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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 E. W. Filer, R. P. Smith, L. S. Darken

The solubility of nitrogen gas in purified iron and low alloy steels is determined for the y region (930° to 1350°C). The diffusivtiy of nitrogen is estimated from the rate of approach to equilibrium. The investigation of aluminum-killed steels, held in nitrogen, discloses precipitation of aluminum nitride, the solubility of which is determined. ALTHOUGH several investigations of the solu-bility of nitrogen gas in y iron have been reported, all have made use of the method adopted by Sieverts in his classic work, whereby the solubility is determined by the pressure or volume change of the gas. The agreement between different investigators* is rather poor, particularly as compared to the self-consistency of results of several individual investigators. The present report represents a portion of our investigation of the equilibrium of nitrogen and nitrogenous atmospheres with iron and steels. The method adopted in this temperature region (910" to 1400°C) consists of holding the specimen in gaseous nitrogen, quenching (or cooling), and determining the nitrogen content by direct analysis (solution in acid followed by distillation and titra-tion of the ammonia).** Up to 1050°C a 20 in. vertical wire-wound (Kan-thal) furnace was used; this was wound in three sections so that by proper adjustment of relative currents, and use of a modulator1 and a commercial controller (using a chromel-alumel control couple), a zone almost 6 in. long could be maintained uniform within a few tenths of a degree. Since the temperature coefficient of the nitrogen solubility is low, the full precision was not utilized and a variation of l° to 2" was tolerated; a variation of a similar amount also occurred occasionally between the beginning and end of the experiment. At higher temperature a vertically mounted, tubular Globar furnace and control unit was used; the zone of uniformity (l° to 2"C) was here limited to about 2 in.; fluctuations with time were comparable to those in the wire-wound furnace. Reported temperatures were measured by use of a platinum-platinum-rhodium thermocouple, which was frequently com- pared with a similar standard couple which was calibrated at the gold and palladium points and also compared with one certified by the Bureau of Standards; error from this source is believed to be less than 1 "C. Nitrogen gas from a commercial cylinder was mixed with slightly over 1 pct H by use of a gas mixer described previously.' This mixture was passed over hot copper and through ascarite and phosphorus pentoxide to remove oxygen and water vapor. The purified gas contained 1.05 pct H. This procedure was adopted to prevent the formation on the specimens of oxide film, which is well known to be nearly impervious to nitrogen; its success was attested by

Jan 1, 1952

By E. C. van Reuth

FIFTY-three alloys have been examined in the Fe-W and Co-W alloy systems in an attempt to verify the finding of o phases in these systems as reported by Goldschmidt.' The alloys were examined metallographically and by X-ray diffraction. The 10-g specimens were made by powder metallurgy techniques. Very fine, high-purity powders were compressed in a double-acting die at 120,000 psi after hydrogen reduction. All compacts were then sintered for 200 hr at 950°C in a helium atmosphere. Metallographic investigation and X-ray diffraction proved this time to be sufficient to allow complete homogenization before the subsequent high-temperature anneal. Each specimen was then sealed into an evacuated silica capsule and annealed at 1400"or 1500 C (except two) for 25 hr. (The 60 pct Fe and 55 pct Co alloys taken to 1610"and 1680°C respectively were held at these temperatures for 1hr. However, since these structures were at equilibrium before the anneal, and in view of their resultant structures, it is assumed that they reached equilib-

Jan 1, 1960

FRANK N. SPELLER,? Pittsburgh,. Pa.-Mr. -Hayward's paper again draws attention to the fact that copper in steel is not the enemy that a good many of us it one time thought it was. He shows clearly that steel with over 0.75 per cent. of copper is as dependable, under the :conditions which he describes, as the same steel without copper. I might add that you-can weld copper-steel- satisfactorily up to that point; in fact, we have succeeded in welding pipe by the lap weld process up to 1 per cent. copper. Notwithstanding the date that have been presented on the effects of copper on the physical properties and corrosion of steel, a maximum copper limitation is still found in many specifications. In some cases the limit is extremely low, such as below 0.05 .or 0.03: per cent., or thereabout. That is a relic of days gone by, and I think the practice should be discouraged. E. F. CONE, New York; N. Y.-Not so many years ago steel-casting makers were very particular as to the amount of copper that existed in the pig iron that they used. They would not use copper-bearing pig iron unless mixed with non-copper iron. I do not know what the practice now is in the particular foundry where I was metallurgist at one time,

Jan 4, 1918

By B. H. Sage, W. N. Lacey

The growing background of experimental information concerning the volumetric and phase behavior of binary and ternary hydrocarbon systems is used as the basis for a comparison of these systems with naturally occurring hydrocarbon mixtures under conditions representative of underground petroleum reservoirs. The qualitative and semiquantitative similarities and differences between the two types of systems are considered in reference to the possibilities and limitations of using experimental data on binary and ternary systems for predicting the volumetric and phase behavior of naturally occurring hydrocarbon mixtures of low molecular weight. The possible influence on such phase behavior of water, hydrogen sulphide, nitrogen, and components of relatively high molecular weight is discussed. INTRODUCTION During the past two decades much effort has been devoted to the study of the volumetric and phase behavior of pure paraffin hydrocarbons and of binary and ternary mixtures of these compounds. Many of these studies were carried out with the direct objective of utilizing a knowledge of the detailed characteristics of binary and ternary mixtures of the lighter paraffin hydrocarbons for predicting the behavior of more complex mixtures. The ability to make such predictions with accuracy would be of great value in petroleum production and refining. Although the behavior of the methane-propane system' served at one time as a qualitative illustration of the probable characteristics of the more complex hydrocarbon mixtures found in nature, it' fell far short of requirements for quantitative predictions. The present paper endeavors to indicate the relation of the more recently accumulated information concerning the behavior of binary and ternary hydrocarbons to this problem. In discussing binary and ternary systems as examples pointing toward the behavior of multi-component systems no effort is made to present new methods of predicting the characteristics of natural hydrocarbon mixtures. Preliminary proposals have been made elsewhere for the prediction of volumetric phase equilibrium and thermodynamic data for multicomponent mixtures, utilizing as a basis the behavior of binary and ternary systems. Numerous other proposals have been made. That based upon the concept of a pseudo-critical state" has proved to be of value to the petroleum industry. Concurrently with this study of binary and ternary systems investigations have been made of natural hydrocarbon systems. Of the many publications reporting such experimental information only a few examples will be mentioned. A number of studies of black oil and natural gas have been made and much attention has been directed to extended and detailed investigations of the behavior of fluids in condensate fieldS 16,17,18,19,20. This work has been supplemented by some studies of the separation of bitumen from natural hydrocarbon liquids The over-all behavior of such systems has been used in predicting the volumetric and phase behavior of naturally occurring mixtures This background of experimental and correlated information concerning the behavior of multicomponent hydrocarbon systems also permits a direct comparison of the characteristics of binary and ternary aliphatic systems with those materials produced from underground reservoirs. PRESENTATION OF DATA The primary limitation encountered in using binary and ternary aliphatic hydrocarbon mixtures as examples of the characteristics of the fluids encountered in underground reservoirs lies in the existing lack of knowledge of the quantitative effect upon behavior of the presence of several important constituents, notably hydrocarbons of high molecular weight, water, carbon dioxide, hydrogen sulphide, and nitrogen. The presence of substantial quantities of hydrocarbons of fairly high molecular weight serves to increase the complexity of the phase behavior of natural systems. No simple systems yet studied give adequate guidance in this regard. The influence of such materials of high molecular weight was indicated earlier",?' to an extent which serves to show that definite limitations now exist in the correlation of simple and complex systems. However, significant progress is being made in filling gaps in the information. For example, similarities in the behavior of fluids in condensate fields with that of binary and ternary systems are becoming more systematically evident. A few studies of the behavior of water in paraffin hydrocarbon systems have been made Results of investigations of mixtures of carbon dioxide and the lighter hydrocarbons also are available Limited work has been reported con-

Jan 1, 1949

By W. N. Lacey, B. H. Sage

The growing background of experimental information concerning the volumetric and phase behavior of binary and ternary hydrocarbon systems is used as the basis for a comparison of these systems with naturally occurring hydrocarbon mixtures under conditions representative of underground petroleum reservoirs. The qualitative and semiquantitative similarities and differences between the two types of systems are considered in reference to the possibilities and limitations of using experimental data on binary and ternary systems for predicting the volumetric and phase behavior of naturally occurring hydrocarbon mixtures of low molecular weight. The possible influence on such phase behavior of water, hydrogen sulphide, nitrogen, and components of relatively high molecular weight is discussed. INTRODUCTION During the past two decades much effort has been devoted to the study of the volumetric and phase behavior of pure paraffin hydrocarbons and of binary and ternary mixtures of these compounds. Many of these studies were carried out with the direct objective of utilizing a knowledge of the detailed characteristics of binary and ternary mixtures of the lighter paraffin hydrocarbons for predicting the behavior of more complex mixtures. The ability to make such predictions with accuracy would be of great value in petroleum production and refining. Although the behavior of the methane-propane system' served at one time as a qualitative illustration of the probable characteristics of the more complex hydrocarbon mixtures found in nature, it' fell far short of requirements for quantitative predictions. The present paper endeavors to indicate the relation of the more recently accumulated information concerning the behavior of binary and ternary hydrocarbons to this problem. In discussing binary and ternary systems as examples pointing toward the behavior of multi-component systems no effort is made to present new methods of predicting the characteristics of natural hydrocarbon mixtures. Preliminary proposals have been made elsewhere for the prediction of volumetric phase equilibrium and thermodynamic data for multicomponent mixtures, utilizing as a basis the behavior of binary and ternary systems. Numerous other proposals have been made. That based upon the concept of a pseudo-critical state" has proved to be of value to the petroleum industry. Concurrently with this study of binary and ternary systems investigations have been made of natural hydrocarbon systems. Of the many publications reporting such experimental information only a few examples will be mentioned. A number of studies of black oil and natural gas have been made and much attention has been directed to extended and detailed investigations of the behavior of fluids in condensate fieldS 16,17,18,19,20. This work has been supplemented by some studies of the separation of bitumen from natural hydrocarbon liquids The over-all behavior of such systems has been used in predicting the volumetric and phase behavior of naturally occurring mixtures This background of experimental and correlated information concerning the behavior of multicomponent hydrocarbon systems also permits a direct comparison of the characteristics of binary and ternary aliphatic systems with those materials produced from underground reservoirs. PRESENTATION OF DATA The primary limitation encountered in using binary and ternary aliphatic hydrocarbon mixtures as examples of the characteristics of the fluids encountered in underground reservoirs lies in the existing lack of knowledge of the quantitative effect upon behavior of the presence of several important constituents, notably hydrocarbons of high molecular weight, water, carbon dioxide, hydrogen sulphide, and nitrogen. The presence of substantial quantities of hydrocarbons of fairly high molecular weight serves to increase the complexity of the phase behavior of natural systems. No simple systems yet studied give adequate guidance in this regard. The influence of such materials of high molecular weight was indicated earlier",?' to an extent which serves to show that definite limitations now exist in the correlation of simple and complex systems. However, significant progress is being made in filling gaps in the information. For example, similarities in the behavior of fluids in condensate fields with that of binary and ternary systems are becoming more systematically evident. A few studies of the behavior of water in paraffin hydrocarbon systems have been made Results of investigations of mixtures of carbon dioxide and the lighter hydrocarbons also are available Limited work has been reported con-

Jan 1, 1949

By J. E. Sherborne, P. H. Jones, E. C. Babson

A study of the Chapman zone in the Richfield field, Orange County, California, indicates that the quantity of oil recovered by present methods will be only a small portion of the oil originally in place. Since the volume of residual oil is believed to be of large magnitude, an experimental water-flooding operation has been initiated in order to determine whether water-flooding offers promise as an economical method of recovering some of this residual oil. A single injection well was drilled between old producing wells, and a water-treating plant using alum flocculation and chlorination was designed and built. Water has been injected into the input well for six months at rates in excess of 100 bbl. per day. Production from one of the neighboring wells has increased materially, the oil production having risen from 7 to 30 bbl. and the water From I to 40 bbl. per day. While definite conclusions regarding the economic success of water-flooding in the Chapman zone are not justified at this time, it has been demonstrated that water can be injected into the zone on a sustained basis and that this water will displace appreciable quantities of oil from the sand. Introduction As a result of an investigation of subsurface conditions in the Chapman zone of the Richfield field, it was concluded that ultimate oil recovery from this zone would probably be low and that natural water encroachment was so localized as to be of little importance from a recovery stand- point. Furthermore, it was found that in many portions of the zone the wells were approaching an unprofitable level of production. When these data were presented to the management of the Union Oil Co.; their reaction was that an attempt should be made to develop methods of recovering at least a portion of the large quantity of oil remaining in this zone. After some investigation, it was decided that wafer-flooding offered the most likely means of accomplishing this end, but reservoir conditions in the Chapman zone differ so widely from those encountered in any of the flooding projects described in the literature that it was difficult to evaluate the probability of success. Despite encouraging results from laboratory tests, it was not even certain that water would displace an appreciable volume of oil from the Chapman sand under reservoir conditions. Therefore, it was decided to initiate a small-scale project, for two purposes: first, to determine whether water would displace oil from the Chapmall sand and, second, to obtain information and experience for future operations if water-flooding appeared to be a promising method of secondary recovery. Reservoir Data The Chapman zone is the upper of the two producing zones in the Richfield field, being found at depths from 3000 to 3700 fi.. The productive portion of the zolle consists of a large irregularly shaped sand body, which is more than 400 ft. thick at the top of the structure. As the margin of the field is approached, the sand is replaced

Jan 1, 1945

By A. Keil

TO measure the absolute conductivity of metallic specimens it is generally necessary to have exact geometrical shapes and good electrical contact with the test-piece. To overcome limitations of the standard methods, an electronic conductivity-meter* Trade name, Sigmatest; model Dr. F. Forster; Reutlingen, Ger-many. has been developed, which works on the principle of inducing high frequency eddy-currents in the specimens and measuring the reaction of these curients on a measuring coil.',' To attach the instrument to the test specimen, a flat area of about 10 mm diam is all that is necessary. The reading is taken off a scale calibrated in pet of International Annealed Copper Standard. The induced eddy-currents are propagated in a circular motion parallel to the surface. Thickness of the layer included in a measurement depends on the frequency used. With a frequency of 60 kc per sec, the penetration of the currents was 0.8 mm at the upper limit of the scale, and 2 mm at the lower limit. The method is limited to nonferrous metals and other applications have been described elsewhere." The object of the present investigation was to detect the formation and growth of surface layers of differing conductivity, and to determine the depth to which these changes could be observed. A well known phenomenon which illustrates the problem is the internal oxidation of certain silver alloys containing base metal solutes, such as copper or cadmium, when they are annealed in an oxidizing atmosphere.4, 5 Until now, the only methods available for following these phenomenon have been metallo-graphic examination and hardness tests.0, 7 Changes in mechanical properties of copper alloys by internal oxidation were recently discussed in a more general way by Martin and Smith." When measuring these conductivity changes it must be remembered that the only absolute values of conductivity are those of 1) the nontreated homogeneous specimen, and 2) the final values obtained with a surface layer of depth comparable to the penetration of the eddy-currents. All intermediate values refer to the mixed conductivities of the transformed surface layer and the untransformed alloy, and are thus readings of relative value only. Experimental Results Specimens were annealed for 1/2 hr at 800°C in hydrogen, and the internal oxidation was carried out by thermal treatment in air at 800°C. Fig. 1 shows the results of the first series of experiments. With internal oxidation of a solid solution of 8 pet Cd in silver, the conductivity rises continuously until the surface layer formed has become thick enough to be the deciding factor (about 400µ). Precipitates of CdO are mainly in the form of points, Fig. 2, and, as a result, the electric contact between the silver crystals is not distorted by them. Brine11 tests were run with a 1.25 mm ball and a 7.812 kg load. The specimen annealed in hydrogen and oxidized to a depth of 400µ had a hardness of 40 Bhn,

Jan 1, 1959

By J. J. Kramer, K. Foster

The orientation distribution of surface-energy -induced secondary recrystallized grains was determined. This work was conducted on thin sheets of a 3 pct Si-Fe alloy annealed under environmental conditions that furor grouth of grains with a (100) plane in the surface of the sheet. The texture was found to be extremely sharp and almost independent of sheet thickness. The distribution varied exponentially with the angular deviation from the {100} plane. It was possible to relate the distribution to the nu-cleation rate of the secondary rains as influenced by the surface-energy difference. THE role of surface energy in the secondary grain growth of cube-oriented grains (grains with a (100) plane in the plane of the sheet) in thin Si-Fe sheets has been previously discussed.1-4 In high-purity sheet material normal grain growth usually occurs until the grains have extended through the sheet. Further grain growth is inhibited by the thermal grooving of the boundaries at the sheet surface. However, additional growth of cube grains can occur by a secondary grain growth process under conditions where the (100) plane has a lower surface energy than other orientations. Apparently for these alloys, cusps exist in the polar plot5 of surface free energy with the lowest cusp energy occurring at the (100) orientations. This has been reported to be the result of preferential adsorption of sulfur on the (100) planes.6 As a result of this process, a distribution of orientations could arise from two possible mechanisms. First, when a cusp is present in the polar plot of surface free energy, there are orientations inside the cusp that have a lower surface energy than elsewhere on the polar plot. Also, at sufficiently high temperatures, flat surfaces whose orientations are inside or just outside the cusp (depending on its shape) can often thermally etch, yielding a microscopically stepped surface of even lower surface energy. As a result, grains oriented close to cube would also have a lower surface free energy, either because of the cusp shape or by thermal etching, and could possibly grow as secondary grains by the surface-energy phenomenon. One should thus observe a distribution in the surface orientation of the cube grains comprising the secondary structure. It is the purpose of this paper to investigate this orientation distribution experimentally and to discuss the factors involved in its formation. For this purpose, the surface orientations of a large number of secondary grains in various sheet thickness were determined by means of the Laue back-reflection X-ray technique. PROCEDURE A vacuum-melted 3 pct Si-Fe alloy containing a nominal impurity content of 0.005 wt pct was processed into strip. A single cold-rolling step of 90 pct reduction was used for each strip regardless of the final sheet thickness. Final strip thicknesses of 0.60, 0.30, 0.15, and 0.075 mm were used. Care was taken to insure that the final strip surface was smooth and flat. All strips of a given thickness were annealed together at 1200°C in dry hydrogen (dew point -70°C) to develop the desired secondary structure and to insure identical environmental annealing conditions. The annealing time was selected to develop a complete secondary structure in the thinner sheets but to permit the thicker sheets (0.60 mm) to have residual primary grains remaining. This was necessary to determine whether growth impingement could lead to one secondary grain consuming another at a greater angular deviation. For the X-ray determination of the surface orientation of the secondary grains, a special specimen holder was used. The camera and holder arrangement could be aligned by X-raying a grain in three positions rotated 180 deg to each other. Thus, with a small beam X-ray focus (1 mm), the surface orientation of any grain could be determined to within one-half a degree. The surface orientations of one hundred cube secondary grains were determined for each sheet thickness. The criteria of a secondary grain were its size relative to the sheet thickness and the number of sides of the grain observed in the sheet surface. (A primary recrystallized grain extending through a sheet will generally have six edges visible in the plane of the sheet, whereas a secondary grain will have many more when growing entirely into primary grains.) Grains were selected as randomly as possible by X-raying every secondary grain found along a line drawn on the strip. No attempt was made to determine the exact orientation of the planes of the surface, as many strips from randomly selected sheets were used. On1y the angular deviation of the surface plane from {100} was measured. In order to assess the volume distribution in the

Jan 1, 1965

By W. A. Clark

The production of sand in an oil well increases operating costs because of abnormal wear in subsurface equipment, the necessity for frequent cleanouts, and the need for a means of disposing of the sand. Moreover, removal of sand from the zone can bring about the creation of cavities from which bodies of formation, sand or shale, may slough into the hole, endangering the shutoff, impeding production or collapsing the liner. The procedure known as gravel packing is attracting attention as a means of controlling these factors and contributing to the productive life of a well. That gravel packing is now substantially beyond the preliminary stage on the Pacific Coast is reflected in the 191,000 bbl. of oil produced monthly by the 66 gravel-packed wells in 11 different producing sectors. Reasons fob Gravel Packing Gravel packing, if properly carried out, can be expected to provide the following benefits: 1. Prevent the movement of sand and thus eliminate sand production and sand fills, and prevent the formation of cavities. 2. Provide a practical, relatively inexpensive, large-diameter hole, which will provide well-known theoretical advantages. 3. Support the walls of the hole by completely filling the space between the liner and the formation, regardless of its irregularities, and afford a support for liners. 4. Provide for more efficient pumping operations in wells by: (a) possibly utilizing the gravel as a gas trap in pumping gaseous fluids, (b) allowing deep submergence of the pump into the oil zone. In a conventional well—that is, where the liner is set in an open hole-. even though perforation sizes are chosen according to known rules based on analysis of sand grains from samples from the zone, there is likely to be some production of sand. This may be due to the miscalculation of

Jan 1, 1940

By W. A. Clark

The production of sand in an oil well increases operating costs because of abnormal wear in subsurface equipment, the necessity for frequent cleanouts, and the need for a means of disposing of the sand. Moreover, removal of sand from the zone can bring about the creation of cavities from which bodies of formation, sand or shale, may slough into the hole, endangering the shutoff, impeding production or collapsing the liner. The procedure known as gravel packing is attracting attention as a means of controlling these factors and contributing to the productive life of a well. That gravel packing is now substantially beyond the preliminary stage on the Pacific Coast is reflected in the 191,000 bbl. of oil produced monthly by the 66 gravel-packed wells in 11 different producing sectors. Reasons fob Gravel Packing Gravel packing, if properly carried out, can be expected to provide the following benefits: 1. Prevent the movement of sand and thus eliminate sand production and sand fills, and prevent the formation of cavities. 2. Provide a practical, relatively inexpensive, large-diameter hole, which will provide well-known theoretical advantages. 3. Support the walls of the hole by completely filling the space between the liner and the formation, regardless of its irregularities, and afford a support for liners. 4. Provide for more efficient pumping operations in wells by: (a) possibly utilizing the gravel as a gas trap in pumping gaseous fluids, (b) allowing deep submergence of the pump into the oil zone. In a conventional well—that is, where the liner is set in an open hole-. even though perforation sizes are chosen according to known rules based on analysis of sand grains from samples from the zone, there is likely to be some production of sand. This may be due to the miscalculation of

Jan 1, 1940

By John C. Calhoun, F. W. Gooch, J. P. Everett

The results of two sets of displacement experiments are reported. In the first set of experiments various solutions of sugar in water were displaced by other solutions of sugar in water. In the second set oils were displaced by water. Each set of experiments was performed on a linear system made of cemented silica sand grains. These displacement tests were made to evaluate the behavior when the ratio of fluid viscosities between the displacing and displaced phases was varied. A further consequence of the test results is a comparison between displacement behavior when the displaced and displacing phases are miscible as with sugar solutions and when they are immiscible as with oil and water. INTRODUCTION Buckley and Leverett1 have presented a theory for the displacement of oil by gas or water based upon the relative permeability concept. This theory presents the displacement of oil as occurring in two phases, an initial or primary phase preceding the breakthrough of the displacing phase and a subordinate or secondary phase during which both oil and the displacing phase flow simultaneously through the same porous section. These authors gave the results of calculations to show that the percentage of oil displaced during the primary phase by water drive would be dependent upon the ratio of the viscosity of the oil to that of the water. No experimental evidence was reported by these authors to substantiate their theory. Qualitatively, however, it has been found to be in agreement with many observed field results. Laboratory investigators have been in general agreement in reporting for air or gas drive2,3 a small primary phase of production and a large secondary phase. Reported investigations on water drive3,4,5 have shown instances where both primary

Jan 1, 1950

By J. V. Gluck, Ping-Wang Chiang

The tellurium-rich region of the Sb-TI-Te ternary system was investigated by means of DTA, metallo-graphic, X-ray, and electron beam microprobe techniques on the sections Sb2Te3-T12Te3, SbTlTe2-Te, SbT1Te2-Sb2Te3, and SbTlTe2-T12Te3. The phase behavior of this region is summarized in terms of four ternary invariant reactions and a schematic reaction diagram is suggested. Isopleths for the sections SbT1Te2-Sb2Te3, Sb2Te,-T12Te3, and SbTlTe2-Te were constructed, and a schematic diagram of the projections of the liquidus lines and invariant planes is presented. No evidence was found to support the existence of the ternary compound "SbTlTe3", or pseudo-binary behavior of the section T12Te3-Sb2Te3, as reported by Borisova and Efremova. Electrical conductivity, Seebeck coefficient, and thermal conductivity measurements were made at room temperature on fully annealed samples. 1 HE phase relationships in chalcogenides are often complex and difficult to resolve, particularly since the approach to equilibrium is a rather slow process. For example, the phase diagram of the T1-Te binary system was in doubt until clarified by Rabenau et al.,1 the phase fields at compositions near Bi2Te3 in the Bi-Te binary system have only recently been satisfactorily elucidated by Glatz,2 and there may still be some question as to the extent of the Sb2Te3 field in the Sb-Te system.3-5 In ternary systems, the existence of the compound "AgFeTe2" was the subject of a number of conflicting reports6-8 and the stoichiometry of the composition "AgSbTe2" was in doubt for a period of time.9 Recently, questions have arisen regarding the existence of certain compounds in the ternary systems Bi-Tl-Te10-14 and Sb-Tl-Te.15 The impetus for studies of these latter systems stemmed from the report of Borisova et a1.10 of a congruently melting ternary compound, "BiTlTe3", which apparently had extremely favorable thermoelectric properties for room-temperature cooling applications. Attempts by other investigators to produce the compound or confirm the transport properties proved to be unsuccessful.12-14 Recently, Chiang and Gluck14 reported studies of the phase relations in the tellurium-rich region of the Bi-T1-Te system which indicated that the section T12Te3-Bi2Te3 was not pseudobinary as suggested by Borisova et a1.10 The contention of Spitzer and sykes12 was supported that the composition "BiT1Te3" was multiphase, with the primary constituent actually being BiTlTe2, a compound whose existence has been well demonstrated.16,17 The investigation reported in the present paper was prompted by a later report of Borisova and Efremova15 on a similar study of the section T12Te3-Sb2Te3 from the Sb-T1-Te system. They also claimed this section to be pseudobinary, and that a ternary compound "SbTlTe," was formed peritectically. Some "preliminary" crystallographic data were given for the compound and thermoelectric transport properties were presented. In view of the questions concerning the behavior of the Bi-T1-Te system and the existence of the compound "BiT1Te3" it was suspected that the Sb-T1-Te system might behave in a similar fashion, particularly in light of the known existence of a compound SbT1Te2, iso-structural with BiT1Te2.17 Consequently, an investigation was undertaken to clarify the phase relationships in the tellurium-rich region of the Sb-T1-Te system. It is the purpose of this paper to present the results of this study, including a representation of the phase relations, isopleths for various composition sections, and the determination of some phase compositions and transport properties. EXPERIMENTAL PROCEDURES Commercially available high-purity (99.999+ pct) elements, purchased from the American Smelting and Refining Co., were used for the sample preparation. All samples were made from thoroughly mixed powders of previously prepared master alloys: SbTlTe2, Te, Sb2Te3, and T12Te3. Stoichiometric quantities of the constituents for each 10-g sample were weighed into a specially cleaned fused silica tube and sealed under a vacuum of better than 5 x 10-5 torr. The sealed constituents were fused and reacted at 650° to 750°C for at least 4 hr under continuous agitation in a "rocking" furnace, and the resulting product was air-cooled. The tube was opened and the sample was ground to a powder. A portion of the powder was rebottled in a DTA tube under vacuum, and the rest of the material was similarly resealed in a separate tube, re-fused in the rocking furnace, and again cooled to make the ingots for electrical and microstructural studies. All samples were subjected to further heat treatments as discussed in the section on experimental results. Each DTA tube was made of 7-mm-OD fused silica tubing with a concentric 2-mm-ID depression about 4 mm long formed in the bottom to accommodate a thermocouple. The size of a DTA sample was 0.5 to 1.0 g. An Aminco Thermoanalyzer whose accuracy was within 2°C18 was used for the DTA measurements. The metallographic samples were prepared by conventional techniques. A solution of FeCL dissolved in a methanol-HC1 mixture was found to be the most satisfactory etchant. Electron beam microprobe scanning and point-count examinations were made on polished and unetched samples using an ARL Electron Microprobe at an electron beam voltage of 20 kv. The detectors were set to receive characteristic La1 radiation. Calibration standards of the pure elements were incorporated in each sample mount; quantitative point counts were calibrated by a method similar to Ziebold

Jan 1, 1969

By Charles L. Guettel

The temperature coefficients of electrical resistance of 31 alloys in the nickel-rich corner of the Ni-Cr-Fe system were determined. The results indicate that a range of binary Ni-Cr alloys has lower temperature coefficients than a specific region of Ni-Cr-Fe alloys which has been reported and quoted by others as providing the lowest coefficients in the ternary system. DESIRABLE properties of resistivity and temperature coefficients of resistance have been the basis for the successful commercial application of various Ni-Cr and Ni-Cr-Fe alloys. In particular, low or negligible temperature coefficients of resistance are necessary for wire used in precision wire wound resistors and potentiometers involved in closely controlled electrical and electronic circuitry. Alloys most successfully applied to this purpose basically have not been ternary Ni-Cr-Fe alloys but rather heat-treated Ni-Cr alloys in the region of approximately 73 to 79 pct Ni and 20 pct Cr with significant additions of other elements such as aluminum, silicon, iron, copper, manganese, and cobalt. While the addition elements play a vital role in the nature and control of the temperature-resistance curve of any one of these alloys, the inherent relatively low temperature coefficient of the binary Ni-Cr base composition itself in the approximate region of 80 pct Ni and 20 pct Cr contributes fundamentally to the eventual negligible temperature coefficient obtained with the applied alloys. W. A. Dean 1 has reported mean temperature coefficients (20' to 100oC) of as-cast samples for the Ni-Cr-Fe system, the nickel corner of which is given in Fig. 1. Dean had to use as-cast samples because alloys from a considerable region of the system were unworkable. Dean refers to the work of Hunter and sebast2 who used annealed wire samples to show that, for chromium contents of 10 to 25 pct, the temperature coefficient increases as the iron content is increased at the expense of nickel. Although the data of Hunter and Sebast were limited in the nickel-rich areas to eight samples of 60 to 91 pct Ni with only four samples containing iron, the possibility that no Ni-Cr-Fe alloy has a lower temperature coefficient than certain binary Ni-Cr alloys should have been given serious consideration. However, Dean's work has been referred to by J. S. Marsh,3 who, quoting Dean, states that for the temperature coefficients "the smallest values-about 0.0001 per oC (100 ppm)—were found for alloys containing about 55 pct Ni and 20 pct Cr" (balance iron). A region such as that reported by Dean would be significant to those trying to develop alloys for the applications described. Therefore, a series of three-pound laboratory open-air induction melts of Ni-Cr and Ni-Cr-Fe alloys were melted, conventionally processed to 0.005 in. diam wire, and continuously strand annealed at 1900° F. The basic Ni-Cr compositions, with balances essentially iron other than usual minor impurities, and the corresponding temperature coefficients of resistance and resistivities are given in Table I. The resistivities are approximate and are not to be considered as a basis for relating them to their position of composition in the ternary system. The wire diameters were determined with a micrometer, and not by weight and density measurements which would be required for accurate resistivity values. However,

Jan 1, 1963

By W. R. Seyfried

THE problem of extracting alumina from clay and low-grade bauxites has been the subject of considerable interest for some time. The basic reason, of course, lies in the fact that known reserves of high-grade bauxite are not inexhaustible and that the present commercial process cannot successfully cope with low-grade bauxites or clay. Ultimately it may be necessary to use these poorer raw materials for all commercial operations. An unprecedented demand for aluminum during the war emergency and the constantly threatened shortage of imported bauxite caused the United States Government to take an active role in this problem. Through the National Academy of Sciences, the War Production Board and the Defense Plant Corporation, it investigated processes and finally selected four to be used in the construction and operation of four experimental plants. Each plant was to be designed in such a way as to facilitate its incorporation into a larger commercial plant should the need arise. The Chemical Construction Corporation process, or "Chemico" ammonium sulphate process as it is better known, was one of the four selected. The extensive literature and patents on record before the war generally follow one of two process-types depending upon the extracting reagent used. One group uses an acid reagent, the other an alkali. The Chemico process uses an acid reagent. For those interested in other processes described in literature, there is a short bibliography at the end of this paper. The basic steps of all acid extraction processes are: (I) to make the aluminum silicates acid soluble, (2) to separate the released alumina from impurities and insoluble gangue, and (3) to recover the reagent for re-use. THE PROCESS AS PLANNED In April 1941, a group of chemists and engineers of the Chemical Construction Corp. became interested in the problem of extracting alumina from clays and low-grade bauxites and, under the leadership of Mr. Blakeslee Barnes, Vice President and General Manager of the Company, first drafted a process in July of that year-five months prior to Pearl Harbor. The work continued in our research laboratories and with a small pilot plant. By June 1943, the work had progressed to a point where it was possible to apply for a patent on the process which was U.S. patent 2,405,426, granted August 6, 1946. Immediately prior to the development of the Salem plant, the process was envisaged to be as follows: I. The first step was to make the aluminum silicates acid soluble. It was planned: (a) Clay or low-grade bauxite would be roasted at 700 to 800°C (1292° to 1472°F), (b) The roasted ore would then be leached with hot aqueous ammonium bisulphate to form a slurry. In this way the

Jan 1, 1947

By C. S. Westerberg, C. P. Heiner

Observation of the clinkering action of coal from the Castle Gate D seam in underfeed stokers over a period of years has given rise to the present investigation of the effect of bony coal on clinkering. Some very costly examples of slagging clinkers in particular cases have been of especial interest to the authors. In such cases coal analyses and ash-softening and fluid temperatures have been found of little value. In general, it was noted that slagging mas accompanied by a somewhat higher ash content of the stoker slack, and the suspicion naturally arose that foreign matter was the troublemaker. One would naturally suspect bony coal and rock impurities because of their occurrence and prevalence within the seam and the relative absence of sulphur or other impurities in the coal mined. The test results given herein indicate that the concentration of the bony coal and rock impurities in the coal determines the clinkering tendencies of the ash during combustion. Castle Gate D Seam Extending from the Utah-Colorado line near Grand Junction, Colo., westward to Greenriver, Utah, and thence in semicircular form north and westward to Castle Gate, and from there southward to Mt. Hilgard in central Utah, is a line of nearly perpendicular cliffs, composed of interbedded massive sandstone and shales, making up the coal-bearing horizon of the Mesaverde formation of Upper Cretaceous age. The cliffs face roughly concentrically toward the south and southeast and the strata, with conformably enclosed coal beds, gently dip away from the face of the cliffs and at right angles to their front line. Back of these cliffs the mountain masses rise to an altitude of from 8000 to 10,ooo ft. above sea level. Stretching away from their foot is a great shale plain, on which the towns are situated and over which the railroad lines and highways run. The Castle Gate mines enter the coal beds at their outcrop; the workings extending within a particular coal bed away from the outcrop and under the mountain mass back from the cliff line (Fig. I). Throughout the Mesaverde formation in the Castle Gate general area, there are from two to five workable coal beds. Usually not all of these are coincidentally of workable size and merchantable quality throughout any given large tract. In the Castle Gate mine area, the base of the Mesaverde horizon and coal measures is marked by a massive, cliffmaking, gray sandstone bed 60 to 80 ft. thick. Locally this is referred to as the "Castle Gate sandstone floor." Frank R. Clark, in U. S. Geol. Survey Bull. 793, designates it as the "Aberdeen sandstone." At Castle Gate the various coal beds are designated by the letters A, B, C, etc., commencing with the lowest bed.

Jan 1, 1942

By C. P. Heiner, C. S. Westerberg

Observation of the clinkering action of coal from the Castle Gate D seam in underfeed stokers over a period of years has given rise to the present investigation of the effect of bony coal on clinkering. Some very costly examples of slagging clinkers in particular cases have been of especial interest to the authors. In such cases coal analyses and ash-softening and fluid temperatures have been found of little value. In general, it was noted that slagging mas accompanied by a somewhat higher ash content of the stoker slack, and the suspicion naturally arose that foreign matter was the troublemaker. One would naturally suspect bony coal and rock impurities because of their occurrence and prevalence within the seam and the relative absence of sulphur or other impurities in the coal mined. The test results given herein indicate that the concentration of the bony coal and rock impurities in the coal determines the clinkering tendencies of the ash during combustion. Castle Gate D Seam Extending from the Utah-Colorado line near Grand Junction, Colo., westward to Greenriver, Utah, and thence in semicircular form north and westward to Castle Gate, and from there southward to Mt. Hilgard in central Utah, is a line of nearly perpendicular cliffs, composed of interbedded massive sandstone and shales, making up the coal-bearing horizon of the Mesaverde formation of Upper Cretaceous age. The cliffs face roughly concentrically toward the south and southeast and the strata, with conformably enclosed coal beds, gently dip away from the face of the cliffs and at right angles to their front line. Back of these cliffs the mountain masses rise to an altitude of from 8000 to 10,ooo ft. above sea level. Stretching away from their foot is a great shale plain, on which the towns are situated and over which the railroad lines and highways run. The Castle Gate mines enter the coal beds at their outcrop; the workings extending within a particular coal bed away from the outcrop and under the mountain mass back from the cliff line (Fig. I). Throughout the Mesaverde formation in the Castle Gate general area, there are from two to five workable coal beds. Usually not all of these are coincidentally of workable size and merchantable quality throughout any given large tract. In the Castle Gate mine area, the base of the Mesaverde horizon and coal measures is marked by a massive, cliffmaking, gray sandstone bed 60 to 80 ft. thick. Locally this is referred to as the "Castle Gate sandstone floor." Frank R. Clark, in U. S. Geol. Survey Bull. 793, designates it as the "Aberdeen sandstone." At Castle Gate the various coal beds are designated by the letters A, B, C, etc., commencing with the lowest bed.

Jan 1, 1942

CONTENTS PAGE UREN, LESTER C.-Increasing Production of Petroleum by Increasing Diameter of Wells. Discussed by A. Beeby Thompson 1 LAHEE, FREDERIC H.-Comparative Study of Well Logs on the Mexia Type of Structure. Discussed by W. A. I. M. van Waterschoot van -der Gracht.... 4 Increasing Production of Petroleum by Increasing Diameter of Wells Discussion of the paper of LESTER C. UREN, presented at the New York Meeting, February, 1925, and issued, as Paper No. 1364-G, with MINING AND METAL-LURGY, October, 1924. A. BEEBY THOMPSON, London, Eng. (written discussion).-The subject discussed in this paper has long been debated by operators in European fields, where very strong views are held regarding the advisability of controlling gas pressures by shutting in wells. While unwilling to theorize on the subject of restricted flow, the writer has always been disposed to associate himself with those who hesitate to impose any obstruction to a natural transitory state that breaks up the oil-containing strata and establishes a feeder system which no subsequent events, natural or artificial, can approach in intensity. In both Russia and Roumania, where the oil is concentrated in discontinuous, disturbed, and irregular lenticles of sand varying, within short distances, in coarseness of grain, extent of impregnation and degree of cementation, it has been the practice to let the wells run wild in order to provoke disruption of strata. By encouraging violent eruptions, an extended feeder system is created and the ejection of enormous quantities of sand, rock, and clay creates a sump and seepage area that it would be difficult to imitate by any artificial means, not excluding actual mining. Before discussing the somewhat novel method suggested for enlarging the infiltration area, the writer would like to confirm the fact that many valuable data applicable to oil are forthcoming from a study of water phenomena. Long association with water-supply problems in many parts of the world has shown how closely the phenomena of underground movements of water and oil are related, so that it is pleasing to note the author's use of water formulas. But there is one great distinction;

Jan 7, 1925

By Wm. R. Webster

This is a contribution for the proposed new discussion on the physics of steel. The former discussion on the subject started with the consideration of five papers presented at the Chicago meeting in 1893, and continued for several years. The Suggested Lines of Discussion, prepared by Doctor Howe, covered a wide field and added greatly to the success of the work. Naturally, the first step in a new discussion will be to remodel and bring up to date the old Suggested Lines of Discussion so as to embody all the important advances in the metallurgy of steel that have a bearing on the physics of steel and keep the papers and discussions within the field of work undertaken. This paper will be devoted to the practical application, in rolling steel, of the effects of carbon, phosphorus, and manganese on its tensile strength, with some suggestions on further research work. Dr. J. E. Stead, in his paper Influence of Some Elements on the Mechanical Properties of Steel,' gave a complete review of all that had been done during the past thirty years. He gave full credit to all investigators who worked on these lines, also their results, with his views on same, and in many cases his own results. All of this data and much new valuable information were put in convenient shape for reference and study. To do this required a great deal of work, which is fully appreciated by the steel manufacturers and investigators. The variations in the values given by the different investigators for the increase of the tensile strength of steel for each 0.01 per cent. of carbon, phosphorus, and manganese were largely due to the steels they worked on, the large or small variations in the amount of the elcments present, and the omission to take into consideration all the factors, from the blast furnace through to finished rolled material, that affect the character of the steel. For instance, a poorly made dirty steel requires considerably more carbon to give the same ultimate strength than a well-made clean steel with the same phosphorus and manganese content.

Jan 1, 1922