the second is the fact that no results are available for days, or typically, weeks after the drilling is done. Thus for development work, coring and drilling must be done on a grid basis and many additional holes are cored to ensure that the entire orebody is mapped. Another disadvantage to cores is the fact that a small volume is sampled, the volume of the core itself. This leads to problems in the mapping out of the orebody when the ore de- posit is not very homogeneous. The PGT probe described in this paper is a new solution to the disequilibrium problem. Basically, the probe measures radiations that come almost directly from uranium itself. The first daughter of uranium, which is protactinium-234 (Pa-234), is only separated from uranium by a 24-day half-life and no disequilibrium problems build up in such a short time. The PGT probe measures the intensity of a one MeV gamma line emitted by Pa-234 and, using this information, calculates the concentration of uranium. The PGT probe is 24" in diameter and 12 feet long. The probe contains a microprocessor which passes the information to a larger minicomputer in the truck. All data is analyzed on site, and the results from a high speed printer are presented to the geologist. Data is also available on 9- track IBM compatible tape for further processing. The PGT probe output is linear with uranium concentration. The only correction factor is for borehole size, and that only becomes important in boreholes bigger than seven inches in diameter. Dead time is compensated in the probe itself and no problems have been encountered in ore zones up to several percent UjO8. In addition to the uranium assay, a conventional gross gamma log is plotted alongside. Grade thicknesses for zones above cutoff are calculated as well as disequilibrium factors. COMPARISONS During its commercial operation PGT logged a series of 18 holes that had been cored and assayed. All of the holes in this series were logged in normal operation by regular field operators. The time to log each hole was generally under an hour, and in typical operation a PGT logging truck will do between 7 and 8 holes a day. The results of the comparison of the PGT and the core assays are presented in a series of figures showing plots of the PGT assay, core analysis and gross gamma measurements. The first three figures show individual holes with the gross gamma plotted along with the core and the PGT assays. All three logs were from holes on the reduced side of a rollfront deposit in South Texas. In Figure 1 we see the two wings of the roll- front at 143 ft and 150 ft separated by a barren zone. The wings are well defined both by the PGT assay and the core. There is approximately a one foot shift which can be attributed to drilling errors. The gross gamma is showing a rather severe discrepancy, being considerably lower and not showing the barren zone. The grade thickness calcula-

Jan 1, 1980

By Ellis H. Gates

BENEFICIATION of the manganese oxide ores at Three Kids Mine near Henderson, Nev., has evolved over a period of years. Commercial application of the process is on a secure basis, and an effective working hypothesis has been formulated to help solve the problems encountered in flotation. An outstanding difference between the Manganese Inc. operation and other flotation processes is the necessity for high recovery of slime mineral values. Part of the manganese minerals in the Three Kids ore deposit occurs as primary slime or as minerals that are easily slimed by grinding. High recovery of this slime portion is essential to an economic overall manganese recovery. The aim of much of the research at Manganese Inc. was to recover these slimed and finely ground minerals by flotation. Early Agglomeration Processes: Tunbridge' in 1880, followed by Everson2 in 1886 and Cattermole" in 1904, discovered that under certain pulp conditions precious metals and sulfide minerals could be agglomerated if enough soap or oil were mixed into the pulp slurry. These agglomerated particles, Which under ideal conditions ranged from 1/16 to 1/4 in. diam, were recovered by screening, tabling, and hydraulic classification. Even flotation by air occluded in the agglomkrate particles by vigorous stirring was suggested. Cattermole nearly succeeded in getting his process into commercial operation, but it was finally abandoned, presumably because he could nat compete with the low reagent requirements of the new agitation froth process. Since Cattermole's time Christensen in 1921, Borcherdt4 in 1926, and Chapman and Littleford- in 1934 have attempted to apply the principles of agglomeration. In the light of current research at Manganese Inc. on conditioning of pulp at high energy input levels, it is interesting to note the variety of equipment such as tumbling mills, mixing drums, and shakers described by Borcherdt in his patent to produce the agglomerated particles. Ore Characteristics: Manganese in the Three Kids ore occurs as a 'complex mixture of manganese oxides commonly Known as wad. The manganese minerals have Been identified as psilorflelane, hollandite, coronadite, and pyrolusite with minor amdunts of rhodonite and rhodochrbsite. The ppincipal gangue miherals are quaktz, opal, kaolinite, montmoril-lonite, calcite, gypsum, fcelesitite, and barite. Most of the mangandse ore minerals are either porous and sponge-like in structure or soft clay-like masses composed of fine grained mineral particles approaching the size range of colloids. Consequently the ore minerals from the Three Kids mine have relatively large surface areas and high void content per unit weight. The specific area of various manganese ore samples measured at the California Research Corp. laboratories ranged from 32 to 58 sq m per g. The great surface area and high void content explains in part the unusually high reagent consumption required in the treatment of this ore. Current Milling Practice: At Henderson6 he ore is crushed to —1 in. and ground with rod mills in a closed circuit with spiral rake classifiers and cyclones. Sulfur dioxide solution is added to the pulp as it leaves the grinding circuit, immediately followed by addition of a reagent mixture of soap, oil, and wetting agent in the form of an emulsion. The reagents are initially well mixed into the pulp during their passage through centrifugal pumps to the conditioning equipment. All reagents are added prior to conditioning. The intense conditioning or mechanical stirring of the pulp, in which large amounts of power are consumed, is the principal difference between the flowsheet used at Manganese Inc. and a standard flotation circuit. As much as 38 kw-hr of energy per dry short ton of ore in a pulp containing 18 to 23 pct solids is used for conditioning. After conditioning, the pulp passes to a flotation circuit that consists of one roughing stage, a scav-

Jan 1, 1958

By C. S. Smith, L. Guttman

It is shown, from a study of geometric probabilities, that the average number of intercepts per unit length of a random line drawn through a three-dimensional structure is exactly half the true ratio of surface to volume. Since the surfaces can be internal or external, the area of grain boundary or of the interface between any two constituents in a micro-structure can be measured. Other metric relations are tabulated that may be of use in studies of the microstructure of polycrystalline, cellular, or particulate matter generally. IN many fields of scientific investigation the structure of cellular aggregates or random arrays of discrete particles imbedded in some matrix is observed on a two-dimensional section and inferences are drawn therefrom as to the real structure in three dimensions. The biologist's microtome slice, the petrologist's thin section, and the metallurgist's plane polished and etched sections are common examples, although the problem is a general one. Scientists have commonly limited their thinking to the same dimensionality as their structures, and the few attempts that have been strictly three-dimensional in character have been laborious and noteworthy. From a metallurgical standpoint it is often of considerable importance to know, in addition to the volume fraction of two or more components in an alloy, the amount of two-dimensional interface between crystals. Such grain boundaries (which may separate either two identical crystals differing only in orientation or two crystals differing in structure, and possibly also in orientation) have a determining factor upon the mechanical behavior. It is at these boundaries that melting commences, that stress-induced corrosion occurs, and that various precipitates (harmful or otherwise) first appear. The boundary is doubtless of equal importance in nonmetallic crystalline aggregates such as rocks, ceramics, and concrete, and the biologist is deeply concerned with the area of cellular membranes. Many synthetic cellular foams involve similar structural problems. The very term structure usually implies the presence of interfaces and a complete understanding of structure involves nothing but an analysis of the geometrical, metrical, and topological relations between the various interfaces (zero, one and two-dimensional) that exist in a three-dimensional structure. Even systems lacking sharp physical interfaces often have interrelated gradients of composition or velocity (as cored crystals or turbulence cells) in which a neutral surface can be treated as a two-dimensional interface. In an earlier paper by one of the authors' the question of cell shape was considered in terms of simple topological principles without regard to physical dimensions. The determination of the actual size of grains in two dimensions is carried out in a routine fashion in innumerable metallurgical laboratories (see, for example, the ASTM standard methods of grain size determination2), though this is done merely to check the uniformity of a product and has no relation to the actual three-dimensional shape or size of the grains. Some authors have discussed the three-dimensional problem but only on the basis of assumptions as to idealized grain shapes.:'-' Quantitative measurements of microstruc-tures to obtain the volumetric relations of various phases have been carried out by petrographers for many years and are of increasing popularity among metallurgists." The present paper will show how, on the basis of no assumptions other than randomness of sectioning (usually realizable in experiment), it is possible to learn a great deal about the three-dimensional structure. The relations to be derived will generally be used on random arrays of cells or other particles, although they are equally applicable to ordered arrays and even to isolated objects of complex shape provided that suitable random sections can be made. Total Area of Interfaces in a Sample Consider a typical microstructure of a single-phase polyerystalline metal, such as that shown pres- in Fig. 1. The plane cross section shown contains a network of lines which subdivides the area into two-dimensional cells. The lines, of course, represent merely the intersection of the two-dimensional plane of sectioning with the two-dimensional interfaces between adjacent three-dimensional cells. The structure also contains points at which two or more lines intersect: in three dimensions the points are, of course, lines. In the more general case there may be in three dimensions isolated particles surrounded by a single interface without contact with others, and both two and one-dimensional features which do not necessarily connect with others. On the two-dimensional section these will appear as areas delineated by a closed line (as at a and b, Fig. 2), as isolated lines

Jan 1, 1954

By R. M. Genevray, M. B. Bever, E. J. Suoninen

THE martensitic transformation in the ß-phase of the Cu-Zn system has been the subject of several investigations. The transformation is known to be reversible and to be affected by stress. Its temperature range has been determined as a function of composition. In the investigation reported here, the effect of tensile stresses on the transformation was investigated quantitatively. Some information was also obtained on the thermoelastic behavior of the martensite formed in the first stages of the transformation. Most of the experiments were done with alloy E of an earlier investigation;' this alloy analyzed 60.49 pct Cu and 39.51 pet Zn by weight. The methods of shaping and heat treatment were also essentially the same as those previously used. The stress was applied to the specimen immersed in a cooling liquid. The transformation was followed by measuring the electrical resistance with a Kelvin bridge and the elongation with a cathetometer. Fig. 1 shows the M, temperature as a function of stress. Resistance and strain measurements gave essentially identical values. The results suggest a roughly linear relation between M. and in the range investigated, up to 12 kg s mm". At higher stresses, plastic deformation begins to interfere seriously with this relationship. The increase of M, with stress is consistent with published work on the effect of stress on the martensitic transformation. The slope of the curve, 4°C per kg mm ", is of the same order of magnitude as the corresponding value calculated for steel.' Fig. 1 also shows the difference, AM, between the temperature of 50 pct transformation on cooling, as measured by changes in length, and that of 50 pct reverse transformation on heating. This difference, which may be considered a measure of the hysteresis, increases with stress; the decrease at highest stresses is probably associated with plastic deformation. Preliminary work using only resistance measurements was done with an alloy containing 60.15 pct Cu and 39.79 pct Zn by weight. The results indicated higher values o-F M, in agreement with the known variation of M. with composition.' The effect of stress on M, (2°C per kg mm-') was of the same order of magnitude as that shown in Fig. 1 for composition E. An increase in hysteresis with stress was also found. The following experiment was made in order to investigate a partially transformed structure. A specimen of alloy E was cooled to — 85°C under a stress of 4.7 kg mm-'. Under these conditions, the martensitic transformation started but did not go to completion. The stress was then released and the specimen cooled to — 105°C. Fig. 2 shows the measured elongation c. The first change in the slope of the curve indicates the beginning of the transformation under stress. Removing the load at —85°C caused a decrease in length to the value corresponding to the elastic elongation of the parent phase resulting from the applied stress. Hence, the marten-site formed in the first part of the experiment apparently disappears completely and without hysteresis upon the release of the stress. The increase in length on further cooling indicates renewed formation of martensite. These conclusions are consistent with the concept of "thermoelastic" martensite," which has been confirmed by test." Acknowledgments The authors are greatly indebted to Professor M. Cohen for his advice and encouragement. They also thank F. Paxton for assistance. Thanks are due the American Brass Co. which supplied the alloys. References E. Kaminsky and G. V. Kurdjumov: Zhur. Tekhn. Fiziki SSSR (1936) 6, p. 984. A. B. Greninger and V. G. Mooradian: Trans. AIME (1938) 128, p. 337. "J. E. Reynolds, Jr. and M. B. Bever: Trans. AIME (1952) 194, p. 1065; Journal of Metals (October 1952). 'A. L. Titchener and M. B. Bever: Trai~s. AIME (1954) 200, p. 303; Journal of Metals (February 1954). " 3. A. Kulin, M. Cohen, and B. L. Averbach: Trans. AIME (1952) 194. p. 661; Journal of Metals (June 1952). "J. K. Pate1 and M. Cohen: Acta Metallurgica (1953) 1, p. 531. 'C. Crussard: Comptes Rendus (1953) 237, p. 1709. ' G. V. Kurdjumov: Zhur. Tekhn. Fiziki SSSR (1948) 18, p. 999. G. V. Kurdjumov and L. G. Khandros: Dokl Akad. Nouk. SSSR (1949) 66. p. 211.

Jan 1, 1957

By J. C. Martin

A theoretical analysis of steam stimulation is presented for single sands. The analysis includes the effect of steam production and most of the effects of heat conduction. The results show the effects of a number of important variables on the performance of an idealized well under steam stimulation. Calculated responses are presented which indicate the effects of steam production, amount of steam injected, water production, formation thickness and formation damage. Results indicate that steam production can cause large reductions in the heat contained in the formation. This effect can be eliminated by drawdown control. Water production reduces the amount of oil produced during stimulation. The optimum amount of steam to inject depends on economic factors as well as the well response. In many cases, the increased temperature resulting from stimulation reduces oil viscosity near the well sufficiently to overcome the effects of formation damage even if the damage is not removed during steam injection. Calculated responses for thin sands are more favorable than anticipated. INTRODUCTION Little has been published on the theory of steam stimulation'-' despite the interest it has created and the wide variation in well responses. The results of the present analysis provide an insight into steam stimulation, and the methods employed provide a foundation for future work. Analyses presented in Refs. 1 and 2 are very limited and apply to gravity drainage conditions. Ref. 3 contains an analysis similar to the one presented here. The idealized models used and the assumptions made in Ref. 3 are different from those used in this paper. The analysis assumes that after steam injection has heated a small portion of the volume within the radius of drainage of a single uniform sand, a shut-in soaking period is allowed before returning the well to production. The effects of gravity, capillarity, transient pressure and water-sensitive sands are neglected. The injection and soaking times are assumed short compared to the stimulated production time. The initial temperature is assumed uniform; thus, the results apply primarily to first-cycle stimulation. The effects of gas production other than steam are neglected, and the water-oil ratio during production is assumed constant. Steam stimulation involves the simultaneous variation of the temperature, pressure and saturations. General mathematical equations for these variations are complicated and can be very difficult to solve. Simplified equations based on idealized models are used to reduce the mathematics sufficiently to allow approximate solutions to be obtained. DISCUSSION INJECTION An idealized model for which heat conduction is neglected is used to represent the behavior of a well during steam injection. The mathematics for this model is presented in Appendix A which also contains an approximate solution for the behavior of the no-conduction model. SOAKING During soaking, the well is shut in. Only the temperature, pressure and saturation distributions at the end of soaking are needed in the analysis. During soaking the heat is considered to be conducted in a uniform medium from an initially uniformly-heated circular cylinder confined to the producing interval. At the end of soaking the saturations and pressures are assumed to correspond to the cold zone. Analysis of the heat flow during soaking is included in the next section. The radius of the heated cylinder is calculated from the following heat balance (for constant quality steam injection). At the end of the soaking period it is assumed that little or no free gas is present near the well, and that the soaking period has been sufficiently long that the steam zone has had time to expand and the steam has condensed. The condition where there is no soaking is considered in the next section. PRODUCTION In this section, an approximate method is presented for solving the equations of heat and fluid flow associated with the production of oil and water during steam stimulation. Where initial pressure drawdowns are sufficient to cause steam to flow into the wellbore, steam production is assumed to occur within a short initial adjustment period (Appendix B). The production practices followed soon after the well is returned to production can have a large influence on the amount of oil produced during the stimulation cycle. Under most conditions, there is a period of time in which some or all of the water in the heated zone is converted into steam and produced. This flashing of hot water is caused by the pressure in the heated zone dropping below

By H. C. Gatos, A. D. Kurtz

WITH the growing interest in the mechanism of self-diffusion of metals, the study of accurate and convenient methods for determining self-diffu-sion coefficients appears highly desirable. It was with this objective in mind that the present investigation was undertaken. Gatos and Azzam1 employed an autoradiographic technique for measuring self-diffusion coefficients of gold. This method involved sectioning of the specimen through the diffusion zone and recording the radioactivity directly on a photographic film. Because of the very short range of the emitted ß rays in gold, the activity recorded on the film was essentially the true surface activity. With proper choice of the sectioning angle, sufficient resolution could be obtained and the entire concentration-distance curve recorded in one measurement. For the boundary conditions of the experiment, where an infinitesimally thin layer of radioactive material diffuses in positive and negative directions into the end faces of a rod of infinite length, the solution of the diffusion equation is C/Cn = 1/v4pDt exp (-x2/4Dt) where C is the concentration of diffusing element (photographic density in this case), C,, is the constant (depending upon amount of radioactive material), x is the diffusion distance, D is the diffusion coefficient, and t is the time. Thus, by plotting the logarithm of the concentration vs the square of the diffusion distance, a straight line results and the slope contains the diffusion coefficient. In this manner, the self-diffusion coefficient of gold can be obtained as a function of temperature. In the present investigation the results reported by Gatos and Azzam1 have been verified, and the autoradiographic technique has been further developed and applied for the determination of the self-diffusion coefficient of gold at a number of temperatures. Furthermore, the energy of activation for the self-diffusion of gold has been conveniently determined. . Experimental Techniques Preparation of Specimens: The inert gold of high purity was received in the form of a rod from which cylinders were cut and machined to a diameter of 0.500 in. The specimens were annealed to a suitably large grain size and the faces were surface ground prior to the deposition of the radioactive layer. The radioactive isotope Au198 was chosen. It was produced in the Brookhaven pile by means of the reaction Au197 + n ? Au108. It decays by ß emission (0.96 mev) to Hg108 with the subsequent emission of a y ray (0.41 mev). 70Au 108 ? 80Hg 108 + -1e°. The half life of the Au108 is 2.7 days so that a strict time schedule had to be maintained in order to secure sufficient activity until the end of the experiments. For this reason, initial activities as high as 10,000 millicuries per gram were used. The gold arrived in the form of foil and was evaporated onto one face of each gold specimen cylinder to a thickness of about 100A. A sandwich-type specimen was formed by welding two such cylinders together. Evaporation of Gold: The gold was evaporated under vacuum from heated tantalum strips which were bent in such a way as to limit the solid angle through which the gold was allowed to vaporize, thus insuring a more efficient utilization of the gold. The specimens rested on flat brass rings which had an inner diameter of 0.475 in. The entire specimen-holding assembly could be manipulated from outside the vacuum system by means of a magnet which attracted a slug of soft iron attached to the assembly. By evaporating inert gold on glass slides under conditions identical to those employed for the radioactive gold, it was found that the thickness of the films was about 100A. Welding: The welding was performed by hot pressing in a stainless steel cylinder. The inside of the cylinder was threaded and fitted for two plugs. The specimens to be welded were placed in the middle of the cylinder and two pressing disks, one at each end, were inserted to avoid shearing stresses as the plugs were tightened. Mica disks were placed between the pressing disks and the specimens to prevent them from welding. The plugs were then tightened with a hand wrench and the entire unit was placed in an argon stream for about an hour to remove the oxygen. The unit was then inserted in the center of an argon atmosphere furnace maintained at about 700°C and left there for about an hour. Because of the difference in the temperature coefficient of expansion of the two metals, as the temperature rose. the pressure on the specimen-rollple increased and a weld resulted Welding was generally satisfactory under the conditions described.

Jan 1, 1955

By Larry D. Patts

Section 317(e) of the Federal Coal Mine Health & Safety Act of 1969 directed the Secretary of the Interior to prepare standards under which all working places in a mine shall be illuminated by permissible lighting while persons are working in such places. Section 317(e) further provides that such working places shall be illuminated within 18 months after such standards are promulgated. In accordance with this section of the Act, there was published in the Federal Register for December 91, 1970, a notice of proposed rulemaking which prescribed the illumination to be provided in the working places of underground coal mines. In light of written comments, suggestions, and objections to this proposed rulemaking, the proposedstandards were withdrawn and reproposed in the Federal Register for Wednesday, October 27,-19h. In light of further comments, suggestions, and objections, a public hearing was held on April 4, 1974, and standards were again reproposed and published in the Federal Register for April 1, 1976. Promulgation of the final lighting standards took place on October 1, 1976, which means that the underground coal mining industry must comply with face illumination requirements by April 1, 1978. As mentioned previously, the first proposed rulemaking for illumination of underground coal mines was published in the Federal Register on October 27. 1971. In early 1972, Consolidation Coal Company (Consol) and the United States Bureau of Mines agreed to a cooperative study of underground face illumination: Consol felt that expertise is this field would become increasingly important. Consol's initial efforts in illumination were aimed at investigating practical lighting systems for underground face equipment. We were concerned with installing unobtrusive lights which provided sufficient face illumination for safety, but at the same time were readily maintainable, electrically reliable, and physically sheltered from damage. We believe that our initial lighting systems did provide sufficient face lighting for safety, but because only prototype components were available for field testing, the resultant poor system reliability and maintainability necessitated drastic improvement before face lighting could become practical. Final Lighting Standards Deem Early Lighting Installations Out Of Compliance On April 1, 1976, the Federal Register contained the final version of the illumination standards (as they were later promulgated in October). When these illumination regulations and measurement techniques were defined and measuring instruments were available, Consol checked their lighting systems underground and determined that the systems were not in compliance with these final illumination standards. More Lighting Hardware Added In An Attempt To Achieve Compliance. After determining that all of our face lighting systems were not in compliance, we began adding additional lighting hardware in order to meet compliance with published regulations. Unfortunately, to date, we have not been able to meet compliance with practical lighting systems. We have determined from our field installations that the required additional lighting hardware, (to meet compliance) with its increased vulnerability and decreased reliability, renders the lighting systems impractical, if not impossible, to reasonably maintain. Our attempts to provide 0.06 footlamberts have also produced adverse operator reaction to the glare and to illumination systems in general. BCOA Members Ask MESA To Demonstrate Practicability Of Compliance With Regulations Industry concern about meeting the impending lighting regulations was mounting, and in May of 1976 a meeting between MESA and BCOA members was held to discuss lighting compliance problems. At this meeting, BCOA offered to work cooperatively with MESA in testing the practicability of various lighting systems mounted on underground mining equipment. Field tests were to be conducted by United States Steel Corporation, American Electric Power Service Corporation, and Consolidation Coal Company. The purpose of this underground field testing was to develop capability to provide adequate face illumination in a safe, workable manner which would not detract from efficiency of operation. BCOA members involved in this cooperative study were to submit necessary machine drawings, sketches, etc. to MESA in order that MESA could perform a "black-box" study and specify the type and location of luminaires to be installed on the test machines. MESA was confident that they could specify lighting systems that would be in compliance and would be practical so as not to detract from efficiency of operation. Consol was first to install lighting hardware under the BCOA/MESA cooperative agreement. As per MESA specifications, Control Products HgV luminaires were installed on a Joy 2BT-2H boring machine at the Williams Mine of Northern West Virginia Region. As of mid-October, 1976, Consol had approximately eight weeks operating experience with the lighting system on this boring machine underground and had drawn the following conclusions: The lighting system installed at Williams Mine (1) does not meet compliance with lighting standards as originally proposed by MESA, (2) does not provide illumination in a safe workable manner, and (3) will detract from efficiency of the mining operation due to operational delays. Although Consol has rearranged lights on this boring machine in an attempt to reduce operator objections, a practical lighting system which is "in compliance" has not been arrived at as of this writing.

Jan 1, 1979

By M. I. Sherman, J. D. H. Strickland

USE of a hydrometallurgical approach to the oxidation of sulfide ores and extraction of metals therefrom may have advantages over the more common smelting techniques when a low grade deposit is difficult to concentrate or the subsequent separation of metals, coexisting in the ore, is laborious by any known smelting operation. For economic reasons, the most promising oxidants are either atmospheric oxygen or electric power. The use of oxygen, or air under pressure, has recently been revised. Pyrrhotite has been converted to iron oxide and elementary sulfur' and a variety of sulfides have been treated by Forward and co-workers.2-4 Generally sulfate is the end form of the sulfur but with galena in an acid medium, elementary sulfur can be formed." For economic reasons chlorine and ferric iron salts are about the only possible alternatives to the atmosphere as oxidizing agents for base metal sulfides. If aqueous solutions of chlorine or ferric iron are employed, the reduction products can be oxidized electrolytically in situ and used again, thus acting as catalysts for electric power as oxidant. The use of ferric salts for this purpose is established hydrometallurgical practicea but, although chlorine gas has been employed in the dry state at an elevated temperature, its use in aqueous solution at or near room temperature has not found favor. The reaction of chlorine water with the soluble sulfide ion has been studied by several workers,7-9 and both sulfate and elemental sulfur are found as end products, the latter being favored by the presence of a low concentration of oxidant relative to that of sulfide in solutions of about pH 9 to 10. Of direct bearing on the work in hand are an early American patent" and a recent Austrian patent." The former advocates stirring powdered ore with an aqueous solution of ferric chloride chlorine oxides and chlorine. In the latter it is claimed that both metal and sulfur can be obtained by electrolysis, in a diaphragm cell, of a metal ore slurry in brine. Details in these patents are scant and no data or explanation is given for the mechanism of the reaction which, in the Austrian work, is attributed to the (unlikely) action of nascent chlorine at the anode surface. No mention is made of possible differences in behaviour between various ores. Apparatus A complication encountered when working with chlorine water is that a serious loss of chlorine occurs by gas partitioning unless an enclosed system is used and any air space in the apparatus is kept very small and constant. Arrangements were made, therefore, to take out samples for analysis without letting air into the system to replace the liquid removed. For convenience in studying a heterogeneous reaction the apparatus was so designed that a reproducible controlled stirring rate could be maintained and the ratio of surface area of ore to volume of solution was approximately constant throughout any experiment. The apparatus used is shown in Fig. 1. The ground ore was placed in the horizontal cylindrical vessel, A, of about 1 liter capacity, heated by a constant temperature circulating bath pumping water through the concentric jacket, B. By adding chro-mate to this water, an ultraviolet radiation filter effectively surrounded the reaction vessel, greatly reducing any possible photochemical decomposition of chlorine solutions. Stirring was effected by glass paddles, C, attached by an axle to a magnet which was rotated by another powerful Alnico magnet, D, outside the glass end, this magnet being itself rotated by an electric motor electronically controlled to constant speed. Speed could be varied from about 150 to 900 rpm and was measured and held to within 1 pct of a given value. The end of the reaction vessel remote from the stirring magnet was closed by another one-ended glass cylinder, E, connected by thin polyethylene bellows, F, clamped by screw clamps and watertight rubber gaskets to the main vessel. Through E, a glass electrode and calomel electrode projected into the solution and a hypodermic syringe pierced a small bung and allowed acid or alkaline to be added to maintain a constant pH. By pushing the fully extended bellows until the two cylinders touched, from 50 to 100 ml of solution could be forced out through a sintered disk into the three-way tap system, G, either to waste (for flushing purposes) or up into a 10 ml burette where the solution could subsequently be measured out for analysis. The ore samples were introduced at H, the tube being stoppered by a thermometer of —1 to +52ºC range, graduated to 0.1°C intervals. To prevent ore from being ground in the end bearings of the stirrer these bearings were pro-

Jan 1, 1958

By H. R. Froning, R. O. Leach

In wertability alteration flooding, a chemical agent is rnoved through a reservoir by the flood water to increase oil recovery by decreasing the degree of wetting of the rock by the oil. Substantial amounts of the chemical may be lost during movement through the reservoir. The extent of the loss, and therefore the economics of the process, depends in some cases on factors which are difficult to reproduce in the laboratory. Therefore, a short-duration, low-cost field test method is needed to permit evaluation of chemical requirements under actual field conditions. This paper describes a small scale rest conducted at a single well for measuring chemical requirements, thereby giving a more reliable evaluation of this important factor in the applicability and economics of the process. In the rest a small wafer slug containing the chemical agent and a nonadsorbed tracer is displaced into the reservoir by a known volume of wafer. The well is then placed on producrion. Chemical loss per barrel of pore volume contacted is calculated from [he fractional recoveries of the agent tested and the nonadsorbed tracer. The method has been used to determine within the actual reservoirs the chemical requirements for both a sandstone and a dolomite reservoir. Several chemical agents are potentially available for wettability alteration flooding, although none is universally applicable. For some applications of the method, chemical costs per barrel of additional oil recovered can be substantially less than one dollar. INTRODUCTION Wettability alteration flooding provides a means of increasing oil recovery from reservoirs by decreasing the degree of wetting of the rock by the oil and increasing the displacement efficiency of the flood water. Earlier studies demonstrated a relationship between oil recovery during waterflooding and the degree of wetting of a rock surface by an oil. The application of wettability alteration flooding to the Harrisburg field of Nebraska provided a field test' of this recovery process. Subsequently, additional laboratory and field tests have developed additional procedures for evaluating wettability alteration flooding, and have indicated where the process may be applicable. Applicability of this process to specific reservoirs is determined by a progression of tests to determine sus- ceptibility of the reservoir to alteration of its wettability, to indicate the degree of recovery improvement and to estimate the amount of chemical required to process the reservoir. The economics of applying improved oil recovery processes depends not only upon the degree of improvement in oil recovery achievable by the process but also upon the process costs and the timing of the income and the investment. Emphasis in this paper is on the expenditure aspects of the process. The work reported in this paper indicates that the chemical investments required for wettability alteration flooding are substantial. For evaluating the economics of a potential flooding application it is imperative that a sound estimate of the chemical requirements be made for the reservoir. Generally, true reservoir conditions are not adequately simulated in laboratory chemical propagation tests. Because of wide well spacings, many years might be required to obtain chemical propagation data from conventional pilots or inter-well tests. Consequently, n short-duration, low-cost method is needed to determine chemical requirements in the field. The potential applicability of wettability alteration flooding is discussed, as well as the economics of wettability alteration with respect to the inherent and imposed restrictions on the timing of income and investments. DETERMINATION OF CHEMICAL REQUIREMENTS In the process of moving a chemical bank through reservoir rock, some of the chemical agent lags too far behind the flood front to be effective or is otherwise lost to the reservoir system. The extent to which these losses occur overshadows the reductions in chemical concentration due to diffusion and to mixing with the reservoir fluids. Experience indicates that almost without exception, chemicals which induce a wetting change undergo either sorption reactions or chemical reactions with mineral constituents of the pore surfaces. Other reactions may occur between the added chemical and the reservoir oil and water. Even in limiting consideration to reactions of the relatively inexpensive inorganic salts, bases and acids, the reactions may be exceedingly complex. Reservoir pore surfaces consist of more than silica in sandstone reservoirs, and more than calcite or dolomite in carbonate reservoirs. Many mineral species are present, each exhibiting specific tendencies to react with an injected chemical. The reactions which occur can consume enough of the agent to have an important effect on economics. These reactions can cause a change in pH of the chemical bank, or may remove some of the active chemical by precipitation, adsorption or reaction to form a new chemical which may or may not be effective in