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DAVID WHITE,* Washington, D. C.-This paper is very timely since the Philippine Islands are presumably open to the enterprise of the American driller, whereas much of the territory in that part of the world is closed to us. The United States has ambitious plans for the operation of a great merchant marine, which is to be oil burning in the main, and it takes but a glance at the world map to see the strategic advantage of oil supplies in the Philippines for such marine operations. It is a little difficult to understand why more attention has not been given to the Philippines, in spite of the difficulties attending development in these islands. A number of American oil companies are, I believe, at the present moment taking an interest in the possibilities of the Philippines. Important factors in the formulation of opinion regarding the importance of the oil deposits of the Philippines, as brought out by Mr. Pratt,1 are the point of view and the breadth of experience of the examining geologist. The average oil geologist, whose experience has been mainly in the Appalachian region, the Mid-continent, or Louisiana, or possibly even in California, on seeing the narrowness of the basins, the closeness of the folding, and the presence of igneous rocks here and there, would be likely to draw unfavorable conclusions as to the possibilities of the Philippine Islands. Geologists visiting that region should be familiar with the geological conditions of oil occurrence in Japan, Formosa, the East Indies, or in the Baku district, and their conclusions should be formulated with the knowledge and understanding of the occurrence of oil in those regions rather than in the United States.

Jan 8, 1920

By B. H. Caudle, L. H. Silberberg

Reservoir depletion by natural water drive is typified by the movement of water from an aquifer into the adjacent oil-bearing formation. Prior studies of this type 01 water movement have generally neglected the resistance to flow in the aquifer and its effect on the movement of water into the oil bearing zone. A method for designing and operating scaled models of such reservoir systems is presented. Experimental data on a model of an edge-water-drive reservoir are shown and discussed. INTRODUCTION Most petroleum reservoirs derive at least a part of their productive capacity from water influx. This water may be injected from the surface or it may come from an aquifer adjacent to the oil zone. In either case, the reservoir engineer must be able to estimate the advance of the water as a function of either the elapsed time or the fluid produced. This paper describes a type of fluid flow model which includes the effect of viscous and gravitational forces in the reservoir and the surrounding aquifer. Natural water influx can be divided into three general (but widely overlapping) categories according to the direction of flow in the aquifer. These are shown schematically in Fig. 1. Fig. l(a) illustrates an edge-water-drive mechanism. In this case, water advances updip along the stratum but the movement of water is essentially horizontal and very little of the oil is actually underlain by water. The bottom-water drive (Fig. l(b)) is characterized by a thick aquifer underlying the oil zone. The water movement is generally vertical in the aquifer. The third category is illustrated in l(c). Referred to as the "thin oil column", this type of oil accumulation consists of oil over water in a relatively thin stratum. Fluid movement is horizontal in both the oil and water zones, except close to the producing well. One characteristic which all three of these types have in common is that part of the water flow takes place in the water invaded region of the oil reservoir while the remainder of the water flow occurs in the aquifer. The resistance to the flow of water usually will not be the same in these two regions. This occurs because the porous rock normally contains only water in the aquifer, while the water-invaded region always contains microscopic globules of bypassed oil (residual oil) which interfere with the flow of water through the rock. The production history of any type of a water-drive system is a function of two phenomena — where the water goes, and how it displaces the oil in the area invaded by the water. It is usually impractical to study these two phenomena at the same time. In most cases one type of analysis is used to predict the gross movement of water in the reservoir, while a different type of analysis is employed to determine the amount of oil to be recovered from the gross volume contacted by the water. The portion of the oil reservoir which is invaded by water is mainly a function of the resistances to fluid flow in the several parts of the flow system. This gross water influx in the three types of natural water drive typically results in water cusping to the production wells either from the side or from below (water coning). In 1747, Muskat described a greatly simplified mathematical model for predicting the area invaded by water in a bottom-water-drive reservoir.1 This model used the Laplace equation and suitable boundary conditions to describe the isopotentials and streamlines in the flow system. The use of this model assumes that (1) the reservoir rock is homogeneous in nature, (2) the oil and water mobilities are equal, (3) there is no oil flowing in the water invaded region, and (4) external forces — such as gravity — do not affect the flow. This method has been used for both natural water drives and water injection projects. In this, as in most models, the method of images is used to reduce the size of the model necessary to describe the reservoir. The assumption of equal viscosities and permea-

Jan 1, 1966

By R. L. Templin

THE increasing use of aluminum and its alloys in commercial fields has demanded a better understanding of their machining properties. This fact is exemplified by problems that have arisen in the automotive and airplane industries, but many in other fields might be cited. As pure aluminum and its alloys in their various commercial conditions show appreciable differences in their machining properties, it is not surprising that quite divergent solutions have been offered for the machining problems encountered. However, if the fundamental requirements of the most suitable cutting tools for these metals are understood, these machining problems lend themselves more readily to satisfactory solutions. Since the machining of free cutting brass and mild steel is understood by most persons accustomed to working these metals, it may serve our purpose better to first make a general comparison of the tools more commonly used in machining these metals with the tools most suitable for machining aluminum, then proceed to a more specific discussion of the individual tools. COMPARISON OF CUTTING TOOLS Cutting tools commonly used for machining free cutting brass usually have little, if any, top and side rake; they are ground on a medium to coarse abrasive wheel and used without any cutting compound or with a cutting compound that has a paraffin base. Those ordinarily used for steel have some top and side rake, are usually ground on a medium to fine abrasive wheel, and are often used with soluble-oil cutting compounds. The proper tools for aluminum and its alloys should have appreciably more side and top rake than the tools for cutting steel; should have very keen edges obtained by grinding with fine or very fine abrasive wheels supplemented in many cases by hand stoning with an oil-stone; and should be used with suitable cutting compounds whenever possible. In many cases, tools suitable for machining aluminum and its alloys are not appreciably different from tools commonly used for cutting hardwoods. The front clearance of a tool most suitable for machining aluminum and its alloys should be about 6°, the top rake from 30° to 50°, making the total angle of the cutting edge of the tool from 35° to 55°. A side

Jan 1, 1928

By C. D. Stahl, S. M. Farouq Ali

This investigation attempts to describe and simulate the alcohol displacement process by means of a cell model, as employed in chemical engineering practice. The proposed model is more simple than previously proposed models. and utilizes parameters chosen on a theoretical basis. The model successfully reproduced the formation of the stabilized bank and the breakthrough of alcohol, the latter depending on one of the model parameters, which may be correlated with the length of the porous medium. Moreover, the effects of the phase behavior of the liquid system involved, as observed in experimental studies, were reproduced. Several variations of the basic model were devised and tested on a digital computer. These included the cases in which: (1) the actual value of fractional flow was used in cell-to-cell computations; (2) the number of cells was varied within the same run; and (3) incomplete rather than complete phase equilibrium was assumed within each cell. The proposed cell model clarifies the basic mechanism of the process. Detailed concentration profiles obtained for each cell, for instance, showed the mechanism of bank formation in relation to the phase behavior characteristics. The results obtained indicated a varying degree of phase equilibrium concommitant with changes in the velocities of the phases in an actual alcohol displacement. This condition was approximated by changing the number of cells during the simulation. Interesting information was obtained on the influence of path length on the efficiency of alcohol displacement, which has been the subject of some controversy. Certain limitations preclude the use of the proposed model as a substitute for experimental studies. The results obtained were, nevertheless, of value in interpreting the experimental results. INTRODUCTION During recent years considerable effort has been directed toward an understanding of alcohol displacement, the process whereby oil and water are recovered from a porous medium by the continuous injection of a solvent. The complex nature of the physical process involved has so far defied a complete mathematical treatment. Other methods of approach, amounting to an overall material balance, have been proposed, yielding useful information on certain aspects of the process.1-3 Taber et al, in particular, defined the displacement mechanism in terms of the phase behavior of the alcohol-oil-brine system invoIved.2 Wachmann reported a mathematical treatment of alcohol displacement subject to certain simplifying assumptions? Donohue proposed the use of a "cell model" for simulating alcohol disPlacement.5 The nature of the assumptions involved limited the utility of the model. The present work attempts to examine the variables involved in the simulation of alcohol displacement and discusses several possible versions of the basic cell model. Under certain conditions the model results are similar to the experimental results. In particular, the spontaneous formation of of the stabilized bank and the effects of the system phase behavior were successfully reproduced. PREVIOUS WORK ON CELL MODELS Cell models and the theoretical plate concept are often used in solving chemical engineering problems in which an explicit mathematical solution may be difficult or impossible to obtain. Examples of such applications occur in distillation, gas-liquid chroma tography,6 reactor technology, absorption, etc. In petroleum engineering, such a model was used by Attra7 to describe non-equilibrium gas drive, and by Higgins and Leigh ton8 to calculate sweep efficiency in water flooding. Aris and Amundsen pointed out the equivalence between the diffusion model and perfectly mixed cells connected in series.9 Deans proposed a three-parameter cell model to simulate two-component

Jan 1, 1966

By R. L. Schmidt, J. D. Verhoeven

The diffusion coefficients and electrotralzsport mobilities of aluminum, gallium, and arsenic have been determined in molten germanium with the capillary reservoir technique. The diffusion coefficients are slightly higher than those determined by the solidification technique of Brirton et a1.1 It was found that aluminium and gallium migrate to the cathode in molten germanium) whereas arsenic migrates to the anode under an electric field. A possible technique for producing p-n junctions by means of electric field freezing is discussed in view of the experimental data. In the past decade or so the literature has abounded with articles concerning the solid-state properties of the semiconducting elements germanium and silicon. It is surprising by comparison how little has been published concerning the liquid-state properties of these materials. In the production of doped germanium or silicon the diffusion coefficient of the dopant in liquid germanium or silicon is an important quantity. Yet, to the best of our knowledge, no one has ever made a direct measurement of the diffusion coefficient of solutes in either molten germanium or silicon. A number of authors'-4 have determined some diffusion coefficients by the indirect technique developed by Burton et al.1 This technique appears to give numbers of the correct order of magnitude but it does depend upon a number of assumptions in the analysis and also requires prior knowledge of the viscosity of the melt. In the present work a more direct measure of the diffusion coefficients of arsenic, gallium: and aluminum in molten germanium has been made. It has been shown independently by two groups of authors5, 6 that, when an electric current is passed through the interface of a solidifying metal containing an impurity, the resulting electrotransport in the liquid boundary layer at the interface offers a mechanism for control over the redistribution of the impurity accompanying the solidification. These authors show that the degree of control is proportional to the mobility, U of the impurity atoms in the liquid boundary layer, where the mobility is defined as the drift velocity relative to the solvent per unit electric field. In principle the results apply to the solidification of a doped semiconductor and offer an interesting technique for control of the doping of a semiconductor. In the present work the mobilities of aluminum, gallium, and arsenic were determined in molten germanium in order to evaluate the potential usefulness of electro-transport as a technique for solute control when applied to the solidification of doped germanium. EXPERIMENTAL PROCEDURE Both the diffusion coefficients and the mobilities were measured using high-purity alumina capillaries and a resistivity technique for analysis. A schematic diagram of the electrotransport apparatus is shown in Fig. 1 and the details of the cell design are shown in Fig. 2. For the mobility experiments electrical contact with the bottom of the capillary was made with graphite, as shown in Fig. 2. In order to prevent electrical contact with the melt the graphite was coated with a thin layer of alumina using a plasma spray torch. The cell assembly, a graphite electrode, and another assembly containing two blank capillaries were fastened to the lavite disk shown in Fig. 1. To make a run the system was evacuated and the doped germanium was outgassed at the operating temperature of 1030°C. The cell and blank capillaries were then submerged beneath the melt and a slightly positive pressure of helium was introduced to fill them. After passing current through the cell for a given time the cell and blank capillaries were raised from the melt and the furnace was shut off. The temperature of the cells dropped below the freezing point of germanium within 1 to 2 min after the furnace was shut off.

Jan 1, 1968

By Kung-Lee Wang, Brian W. Mackenzie, Warren E. Morrison, DeVerle P. Harris, George F. Sharrard

The term "mineral economics" is applied to a wide range of activities in the mineral industries. Earlier chapters have described the application of economic concepts to the mineral industries-supply, demand, conservation, tariffs, etc. The solution of mineral economics problems is often assisted by the application of quantitative methods. The purpose of this chapter is to describe a number of quantitative methods-econometric, operations research, and management science techniques-which find application in the analysis of mineral economics problems. These methods include input-output analysis, trend analysis, forecasting techniques, simulation, multivariate statistical analysis, mathematical programming, and market research techniques. The purpose of this introductory section is to provide a mineral economics framework for the application of these methods. Mineral economics is a subdivision of economics that is justified by a sufficient number of economic problems in the mineral industry requiring special experience and an unusual combination of skills. These problems are concerned with the conversion of minerals as geologic resources to minerals as economic goods. The mineral conversion process is outlined in Fig. 8.A.1. The physical occurrence of mineral deposits in nature and the market demand for mineral products in the economy provide the basic stimuli. The conversion process embodies a number of sequential stages-exploration, the development of mineral deposits, and mineral processing facilities and, consequently, productive activity to supply market demand. Changes in demand and the depletion of deposits illustrate the dynamics of the process. Mineral economics applies economic con-

Jan 1, 1976

By M. M. Rao, P. G. Winchell, R. J. Russell

A detailed analysis has been used to correlate the avalable thermodynami c da In on iron-ric11 Fe-Ni (41loys in the body-centered a, and the face-centered y phases. The inp ut injovrt~ation required by the a am lysis consists of tile heat of the a, to y transformation at 1123°K, the heat of mixing of y at 1123°K, tile specific heats of both a, and y (decomposed into Debye, electronic, and magnelic contributions), and the positional and magnetic entropies of both a, and y. PYLrrzary oirt.bul of the analysis is the free energy of each phase as a Junction of temperature and composition. FOr Fe-Ni alloys the adjustment of twenty-one parunletevs allows the accurate reproduction of enthalpy data for both phases, the heat of mixing- for y, the a/y equilibrinm compositions in the Fe-Ni phase diagram, and the usually accepted enthalpy and entropy of a and y iron. Also obtaitzed are fuirly accurate reproductions of electronic specific heat coefficients predicted from electron- to-atom ratio interpolations and To temperatuves eslimanted from transformation studies. Also considered in the calculation are the elastic constants, Curie temperatures, saturation magnlelizalion values, and indications of short- range order. The measnred activity coefficient of iron in anstetnite could not be accurately matched. The major source of uncertainty in the model is thought to be the magnetic contribution to the entropy of austenite. Calcrclations were extended to Fe-ni-C alloys using available carbon-acliuity data. The free energy of transformation from martensile to r at fixed composition was obtained as a function of nickel and carbon contetzt, and binary thetal-carbon phase diagrams Were estimaled as a function of nickel contenl. We needed thermodynamic information for Fe-Ni and Fe-Ni-C alloys at temperatures between 400" and 800°K in order to interpret the results of several phase-transformation studies. The most recent theoretical analysis of the thermodynamics of Fe-Nialloysl was based on a lumped-parameter, regular-solution model and used the Fe-Ni phase diagram available at that time.' Because significant difficulties were encountered in attempting to extend this analysis to Fe-Ni-C alloys, and because more experimental data has become available recently, we decided to attempt a new correlation. The analysis used here allows the extrapolation of measured and calculated thermodynamic values to lower temperatures and the extension of the thermodynamic analysis to Fe-Ni-C alloys. The structure of this correlation consists of expressions containing a total of twenty-one adjustable parameters. The forms of these expressions are discussed in the next section; however, a less formal summary is presented now to provide a physical overview of the model and to indicate its connections to prior work. Primary input information for this correlation is described below. The measured values of the specific heat of iron3 and its analysis475 and theoretical estimates of the specific heat of y* iron at low tempera- loys at 1123°K has been measured by solution calori-metry.7 The enthalpies of both a, and y have been measured most recently by Scheil and Saftig,B who used a dry-ice calorimeter. These data are used to formulate expressions for the heat of mixing of y and the heat of transformation of a, to y both at 1123°K. The a and y solubility limits in the Fe-Ni phase diagram have been redetermined recently9 by methods which assure a close approach to equilibrium. The a to y transformation can occur without change in nickel content or free energy at a temperature called TO; TO temperatures for various nickel contents have been estimated from transformation studies. The computed free-energy functions are adjusted by means of the parameters to fit both the phase diagram and the TO temperatures. Primary emphasis is placed on the phase diagram fit. Iron activities have been measured in Fe-Ni austenite10 between 973" and 1173°K. These activity data, which cannot be fitted accurately with our model, indicate that iron is substantially ideal in iron-rich austenite. Secondary, but helpful, information for the present correlation is provided by neutron diffraction and saturation magnetization measurements on both body-centered and face-centered Fe-Ni alloys."-'3 These results were interpreted11 in terms of composition-insensitive, localized magnetic moments on both iron

Jan 1, 1968

By Andrew Cosgarea, William R. Upthegrove, Morteza Mirshamsi

The capillary-reservoir technique was used with lead-210 and cadmium-115m to determine the self-diffiLsion coefficients of both cadmium and lead in the liquid binary Cd-Pb system. The self-diffusion coefficients of pure cadmium and pure lead were obtained and were compared with the theoretical predictions. Good to excellent agrement between the experimental and predicted values was obtained. The self-diffusion coefficients of cadmium were tneasuved in alloys containing 2.50, 9.13, 17.40, 31.00, 45.00, 69.00, and 97.00 lot pct Cd by determining- the amount of cadniiutn-115m which diffused out of a small-bore capillavy into an infinite reservoir during- a given time peviod. Sinzila7-measurements were made with lead-210 to determine the self-diffusion coefficients of lead in these identical alloys. Diffusivities were determined from measurenzents performed in the temperature interval of 290" to 480°C. The results were correlated with the Ar-vhenius equation, and the maximum variation of the equation parameters (Q and Do) was also inrestigated . THE theory of diffusion in liquids, particularly liquid metals, is relatively undeveloped in contrast to that for the gaseous and solid states. Although the practical application of liquid metals as heat-transfer media has become increasingly important, few liquid-metals systems have been investigated. Experimental data of fundamental significance in this field are not readily obtained, which may explain but not justify the present lack of knowledge. What work has been completed is primarily restricted to liquid diffusion of pure metals; little work has been done in liquid-metal diffusion of binary mixtures. A review of liquid-metal diffusion theory and research is available elsewhere.1-4 In an effort to add to the knowledge of liquid-metal systems and to increase the basic understanding of the diffusion process in liquids, a study of diffusion in the binary-liquid system, Cd-Pb, was undertaken. The capillary-reservoir technique5 was employed to measure the self-diffusion coefficients of cadmium and lead in molten binary alloys. Measurements were made with seven selected compositions and over a temperature range from 290° to 480°C. The experimental apparatus consisted essentially of the following items: constant-temperature bath, diffusion cells, capillaries, capillary-filling device, and a radioactive tracer counting system. EXPERIMENTAL APPARATUS Constant-Temperature Bath. A cylindrical steel vessel, 8 in. in diam and 15 in. deep, surrounded by an insulated heating coil was used with a sodium-potassium nitrate salt mixture heating medium. The bath was maintained slightly below the desired control temperature by the furnace-heating element; and a 250-w heater, actuated by a Bayley proportional temperature controller, was utilized for the final control of the temperature. A constant-speed mixer stirred the salt to insure a uniform temperature within the bath. Four calibrated Chromel-Alumel thermocouples were placed at various positions in the salt bath to verify the absence of temperature gradients. The observed temperature variation during any diffusion run was less than 0.l°C. The entire furnace assembly was mounted on four shock absorbers to exclude building vibrations and the stirrer propeller blades were adjusted so not to induce vibrations within the reservoir. A schematic diagram of the furnace and the constant-temperature bath is shown in Fig. 1. Diffusion Cell. The diffusion cells and associated parts were the same, except for slight modification, as the one used by walls1 in this laboratory, and are shown in detail elsewhere.' A graphite crucible, 4 in. long and 40 mm (1-1/2 in.) ID, enclosed in a 60-mm (2-1/4 in.) Pyrex tube cell about 18 in. long, was used as a container for the melt. The reservoir (molten alloy in the graphite crucible) was usually about 2 to 2-1/2 in. deep. Graphite was used because of its satisfactory nature as a refractory material and the low solubility of carbon in molten Cd-Pb alloy.677 The Pyrex cell was closed at the bottom and fitted at the top (open end) with a 2-in. Dresser coupling. A brass flange was welded to the top of the coupling. The upper part of the diffusion assembly was bolted to this flange with an O-ring seal. The lower part of the diffusion cell was supported in a 3-in. brass cylinder which was open to allow for circulation of salt around the cell. The top assembly consisted of two synchronous motors, a drive shaft, a thermocouple well, and controlled-atmosphere inlets and outlets. One motor was used for rotation of the capillaries at a rate of 1/2 rpm in the reservoir during the diffusion run. The other motor was used for the vertical positioning of the capillaries and the capillary holder by means of a simple screw drive. The capillary holder and drive assembly were lowered into the reservoir for the run and raised after the desired diffusion time at a rate of approximately 0.4 in. per min. Capillary holders were made of graphite. These

Jan 1, 1967

By Dale A. Vaughan, Oliver M. Stewart, Charles M. Schwartz

Solid-solubility limits at 1500°, l000q and 500°C for carbon, nitrogen, and oxygen in high-purity tantalum were determined by X-ray lattice-parameter methods. For carbon, the solubility was found to be 0.17 at. pct at 1500°C, and less than 0.07 at. pct at 1000°C. A nitrogen solubility of 3.70 at. pct at 1500° C decreases linearly with temperature to 2.75 at. pct at 1000°C, and 1.8 at. pct at 500°C. In the case of oxygen, the solubility was found to be 3.65 at. pct at 1500°C, 2.95 at. pct at 1000°C, and 2.5 at. pct at 500°C. The phases Ta2C, the low-temperature modification of Ta205, and Ta,N of unknown composition but which has a superlattice structure based upon the original bcc tantalum lattice have been identified as the initial precipitates in the respective systems. Metallographic methods were employed to verify the X-ray analyses. The etching behavior of Ta is discussed in terms of lattice i?rzperfections and precipitate phases. The excellent fabricability, high melting point, and nuclear properties of tantalum are responsible for interest in this refractory metal. Data on the solid solubility of the interstitial elements (oxygen, nitrogen, and carbon) in tantalum and on the precipitate phases are somewhat limited. The significant contributions are discussed below. Because the purity of electron-beam melted tantalum (only recently available) is considerably higher than that used in previous studies, the present investigation was initiated. Gebhardt et all-3 have investigated the tantalum-oxygen and tantalum-nitrogen systems with particular reference to the changes in physical properties and to the rates of reaction between these gases and the metal. The solubility of oxygen in tantalum was reported2 to be 3.7 at. pet at 1500°, 2.3 at. pet at 100O°C, and 1.4 at. pct at 750°C. Schonberg4 reported that several oxide phases (Ta40, Ta,O, TaO and Ta,05) exist while X-ray studies by Gebhardtl showed only two oxides, Ta,05 and an unidentified phase which was associated with a platelet-type precipitate. La-gergren and Magneli,' however, questioned the existence of compounds other than the two allotropic modifications of Ta,05 for the tantalum-oxygen system. In the case of nitrogen, the solubility was estab- lished by Gebhardt3 to be of the order of 7 at. pct at 1800°c. The solubility was reported to decrease rapidly with temperature, and, although no limits were established, a precipitate phase was observed by Gebhardt except when the high-nitrogen specimens were cooled very rapidly from the reaction temperature of 1800c. He reported the initial precipitate phase to be a tetragonal distortion of the bcc tantalum lattice while Schonberg6 reported the phase lowest in nitrogen Jo be a cubic super-lattice with a cell size of 10.11 A. Two other nitride phases, Ta,N and TaN, were reported; these appear to be isomor-phous with the carbides of tantalum. The tantalum-carbon system was investigated by Ellinger7 and by Lesser and Braurer. Two compounds, Ta,C and TaC, were reported to exist, each with a range of composition. The solubility of carbon in tantalum was found to be practically nil at all temperatures. Thus, of the interstitial elements which are present in small amounts in high-purity tantalum, carbon might be expected to form precipitates. The present investigation was initiated to obtain additional data on the solid-solubility limits of these interstitials at 1500°, 1000°, and 500' with particular emphasis on the distribution and the identification of the precipitate phases. EXPERIMENTAL WORK AND RESULTS In the present investigations of the solid solubility and of the precipitate phases in the systems tantalum-nitrogen, -oxygen, and -carbon, high-purity tantalum was reacted with high-purity gases, homogenized at 1800°c, and annealed at and quenched from 1500°, 1000,

Jan 1, 1962

By Anderson, Burton E.

FOR several centuries diamond mining has been an adventurous, profitable and enticing industry in Brazil. Some of the world's most valuable diamonds have been found in this country. Two of the most famous stones are the "Estrella do Sul" (Southern Star), weighing 2541/ karats, and the "Branganca," weighing 1680 karats in the rough and 367 karats cut. For a great number of years the stones extracted and sold were mostly the white diamonds used for jewelry. Within the last thirty years black diamonds have been developed as an abrasive cutting material and in these black diamonds the State of Bahia, Brazil, has a monopoly of the world supply. Carbons, as they are commonly called, are being used for core-drilling, polishing, cutting, wire-drawing, and vari-ous other applications in which such a hard substance is required. Bernard Bandler & Sons, of New York City, have selected, graded and delivered these carbons to the United States markets.

Jan 1, 1932

By Carle R. Hayward

GENERAL conditions in the lead industry have registered a distinct improvement. The first signs of a strengthening market were found in an increasing demand for scrap. There is keen competition for old battery plates both by large and small dealers. The large operator smelts them either alone or in combination with ores or other lead-bearing material, giving an antimonial lead for which there is brisk demand. The small operator usually has three alternatives. He may simply melt out the metallics in a kettle at low temperature, giving an antimonial lead and a pulverulent lead oxide; he may fuse under oxidizing conditions, giving a soft lead and lead-antimony slag; or he may fuse under reducing conditions, giving a relatively low-grade antimonial lead and a low-antimony slag. In each case the metal product is used or sold, and the dross or slag sold to a large smelter. It will be interesting to see what the final outcome will be of this situation which is generally conceded to be unsatisfactory.

Jan 1, 1937

By H. J. Maguire

(Presented by invitation at a meeting of the Spokane Local Section, Feb. 17, 1912.) THOSE familiar with mill-practice understand the work required of an average bucket-elevator, but I wish to call special attention to the wear on the buckets. I have been studying in what manner the life and service of the bucket might be improved, and I feel that an adjustable lip, attachable to each bucket without the aid of rivets, will be of material advantage. For illustration, consider the feed-elevator of a typical mill in the Cur d'Alène district. The ore is carried by water in a launder from the feed-rolls and dumped in the "boot" of the elevator, directly in front of the ascending bucket. Middlings from the return-rolls are similarly handled. Under this condition the bucket not only carries the ore, but also picks it up, and this latter requirement determines the life and service of the bucket. It might be said that it would be better practice to convey the feed to the elevator and dump it directly into the bucket, but at one mill at which this plan was tried the results were disappointing and the rubber belt was badly worn. The wear of the bucket is confined to the lip and the corners which have to pick up the material. When the lip on a corner of a 7- by 12-in. malleable cast-iron bucket is worn down about 3 in., the bucket is of no further value as a carrier and has to be replaced. The worn bucket, containing about three¬quarters by weight of the metal of the original bucket, has a scrap value of about 10 per cent. of that of a new bucket. To the cost of the bucket, however, should be added the time-cost of replacing the old bucket by a new one. This time-cost is considerable when the loss per hour, to cease operating the mill, is about $200. It is out of the question to put lips on a bucket unless the latter was originally fitted with this device. For if it is attempted to fit lips upon buckets not originally provided with

Sep 1, 1912

By I. H. Silberberg, R. L. Reed, O. K. Kimbler

interfacial films have frequently been observed at interfaces between certain crude oils and water. Several investigators have postulated that the presence of these films should influence the efficiency of oil recovery in water drive or waterflood operations. They may also influence the stability of emulsions which are sometimes a problem in petroleum production, and may be a factor in the fonation of paraffin deposits in oil well tubing and flow lines. This paper presents a technique with which a modified Langmuir film balance may be used to study the compressibility and collapse pressure of these natural interfacial films. Experimental data are presented for several nude oil-water systems. Data developed are used to infer the phase state of the film as a function of such variables as rate of reduction of interfacial area, ionic composition of the subtrate and pH of the subtrate. A film of known physical characteristics is shown to have a sinnificant effect on oil recovery from an unconsolidated sand pack. Possible applications of these results to petroleum production are discussed. INTRODUCTION The use of water to displace petroleum from reservoir rocks is of major importance both as a primary and a secondary recovery process. As water invades the rock, oil is completely displaced from some pores and left as a discontinuous phase in other pores. The manner in which water moves from pore to pore is strongly influenced by capillary forces. In view of the complexity of reservoir fluid systems, there can be little doubt that complicated interactions take place at both the liquid-solid and oil-water interfaces. One of the more interesting, and least understood, of the phenomena which take place at the oil-water interface is the formation of interfacial films. These films are believed to result from the adsorption of high molecular weight polar molecules at the interface.l.2 Presence of such molecules may cause a striking alteration in interfacial tension. When the oil-water interfacial area of certain crudes is rapidly reduced, a thin region (film) about the interface assumes the appearance of a solid membrane, and striations, wrinkles and gross distortions may occur. If such a film is solid, it should greatly alter the interfacial tension normally assumed to exist between the oil and water phases. If the membrane is continuous, a solid phase would separate the oil and water. Interfacial films between crude oil and water were observed in 1949 by Bartell and Niederhausers who commented upon the apparent rigidity of the films and their possible importance in the petroleum industry. Morrell and Egloff4 had earlier attributed the extreme stability of emulsions of sea water in fuel oil to very stable asphaltic films. Numerous investigators have observed rigid films in the course of crude oil-water interfacial tension determinations by the pendent drop method. Several investigators5,6,2 have separated inter-facially active materials from crudes and attempted to characterize them chemically. Reisberg and Doscher,2 using Ventura crude, showed the interfacial tension against water (as measured by the pendent drop method) to be affected by aging, contraction and expansion of the interface, and the pH of the water. These investigators attributed the adhesion of oil to a water-wetted surface and the distortions of flow paths in glass capillaries to the presence of rigid films. Dodd7 has studied the interfacial viscosity of adsorbed films and found them to be non-Newtonian in behavior. Craighead and Harvey8 reported a series of displacements in tubes packed with 60 mesh glass beads. They interpreted the results as indicating an effect of stearic acid films on waterflood recovery and imply that natural films may produce similar results.

Jan 1, 1967

By J. C. Melrose

The contact angle is one of the boundary conditions for the differential equation specilying the configuration of fluid-fluid interfaces. Hence, applying knowledge concerning the wettability of a solid surface to problems of fluid distribution in porous solids, it is important to consider the complexity of the geometrical shapes of the individual, interconnected pores. As an approach to this problem, the ideal soil model introduced by soil physicists is discussed in detail. This model predicts that the pore structure of typical porous solids will lead to hysteresis effects in capillary pressure, even if a zero value of the contact angle is maintained. The model is generalized to situations in which the contact angle takes on values between zero and 40 degrees. For the imbibition branch of the capillary- pressure function, the model predicts a considerable departme ftom the usually assumed cos 0 relationship. In fact, according to the model, it is possible that a displaced wetting phase will not be able to reimbibe, even when the contact angle does not exhibit hysteresis. INTRODUCTION The subject of capillarity in porous media has long been of interest in many branches of engineering and applied science. The earlier investigators were those concerned with the physics of soils. 1-5 More recently, petroleum engineers and others dealing with the problems of petroleum production from reservoir rock have given much attention to the subject.6-10 Also, important additions to the literature of capillarity have been contributed from the field of chemical engineering.11-12 These attest to the wide range of industrial applications in which capillary phenomena play a role. The present paper is concerned with the role which wettability plays in capillary action in porous media. As is well known, capillary-rise (or capillary pressure) phenomena have frequently been interpreted with the aid of a model employing the concept of a cylindrical capillary tube. This approach has enjoyed a certain degree of success in correlating experimental results.13 The generalization of this model, however, to situations which involve varying wettability, has not been established and, in fact, is likely to be unsuccessful. In this paper another approach to this problem will be discussed. A considerable literature relating to this approach exists in the field of soil science, where it is referred to as the ideal soil model. Certain features of this model have also been discussed by Purcel114 in relation to variable wettability. The application of this model, however, to studying the role of wettability in capillary phenomena has not previously been attempted in detail. In the present paper, additional features of the model are introduced. These features are critical in determining the quantitative behavior of the model. GENERAL FEATURES OF CAPILLARY HYDROSTATICS BASIC PRINCIPLES When the interstices of a typical porous solid are occupied by two or more immiscible fluid phases, the fluids are microscopically commingled. Hence, fluid-fluid interfaces are found within a certain fraction of the pore openings. The fundamental equation of capillarity specifies the configuration of these fluid-fluid interfaces. This is known as the Laplace equation, when derived from mechanics, and as the Gibbs-Kelvin equation when derived thermodynamically.15 Given two fluid phases, a and ß, in hydrostatic equilibrium, the Laplace equation states that the respective fluid pressures in regions close to the interface are related by Here oaß is the surface or interfacial tension and rl and r2 are the principal radii of curvature of the surface or interface. The pressure difference, Pa-Pß, is the capillary pressure, PC. As Buff15 has shown, Eq. 1 states the condition for hydrostatic equilibrium within the two-phase confluent region, which is referred to as the interface. It thus can

Jan 1, 1966

By R. A. Flinn, R. D. Pehlke, D. R. Glass, P. O. Hays

Knowledge of the depth of penetralion of an oxygen jet into the bath of the oxygen converter and of the correlation of penetration with driuing pressuve, lance heighl, and nozzle throat area is vital to the understanding of converter operation. If the penetration is too shallow, then severe and hazardous slopping takes place. On the other hand, if the jel penetrates entirely Lhvough lhe bath for an apprcciublc period of time, bottom damage occurs. In addilion to measurement of the penetralion of the jel, knou~ledge of the circulatory movement in the bath is also of interest in order to evaluale various theories oj-concerter operating behavior which have been published. In this investigation, experimental converters were buill of IOU- , 300-, and 4000-lb capacity. Four independent methods were used to determine penelralion: the onset of bottom marking, a nitrogen bubbler probe, observation througlt an optical syslew built into the oxygen lance, and direcl viewing of the jet issuing from the bottom of the vessel. Good correlation zuas obtained, and empirical relalions for pvedicling perletration were found. These relations were conjzrmed by bottom marking tests in 55- and 110-ton vessels. Within the operaling conditions employed in these tests, the depth to which a single oxygen jet penetrated zuas found lo vary according to the relatiorl ThE technical literature is replete with data concerning the successful use of the basic oxygen furnace or converter in steelmaking. Experimental data are lacking, however, on the vital factors of the depth of penetration of the jet into the bath and the induced circulation. Commercial operating conditions usually have been the result of cut and try experiments in lance manipulation until satisfactory results were obtained. There have been, however, two hotly argued opposing theories concerning desirable depth of penetration and these are exemplified by the Schwarz and Miles patents1,2 on one hand and the Suess patent3 on the other. The Schwarz patent teaches that the jet, issuing from the nozzle at supersonic speed, penetrates deeply "so that the reactions between the iron and the oxygen and between the oxygen and the rest of the smelting components take place in the center of the bath". Specific operating suggestions are given by Miles.2 By contrast, the Suess patent calls for surface Circulalion was investigated by lour methods: by direct observation in 200-lb open baths, by the use of graphite rudders in the 300- and 4000-lb converlers, by direct observalion through an oplical system in the lance, and by various models al room temperature. All were in excellent agreement and indicated that the motion of the bath ulas up at the center, radially outluavd at the surface, and down at the sides. Experi-ments in small and in commercial vessels indicate that it is essential to operate with a jet penetration of approximately 50 pct of the bath depth. Surface blowing results in low oxygen eficienty and in hazardous conditions which may render the process inopeuable. RejYactory dartzage al the bottom of the vessel is only encountered when the jet penetrates to the bottom, and this can be avoided by properly applying the penetration formula. The application of this en/pirical formula in commercial peraations is best when limited to combinations of lance size, pressure, and height which are typically encounteved in the use of a single-hole lance. blowing so that "...the oxygen jet does not penetrate deeply into the molten metal bath and is confined to an impingement area at the central portion of the bath surface". These references are given merely to illustrate the basic differences between the two schools of thought and to point out the need for measurement of penetration for the sake of the operator. For example, it is shown later that inefficient and even dangerous conditions can arise if improper blowing conditions are used. Differences are also evident between the two schools of thought as to the mixing, circulation, and agitation which is to be accomplished by the jet. The Schwarz patent states that "surface contact is not sufficient in most cases to bring about quick reaction, the same as the blowing of the gas over the bath surface or the mere blowing of the gas onto the bath surface". The patent goes on to call for active mixing. In contrast the claims of the Suess patent call for "discharging a stream of oxygen ... to an extent to avoid material agitation of the bath by the oxygen stream". In this patent the circulation is said to be downward in the center and up at the sides of the vessel. A number of investigators4-12 have explored penetration and circulation in transparent models. In general, it is agreed in these tests that the circulation is upward at the center (along the sides of the jet cavity),

Jan 1, 1968

By M. H. Waxman, L. J. M. Smits

A simple physical model was used to develop an equation that relates the electrical conductivity of a water-saturatedshaly sand to the water conductivity and the cation-exchange capacity per unit pore volume of the rock. This equation fits both the experimental data of Hill and Milburn and data obtained recently on selected shaly sands with a wide range of cation-exchange capacities. This model was extended to cases where both oil and water are present in the shaly sand. This results in an additional expression, relating the resistivity ratio to water saturation, water conductivity and cation-exchange capacity per unit pore volume. The effect of shale content on the resistivity index - water saturation function is demonstrated by several numerical examples. INTRODUCTION A principal aim of well logging is to provide quantitative information concerning porosity and oil saturation of the permeable formations penetrated by the borehole. For clean sands, the relationships between measured physical quantities and porosity or saturation are well known. However, the presence of clay minerals greatly complicates log interpretation, particularly the electrical resistivity and SP logs, and considerably affects evaluation of hydrocarbon-bearing formations. The conductance and electrochemical behavior of shaly sands and their relation to log interpretation have been studied by many workers. wylliel and Lunch2 reviewed this work in some detail. Virtually all laboratory measurements of electrical resistivity and electrochemical potential of shaly sands published to date are the work of Hill and Milburn.3 Their measurements were made on about 300 cores covering a large variety of sedimentary rocks, and a wide range of equilibrating NaCl solution concentrations. Hill and Milburn described their conductivity data by an empirical equation in which the shaly sand conductivity Co was expressed as a function of the solution conductivity C and two parameters b and F01 . The quantity b was shown to be a measure of the effective clay content of the rock, being approximately proportional to the cation-exchange capacity of the rock divided by its pore volume. The latter ratio is designated as 9, in this paper and has the dimensions meq/ml or equiv/liter. Qv is identical with the term representing the concentration of fixed charges in the Meyer-Sieved and Teorel15 theory of permselective membrane behavior. F01 is a formation resistivity factor referred to a hypothetical equilibrating solution resistivity of 0.01 ohm m at 25C,* where clay effects presumably are minimized. F01 was correlated to porosity by an Archie-type equation.6 The Hill-Milburn equation describes their data with a standard deviation of approximately 1 percent and a maximum deviation of + 10 percent. Shaly sands behave as permselective cation-exchange membranes, their electrochemical efficiencies increasing with increasing clay content. The electrochemical potential data of Hill and Milburn were expressed graphically, and demonstrate that the membrane efficiency (or cation transport number) of these sands is a function only of the b value (i.e., Qv) and the respective salt concentrations of the two solutions forming the liquid junction in the sand. The diffusion potentials are not dependent on F01 or any parameter relating to the porosity or pore geometry of the rock. The Hill-Milburn resistivity equation correctly predicts a decreasing sand conductivity Co with decreasing solution conductivity C?. However, at some low value of C,, the calculated Co-C, function goes through a minimum; with further decrease in C?, the predicted sand conductivity increases sharply. As pointed out by Hill and Milburn, an increasing value of Co with decreasing C, is physically meaningless. Since this occurs below the range of practical values of C,, the usefulness of the empirical equation is not affected when

Jan 1, 1969

By Robert H. Richards

The extent to which sizing by sieves should be carried, as a preliminary to the separation, by jigging, of minerals of different specific gravities, has been a matter of controversy for many years. The subject has been investigated by several authorities, yet the ground does not seem to have been completely covered, nor are the questions involved entirely settled. For my present purpose I shall refer to but three investigators—Rittinger, Munroe, and Hoppe. In seeking additional light, I have gone over part of the old ground which has been considered satisfactorily settled; and since these preliminary tests have thrown light on some points, they have been included in this paper. In the investigations here described, I have confined myself, for several reasons, wholly to small sizes—grains of 0.1 inch in diameter and less. Rittinger's work was mainly done upon larger sizes, and there is much need among millmen of information concerning the smaller sizes. Moreover, these sizes brought the investigation within the means at my disposal. The laws that have been claimed as the laws of jigging by the several authorities are: 1. The law of equal-settling particles. 2. The lam of interstitial currents. 3. The law of acceleration. 4. The law of suction. The first of these has been considered by investigators, generally, to be the most important of all, and the larger part of the work of jigging is thought to be governed by it. But that it does not cover the whole of jigging is clear to all; and to account for the increased efficiency which we may call the extra jigging-catch, the other three laws have been advanced. The investigation described in this paper was undertaken to determine, as far as possible, to what extent each of the four laws con-

Jan 1, 1895

ALBERT SAUVEUR, Chairman. A. A. STEVENSON, Vice-Chairman. HERBERT M. BOYLSTON, Secretary, Abbot Bldg., Cambridge, Mass. John Birkinbine, William Kelly, J. S. Unger, William H. Blauvelt, Charles Kirchhoff, Felix A. Vogel, James Gayley, Richard Moldenke, Leonard Waldo, Henry D. Hibbard, Joseph W. Richards, William R. Walker, Henry M. Howe, C. F. W. Rys, William R. Webster, Robert W. Hunt, E. Gybbon Spilsbury, Frederick W. Wood. J. E. Johnson, Jr., The innovation of a special meeting under the auspices of the Iron and Steel Committee was well justified, if we accept as a criterion the number of papers presented at the meeting held on Oct. 16 and 17 in New York and the attendance at that meeting. Twenty-four papers were read, and most of these were widely discussed orally, while doubtless the written discussions will be even larger in extent. Discussions will be received up to Dec. 1, 1913. The attendance at the meeting of 106 members and 75 guests is an evidence of the wide anti growing interest in the Institute of men interested chiefly in iron and steel. It is especially interesting to note this large attendance at a meeting where very little of a social nature was introduced into the program. An informal dinner for the men at the Engineers' Club closed the meeting. At this dinner were present about 70 members and guests. One of the Vice-Chairmen and the Secretary of the new Committee on Petroleum and Gas told of the important plans in prospect of that Committee. Brief impromptu speeches by a considerable number of the members and guests were enjoyed. Professor Marburg reiterated his previous assertion that he believed that the Institute and the American Society for Testing Materials, as well as some of the other technical societies, were all fighting for one good cause; that there was room in the field for all of these societies with their various points of view; and that they should march shoulder to shoulder. The success of this dinner was due largely to the efforts of Mr. Johnson who had the affair in charge.

Jan 11, 1913

By Edward W. Parker

This plant was built in 1907 at the Bankhead mines to manufacture briquettes by the Zwoyer process under license from the Zwoyer Fuel Co., of New York, N. Y. The building was constructed to contain two units, each of a capacity of 10 tons per hr.; one unit was installed at the time the building was constructed, and the second unit is now being built. The coal used is an anthracite, which is more friable than that of Pennsylvania, and, as a consequence, a larger percentage of dust or waste is produced, which was formerly thrown upon the slack-pile as waste, but is now passed to the ? dust-bin " in the breaker, from which it is conveyed to the briquette-plant.

Jan 5, 1908

By Eckley B. Coxe

The subject of this paper will be treated as briefly as possible under the following heads : I. The latest designs of some of the machinery used at these collieries in the preparation of coal. 11. The means employed for elevating, conveying and transporting the coal and slate in and about the breaker. 111. The means employed for raising the coal from the mines to the top of the breaker. IV. The iron breaker as a structure. V. The preparation of the coal as effected in the iron breaker. A key to the plates and the letters and numbers designating different parts, will be found at the end of the paper. I. Preparing Coal. Anthracite coal as it comes from the mines is not marketable. The "run of mine" cannot, as in the case of bituminous coal, be sold. Anthracite, being very compact and practically free from volatile combustible matter, burns only at the surface, and it is, therefore, deemed important to have the lumps as nearly of a uniform size as possible, so that between them a large amount of surface will remain exposed to the action of the air without checking the draught too much, or allowing enough air to pass to cool the coal below the ignition-point, In other words, if the pieces of coal of the size of a chestnut and smaller are mixed with lumps of the size of an egg they fill the air-passages and prevent a free draught. It has long been recognized, therefore, that one of the most important points in preparation is to have a uniform sizing, and also to make as large a number of different sizes as can be produced without too

Jan 1, 1891