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By M. C. Leverett

Knowledge of the theory underlying the behavior of mixtures of fluids in reservoir rocks is essential to the proper solution of certain types of problems in petroleum production, but is as yet incompletely developed. The object of this paper is to show the application of well established thermody-namic and physical principles to these problems, and thus to assist in the development of the basic theory. For convenience the problems to be considered here may be divided into two groups: 1. Static problems, involving only the static balance between capillary forces and those due to the difference in densities of the fluids; i.e., gravitational forces. 2. Dynamic problems, involving analysis of the motion oi mixtures of immiscible fluids in porous media under the influence of forces due to gravity, capillarity, and an impressed external pressure differential. Capillary Equilbrium in Sands Under this heading the static type of problem will be discussed and the results of experimental investigations on the capillary properties of unconsolidated sands will be presented. Although the discussion of this section is, in a sense, prefatory to the treatment of problems of mixture flow, the concepts developed here have considerable intrinsic importance apart from their ap-plication to flow problems. For, it is reason-able to postulate that the reservoir fluids are, owing to their long existence in undis- turbed mutual contact prior to exploitation, in substantial equilibrium. It follows that their distribution in the reservoir at the time of tapping should be entirely predictable from the theory of capillary equi librium, provided certain experimentally measurable properties of the reservoir rock are known. Knowledge of the distribution of the several fluids in the reservoir is, ol course, helpful in the estimation of reserves and in other problems. It is to be emphasized that throughout the discussion of capillary statics it is assumed that the fluids are in equilibrium from the capillary standpoint. Thus, water, where it is referred to as being in a reservoir, will be understood to be interstitial water, present at the time of drilling the reservoir, commonly termed "connate" water. The theory developed here is perfectly general for any porous solid, whether a carefully prepared unconsolidated sand or a natural sandstone from an oil reservoir. At present, however, only problems involving clean, unconsolidated sands can be made to yield numerical solutions, since only such sands have been adequately investigated experimentally. Experimental evaluation of the pertinent properties 01 natural reservoir rocks will permit the extension of the numerical treatment to problems involving these materials. We shall now consider in some detail the static equilibrium of fluid mixtures in porous solids: that is, the manner in which the reservoir fluids are distributed vertically whell the Forces due to capillarity are just balanccd by those due to gravitation.

Jan 1, 1941

By M. C. Leverett

Knowledge of the theory underlying the behavior of mixtures of fluids in reservoir rocks is essential to the proper solution of certain types of problems in petroleum production, but is as yet incompletely developed. The object of this paper is to show the application of well established thermody-namic and physical principles to these problems, and thus to assist in the development of the basic theory. For convenience the problems to be considered here may be divided into two groups: 1. Static problems, involving only the static balance between capillary forces and those due to the difference in densities of the fluids; i.e., gravitational forces. 2. Dynamic problems, involving analysis of the motion oi mixtures of immiscible fluids in porous media under the influence of forces due to gravity, capillarity, and an impressed external pressure differential. Capillary Equilbrium in Sands Under this heading the static type of problem will be discussed and the results of experimental investigations on the capillary properties of unconsolidated sands will be presented. Although the discussion of this section is, in a sense, prefatory to the treatment of problems of mixture flow, the concepts developed here have considerable intrinsic importance apart from their ap-plication to flow problems. For, it is reason-able to postulate that the reservoir fluids are, owing to their long existence in undis- turbed mutual contact prior to exploitation, in substantial equilibrium. It follows that their distribution in the reservoir at the time of tapping should be entirely predictable from the theory of capillary equi librium, provided certain experimentally measurable properties of the reservoir rock are known. Knowledge of the distribution of the several fluids in the reservoir is, ol course, helpful in the estimation of reserves and in other problems. It is to be emphasized that throughout the discussion of capillary statics it is assumed that the fluids are in equilibrium from the capillary standpoint. Thus, water, where it is referred to as being in a reservoir, will be understood to be interstitial water, present at the time of drilling the reservoir, commonly termed "connate" water. The theory developed here is perfectly general for any porous solid, whether a carefully prepared unconsolidated sand or a natural sandstone from an oil reservoir. At present, however, only problems involving clean, unconsolidated sands can be made to yield numerical solutions, since only such sands have been adequately investigated experimentally. Experimental evaluation of the pertinent properties 01 natural reservoir rocks will permit the extension of the numerical treatment to problems involving these materials. We shall now consider in some detail the static equilibrium of fluid mixtures in porous solids: that is, the manner in which the reservoir fluids are distributed vertically whell the Forces due to capillarity are just balanccd by those due to gravitation.

Jan 1, 1941

By J. S. Aronofsky, R. Jenkins

A simple means of predicting the flowing well pressure history in a natural gas reservoir has been developed. The differential equation for unsteady radial flow of gases through porous media was solved by numerical methods using electronic punch card machines. The results obtained from these calculations are presented in a generalized form which is believed to be most convenient for engineering use. These results are compared with those presented in a paper by Bruce, et al4. An effective radius of drainage has been defined which permits the equation of steady state gas flow to be used easily to predict well pressures in gas reservoir depletion. An equivalent effective radius of drainage is defined for liquid flow systems and a comparison is made of the gas solution to the liquid solutions. INTRODUCTION This paper presents a numerical method for describing the transient flow of gases radially through a porous medium from which the production rate is specified. The results obtained from these calculations are presented in a generalized form which is believed to be the most convenient for engineering use. The principal application of these calculations should be to flow in natural gas reservoirs, in the interpretation of pressure drawdown tests, in the estimation of reserves, and in calculation of injection pressures required in gas injection and cycling operations. The evaluation of natural gas wells is based upon back-pressure tests in which measurements of production rate and flowing well pressure are made for periods of one, two, or more days. The flow is assumed to have stabilized at this time, and the observed values of pressure and production rate are used with standardized formulae to determine the well's allowable production rate. Furthermore, the results obtained from such a test of short time duration are extrapolated in such a manner to allow a prediction of what the well pressure will be at some future time for a specified (but possibly untested) flow rate. The manner of conducting such back-pressure tests suggests several questions as follows: 1. 'What is the definition of stabilized flow and what factors determine the length of time required for the flow to become stabilized? 2. How may the recorded values of pressure and rate be utilized? 3. As the well is produced and the reservoir pressure falls, how will the flowing well pressure change? Can this flowing well pressure be predicted from the back-pressure test? 4. Are the results obtainable from the test influenced by a particular procedure used in obtaining the results? 5. Is it possible to estimate the gross reservoir permeability from back-pressure data? It is not within the scope of this paper to provide solutions Or even to discuss adequately all the above questions. However. in considering such matters, the

Jan 1, 1955

By Edward Saibel, W. T. Lankford

DURING the course of an investigation of the plastic flow of aluminum aircraft sheet under combined loads, several problems arose in which analyses of the conditions leading to unstable plastic flow were needed. In order to provide these analyses, and in the hope of attaining a better understanding of the general problem of unstable plastic flow, the present study was undertaken. It is well known that unstable plastic flow is associated with a form of mechanical instability frequently observed during the plastic deformation of ductile metals. This instability is characterized by the fact that, at its onset, plastic straining will proceed at a constant magnitude of the externally applied forces. It is further typical that the resulting unstable flow is generally accompanied by the formation of a neck, a local bulging, or some other form of heterogeneous deformation. Perhaps the most familiar example of unstable plastic flow to the metallurgist is the formation of the neck in the ordinary tension test. It is well known that in this test most metals exhibit a maximum in the externally applied load, followed by the process commonly referred to. as "necking down." Instability in the simple tension test has been frequently discussed and numerous investigators 1,2.3,12 have derived the criterion for instability in terms of a critical rate of strain hardening. It is the purpose of the present study to extend the criterion for unstable flow to the more general case where the body undergoing flow is subjected to combined loads. It is hoped that the problems considered will provide a more consistent picture of the general features of this important form of mechanical instability. The most practical implications of instability in plastic flow arise in connection with sheet metal forming operations. In the formation of a great many sheet metal parts, the deformations are produced primarily by stretching. If the conditions which lead to unstable flow are fulfilled in such a formation, and if the resultant instability leads to a pronounced localization of flow, then the useful limit of ductility of the material will have been reached. It is also essential that the effects of instability be taken into consideration in any study of the plastic flow and rupture of metals under combined stresses. In general, when unstable plastic flow is initiated, straining becomes localized, the geometry of the test specimen changes, and the state of stress in that portion of the specimen undergoing plastic flow is no longer under external control. In many past studies of the effects of combined stresses on flow and rupture, account has not been taken of the fact that, although a given test may be started under constant

Jan 1, 1947

By P. D. Hunt, I. Johnson, M. G. Chasanov, H. M. Feder

The solubilities of the transition metals from scundium to nickel, inclusive, in liquid cadmium were determined by sampling saturated solutions. At 400°C these solubilities (ppm) are:Sc, Co, 22; Ni, 12000. Relative partial molal enthalpies and excess partial molal entropies at infinite dilution for the solutes Cr, Mn, Fe, and Co are compared zoitlz similar data for the post-transition metals. Three new intermetallic phases, ScCd,, TiCd, and Ti,Cd, encozaztered in the course of this work, are reported. Measurements of the solubility of the 3-d transition metals in liquid cadmium have been reported' only for iron. The present measurements for the entire series were made as an aid to the study of the systematics of alloy formation. EXPERIMENTAL The apparatus and sampling techniques used for the solubility determinations were similar to those described by Martin etal.' Temperatures were measured with a Pt/Pt-10 pct Rh thermocouple sheathed in recrystallized alumina and immersed in the solution. The thermocouple was recalibrated periodically during the course of the investigation. Thermocouple voltages were measured to the neares 0.01 mv with a Rubicon model 2732 potentiometer. A scaled-down version of the apparratus, in which the total metal charge was about 90 g, was employed to measure the solubility of scandium. Two-mm ID Vycor filter pipets were used to sample the scandium-cadmiurn solutions; the samples weighed about 2g- Cadmium with a minimum purity of 99.95 pct was used; the only impurities detected spectrochem-ically were C'u and Mg, both less than 10 ppm. The purities of the other metals were: scandium, 99.9 pct; titanium. 99.92 pct; vanadium, 99.9 pct; chromium, 99).99 pct; manganese, 99.9+ pct; iron, 99.90 pct; cobalt, 99.95 pct; and nickel, 99.96 pct. Solidified melts were routinely analyzed spectro-graphically. No significant contamination by the crucible, sampling pipets, or other materials of construction was observed. The entire specimen obtained by sampling was dissolved to preclude analytical errors due to segregation on cooling. Colorimetric methods3 were used for the analyses of cobalt (2-nitroso-l-naphthol), manganese (permanganate), nickel (dimethylglyoxime), titanium (peroxide), and vanadium (thiocyanate).4 Chromium, iron, and scandium were neutron-irradiated to produce The dissolved samples were gamma-counted to determine solute concentration.For the separation of intermediate phases from cadmium-rich alloys selective leaching by saturated ammonium nitrate solutions was employed. The concentration of cadmium in the successive leaches was followed polarographically and the process was terminated when the rate of cadmium dissolution decreased markedly. For the further investigation of intermediate phases 1/4- in. diam powder compacts were pressed at 80,000 psi and annealed in argon at 315" to 330°C for 10 days. Larger quantities of alloys were prepared in sealed tantalum capsules heated in a rocking furnace.

Jan 1, 1962

By E. Brunner, E. S. Mardock

A method of measuring oil saturations in cores or sand packs by neutron scattering is described. This method permits local SatUrations to be measured in a core enclosed in a steel pressure vessel without interrupting the flow. calibration data and a saturation distribution measurement obtained with the apparatus are included by way of illustration. Introduction In laboratory flow experiments designed to study the mechanism of oil production it is frequently necessary to measure the oil saturation in a core or sand pack containing Oil, gas, and perhaps brine. It is sometimes desirable that the saturation measurement refer to a relatively small portion of the core, so as to eliminate end effects; that it be made without interrupting the flow, and that it be applicable to a core enclosed in a steel Pressure vessel capable Of withstanding the Pressures encountered in petroleum reservoirs. None of the usual methods of measuring saturation meets all Of these requirements. To measure the gas saturation by observing the apparent compressibility of the gaseous Phase1 would require the interruption of the flow and would give an average saturation for the whole core. An electrical conductivity method is available for measuring brine saturations,2,3 but it is not applicable to oil. A radioactive tracer might be used if a suitable substance could be found that would dissolve in the oil, emit gamma radiation, and not be adsorbed on the sand, the steel core holder, or in an aqueous- phase. The large gamma-ray background from the mass of radioactive oil in other parts of the apparatus might, however, be undesirable. There remain for the saturation measurement methods involving the absorption or scattering of some penetrating radiation produced outside the apparatus. It might be possible to use X-rays or gamma rays; but these radiations would be so much less strongly absorbed and scattered by the oil than by the steel walls of the core holder and by the sand that it seems doubtful that much precision could be attained. In a beam of neutrons, however, there is a radiation that is very penetrating and, moreover, its scattering by substances containing hydrogen, such as oil, is qualitatively different from that occasioned by other materials. It would seem possible, and has proved to be quite practicable, to measure oil saturations accurately under the required conditions by means of neutron scattering. The first, to our knowledge, to suggest neutron scattering as a means of measuring oil saturation were F. Brans and ,. A. Bottema,4 of the Amsterdam laboratories of the Bataafache Petroleum Maatschappij, who made a few preliminary experiments to test the method while they were engaged in exploring the possibilities of neutrons for well-logging purposes. A comprehensive account of neutrons and their behavior will be found, together

Jan 1, 1946

By E. S. Mardock, E. Brunner

A method of measuring oil saturations in cores or sand packs by neutron scattering is described. This method permits local SatUrations to be measured in a core enclosed in a steel pressure vessel without interrupting the flow. calibration data and a saturation distribution measurement obtained with the apparatus are included by way of illustration. Introduction In laboratory flow experiments designed to study the mechanism of oil production it is frequently necessary to measure the oil saturation in a core or sand pack containing Oil, gas, and perhaps brine. It is sometimes desirable that the saturation measurement refer to a relatively small portion of the core, so as to eliminate end effects; that it be made without interrupting the flow, and that it be applicable to a core enclosed in a steel Pressure vessel capable Of withstanding the Pressures encountered in petroleum reservoirs. None of the usual methods of measuring saturation meets all Of these requirements. To measure the gas saturation by observing the apparent compressibility of the gaseous Phase1 would require the interruption of the flow and would give an average saturation for the whole core. An electrical conductivity method is available for measuring brine saturations,2,3 but it is not applicable to oil. A radioactive tracer might be used if a suitable substance could be found that would dissolve in the oil, emit gamma radiation, and not be adsorbed on the sand, the steel core holder, or in an aqueous- phase. The large gamma-ray background from the mass of radioactive oil in other parts of the apparatus might, however, be undesirable. There remain for the saturation measurement methods involving the absorption or scattering of some penetrating radiation produced outside the apparatus. It might be possible to use X-rays or gamma rays; but these radiations would be so much less strongly absorbed and scattered by the oil than by the steel walls of the core holder and by the sand that it seems doubtful that much precision could be attained. In a beam of neutrons, however, there is a radiation that is very penetrating and, moreover, its scattering by substances containing hydrogen, such as oil, is qualitatively different from that occasioned by other materials. It would seem possible, and has proved to be quite practicable, to measure oil saturations accurately under the required conditions by means of neutron scattering. The first, to our knowledge, to suggest neutron scattering as a means of measuring oil saturation were F. Brans and ,. A. Bottema,4 of the Amsterdam laboratories of the Bataafache Petroleum Maatschappij, who made a few preliminary experiments to test the method while they were engaged in exploring the possibilities of neutrons for well-logging purposes. A comprehensive account of neutrons and their behavior will be found, together

Jan 1, 1946

By R. W. Gurry

Thermodynamic calculations indicate that boron is a better deoxidizer than silicon but probably is not quite as effective as aluminum. Boron should, therefore, be readily oxidized out of the open-hearth bath, which implies that it is not recovered in significant concentration from any scrap charged; also that, if added in the ladle, it tends to oxidize out during teeming unless protected by the presence of a better deoxidizing agent. These conclusions do not apply to liquid cast iron, in which the oxygen content is much lower than in liquid steel. The possibility of conserving certain strategic alloying elements widely used in steelmaking, notably manganese, chromium and molybdenum, by the use of boron, which in small concentration appears to be extraordinarily effective in promoting hardenability, raises a question as to what extent any boron present in the scrap charged into the open hearth is oxidized out during melting and subsequent refining. This question is significant because the optimum concentration of boron in the finished steel, which is fairly critical, would be very difficult to attain if the boron in the charge were largely retained in the metal. Moreover, unless boron is substantially eliminated in the open-hearth process its use on a large scale would eventually make it impossible to produce boron-free steel except by restricting the charge to virgin material. There is at present, unfortunately, virtually no satisfactory direct evidence to provide an answer to this question; but there are indications from practice that boron is oxidized out in the open hearth in the production of medium or low-carbon steel, although it may be retained if the carbon content remains fairly high; that is, if the oxygen is kept fairly low. In the absence of direct data, it is necessary to rely upon the indications of indirect evidence, the best approach now available being a thermodynamic calculation of the deoxidizing power of boron in liquid steel by the general method used so successfully by Chipman1 in his study of the reactions in the open-hearth process. The thermal data for boron, upon which such a calculation must be based, are reasonably satisfactory; the only quantities not directly determined are the entropy of melting of boron, the activity coefficient of boron in liquid steel, and the activity coefficient of B2O3in an open-hearth slag; but these values may be estimated with ample accuracy. The results of this calculation, which is presented later, are given in Table I, together with corresponding data for other deoxidizing elements. This table shows the calculated residual content of oxygen in equilibrium with different residual concentrations of the deoxidizer in the metal;

Jan 1, 1944

By R. W. Gurry

Thermodynamic calculations indicate that boron is a better deoxidizer than silicon but probably is not quite as effective as aluminum. Boron should, therefore, be readily oxidized out of the open-hearth bath, which implies that it is not recovered in significant concentration from any scrap charged; also that, if added in the ladle, it tends to oxidize out during teeming unless protected by the presence of a better deoxidizing agent. These conclusions do not apply to liquid cast iron, in which the oxygen content is much lower than in liquid steel. The possibility of conserving certain strategic alloying elements widely used in steelmaking, notably manganese, chromium and molybdenum, by the use of boron, which in small concentration appears to be extraordinarily effective in promoting hardenability, raises a question as to what extent any boron present in the scrap charged into the open hearth is oxidized out during melting and subsequent refining. This question is significant because the optimum concentration of boron in the finished steel, which is fairly critical, would be very difficult to attain if the boron in the charge were largely retained in the metal. Moreover, unless boron is substantially eliminated in the open-hearth process its use on a large scale would eventually make it impossible to produce boron-free steel except by restricting the charge to virgin material. There is at present, unfortunately, virtually no satisfactory direct evidence to provide an answer to this question; but there are indications from practice that boron is oxidized out in the open hearth in the production of medium or low-carbon steel, although it may be retained if the carbon content remains fairly high; that is, if the oxygen is kept fairly low. In the absence of direct data, it is necessary to rely upon the indications of indirect evidence, the best approach now available being a thermodynamic calculation of the deoxidizing power of boron in liquid steel by the general method used so successfully by Chipman1 in his study of the reactions in the open-hearth process. The thermal data for boron, upon which such a calculation must be based, are reasonably satisfactory; the only quantities not directly determined are the entropy of melting of boron, the activity coefficient of boron in liquid steel, and the activity coefficient of B2O3in an open-hearth slag; but these values may be estimated with ample accuracy. The results of this calculation, which is presented later, are given in Table I, together with corresponding data for other deoxidizing elements. This table shows the calculated residual content of oxygen in equilibrium with different residual concentrations of the deoxidizer in the metal;

Jan 1, 1944

By E. F. Sturcken, J. W. Croach

A grain orientation distribution function, P(u,F), was developed for use in predicting physical properties in oriented metals. Examples are given of the use of the function to predict thermal expansion coefficients in rolled uranium rods and plate. The P(u,F) function was synthesized from X-ray difpaction intensity measurements, Ii, norrnally used to plot inverse pole figures. The symbols u and F specify the angles that the crystallographic axes of the grain make with the normal to the sample surface and P(u, F) gives the number of grains oriented in each direction, (u,F). P(u,F) is obtained from a least squares fit of the Ii to an orthonormal set of spherical harmonic functions. The P(u, F) function was also used to define a quantity, J, which is a measure of the departure of the orientation distribution from unifomzity (or "randomness"). The J parameter may be used to follow, quantitatively, the amount of preferred orientation induced as a function of mechanical working or heat treatment. An example is given of the application of the J parameter to prefevred orientation studies of hot- and cold-rolled uranium rods and hot-rolled uranium plate. Because P(u,F) is derived from relative intensity measurements by the powder diffraction technique, it is applicable to material with large absorption coefficients and/or grain size and is particularly suitable for characterizing the preferred orientation of large numbers of samples such as fuel elenzents for a nuclear reactor. IN general the physical properties of an oriented metal depend on the direction in which the properties are measured. Hence to predict physical properties the grain orientation must be known as a function of the direction of the specimen. The conventional methods of expressing preferred orientation measurements are the pole figure1 and the inverse pole figure.2-8 Both methods are difficult to use for predicting physical propertiess because they are graphical and because they are stereographic projections and hence are not "area-true." In the present report a quantitative orientation distribution function, P(u,F), is synthesized from pole density measurements normally used to plot inverse pole figures. For inverse pole figure plots the pole densities, pi, are obtained by powder dif-fractometer intensity measurements of their reflections from a flat surface of the sample, normal to the direction of interest. Each pole density, pi, represents a single orientation, i, and is proportional to the volume of material with orientation, i; hence a set of pi gives an approximation for the general orientation for the sample direction measured. The expression8'7 for calculating the pole densities, pi, from the diffraction measurements was previously

Jan 1, 1963

By W. O. Philbrook, A. H. Jolly, T. R. Henry

IN the course of a study of slag-control methods, the authors devised a laboratory technique by which the basicity of basic open-hearth furnace slap could be estimated with sufficient accuracy to make the method of possible interest for slag-control purposes. The process consisted of measuring the slight basicity of an extract of the powdered slag in water. The procedure was presented, for the benefit of those who might care to experiment with it, in a paper submitted in the 1944 McKune Award Contest and presented at the 1944 Open-hearth Conference in Pittsburgh.1 Interest expressed at that meeting and favorable operating experience with the method at a neighboring plant, as described in a related paper by Michael Tenenbaum and C. C. Brown,2 have encouraged us to present further details of the development, technique, and pitfalls of the method and some additional data not included in our first report. At the outset it must be admitted that this method of estimation of slag basicity is not perfect; neither is any other that we know of. It is subject to somewhat greater errors than would be desirable, but compares favorably with other techniques in this respect. It has the disadvantage that it places the final determination of slag basicity in the hands of a laboratory technician rather than the furnace operator, although it can be operated in a control laboratory adjacent to the furnaces. It requires close attention to certain details, as do most laboratory procedures. On the favorable side, it eliminates the "human factor" of personal judgment inherent in estimation from pancakes or powdered samples. The procedure can be placed in practice much more rapidly and presents much less of a training problem than visual methods of estimation. The principle and operation of the method are so simple that it would not be surprising if others have experimented with the same or similar procedures, but we are not aware of any prior publication of details. Our own shop has been operating fairly successfully for several years with the aid of slag pancakes. Since the past year or two have not been favorable for the expenditure of time and energy where the need was not urgent, we have not introduced the new practice for actual slag control and hence do not have extensive operating data. In presenting this method, therefore, we make no claims as to theoretical justification nor guarantees as to practical applicability, but offer it as an empirical observation. We believe it has sufficient merit to warrant its investigation by those just instituting a slag-control program or in search of supplementary methods for judging slag basicity PRINCIPLE OF THE METHOD It is well known that when burnt lime or slaked lime is shaken up with water it

Jan 1, 1945

By Y. Dardel

Since the first determination of Dumas1 in 1880, many authors have tried to measure the solubility of hydrogen in solid aluminum, or at least the amount of dissolved gas in it. However, the interpretation of the results which have been obtained is still difficult. Sieverts? then Baukloh and Oesterlen,a during their gassing experiments could not determine any solubility of hydrogen in solid aluminum. On the other hand, Portevin, Chaudron and Moreq4 leaving the determination of the hydrogen solubility beyond the scope of their experiments, measured only the amount of gas that they could extract by high voltage positive ion bombardment and found up to 151 cm3 of gas per I00 g of metal. Winterhager,6 by repeated vacuum extraction during severe cold rolling, extracted up to 161 cm3 per 100 g. In both series of experiments, the extracted gas contained chiefly hydrogen with a small amount of nitrogen, carbon monoxide, carbon dioxide and methan. Later, Schmidt and von Schweinitze as well as Chaudron and Moreau7 showed the importance of the adsorbed layer of hydrogen, the extracted quantities being proportional to the surface and not to the weight of the sample, when its cleaning was not perfect. In earlier experiments, Steinhausers extracted from more massive samples nothing but a little amount (< 0. 5 cm3 per I00 g) of hydrogen, carbon monoxide and methane. Thus, according to these experiments the quantity of dissolved gas is probably very small and the effect of the surface could falsify the results of the extraction. However, owing to the care taken by Chaudron and his coworkers, it was clear that all the hydrogen extracted could not come from the superficial layer, or that the links which bound hydrogen to the surface were so strong that the usual method of cleaning could not destroy them. After the main parts of the experiments reported here had already been carried out, Eborall and Ransley9 published the results which they obtained with an analysor having an accuracy of 0.03 cm3 per I00 g, while that of the usual apparatus was only about 0.2 cm3 per I00 g. During all their experiments the adsorbed layer would have been a difficulty, for the value of the adsorbed hydrogen was approximately equal to that of the dissolved amount. Table i—Amount of Adsorbed and Dissolved Hydrogen (After Eborall and Ransley) Extraction Hz Adsorbed „ h2 dissolved Temperature Calculated Extraction OCcma 500 0.057 0.050 600 0.062 o.096 Since always keeping the same adsorbed layer is very difficult, an error in the correction for the adsorption can be made when using the apparatus of. Eborall and Ransley, as well as the earlier apparatus.

Jan 1, 1949

By G. A. Croes, N. Schwarz

The dimensionless groups, to which the variables that govern the displacement of oil from reservoirs by liquids can be combined, are derived. Three types of displacement are considered, viz. cold-water drive, hot-water drive and solvent injection. The derivation of the dimerzsionless groups is carried out by means of the relevant basic equations (in-spectional analysis). The resulting sets of groups are afterwards completed by means of dimensional analysis. The form of the groups is given in such a way that they can be adapted to suit the various boundary conditions that are encountered in practice. The physical meaning of the groups is discussed. They have all been brought together on a chart, from which their mutual relation and their corresporzdence to related dimensionless groups in common use in other engineering sciences can be read off. The limitations of dimensionally scaled model experiments as a useful tool for studying liquid flow in porous media, as occurring in oil reservoirs, are discussed. The use of models to study fluid mechanics has an appeal for everyone endowed with natural curiosity. What active boy has not played with ship and airplane models, or crude models of dam and drainage systems Even in the most advanced technical engineering, such models play a fundamental and indispensable role. "And yet in few departments of the physical sciences is there a wider gap between theory and practice, between scientific knowledge and the state of art, than in the use of models to study hydrodynamic phenomena." Garrett Birkhoff1 INTRODUCTION Laboratory displacement experiments are extensively used to investigate, directly or indirectly, the production behavior of petroleum reservoirs. Such experiments are representative of the reservoirs as a whole, if they are carried out with models that are "properly scaled." The performance of oil reservoirs is governed by the values of a number of variables, which can be combined to dimensionless groups. Two general methods are available for the derivation of these groups. In the first of these, dimensional analysis, combination of the variables is done essentially by trial and error. Its only premise is knowledge of the complete set of relevant variables. In the second method, inspectional analysis, the dimensional homogeneity of the equations describing the behavior of the system to be studied is used. The resulting dimensionless groups can be divided into: (a) independent (variable) groups, such as dimensionless length, time, etc.; (b) dependent groups, giving the dimensionless form of the variables, such as recovery and pressure, that can, at least in principle, be measured during an experiment; (c) similarity groups, which are independent constant groups, such as ratio of length to height of the reservoir and ratio of

Jan 1, 1957

By J. L. Lummus, Frank O. Jones

A field procedure for determining graphite in drilling mud is presented which is sensitive to 0.25 lbs/bbl and accurate to 20 per cent. The method, utilizing oil flotation principles, is suitable for use in all oil-free water base muds except those containing ligno-sulfonates, lignites, or surface active agents. INTRODUCTION Graphite was proposed as a drilling lubricant as early as 1940, but has not been used extensively until recently.&apos; Graphite has been substituted for oil in certain instances to avoid oil contamination of core samples since it has been found that graphite does not interfere with routine core analysis. A major difficulty in using graphite is the lack of a satisfactory field test for determining the concentration of graphite in mud. DISCUSSION OF METHOD Several possible methods of analysis were investigated, including chemical separation, density fractionation, radioactive tracers, and oil flotation.&apos;, &apos; The investigation indicated that a satisfactory method for field use could be devised using an oil flotation method. It was found that toluene shaken with a highly diluted mud sample would recover sufficient graphite to be apparent in the oil phase. Refinement and standardization of technique made it possible to detect as little as 0.25 lb/bbl graphite and to estimate graphite content to within 20 per cent by using a visual comparison method. The test is limited to oil-free water base muds. Quebracho, phosphates, or barytes in the mud do not interfere with the test but surface active agents, lignosulfonates&apos; and lignites evidently render !he graphite water-wet so that none may be recovered by oil-flotation. PROCEDURE Instructions for determining graphite in mud: 1. Collect representative one gallon sample.- from mud stream. Transfer immediately 350 ml portions of this Sample into four mixing cans labeled A, B, C, and D. Measure out graphite (same as is used to treat mud) for addition to cans as indicated below, using either a specially designed scoop or a balance. Can: A B C D Grams Graphite to Add: none 2 4 6 Stir samples B, C, and D for 15 minutes with propeller type mixer. 2. Clean and rinse well with water four 250 ml volumetric flasks labeled I, 11, 111, and IV. Using a 5 ml hypodermic syringe, transfer the indicated volume of samples from cans A, B, C, and D into designated flasks as follows: From Can: A B C D To Flask: I II III IV Add This Volume of Mud: 4 ml 2 ml 2 ml 2 ml 3. Measure 100 ml fresh or distilled water to each flask and swirl gently to disperse mud. Add exactly 5 ml toluene to each flask. Stopper and shake each

Jan 1, 1953

By Harry H. Power

The Specific purposes of forma! engineering education include training in the basic sciences, the engincering-prob]em method, the rudimentary development of technical skills, an appreciation of values and costs, and an understanding of the art of engineering as distinguished from its science, Two major divisions of an educational program in engineering are recognized: (I) the scientific-technological, and (2) the humanistic-social. Hence, the entire curriculum for the four-year program in specialized petroleum engineering schools must be designed to give the student an initial impetus in the directions indicated. In accordance with suggestions from the Engineering Council for Professional Development, Inore attention is being given to the fundamental approach in the undergraduate curriculum. This paper presents a cross-sectional viewpoint of the various educators in the petroleum engineering schools concerning course contents in the specialized curricula An outline is suggested for the content of the specialized courses wherein the engineering problem method or quantitative approach is emphasized. Although the particular viewpoints of the author have been stressed, yet due acknowledgment is made to a considerable number of petroleum engineering educators and in in industry interested in educational work, for their contribution of course outlines or helpful suggestions with respect to programs that will be of maximum value to students, institutions, and the industry they serve. Although "standardization" of course material is not suggested, the advantage to be gained by cooperative determination of purpose and scope are apparent paiticular1y from &apos;he standpoint of the proper accreditment of petroleum engineering schools by petroleum engineering educetors who have laid a basis from which to measure educational values. Petroleum engineering has "come of age" and deserves the same careful attention with respect to. curricula that has been accorded other engineering branches. Introduction Engineering schools have a major responsibility to the public, to industry and to the professions they serve. The specific purposes of formal education include training in the basic sciences, the engineering-problem method, the rudimentary development of technical skills, an reciaciation of values and costs, and an understanding of the art of engineering as distinguished from its science. Other purposes implied include the ability to read, write, and speak the English language effectively, an understanding of social and human relationships, a knowledge of the duties of citizenship, a broad appreciation of cultural interests, and an indoctrination in professional standards and relations. Throughout these educational processes is the development in the student of habits of accuracy, thoroughness, powers of analysis, creative ability and integrity with respect to all phases of his work. Major Divisions of Program In the Report of the Society for the Promotion of Engineering Education,† two † Report of Committee on Engineering Education after the War, dated January 1944.

Jan 1, 1945

By Edward C. J. Urban

THE nature of certain pernicious dusts commonly encountered in the removal of iron ore from the underground mines of the Lake Superior district is recognized, and appropriate measures for the protection of individuals subjected to these dusts have been applied in most mines for more than to years. Undoubtedly the principal concern has been demanded by dusts that contain as a constituent silicon dioxide in its free or uncombined state, the mineral we all know as quartz or chert. Investigators1 agree that among the factors that determine injurious exposure are: the composition of the dust, the concentration suspended at the breathing level and the duration of the exposure. We have on hand data that describe the experience of several underground iron-ore mines in the Upper Peninsula of Michigan and Wisconsin in regard to these factors, which in a large measure also reflect the general experience of the other mines of the area. We believe that a discussion of these data will indicate the effectiveness of the dust-control methods that have been considered good practice and that have been employed over a long period of time. A silicosis-prevention program was ini¬tiated by the iron mines of the Upper Peninsula in 1934 and records of mine dustiness are available from that date to the present time. For dust conditions previous to 1934 the results of observations conducted in other industries can be utilized together with local information pertaining to the development and initial application of rock-drilling equipment. DEVELOPMENT OF ROCK DRILLS The earliest percussion rock drill that later had any industrial use was patented in this country in 1851.2 This machine was later modified and improved in many respects but its piston-type design remained standard for drilling equipment in most mines for the next 63 years.3 The piston drill was operated either by air or by steam. It employed a solid drill steel, fastened directly to the reciprocating piston. The drilling was done dry except in holes directed at an angle below the horizontal. For these water was manually injected into the hole and the pumping action of the rod expelled the sludge. The dry cuttings from drillings inclined above the horizontal fell from the hole by their own weight. A development of major importance from the standpoint of dust generation and control occurred with the invention by J. G. Leyner of a hammer-type rock drill that embodied the essential feature of a drill steel with a hollow core. His patent was secured in 1897. The machine was a radical departure in drilling method. The steel was held loosely in a chuck while

Jan 1, 1947

By J. P. Newell, R. W Storey

This paper describes the development of a continuous float-and-sink process to produce coal low enough in ash content to be suitable for production of electrodes. The cleaned coal had a combined iron and silicon content of 0.239 pct. The efficiency of recovery was 84 pct. AUGER mining is a form of continuous mining in that it completely replaces with a one-cycle operation the older conventional cut, drill, shoot, and load method of mining. Relatively new, having been utilized only within the last few years, it is even more continuous in its production of coal than some other forms of continuous mining being practiced in this country today. There are at present coal recovery augers in operation working along strip-mined highwalls from the outside. This paper will deal with underground mining, specifically with an experiment which was carried out with a machine developed for this purpose. The location of this experiment was in Pike County in eastern Kentucky in the upper split of the No. 3 Elkhorn seam. Coal height was 32 in. and roof conditions were very bad, with 10 in. of soft draw slate coming down with every cut in conventional mining. The coal is high-grade bituminous, excellent for metallurgical coking. Underground auger mining fills a need for a method of recovering coal in thin seams, under bad roof conditions or in split seams. In many cases it might save money by eliminating the handling of excessive quantities of rock. In fact, if the coal can be recovered, as in the case of this experiment, without mixing with any impurities outside the seam, it may be possible to load or ship a satisfactory product with little or no preparation or cleaning expense. The need for some economical method for recovering coal from thin seams is becoming more pressing as the more profitably mined seams are exhausted. Basic Principles of Auger Mining The principles of the auger, or screw conveyor, have long been used in drilling small diameter holes for blasting and other purposes. These same fundamentals apply to large diameter drilling. However, considerably more attention was given to designing a cutting head that would not pulverize the coal and consequently would require a minimum of power to drive it. The head, as designed for this job, consists of a cylinder 25 in. in diam with steel bits set in 3 positions spaced around the forward rim. A conventional coal drill bit, at the head of a bursting cone in the center of the cylinder, trails the forward rim slightly, see Fig. 1. The bursting cone and auger connections are anchored to the cutter barrel by 3 arms spaced at 120". This head design proved to be very satis-

Jan 1, 1953

By J. P. Newell, R. W. Storey

This paper describes the development of a continuous float-and-sink process to produce coal low enough in ash content to be suitable for production of electrodes. The cleaned coal had a combined iron and silicon content of 0.239 pct. The efficiency of recovery was 84 pct. AUGER mining is a form of continuous mining in that it completely replaces with a one-cycle operation the older conventional cut, drill, shoot, and load method of mining. Relatively new, having been utilized only within the last few years, it is even more continuous in its production of coal than some other forms of continuous mining being practiced in this country today. There are at present coal recovery augers in operation working along strip-mined highwalls from the outside. This paper will deal with underground mining, specifically with an experiment which was carried out with a machine developed for this purpose. The location of this experiment was in Pike County in eastern Kentucky in the upper split of the No. 3 Elkhorn seam. Coal height was 32 in. and roof conditions were very bad, with 10 in. of soft draw slate coming down with every cut in conventional mining. The coal is high-grade bituminous, excellent for metallurgical coking. Underground auger mining fills a need for a method of recovering coal in thin seams, under bad roof conditions or in split seams. In many cases it might save money by eliminating the handling of excessive quantities of rock. In fact, if the coal can be recovered, as in the case of this experiment, without mixing with any impurities outside the seam, it may be possible to load or ship a satisfactory product with little or no preparation or cleaning expense. The need for some economical method for recovering coal from thin seams is becoming more pressing as the more profitably mined seams are exhausted. Basic Principles of Auger Mining The principles of the auger, or screw conveyor, have long been used in drilling small diameter holes for blasting and other purposes. These same fundamentals apply to large diameter drilling. However, considerably more attention was given to designing a cutting head that would not pulverize the coal and consequently would require a minimum of power to drive it. The head, as designed for this job, consists of a cylinder 25 in. in diam with steel bits set in 3 positions spaced around the forward rim. A conventional coal drill bit, at the head of a bursting cone in the center of the cylinder, trails the forward rim slightly, see Fig. 1. The bursting cone and auger connections are anchored to the cutter barrel by 3 arms spaced at 120". This head design proved to be very satis-

Jan 1, 1953

By R. J. Borg, C. E. Birchenall

Vapor pressures of eight compositions of Mg-Cd have been determined by the Knudsen effusion technique. Measurements are made at several temperatures for each alloy and the results interpolated to a common temperature for the calculation of the activities. It is not possible to obtain values for the partial molar enthalpies because of the narrow temperature range spanned by the measurements. The results show less precision than those obtained for pure Cd which are also reborted. These alloys are extremely susceptible to corrosion which provides a possible explanation for the lack of precision. Nevertheless, the values of the activity are in good agreement with the results of electromotive force measurements previously reported for the Mg-Cd system. MAGNESIUM and cadmium are mutually soluble in all proportions in the solid state and form a single phase which has the hexagonal close-packed structure. X-ray investigations of this system1,2 have revealed a rapid variation in the relative dimensions of the unit cell occurring at approximately 50 at. pct. The rate of change of the c/a ratio with composition increases markedly for alloys containing more than 50 at. pct Cd. The purpose of this investigation was to determine the activity of Cd in the neighborhood of 50 at. pct and to discover whether or not the thermo-dynamic properties undergo a similar rapid change. The activities are calculated from vapor pressure data obtained by the Knudsen effusion method. Unfortunately the precision of the data from which the thermodynamic values are calculated is insufficient to establish unequivocally a departure from the normal trend. The results are reported primarily because they substantiate the only previously reported activity measurements3 and because they include values for pure Cd which in contrast to those of the alloys show excellent precision. The Cd-Mg system is known to contain several ordered phases. However, this investigation was made at temperatures considerably above the transition temperatures, and the alloys may be regarded as nearly random solid solutions. EXPERIMENTAL Apparatus—The effusion cells are machined from solid tantalum rod. The lids consist of threaded, flanged rings of tantalum onto which are welded shallow cups of 4 mil molybdenum foil. The orifice, which is located at its center, is made by grinding off a small dimple produced with a sharpened punch. Such an orifice has been mounted in plastic, sectioned, and the thickness of the orifice edge measured in a microscope. The maximum thickness is 0.00016 in., and the Clausing factor is consequently equated to unity. The area of the orifice is determined by tracing its projection on the screen of the metallograph at a known magnification and measuring the area of the tracing with a planimeter. Excellent temperature control is achieved with a 4 by 18-in. alundum core, gradient-wound, furnace

Jan 1, 1960

By G. P. Gladis, R. H. Atkinson

PALLADIUM has been used for jewelry for many years, particularly in conjunction with gold. This use increased in amount during the war, as palladium and gold were only moderately used for war purposes while demands for platinum and some of the other members of the platinum group were so great that their use in jewelry was prohibited. Palladium hardened with a small percentage of ruthenium has the necessary technical properties and appearance for good jewelry, and it is sufficiently rare to be desirable for luxury items-at least 100 times as rare as gold. Although both visual and spectrophotometric examination demonstrated that the color of palladium was almost the same as that of platinum, a few jewelers found the surface of palladium, even after some polishing, rather dark in areas that had been repeatedly heated during the soldering necessary to assemble certain types of handmade ornaments. This phenomenon is not to be confused with the thin, bluish oxide film that can be produced by heating in air over the range 400° to 800°C., as that film is easily reduced by dipping in warm 5 per cent formic acid or in warm methanol. It was suspected that the difficulty arose from heating in atmospheres that were alternately oxidizing and reducing, as Wise and Vines1 had found that this opened the grain boundaries of palladium and palladium-silver alloys in the same manner as in pure silver, as reported by Martin and Parker.2 This damage is caused by the reaction between oxygen in solid solution in the metal, acquired when heated under oxidizing conditions, and hydrogen diffusing in from subsequent heating under reducing conditions; the steam cannot diffuse out and therefore builds up sufficient pressure to disrupt the metal near the surface. Copper and various other metals can be damaged similarly, but platinum is nearly immune; therefore the problem was new to the platinum jeweler. Sulphur in the fuel gas also can cause trouble but did not appear to be dominant in the present instance. Metallographic examination of both pure palladium and ruthenium-palladium showed that the usual torch using oxygen and city gas as normally operated did in fact cause the surface and subsurface damage that had been observed, and also disclosed that a reducing flame caused more damage than an oxidizing flame and was very damaging even in the absence of any intentional swing in atmosphere from oxidizing to reducing (Fig. 7); besides the surface damage, there was serious loss of ductility. A full explanation of the mechanism of attack is not evident at the moment, but may be allied to the attack that occurs on heating catalytically active metals in nonequilibrium atmospheres.

Jan 1, 1946