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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 Kenneth E. Gray

The turbulent flow drag coefficients, or friction factors, have been experimentally determined for the cut-tings normally encountered in drilling operations. The gas law and average drag coefficients for characteristically flat particles (limestones and Shales) and for angular to sub-rounded particles (sandstones) were used to extend Newton's equation to a more useful form. The resulting equations are expressions for the slip velocity of a particle as a function of the particle size and shape, the bottom-hole injection Pressure, and the Bottom-hole temperature. The velocities necessary to lift actual rock cuttings as observed in the laboratory were compared with velocities predicted from the derived equations. Results indicate that there is no single correct circulating velocity and that the commonly used 3,000 ft/min linear velocity may he sufficient to lift only very mall particles. The advantage, in terms of horsepower requirements, of cycling high pressure air to obtain lower compression ratios was shown. INTRODUCTION A promising departure from standard rotary hydraulic drilling is air or gas drilling. In many instances the rate of penetration and bit life increases resulting from this method have been very substantial. Further the application of air drilling in areas of lost circulation or water sensitive pay zones has been highly successful. Purpose For the drilling contractor, the practical question remains, "How much air pressure and volume should I have?' lt is necessary to have a reasonable knowledge of the air velocities and pressures required in air drilling operations for the proper design and most advantageous use of surface equipment and for adequate removal of cuttings from the borehole. Eased on experience, most operators agree that at least 3,000 ft/min linear velocity is necessary for satisfactory hole cleaning.' It was the purpose of this investigation to evaluate the drag coefficients, or friction factors, for the cuttings normally encountered in drilling operations, i.e., sandstones, limestones and shales, and to utilize the values obtained to develop an expression for the minimum velocities and pressures (hence the volumes) necessary to lift these cuttings. THEORY Several investigators have done extensive work on the ability of drilling mud to lift bit cuttings. They conclude that the ability of a drilling mud to lift cuttings is dependent on the density difference between the rock being drilled and the drilling mud, the cutting size and shape, the mud flow constants, and the flow state (laminar, transitional or turbulent) of the mud. However, drilling muds are not true fluids but have a variation of viscosity with velocity in laminar flow and a constant apparent viscosity in turbulent flow. A survey of the literature revealed that no experimental work had been done to determine the velocities necessary to lift actual rock cuttings using a compressible fluid such as air or gas. In 1953, Nicolson6 stated that in air drilling fluid mechanics the particles could be assumed spherical in shape and that ; constant drag coefficient of 0.5 could be used due to the highly turbulent flow of the circulating air. By equating the turbulent resistance on the particle to the gravitational force on the particle, he obtained the expression, ^ = 2.67^y ,.......(1) where V, is slip velocity of spherical particle, ft/sec; D is particle diameter, in.; p, is particle density, 1b/ft8; and p, is fluid density, lb/ft3. However, as stated earlier, most operators seem to agree that adequate hole cleaning can be obtained by circulating a sufficient volume of air to give a linear velocity of 3,000 ft/rnin in the annular space. Basic Equation The velocity with which a solid particle freely falls through a fluid will increase until the accelerating force, gravity, is equal to the resisting forces, buoyancy due to the fluid displaced by the particle and friction due to the relative motion of the particle through the fluid. When the accelerating and resisting forces become equal,

By J. L. Tomlinson, B. D. Lichter

Electrical resistivities 01 liquid Cd-Bi, Cd-Sn, Cd-Pb, In-Bi, and Sn-Bi alloys were measured using an electrodeless technique. The resistivities ranged from 50 to 160 microhm -cm, temperature dependences were positive, and no sharp peaks in the composition dependence of the resistivity were observed. On the basis of these observations, it was concluded that the alloys are typical metallic liquids. The electron con-cent9,ation was calculated from the measured resis-tizlity and available thermodynamic data using a model which attributes electrical resistivity to scattering by density and composition flzcctuations. A correla-tion was shown between the departure of the electron concentration from a linear combination of the pure component valences and the value of the excess integral molar free energy. Calculation of the temperature dependence of the electrical resistivity showed a need for more detailed thermodynamic data in these systems and led to suggestions for improvement in the concept of residual resistivity in the fluctuation scattering model. THE electrical resistivity of liquid metals provides information regarding interatomic interactions and their effects upon structure. In this experiment an electrodeless technique was used to measure the electrical resistivities of liquid alloys of Cd-Bi, Cd-Sn, Cd-Pb, In-Bi, and Sn-Bi, and the results were used with thermodynamic data to calculate a parameter which reflects the tendency toward localization of electrons due to compositional ordering. It was found that the resistivities of these alloys are generally metallic in magnitude and temperature dependence. The electrical and thermodynamic properties are discussed in terms of the fluctuation scattering model'22 which supposes that the electrical resistivity arises from scattering due to a static average structure and departures from the average due to fluctuations in density and composition. Further, this model is compared with the pseudopotential scattering model of Ziman et al.3-5 EXPERIMENTAL PROCEDURES Alloy samples were prepared from 99.999 pct pure elements obtained from American Smelting and Refining Company (except tin which was obtained from Consolidated Smelting and Refining Company.) J. L. TOMLINSON, Member AIME, formerly Research Assistant Division of Metallurgical Engineering, University of Washington, Seattle, Wash., is now Physicist, Naval Weapons Center, Corona Laboratories, Corona, Calif. 0. D. LICHTER, Member AIME, is Associate Professor of Materials Science, Department of Materials Science and Engineering, Vanderbilt University, Nashville, Tenn. This work is based on a portion of a thesis submitted by J. L. TOMLINSON to the University of Washington in partial fulfillment of the requirements for the Ph.D. in Metallurgy, 1967. Manuscript submitted May 31, 1968. EMD Weighed portions were sealed inside evacuated silica capsules, melted, and homogenized before the resistivity was measured. The resistivity of a liquid alloy was measured by placing the sample inside a solenoid and noting the change in Q. According to the method of Nyburg and ~ur~ess,~ the resistivity of a cylindrical sample may be determined from the change in resistance of a solenoid measured with a Q meter as T7--5--W =R7JT^ ='Kc-lm(Y) [1] where L, R, and Q = wL/R are the inductance, series resistance, and Q of the solenoid. The subscript s refers to the solenoid with the sample inside; the subscript 0 refers to the empty solenoid. Kc is the ratio of the sample volume to coil volume and y = 2 [bei'0(br)-j ber'o(br)~\ br\_bero(br) +j bei0 (br) expressed with Kelvin functions which are the real and imaginary parts of Bessel functions of the first kind with arguments multiplied by (j)3'2. The argument of the function Y is hr where r is the sample radius and b2 = po~/p, i.e., the permeability of free space times 271 times the frequency divided by the resistivity in rationalized MKS units. Since Eq. [I] cannot be solved explicitly for p, values of Kc. lm(Y) were tabulated at increments of 0.1 in the argument by. A measurement of Q, and Q, determined a value of Kc . lm (Y) and the corresponding value of br could be read from the table. From the known r, uo,, and w, the resistivity, p, was determined. The change in Q was measured after letting the encapsulated Sample reach equilibrium inside a copper wire solenoid. The solenoid was contained in an evacuated vycor tube in order to retard oxidation of the copper while operating at high temperatures and heated inside a 5-sec-tion nichrome tube furnace capable of obtaining 900°C. Temperature was determined with two chromel-alumel thermocouples, one in contact with the solenoid 30 mm above the top of the sample and the other inserted in an axial well at the other end of the solenoid and secured with cement so that the junction was 2 mm below the bottom of the sample. Temperature readings were taken with respect to an ice water bath junction, and the voltage could be estimated to the nearest thousandth of a millivolt. The lower thermocouple was calibrated by observing its voltage and the Q of the coil as the temperature passed through the melting points of samples of indium and tellurium. The upper thermocouple reading was systematically different from the lower thermocouple reflecting the temperature difference due to a displacement of 60 mm axially and 6 mm radially. Calculations show that the gradient over the sample was less than 2 deg. Q was measured by reading a voltage related to Q from a Boonton 260A Q meter with a Hewlett Packard

Jan 1, 1970

By J. Husson, R. Iffly, M. Gondouin

A systematic variation of well deliverability, as reflected from isochronal back-pressure tests performed at regular intervals, has been observed in some gas condensate wells producing at high rates. The same effects have been obtained using a numerical model of gas and condensate flow which takes into account secondary gasoline deposited in the pore space as a result of pressure reduction, and non - Darcy flow of gas in the vicinity of the wells. Matching calculated values with previous test results has been possible, and future predictions have been obtained. An application of this method to the Hassi Er R'Mel gas-condensate field in Algeria is tentatively shown. INTRODUCTION Flow capacity of gas wells is generally derived from an analysis of back-pressure tests. The empirical equation q = C (?p2)n used by Rawlins and Schellhardtl can be derived rigorously assuming that steady-state radial flow of a dry gas of constant viscosity and compressibility is established during each flow period of the well tests. Furthermore, when Darcy's law applies in the entire flow region, the theory predicts that the exponent n is equal to 1. In low-permeability reservoirs, it was soon discovered that the time required to reach a stabilized flow often exceeded the duration of the flow periods normally available for testing wells. Consequently, transient gas flow had to be considered instead of the steady-state assumption previously used. This led to the isochronal testing procedure established by Cullender2 which has largely replaced conventional back-pressure testing. For dry gas fields, this method yields definite values of C and n equivalent to those of the empirical equation. These values should remain constant for each well as long as the permeability of the formation and the characteristics of the gas (viscosity and compressibility) do not change appreciably. This is the case when reservoir pressure remains -close to the original value and when the formation near the wellbore remains free of plugging. Under those conditions, stabilized flow potential curves of gas wells can be established from a single sequence of isochronal flow and shut-in periods. An analysis of a pressure build-up following a longer production period provides additional data on the transmissivity (k h/ u) of the reservoir, and eventually on the 'drainage radius rd of the well, which can be related to the value of C so that future performance of the well can be predicted using the concepts developed by A. Houpeurt.3 At high flow rates, Darcy's law no longer applies in the vicinity of the wellbore, and inertial effects in the high velocity gas flow introduce additional pressure drops. As a consequence, exponent n of the backpressure tests becomes smaller than 1, and a slight curvature of the log-log plot of ?p2 vs q can be predicted when going from very low to high rates of flow (Elenbaas and Katz).5 The effects of variations of viscosity and compressibility with pressure on the radial flow of dry gas in an infinite reservoir were taken into account by Jenkins and Aronofsky.7 Numerical solutions of the transient flow of an ideal gas in finite radial reservoirs were presented by Bruce, Peaceman, Rachford and Rice.8 In the case of gas condensate wells, however, the presence of gasoline in the pore space as soon as reservoir pressure is reduced below the dewpoint pressure further complicates the interpretation of flow tests so that the prediction of stabilized well performance becomes very difficult. Field observation shows that both C and n derived from isochronal tests vary in time, even when reservoir pressure has not changed appreciably. Such a variation cannot be attributed to any change of the gas characteristics, and must result from the effect of a gasoline saturation on the gas flow.

By David C. Jonson, W. Bruce MacKenzie, Arthur A. Bookstrom, Vaughn E. Surface, Neil K. Muncaster, Stewart R. Wallace

In mid-Tertiary time a wet silici-alkalic magma penetrated the Precambrian rocks of what is now the Tenmile Range of Central Colorado and formed the Climax Stock. The stock is a composite one and was intruded in four separate irruptions, each giving rise to a major hydrothermal event. The first three of these produced large stockwork ore bodies that cap and flank the tops of their respective source intrusives; the fourth, and last, yielded almost no commercial mineralization. The ore bodies and their related zones of alteration are circular to ring-shaped in plan and arcuate in section. The different phases of the stock are so positioned with respect to each other that many of the circular and arcuate zones of mineralization and alteration overlap or are juxtaposed. Evidence of a time separation between the different ore bodies is found in certain dikes that were intruded between periods of mineralization and are well mineralized in one ore body but are barren in another. If it is assumed that the parent magma at Climax contained 10 per cent "water," that the "water" contained 0.1 grams per liter of molybdenum, and that the processes of extraction were 100 per cent efficient, then approximately 10 cubic miles of magma would be required for the formation of each ore body. The volume requirements, taken in conjunction with the cross-sectional areas of the different phases of the stock to explored depths, suggest to the authors that each magma chamber was columnar, extended to a depth of thousands of feet, and was connected with a much larger master reservoir. The repetition of similar intrusive, structural, and hydrothermal events, indicates periodic tapping of this reservoir. A regular chemical evolution of the parent magma is suggested by the systematic change in metal ratios and differences in the sites of deposition, relative to the source intrusive, in each of the four separate igneous hydrothermal stages. The preparation of ground was due to changes in magmatic and/ or hydrothermal pressures within the igneous-hydrothermal columns; small, repeated, up and down movements of the rock enclosing the tops of the columns formed the stockwork fractures into which the mineralizers penetrated. The forceful emplacement of each successive phase of the Climax Stock resulted in a slight doming and rotation to the westward of the earlier-formed geologic features. Postore normal displacement along the Mosquito fault is estimated at about 9000 feet. Part of one ore body was cut by the fault and lies at depth below the Paleozoic sedimentary strata on the hanging wall. On the footwall side of the fault, subaerial erosion and glaciation removed a large part of one ore body and uncovered the top of a second.

Jan 1, 1968

By Milton E. Wadsworth, W. Martin Fassell, William H. Dresher

A study of the rate of dissolution of molybdenite (MoS2) in alkaline solution was carried out under carefully controlled conditions. Effects of temperature, oxygen over-pressure, and KOH concentration were evaluated. Studies were made in the temperature range 100°C to 175°C and in the pressure range 0 to 700 psia of oxygen. Under these conditions molybdenite was found to leach according to a linear mechanism. Both oxygen over-pressure and KOH concentration were found to control the rate of leaching. The mechanism has been explained in terms of adsorption of oxygen at the molybdenite surface followed by configurational rearrangement of the adsorbed molecules. The hydroxyl ion dependency is believed to be diffusion-controlled. Laboratory batch studies have shown that molybdenite can be readily dissolved in alkaline solutions under moderate conditions of temperature and pressure. Commercial application of this process to the production of ferro-molybdenum and molybdenum chemicals is promising in view of the ease of dissolution of molybdenite and the relatively noncorrosive conditions involved in the process. HIGH temperature-high pressure techniques have long been used to great advantage in the organic chemical industry, the petroleum industry, and the paper industry. Only recently, however, have these methods been used to extract metals from their ores on a commercial scale. The Chemical Construction Corp., together with interested producers of nickel and cobalt, has done much to develop methods of producing nickel and cobalt powders by the use of high temperature-high pressure techniques.' The Howe Sound Co. is currently operating a plant near Salt Lake City in which the new Chemical Construction Corp. technique is applied to cobalt-arsenic sulfide concentrates. In this method the concentrates are leached in a dilute solution of sulfuric acid under air pressure at a high temperature. Near Edmonton, in Alberta, Canada, the Sherritt Gordon Co. is also using the new method in conjunction with its ammoniacal leach process.' National Lead Co., at Fredricktown, Mo., is operating a process similar to that of Howe Sound. In spite of the rapid growth of high temperature-high pressure hydrometallurgical processes, there has been very little work done on fundamental principles involved in this type of process. Conse- quently the literature lacks any significant data in this field. Oxidation of pyrite,3 phalerite,4 galena,5 and recently molybdenite" in alkaline solutions has been reported to some extent. This investigation was initiated, therefore, to broaden the application of high temperature-high pressure hydrometallurgy and also to contribute some insight into the basic mechanisms of oxidation in an aqueous medium under these conditions. In addition to the immediate consequences of these processes much valuable information remains to be learned about fundamental reactions when they are carried out at temperatures and pressures slightly higher than those normally encountered. Leaching of molybdenite by alkaline solutions under oxygen pressure has recently been reported in the Russian literature by E. S. Usataya,8 who found that leaching rate increased with an increase in the pH of the solution—the strongest effects being observed at a pH of 10—and also with an increase in temperature. Usataya also has reported the formation of a protective film on the surface of the molybdenite when the leaching solution was weakly alkaline, neutral, or acidic. He believes that this oxidation process explains the migration of Mo+ + in the oxidation zones of molybdenite ore deposits and the subsequent impoverishment of the ores. Equipment: The high temperature-high pressure reaction unit used in this work was especially designed for kinetic studies of this nature, emphasis being placed on accuracy of measurement and precision of control. As details of the unit's construction and operation have been discussed elsewhere,7 Only basic features and principles of operation will be discussed at this point.

Jan 1, 1957

By William I. Watson

Problems encountered in beneficiating mineral raw materials become increasingly difficult as there is a shift to lower grade and more complex raw materials, and because of the economic need to strive for ever higher recoveries, higher grade products, and lower processing costs. Methods of attacking the many problems should include not only the familiar chemical and physical tests and equipment, but such techniques as X-ray analysis, infra-red analysis, differential thermal analysis, and the use of electron and X-ray microscopes. Many people in the mineral-treating field are unfamiliar with these newer methods and techniques. The differential thermal analysis method, in particular, does not seem to be very well known, even though it offers interesting possibilities in the study of many ore treatment problems.

Jan 7, 1959

By S. S. Marsden, S. H. Raza

An experimental study of the flow of line-textured. aqueous foams through Pyrex tubes is described. The foams range in quality F (ratio of gas volume to total volume) from 0.70 to 0.96 and behave like pseudoplastic fluids. At lower flow rates they exhibit laminar flow ad have apparent viscosities which increase with quality, and which cover a range of 15 cp to 255 poise for tubes of 0.25- to 1.50-mm radius rj. At higher flow rates a plug-like type of flow is developed, the extent of which increases with both T and ri. When the same foams flow through either open or packed Pyrex tubes, remarkably high streaming potentials ?E are often generated. These can easily reach 50v if nonionic foaming agents are used, but are at least an order of magnitude less for ionic foaming agents. A linear relationship between ?E and the pressure differential ?p is observed; this usually extrapolates to positive values of ?p at ?E of zero. The slope of the line increases with both F and ri. An equation was derived to describe the streaming potential of non- Newtonian fluids in circular tubes and was used to correlate experimental results. The calculated < potentials are of the right order of magnitude. INTRODUCTION Foams are both unusual and inniguing in their physical properties, and have been the subject of many scientific studies. However, present knowledge of foams is still fragmentary, specific and often contradictory. Apparent viscosity of foam is the physical property of greatest interest to both rheo1ogists and engineers. sibreel reported that the apparent viscosity decreased with increasing shear rate in a manner similar to some non-Newtonian fluids. Penny and Blackman2 reported that fire-fighting foams had both a limiting shear stress and a tensile yield stress. There is little doubt that some foams at least behave like non-Newtonian fluids, and have apparent viscosities considerably higher than those of either constituent phase. The high apparent viscosity of foam with its concomittant effect on mobility ratio and sweep efficiency no doubt prompted several attempts by research groups to use foam as a displacing agent in porous media. Based on recent experience, most of these groups probably succeeded in completely blocking fluid flow in the porous media and then abandoned their efforts. Two groups apparently found the successful combination of experimental parameters at about the same time.3,7 Others have recently added to our knowledge of foam flow in porous media and its use as a displacing agent.8-13 An experimental problem encountered by Fried3 was a transient blockage of foam flow in porous media when distilled water was used to prepare the foam-producing solution. Fried surmised that this was due to an electrokinetic effect and he eliminated it by using electrolytes in preparing foaming solutions. He also measured the streaming potential of a number of foams in capillary tubes which he found to be appreciably higher than those obtained when the constituent liquid flowed under comparable conditions. This paper presents results of a more comprehensive study of the streaming potential generated by aqueous foam flowing in both open and packed Pyrex tubes. It also adds to knowledge of the rheology of these foams as deduced from their flow behavior in open tubes. APPARATUS AND PROCEDURE A diagram of the apparatus used is shown in Fig. 1. Details of its construction, testing and use are described elsewhere.14 Careful selection of materials, extreme cleanliness and rather elaborate electrical insulation and shielding were necessary to obtain reproducible results (±5 percent). Both streaming potential and streaming current were measured with an electrometer. The design of the foam generator developed for this work is novel (Fig. 2). It will produce uniform fine-textured foams at pressures sufficiently

By H. D. Outmans

Present first-order theory for frontal stability and viscous fingering of immiscible liquids is improved by including the nonlinear terms in the equations describing conditions at the interface of the liquids. This leads to the revision of several conclusions which were based on first-order theory. They concern the growth rate and changing shape of a sinusoidal disturbance, particularly in relation to the wave number of this disturbance. Nonlinear aspects of effective interfacial tension are discussed and it is shown that this tension is not simply a positive proportionality constant in a linear relation between pressure difference and curvature at the interface. Scaling requirements are determined from the dimensionless groups which govern fingering. Gravity and interfacial tension invalidate a previously formulated conclusion that the shape of a finger after a given displacement is independent of the displacement velocity. Also, similarity of fingering (and, hence, of sweep efficiency in case of an unstable front) requires geometrical similarity of the initial disturbance in the model and the reservoir with a scale factor which is the same as the one for scaling down the dimensions of the reservoir. INTRODUCTION The critical velocity at which the transition zone in the vertical displacement of immiscible liquids becomes unstable was calculated by ill. More recently, the same was done for nonvertical displacements and it was also shown that the stability is affected by an effective interfacial tension between the liquids. 2-4 Although in the oil reservoir a stable front is always desirable from a recovery point of view, the necessary velocity may have to be so low that the corresponding production rate is not economical. In that case, a knowledge of the fingering unstable front is necessary for predicting recovery at break- through. Studies in this direction have not gone beyond the very moment at which fingering first occurs.5,6 Conclusions about stability and fingering in these references are all based on linear theory. In this theory the nonlinear terms in the equations describing conditions at the front are neglected. The usual justification for this lack of mathematical rigor is that the nonlinear terms can be made small relative to the linear terms and, supposedly, small causes produce only small effects. It has been recognized, however, that this is not necessarily true in the nonlinear problems of hydrodynamics.7 The hydro-dynamic stability and fingering of the front between two liquids, accelerated in a direction normal to the front, for instance, is strongly influenced by the nonlinearity of the boundary conditions.8-10 Since these boundary conditions are not unlike those arising in the problem of stability and fingering of the front during a slow immiscible displacement in porous media, it was thought that there, too, the nonlinear terms should be taken into consideration. A summary of the results obtained in linear theory and a comparison with experimental data precede the nonlinear theory developed in this paper. This summary serves to introduce some quantities which will be used in the further develop ment. It should also be pointed out that the method of higher-order approximation by which the nonlinear stability problem is solved has application in other reservoir studies.11 SUMMARY OF LINEAR THEORY 1. A plane interface remains stable if its velocity is smaller than a critical velocity. vc = (p2-p1)gn/(l/A2- l/A1 .........(1.1) This equation is derived for uniform flow in a thin layer inclined to the horizontal plane. The displacement takes place in a direction normal to the intersection of this layer and the horizontal plane. The undisturbed (line) interface is normal to the velocity. Fluid 1, the upper fluid (gas), is displacing Fluid 2 (oil). (VcQS would be the injection rate in cc/

By R. F. Mehl, R. W. Parcel

THE rate of the decomposition of austenite in eutectoid steels, forming only pearlite, may be expressed fundamentally in terms of the rate of nucleation and the rate of growth of pearlite nodules. This matter has received much attention in recent years. (The basic references are listed in ref. 1; references of particular import to the present work will be given separately.) Systematic data have been developed for plain carbon eutectoid steels.:! Although the physical factors affecting the rate of nucleation, N, in case of plain carbon steels have presumably been identified, they cannot as yet be evaluated quantitatively.&apos; Several somewhat successful attempts, however, have been made to calculate the rate of growth, G. In the latter case the important factors determining the edgewise growth of pearlite have been assumed to be: 1—the interlamellar spacing; 2—the concentration extremes and concentration contours of carbon in austenite in front of the growing pearlite interface; and 3—the rate of diffusion of carbon in austenite.* The only systematic data on N and G for pearlite in alloy eutectoid steels are those for Co-steels;6 there are no data on alloy eutectoid steels in which the alloying element is known to decrease the rate of formation of pearlite, apart from a few scattering data reported earlier&apos; for steels containing manganese. This paper reports a systematic study of N and G for eutectoid alloy steels containing molybdenum and nickel, respectively. In order to provide information of help in understanding the results, new data are presented on the effect of molybdenum on the interlamellar spacing of pearlite, So; data on the effect of nickel on So have already been published.&apos; The alloys used were in five groups: 1—Pure Fe-C-Mo alloys (Table I) were supplied by the Climax Molybdenum Company of Michigan, Detroit. They were made from Armco ingot iron of standard analysis, Acheson graphite, and ferro-molybdenum, melted in silica-lined crucibles in a high frequency induction furnace. The ferromolyb-denum was added to the melted steel, followed in 5 min by 0.08 pct Al. The ingot as-cast measured 23/4x 31/4x10 in.; it was hot-forged at 1150°C to a bar 1 in. sq.

Jan 1, 1953

By Norman P. Goss

The Chairman.—Thank YOU, Mr. Goss Gentlemen, I believe we have heard one of the finest papers, especially since Mr. Goss has been very generous in his frank discussion of continuous casting. One point he has brought out which 1 think some of us have not thought through to the same extent that he has—that the continuous casting process offers the small producer an opportunity to compete with the larger, more conventional and presumably better established industries. The meeting is now open for discussion. Are there any questions concerning the first two papers? J. A. Malone.*—I should like to ask Mr. Goss whether there is any special problem involved in the first part, the upper part of the mold before he gets to the first graphite lubricant area. N. P. Goss.—You mean in the forming chamber where chilling first takes place? J. A. Malone.—Yes. N. P. Goss.—So far I have not had any trouble in this part of the setup. My only

Jan 1, 1945

By R. S. Rickard, H. D. Peterson, J. D. Miller, M. C. Fuerstenan

Pure chrysocolla is floated with chelating agents that form insoluble complexes with copper at ambient temperature. Complete flotation is obtained with potassium octyl hydroxamate as collector at pH 6. Flotation response is enhanced with increased temperature when low additions of hydroxamate are involved. A natural ore was floated with 0.4 1b per ton octyl hydroxamate at pH 6.5 and 58°C, and a flotation recovery of 76% was obtained with a concentrate grade of 31.6% copper. The flotation characteristics of the oxide copper minerals, malachite, azurite, and cuprite, have not presented the difficulty for concentration as have those of the copper silicate, chrysocolla. The copper carbonates and oxides respond reasonably well to flotation with conventional collectors, whereas chrysocolla will not respond to flotation with fatty acids or xanthates under normal flotation conditions. In this view then, other reagents will have to be devised to function as collectors for chrysocolla. The most obvious general class of reagents for this purpose would seem to be the organic copper chelating compounds. The utility of chelating agents as collectors in flotation systems has already been demonstrated. For example Vivian1 has floated cassiterite using ammonium nitrosophenylhydroxylamine. Holman2 studied the flotation of nickel oxide ores with dimethylglyoxime and also suggested the use of taurine on oxidized lead ores. A rather detailed study on the application of certain chelating agents to some flotation systems was presented by Gutzeit.3 This work indicated that the formation of surface insoluble chelates is probably responsible for flotation in many cases. The role that soluble chelating agents assume was also presented, that is with effective removal of polyvalent cations by complex formation, effective depression of quartz can be obtained. DeWitt and Batchelder4,5 have shown that oximes function well as collectors for chalcocite, malachite, azurite, and cuprite. Ludt and DeWitt6 have presented the possibility of using dyes, such as octyl malachite green, as a collector for chrysocolla. These works presented by DeWitt et al suggest that organic copper chelating compounds offer considerable promise for concentrating chrysocolla, but that the most suitable chelating reagent from the standpoint of cost and flotation response has yet to be determined. The present investigation was undertaken to study the flotation response of chrysocolla to selected copper chelating compounds, that is ethylenediamine, hexamethylenetetramine, potassium octyl hydroxamate, dimethylglyoxime, and benzoin a-oxime. EXPERIMENTAL MATERIALS Chrysocolla: The chrysocolla used in the microflo-tation studies was from New Mexico and analyzed 20.8% copper. X-ray diffraction showed this material to be amorphous in character, but some faint lines of quartz were noted. A natural oxide copper ore from Utah was also used in the investigation. This ore contains malachite principally but also contains chrysocolla and tenorite together with some sulfide copper. The sulfide copper comprises from 15 to 20% of the total copper content of the ore. Water: Conductivity water was used in the microflo-tation experiments, while Golden tap water was used in the experiments with the natural ore. Reagents: Reagent grade n-amyl alcohol was used as frother in the experiments with pure mineral, while MIBC was used in the work with the ore. Ethylenediamine, hexamethylenetetramine, dimethylglyoxime and benzoin a-oxime were reagent grade in quality. Pure potassium octyl hydroxamate was prepared as follows: 1) 1.0 mole of KOH in 140 cc of methanol was combined with 0.6 mole of hydroxyl-amine hydrochloride in 240 cc of methanol at 40°C (KC1 precipitates under these conditions and to effect complete removal of KCl, the system was cooled to 10°C and filtered), 2) a light methanol wash was then given the KC1 cake, 3) the filtrate was agitated at room temperature and 0.33 mole of the methyl ester of the organic acid (i.e. methyl octanoate) was

Jan 1, 1965

By T. W. Healy, P. Somasundaran, K. Ananthpadmanabhan

Hydrolyzable surfactants such as fatty acids and amines undergo, in addition to micellisation and precipitation, various associative interactions in aqueous solutions to form ionomolecular complexes such as acid-soap, dimers, etc., depending upon the solution conditions such as pH. The interaction of these collector species with the mineral surface and with other dissolved species in solution will play a significant role in determining the interfacial processes such as adsorption and flotation. Marked differences in the hydrophobicity imparted to the mineral surface depending upon the solution conditions such as pH can be attributed to possible differences in surface activities of the foregoing complexes. This aspect of solution chemistry of flotation system is discussed here for two widely used collectors, namely, oleic acid and dodecylamine. Equilibrium species distribution diagrams, based on the available literature data and on estimates of energy of interactions between molecules, have been obtained for oleic acid and dodecylamine solutions.

Jan 1, 1980

By AIME AIME

THE Coal Division holds its fall meeting in the Pocahontas coal field, at the West Virginian Hotel, Bluefield, W. Va., Oct. 9 and 10. The first day will be a busy one-two sessions for the presentation of papers and a dinner in the evening. Hon. E. Fudge, Assistant Undersecretary, Mines Department, and R. V. Wheeler, head of the Mines Research Board of Great Britain, will be the guests of the Division. Mr. Wheeler will discuss the British Mining Act as relates to the coal industry. George S. Rice, Chief Mining Engineer, U. S. Bureau of Mines, will present an account of the recent meeting at Buxton in England, of representatives of England, Germany, France, Belgium and the United States to formulate a plan and to correlate research work now in progress in the various countries. The second day the members will be the guests of the operators on a trip through the Pocahontas field. The work of preparation for the meeting is being actively pushed by committees headed by T. H. Clagett, R. M. Lambie and H. D. Smith, and a good attendance, both local and from the general membership of the Division, is anticipated. Because many will make the trip by car the principal automobile as well as rail-road connections to Bluefield are given here. The program for Friday, Oct. 9, follows:

Jan 1, 1931

New York Meeting, October 16 and 17, 1913.-The One Hundred and Sixth meeting of the Institute for the reading and discussion of professional papers will be held in New York City, on Thursday and Friday, October 16 and 17, 1913. Headquarters will be at the Institute office in the Engineering Societies Building, 29 West 39th Street. The sessions will be held in one of the assembly rooms of the building. Because of the many valuable papers on iron and steel obtained with the assistance of the Iron and Steel Committee, which papers could not appropriately be presented and discussed at the Montana meeting, this October meeting of the Institute is held for the purpose of reading and discussing these papers, most of which will be printed and distributed in advance. The members of the following societies have been invited to attend the meeting, and several have accepted and declared their intention of taking part in the proceedings: American Society for Testing Materials, American Iron and Steel Institute, American Society of Mechanical Engineers, American Society of Civil Engineers, American Institute of Electrical Engineers, American Foundrymen&apos;s Association. The meeting will be conducted under the auspices of the Iron and Steel Committee, and the latest revised program of the proceedings will be found on page xi, under the notes of this Committee.

Jan 10, 1913

By Fred W. Stiefel

To open the Fisher Hill mine of the Republic Steel Corporation, it was necessary to sink an inclined shaft into the rock and excavate stations, drifts, and ore pockets. This inclined shaft, or slope, q ft. 8 in. high by 28 ft. 2 in. wide, has compartments for two 5-ft. gauge ore-skip tracks of 120-lb. rail, one 5-ft. gauge man-skip track of 60-lb. rail, a concrete stairway, and service pipes consisting of a 12-in. compressed-air line, an 8-in. pump-discharge line, and a 4-in. water-supply line. When we were requested to investigate the work, the progress being made (by another organization) amounted to only 2 ½ ft. advance in 24 hr. We reported that progress of at least 6 ft. per day could be made. As a result, the Defense Plant Corporation, through the Republic Steel [ ] Corporation, entered into a contract with us to sink the shaft. The contract contained a penalty and bonus clause predicated upon an advance of 150 ft. per month. The average advance was 7.8 ft. per day; that in the best six-day week was 60 ft. and that in the best month, 215.5 ft. in 25 working days. The drilling was performed by 3 ½ -in. wet drifter drills mounted on five 8-ft. columns (see accompanying illustration). Even though a full-face drilling and mucking operation is customarily desirable, the steep slope, with the accumulation of water and fine debris at the face, made a modified heading and bench operation preferable. The heading and bench were of equal height. The five columns, instead

Jan 1, 1945

By E. H. Bunce

CONTINUED progress in zinc metallurgy has been shown during 1933 by the adoption of new methods as well as the modernization of old processes and equipment, and by the initiation of new fields of activity for future advancement. The use of suspension roasting continued to grow as its advantages and adaptability became increasingly, apparent. The process developed by the National Smelting Co., Ltd., several years ago, of completely roasting on large sintering machines with utilization of the gas for acid manufacture has worked so successfully that an additional machine was installed during the year. At both the Swansea and the Avonmouth Works all of the ore for smelting is now roasted on the large sintering machines, thereby completely eliminating the old hearth-roasting furnaces. Work continued on obtaining partial purification of zinc ores from lead and cadmium by close control of conditions on the sintering machine, and in a few instances by chlorine additions to the ore before sintering. Ores so treated were either partially roasted or com-

Jan 1, 1934

By Gerhard Derge

THE orientation relationships resulting from allotropic transforma-tions and the formation of segregate structures in metals and alloys have been the subject of the eight earlier papers in this series1. A brief summary of orientation studies has also been given by Sachs2. A survey of these papers discloses that the factors that determine the orientation relationship of a precipitated phase to its parent solid solution, as Well as the outward form and appearance of the new phase, are not completely understood. It is now evident that crystallographically analogous systems, as a rule, exhibit the same type of Widmanstätten figure and orientation relations, so that useful information is not to be expected from examination of a new alloy involving lattice combinations of which the orientation relationships are already known. Therefore, the determina-tion of the relations existing between lattice types that have not already been studied seems to be the most promising mode of attack upon the problem; both of the systems reported in this paper represent new com-binations of lattice types.

Jan 1, 1937

E. P. Pfleider, University of Minnesota I would like to ask Bob Merrill whether he considers that horizontal concave curvature of a slope has any stabilizing effect, such as Jenike 1 suggested several years ago. R. H. Merrill, U. S. Bureau of Mines, Denver Federal Center The stabilizing effect is due to the restraint offered to radial movement by the curvature. We found in laboratory tests that if we constrained the rock with the same stresses as those measured in the pit then it would sustain a maximum stress about two or four times greater than when the same rock type was unconstrained. We are therefore definitely of the opinion that a constrained situation in a slope is favorable towards stability. G. A. Leonards, Purdue University I was interested in Mr. Lane&apos;s observations concerning the correspondence between rate of slide movement with rise of reservoir. Perhaps the most interesting feature is that the rate of movement at the time the rock slope failed was less than the rate at an earlier time when it did not fail. This is difficult to explain from current slope stability theory. K. S. Lane, U. S. Army Corps of Engineers I believe that reduced rate of movement is the result of the progressive type of failure, such as described by Patton and Deere. which occurs along the sliding surfaces. It is difficult to analytically define the progressive failure condition for inclusion in slope stability conditions, but its existence should be recognized in design. We should also realize that many apparently stable slopes undoubtedly contain overstressed regions. To design a slope with no overstressed region would be uneconomical and conservative. D. H. Deere I would pose the question-"What is the meaning of a factor of safety of one?" We were involved in the design of a large, irregularly shaped, underground cavity with an unsupported span of several hundreds of feet. Tests on rock specimens indicated a strength of 1300 lb per sq in. The RQD would have been between 90 to 100 percent indicating excellent structural continuity. In-situ stress determinations indicated an approximately hydrostatic state of stress at a level of 1400 lb per sq in. Calculation of stress concentrations at the walls indicated that the stresses there would be about 3000 to 4000 lb per sq in. Admittedly the rock is in a confined condition everywhere except at the very skin of the wall and the rock walls would thus on the average be somewhat stronger. Allowing for the effect of restraint the factor of safety was found to be less than 0.5 over a region several feet into the wall. Construction was started, using rockbolts only to support the walls. Failure around the immediate skin occurred after each

Jan 1, 1967

By M. Tanaka, S. Kita, Y. Jinnouchi, Y. Sawada

This paper generalizes the results of the recent theoretical and experimental investigations on the air-pulsated jigs in Japan. The pulsating mechanism is analyzed as a special vibratory system, and the jigging mechanism as a mass system subjected to the law of hindered settling. The results of investigations on the following items are reviewed: dynamics of the pulsating mechanism; pulsation in a practical TACUB jig development of a new type of air valve; uniform pulsation in a large Baum jig; motion and mobility of bed particles; separating speed in hindered conditions; and standard deviation in practical jigs.

Jan 1, 1985