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THE meeting was opened, Tuesday evening, May 25th, by an address from the President, R. W. Raymond. The following persons having been duly proposed for members and associates of the Institute, were recommended by the Council for election. They were unanimously elected MEMBERS. Florian Alexander, - Newark, N. J. Charles A. Ashburner, - Philadelphia, Pa. Phineas Barnes, - Pittsburgh, Pa. J. Y. Bergen, - Chicago, 111. Leopold C. Bierwirth, - Dover, N. J. Charles E. Billin, - Philadelphia, Pa. Jerome L. Boyer, - Temple, Berks County, Pa. William S. Cherry, - Streator, Ill. Thomas Couch, - Salt Lake City, Utah. W. S. De Camp, - Boonton, N. J. Thomas Donaldson, - Boise City, Idaho. H. Firmstone, - Longdale, Va. Franz Fohr, - New York City. Richard George, - Dover, N. J. John M. Hartman, - Philadelphia, Pa. C. W. Kempton, - Newburyport, Mass. James B. Lewis, - Dover, N. J. James F. Lewis, - Amenia, Dutchess County, N. Y. Arthur H. Meyer, - St. Louis, Mo. Edward H. Morrison, - Boonton, N. J. Charles J. Norwood, - Lexington, Ky. John R. Peters, - Dover, N. J. Charles I. Rader, - Vinton Furnace, Ohio. W. M. Rees, - Stockton, Luzerne County, Pa. George Richards, - Dover, N. J. Alexander H. Sherrerd, - Scranton, Pa. W. S. Sweeny, - Easton, Pa. W. J. Taylor, - Chester, N. J. Walter Tefft, - Mineville, Essex County, N. Y. J. Alexander Tyler, - New York City. J. D. Weeks, - Pittsburgh, Pa. William Wheatley, Jr., - New York City. Moses D. Wheeler, - Virginia, Nevada. Henry Woods, - Streator, III.

Jan 1, 1876

By E. F. Reed

CONSIDERABLE deep hole prospect drilling has been done in the last few years in the Globe-Miami mining district about 70 miles east of Phoenix, Arizona, and in the San Manuel-Tiger area about 50 miles south of the Globe-Miami region. More than 205,000 ft of churn drilling have been completed by the San Manuel Copper Corp. at their property in the Old Hat Mining District in southern Pinal County. The deepest hole on this property is 2850 ft; there are 49 holes deeper than 2000 ft. At the adjoining Houghton property of the Anaconda Copper Mining Co., where only one hole reached 2000-ft depth, there were 27,472 ft of churn drilling and 3436 ft of diamond drilling. Three churn drill holes were deepened by diamond drilling methods. Near Miami in the Globe-Miami district the Amico Mining Corp. drilled four holes by combined churn and rotary drilling methods, the total amounting to 13,879 ft, of which 2256 ft were drilled with a portable rotary rig. In the same district, besides doing a large amount of shallow prospect drilling, the Miami Copper Co. drilled two holes of 2560 and 3787 ft, respectively, which were completed by churn drilling methods. The rocks encountered in drilling at San Manuel and Tiger are described by Steele and Rubly in their paper on the San Manuel Prospect' and by Chapman in a report on the San Manuel Copper Deposit? The rocks are well-consolidated Gila conglomerate, quartz , monzonite, and monzonite porphyry. In some places these formations stand very well while being drilled, and three holes were drilled without casing, the deepest of which was 2200 ft. In other holes faulted and fractured ground made drilling difficult. In the Globe-Miami district the deep drilling was done in the down-faulted block of Gila conglomerate east of the Miami fault and in the underlying Pinal schist. The geology of this area is described by Ransome.3 In the Amico holes the conglomerate varied from material consisting entirely of granite boulders and fragments to a rock made up of schist fragments in a sandy matrix; in the Miami Copper Co. holes there were more granite boulders and the material was poorly consolidated. Drilling was much more difficult and expensive in the Miami area than in the San Manuel district, mainly because of the depth of the holes and the formations drilled. All the deep hole prospecting described in this paper was done with portable rigs. The churn drill rigs were of several types, of which the Bucyrus-Erie were the most popular. Bucyrus-Erie 28L, 29W, and 36L rigs were used on some of the deeper holes on the San Manuel property. A few Fort Worth spudder types were tried, and the deepest hole at San Manuel was drilled with a Fort Worth Jumbo H. The spudder type is considerably larger than most other rigs used on this work and required a larger location site. The spudders were belt-driven machines with separate power units, and time required for setting up and moving was much longer than with the more portable drills. All the churn drilling was done by contractors or with machinery leased from them. A few of the contractors had complete equipment, including most of the necessary fishing tools. Unusual and special, fishing tools were obtainable from the supply companies in the oil fields of New Mexico or in the Los Angeles area. Most of the contractors used equipment with standard API tool joints, so that much of it was interchangeable. Failure of tool joints is one of the principal causes of fishing jobs. It can be minimized if the joints are kept to the API specifications and the proper sized joints are used in the various holes. The minimum sizes that should be used with various bits are as follows: 12-in. and larger bits, 4x5-in. tool joints; 10-in. bits, 3 1/4x4 1/4-in. tool joints; 8-in. bits, 2 3/4x 3 3/4-in. tool joints; 6-in. bits, 2 1/4 x3 l/4 -in. tool joints; 4-in. bits, 1 5/8 x2 5/8-in. tool joints. Two rotary drill rigs were tried at San Manuel on the same hole, and a portable rotary drill rig was used on the Amico drilling for test coring the formation and for drilling in holes 3 and 4. Rotary drilling differs from churn drilling or cable tool drilling in that the bit is revolved by a string of drill pipe and the cuttings are removed from the hole by a thin solution of mud pumped through the drill pipe. The principal parts of a rotary rig are the power unit, a rotating table to revolve the drill pipe, hoists to raise and lower the pipe and to handle casing, and a pumping system to circulate the drilling liquid. The rig used on the Amico property at Miami was mounted on a truck. The larger rig used on the San Manuel property was hauled by several trucks and had separate turntable and pumping units. Diamond drill coring equipment was used successfully with the rotary rig in the holes on the Amico property, To allow for 2 3/8-in. drill pipe with tool joints, 3 1/2-in. core barrels and bits were used. With the standard 3 1/2-in. core barrel there was considerable difficulty in maintaining circulation with mud, so a barrel was designed with a smaller inner tube and a broad-faced bit. This allowed coarser material to circulate between the barrels. Rock bits of 5 5/8 to 3 7/8 in. were used with the rotary rig for drilling between core runs. Diamond drill equipment is much lighter than churn drill tools, so that fishing tools can usually be obtained from supply houses by air express when needed. Three churn drill holes on the Houghton property at Tiger were deepened by diamond drilling with Longyear UG Straitline gasoline-driven-machines. The open churn drill hole was cased with 2 1/2-in. black pipe. In deep hole churn drilling, casing is one of the most important items, especially in drilling in unconsolidated material like the formations drilled by

Jan 1, 1952

By M. R. J. Wyllie, F. Morgan, P. F. Fulton

The importance of formation factor, F, not only in electric logging but as a fundamental rock parameter has recently been stressed.',: The desirability of investigating the range of variation of the resistivity index exponent, n, in the relationship I = S ;", where I is the resistivity index and Sw the water saturation as a fraction of the void volume of a porous medium, has also been urged.3 The magnitude and variation of n with saturation and rock texture is a subject not only of theoretical interest but also one of prime importance in the interpretation of electric logs. A simple technique has recently been developed which enables both F and u to he measured with high accuracy and which may also find acceptance as a convenient method for the determination of irreducible saturation attainment in the restored state method of core analysis. Experience has taught that reproducible measurements of F are possible only if the resistance measuring electrodes are so arranged with respect to a plane face on a porous medium that they are able to make electrical contact with substantially all entry pores in that plane. In practice this may be achieved by using a platinized-platinum gauze electrode backed by some absorbent material (such as felt) which has been saturated with a fluid identical with that used to saturate the porous medium. Applicatiorl of pressure to the electrode and absorbent material then forces the gauze against the plane face of the porous medium and simultaneously squeezes saline solution through the meshes of the gauze. By this means the electrode is in continuous aqueous contact with all pores and satisfactory and reproducible low resistance contact with the porous medium is achieved. Clearly this method, although satisfactory for measurements of F, cannot be applied to the making of continuous resistance measurements on a porous medium while capillary pressure desaturation is being carried out. However, accepting the principle that for satisfactory results electrical contact must be made between a measuring electrode and all pores adja- cent to that electrude, methods of bringing electrodes into intimate contact with the surfaces of porous media were investigated. Two methods were ultimately found to be satisfactory: in the one, the metal electrode is formed on the required portion of the porous medium by the use of a metal spray gun, while in the second the electrode is painted on with an ordinary camel's hair brush. The first method has the advantage of permitting the use of any metal which can be sprayed, but has the disadvantage of requiring rather elaborate and expensive equipment. The second method is presently limited to silver electrodes although in principle other metals, e.g. platinum or gold, could be used. Moreover, the method is so simple and cheap, and has been found to be so satisfactory that it will be described in some detail. The core being investigated is cut into a right circular cylinder and is extracted and dried in the usual manner. The ends are then lightly painted with silver conducting paint* of the type used in printed electrical circuits. The quantity of paint used is not critical but the recommended, minimum compatible with entirely coating the core ends is recommended, particularly on the end that contacts the barrier. The core is then dried at atmospheric temperature for one hour or for shorter periods at any suitable elevated temperature up to about 110°C. It will be found that silver coatings so prepared are not only strongly adherent but also permeable and the core may be the core may be desaturated by the ordinary capillary pressure technique through one of the coated faces. The same permeability is characteristic also of thin metal coatings formed using the spray-gun technique. An ordinary Lucite capillary pressure desaturation cell has been adapted to a form suitable for measuring the resistivity of the saturated silver faced cores both at 100 per cent saturation (i.e., F) and at intermediate saturations down to the irreducible minimum. This has been achieved as follows: A Coors porcelain barrier, having a displacement pressure of c 30 psi was grooved across a diameter. Dimensions of this groove were c 1 mm deep and 1 mm wide at the top. The groove was then painted thickly with silver conducting paint, the paint in the groove being extended lightly over the edges of the groove for a distance of c 1 mm on each side. A 30 gauge silver wire was then arranged in the groove in a form of a spring bow, each end of the silver being held at diamet~ically opposite ends of the groove by means of plastic cement. The arc of the bow at its highest point was arranged to be a millimeter or so above the face of the barrier, while one end of the bow wire was led by means of a pressure-tight connection through the wall of the capillary pressure cell. The groove in the barrier was then Surrounded by suitably cut portions of Kleenex in the conventional manner so as to ensure capillary continuity from core to barrier, and the core placed on the barrier. The weight of the core distorted the silver spring bow and good electrical contact was thereby made between the outside of the cell and the lower painted silver electrode. Electrical connection to tile top painted silver

Jan 1, 1951

By M. R. J. Wyllie, F. Morgan, P. F. Fulton

The importance of formation factor, F, not only in electric logging but as a fundamental rock parameter has recently been stressed.',: The desirability of investigating the range of variation of the resistivity index exponent, n, in the relationship I = S ;", where I is the resistivity index and Sw the water saturation as a fraction of the void volume of a porous medium, has also been urged.3 The magnitude and variation of n with saturation and rock texture is a subject not only of theoretical interest but also one of prime importance in the interpretation of electric logs. A simple technique has recently been developed which enables both F and u to he measured with high accuracy and which may also find acceptance as a convenient method for the determination of irreducible saturation attainment in the restored state method of core analysis. Experience has taught that reproducible measurements of F are possible only if the resistance measuring electrodes are so arranged with respect to a plane face on a porous medium that they are able to make electrical contact with substantially all entry pores in that plane. In practice this may be achieved by using a platinized-platinum gauze electrode backed by some absorbent material (such as felt) which has been saturated with a fluid identical with that used to saturate the porous medium. Applicatiorl of pressure to the electrode and absorbent material then forces the gauze against the plane face of the porous medium and simultaneously squeezes saline solution through the meshes of the gauze. By this means the electrode is in continuous aqueous contact with all pores and satisfactory and reproducible low resistance contact with the porous medium is achieved. Clearly this method, although satisfactory for measurements of F, cannot be applied to the making of continuous resistance measurements on a porous medium while capillary pressure desaturation is being carried out. However, accepting the principle that for satisfactory results electrical contact must be made between a measuring electrode and all pores adja- cent to that electrude, methods of bringing electrodes into intimate contact with the surfaces of porous media were investigated. Two methods were ultimately found to be satisfactory: in the one, the metal electrode is formed on the required portion of the porous medium by the use of a metal spray gun, while in the second the electrode is painted on with an ordinary camel's hair brush. The first method has the advantage of permitting the use of any metal which can be sprayed, but has the disadvantage of requiring rather elaborate and expensive equipment. The second method is presently limited to silver electrodes although in principle other metals, e.g. platinum or gold, could be used. Moreover, the method is so simple and cheap, and has been found to be so satisfactory that it will be described in some detail. The core being investigated is cut into a right circular cylinder and is extracted and dried in the usual manner. The ends are then lightly painted with silver conducting paint* of the type used in printed electrical circuits. The quantity of paint used is not critical but the recommended, minimum compatible with entirely coating the core ends is recommended, particularly on the end that contacts the barrier. The core is then dried at atmospheric temperature for one hour or for shorter periods at any suitable elevated temperature up to about 110°C. It will be found that silver coatings so prepared are not only strongly adherent but also permeable and the core may be the core may be desaturated by the ordinary capillary pressure technique through one of the coated faces. The same permeability is characteristic also of thin metal coatings formed using the spray-gun technique. An ordinary Lucite capillary pressure desaturation cell has been adapted to a form suitable for measuring the resistivity of the saturated silver faced cores both at 100 per cent saturation (i.e., F) and at intermediate saturations down to the irreducible minimum. This has been achieved as follows: A Coors porcelain barrier, having a displacement pressure of c 30 psi was grooved across a diameter. Dimensions of this groove were c 1 mm deep and 1 mm wide at the top. The groove was then painted thickly with silver conducting paint, the paint in the groove being extended lightly over the edges of the groove for a distance of c 1 mm on each side. A 30 gauge silver wire was then arranged in the groove in a form of a spring bow, each end of the silver being held at diamet~ically opposite ends of the groove by means of plastic cement. The arc of the bow at its highest point was arranged to be a millimeter or so above the face of the barrier, while one end of the bow wire was led by means of a pressure-tight connection through the wall of the capillary pressure cell. The groove in the barrier was then Surrounded by suitably cut portions of Kleenex in the conventional manner so as to ensure capillary continuity from core to barrier, and the core placed on the barrier. The weight of the core distorted the silver spring bow and good electrical contact was thereby made between the outside of the cell and the lower painted silver electrode. Electrical connection to tile top painted silver

Jan 1, 1951

By H. L. Shergold, O. Mellgren

Concentration of fine quartz particles at the iso-octane/water interface has been investigated under different conditions of pH and dodecylamine concentration. The results obtained from the related studies on the effect of amine concentration and pH on the interfacial tension, adsorption density, electrokinetic potential, contact angle, and concentration of the various amine species in the system are presented. A good correlation was obtained between these different variables. It is well-known that very fine mineral particles are difficult to float in conventional flotation machines. Flotation rate studies have revealed that the rate of flotation of fine mineral particles is much smaller than that of coarser size fractions. The theories accounting for this behavior have been discussed by Arbiter and Harris1 and also Meloy.2 Theoretically, a hydrophobic fine particle might never make contact with a bubble because of the presence of an energy barrier in the vicinity of the air/water interface.' This energy barrier will have electrostatic, hydrodynamic, and Van der Waals force components. It was thought that by using an oil phase instead of air the energy barrier would be decreased so that fine particles could be concentrated at the oil/water interface more readily than at the air/water interface. The technique used involves dispersing the fine particles in water, containing the appropriate chemical reagents, and injecting a fine dispersion of iso-octane oil droplets into the pulp. After vigorous conditioning, the pulp is passed into a separating column where the oil droplets coated with a layer of mineral particles rise to the surface to form a separate layer. Air is introduced into the base of the separating column to ensure that heavy agglomerates of oil and particles report with the organic layer. This technique has been described previously4 and adopted by Lai and Fuerstenau5 who studied the alumina-dodecyl sulfonate system. The interfacial phenomena in the system composed of hematite, water, and iso-octane in the presence of sodium dodecyl sulfate have been studied and the results reported" earlier. This paper describes the results obtained from investigations into the interfacial phenomena in the quartz/water/iso-octane system in the presence of dodecylamine. The technique used in measuring the interfacial tension, electrokinetic potential, contact angle, and adsorption density were similar to those described previously? Materials Selected pieces of a high purity natural quartz, from the Isle of Man, were crushed in a laboratory jaw crusher and pulverizer. The — 52+72 mesh size fraction was retained and leached with successive washes of hot concentrated hydrochloric acid to remove iron impurities. When no iron was detected in the solution by ammonium thiocyanate, the quartz was washed thoroughly with distilled water until the conductivity of the wash water assumed that of the distilled water. Samples of 25 g of the —52+72 mesh quartz were ground for 5.25 min in an agate vibratory mill. The ground product was 100% —44 m and 57% —10 am, as determined by the Andreasen pipette. The specific surface area of the sample used for the adsorption and flotation tests was 0.94 sq m g-l. This corresponds to a mean particle diameter of 2.4 am. The —44 am quartz sample was stored under vacuum in the presence of silica gel crystals. For the contact angle determination between the three phases, quartz, iso-octane, and water, a piece of the natural quartz was ground into a block about 15 mm long, 15 mm wide, and 5 mm thick. One surface of the block was then polished by successively finer grades of silicon carbide "paper." The final polishing was conducted with alumina on a "hyprocel" paper. The polished quartz specimen was cleaned using nitric acid and ethyl alcohol followed by a wash with distilled water and then stored under distilled water. This pro-

Jan 1, 1971

By A. E. Jenkins, L. A. Baker, N. A. Warner

The electromagnetic levitation technique has been successfully applied to rate studies of the de-carburization of liquid Fe-C alloys from 5.5 to zero pct C at 1660°C using gas mixtures containing 1 to 100 pct CO2 with CO or helium as diluents. The rate was shown to be independent of carbon concen -tration in the melt and only slightly affected by total pressure. The results were shown to be consistent with control either wholly or predominantly by gaseous diffusion. As well as avoiding side reactions with the crucible, levitation allowed precise calculation of reaction rates since the geometry of the system was accurately known. It also enabled interpretation using the established mass-transfer correlations for a gas flowing past a single sphere, The existence of gaseous-diffusion control and the extremely high rates of reaction reported for gas flowing past small spheres are of great practical significance in relation to current investigations into the use of spray-refining techniques in continzcous steelmaking. PREVIOUS work on the kinetics of carbon removal from liquid iron has generally involved the use of oxygen as the gaseous oxidant. Investigations have been made on commercial steelmaking furnaces and in addition laboratory-scale experiments have been attempted with a slag phase present. The general lack of agreement and the obvious difficulty in interpreting the results is at least partly due to the complexity of the systems used. This work has been reviewed by carter1 and more recently by Bods-worth2 and ward.3 The gas-liquid metal reactions have also been studied with slag-free melts by the conventional technique of blowing oxygen onto the melt contained in a crucible. The reaction between the oxidant and carbon could be followed by sampling either the melt or the gas phase. Side reactions with the crucible material have precluded direct interpretation of the results. Fujii, 5-7 using O-A mixtures, attempted to correct for the crucible reaction and reported that the reaction between carban and oxygen occurred at the melt surface and was controlled by gaseous diffusion for carbon contents greater than a critical value and by carbon-diffusion control in the metal for carbon contents less than the critical. The critical value was given as approximately 0.15 pct C. However, whereas this was the case for oxygen contents in the gas stream up to 10 pct, between 10 and 20 pct the rate was found to be approximately independent of oxygen content, and Fujii attempted to explain this observation by postulating the presence of an oxide "film".7 Turkdogan et a1.' have studied iron fuming during decarburizing and suggested gaseous-diffusion control of the reaction above a critical carbon concentration, given as approximately 2 pct C. Filippov9-12 reports in a similar manner to Fujii but makes no mention of the crucible reaction with the carbon in the melt, even though this would be expected with the temperature, crucible material (MgO), and carbon contents used. Both CO2 and O2 were used as oxidant gases. In the present work the decarburization of liquid Fe-C alloys was studied using an adaptation of the electromagnetic levitation technique, and thus the complexities introduced by crucible side reactions were eliminated. In this technique a single sphere of the Fe-C alloy is freely suspended and heated by electromagnetic induction in a flowing stream containing the oxidant gas. The full range of carbon levels up to saturation was studied, the temperature of the melts in this instance being held constant at 1660°C. The oxidant was CO2 which was used either pure or in association with a diluent gas, the total gas pressure being maintained either at 1 atm or at a reduced pressure. Thus the reaction under study was:

Jan 1, 1964

By K. E. Gray, G. M. Myers

In previous publications,5 results of single-blow bit tooth impacts on saturated rocks at various stress states were reported. This paper extends these earlier works to include study of bit impact tests on salt water-saturated Berea and Bandera sandstone samples under conditions of elevated confining and pore pressure. During the tests dynamic filtration and deposition of a mud cake were occurring due to the presence of drilling mud in the borehole and a borebole-to-formation pressure differential. Results indicate that saturation of these sandstones with salt water tends to make them weaker than when saturated with nonreactive fluids. Plastic failure often occurs even when extremely high fluid-loss muds are present in the borehole. The failure mode tends toward plasticity with decreasing fluid loss. Brittle failure of sandstones in mud-filled holes is apparently relatively rare. Depending on the stress level, and the associated failure mode, withdrawal of the bit tooth induces a tensile force that seems rather important relative to the quantity of rock removed by vertical tooth impact. INTRODUCTION A vast majority of the oil wells drilled today involve the use of colloidal muds having a measurable mud filtrate loss. It is known from field experience that reduction of the water loss of a mud generally results in a reduction of the penetration rate. This paper describes an investigation of crater formation at simulated bottom-hole pressure conditions for drilling fluids having different water losses. The literature on single bit tooth impact (cratering) at atmospheric conditions is extensive, but only a limited amount of work has been performed at the stress conditions similar to that found in oil wells. Spherical penetrator cratering tests on rocks at hydrostatic pressure were performed by Payne and Chippenda1e.1 Chisel impact studies on limestone with independently varying overburden and borehole pressure and atmospheric pore pressure were reported by Garner, et al.2 Gnirk and Cheatham3 performed "static" penetrator tests on dry rocks at equal overburden and borehole pressures. Podio and Gray4 studied the effect of pore fluid viscosity at atmospheric pore and borehole pressures and varying overburden pressures. Their results illustrated the importance of fluid saturation of the rock. Yang and Gray5 reported single tooth impact tests on saturated rocks at elevated borehole, pore and confining pressures, but with equal pore and borehole pressures. For the work reported in Refs. 4 and 5, filtration across the hole bottom purposely was avoided. Maurer6 has investigated the effect of independently varying pore and borehole pressures at elevated overburden pressures by using a zero water-loss mud in the borehole. His tests were carried out under conditions that allowed independent control of overburden, pore and borehole pressures, but without control of filtration at the hole bottom. EXPERIMENTAL APPARATUS AND PROCEDURE APPARATUS The single blow chisel impact apparatus used by Garner,2 as modified for this study, is shown in Fig. 1. A cross section of the pressure vessel is shown in Fig. 2. Several pieces of auxiliary equipment were added to the original apparatus in order that the borehole and pore pressure could be applied in a manner analogous to the actual bottom-hole situation. The pore-pressure system included a filtrate volume-measuring transducer and had sufficient surge capacity to allow filtrate to be injected into the sample without significant changes in pore pressure at points remote to the borehole. The borehole-pressure system contained a cross connection to the pore-pressure system so that both systems could be pressured simultaneously. The borehole-pore pressure differential was applied rapidly by the use of a quick and full-opening valve. The operation of this valve triggered two industrial

Jan 1, 1969

By M. A. Dayananda, R. E. Grace

Vapor-solid diffusion couples were employed in a study of ternary diffusion in the single-phase copper-rich corner of the Cu-Zn-Mn system Interdiffusion coefficients were measured at three different compositions corresponding to the intersections of diffusion paths determined at 850°C. Intrinsic diffusion coefficients were determined at two compositions by the Philibert-Guy method. New relations between the various intrinsic diffusion coefficients are also presented. MOST of the investigations of ternary diffusion have been made with "sandwich" couples formed by welding together two homogeneous solid solutions with or without markers placed at the interface. With such couples Kirkaldy and his coworkers1,2 have determined interdiffusion coefficients which describe ternary diffusion in the substitutional alloy systems, Cu-Mn-A1 and Zn-Cu-Al. Guy and Leroy3 have reported intrinsic diffusion coefficients for Co-Ni-Cr alloys as a function of composition using the analysis of Philibert and Guy.4 The use of semi-infinite diffusion couples, for example, vapor-solid couples, where the diffusing species are supplied from a vapor source in contact with a diffusion disk, has so far been confined to studies of binary diffusion. Balluffi et a1.5,6 have successfully determined the interdiffusion as well as the intrinsic diffusion coefficients in several binary metallic systems employing vapor-solid couples with markers initially placed at the vapor-solid interface. They have also discussed the general advantages and limitations of such couples. Vapor-solid diffusion couples can successfully be employed in ternary diffusion studies. The importance of such couples in ternary diffusion lies in the fact that inert markers lie close to the vapor-solid interface, and the composition of the marker plane is virtually known before experimentation begins. Another minor advantage is that the method of Philibert and Guy4 may be used with three alloys instead of four. Lastly, the diffusion paths need not be S-shaped, as pointed out by Meijering7 for "sandwich" couples. The Cu-Zn-Mn system is convenient for ternary diffusion studies because of the large single-phase field in the copper-rich corner. The vapor pressure of zinc above such alloys is known, and X-ray measurements indicate that the molar volume is nearly constant over a wide range of compositions.8,9 It is the purpose of this paper a) to extend the analysis of Balluffi and seigle5 to permit an evaluation of interdiffusion coefficients in ternary vapor-solid couples, b) to use the method of Philibert and Guy to determine intrinsic diffusion coefficients with such couples, and c) to present experimental data on both interdiffusion and intrinsic diffusion coefficients for the Cu-Zn-Mn system at 850°C. INTERDIFFUSION IN TERNARY VAPOR-SOLID COUPLES The analysis of Balluffi and seigle5 is extended in this section to a vapor-solid couple where two solutes diffuse from a vapor source into a ternary solid solution. To take into account the expansion of the diffusion disk caused by the absorption of mass from the vapor phase, the total fluxes are expressed on the basis of a coordinate system that moves with the velocity of the vapor-solid interface; thus. where D3ij are the intrinsic diffusion coefficients,4 v(x, t) is the local Kirkendall velocity of mass flow, and F(t) is the negative velocity of the vapor-solid interface (x = 0). Both these velocities are based on a fixed coordinate system far removed from the diffusion zone. Using the continuity relations and Darken's method1' for a ternary system in which components 1 and 2 diffuse from the vapor phase into a solid of negligible vapor pressure, one obtains

Jan 1, 1965

By A. R. Gregory

A shear wave velocity laboratory apparatus and techniques for testing rock samples under simulated subsurface conditions have been developed. In the apparatus, two electromechanical transducers operating in the frequency range 0.5 to 5.0 megahertz (MHz: megacycles per second) are mounted in contact with each end of the sample. Liquid-solid interfaces of Drakeol-aluminum are used as mode converters. In the generator transducer, there is total mode conversion from P-wave energy to plain S-wave energy. S-wave energy is converted back to P-wave energy in the motor transducer. Similar transducers without mode converters are used to measure P-wave velocities. The apparatus is designed for testing rock samples under axial or uniform loading in the pressure range 0 to 12,000 psi. The transducers have certain advantages over those used by King, 1 and the measurement techniques are influenced less by subjective elements than other methods previously reported. An electronic counter-timer having a resolution of 10 nanoseconds measures the transit time of ultrasonic pulses through the sample; elastic wave velocities of most homogeneous materials can be measured with errors of less than 1 percent. 5- and P-wave velocity measurements on Bandera sandstone and Solenholen limestone are reported for the axial pressure range 0 to 6,000 psi and for the uniform pressure range 0 to 10,000 psi. The influence of liquid pore saturants on P- and S-wave velocity is investigated and found to be in broad agreement with Biot's theory. In specific areas, the measurements do not conform to theory. Velocities of samples measured under axial and uniform loading are compared and, in general, velocities measured under uniform stress are higher than those measured under axial stress. Liquid pore fluids cause increases in Poisson's ratio and the bulk modulus but reduce the rigidity modulus, Young's modulus and the bulk compressibility. INTRODUCTION Ultrasonic pulse methods for measuring the shear wave velocity of rock samples in the laboratory have been gradually improved during the last few years. Early experimental pulse techniques reported by Hughes et al.2 and by Gregory 3 were beset by uncertainties in determining the first arrival of the shear wave (S-wave) energy. Much of this ambiguity was caused by the multiple modes propagated by piezoelectric crystals and by boundary conversions in the rock specimens. Shear wave velocity data obtained from the critical angle method, described by Schneider and Burton4 and used later by King and Fate sand by Gregory, 3,6 are of limited accuracy, and interpreting results is too complicated for routine laboratory work. The mode conversion method described by Jamieson and Hoskins7 was recently used by King 1 for measuring the S-wave velocities of dry and liquid-saturated rock samples. Glass-air interfaces acted as mode converters in the apparatus, and much of the compressional (P-wave) energy apparently was eliminated from the desired pure shear mode. A more detailed discussion of the current status of laboratory pulse methods applied to geological specimens is given in a review by Simmons.8 A new shear wave velocity laboratory apparatus has been developed for testing rock samples under elevated pressures. This apparatus employs liquid-solid interfaces as mode converters. The technique for generating pure shear waves at liquid-solid interfaces was developed from studies of critical angle methods.6 Two identical transducers are placed in contact with opposite ends of the rock sample, one transducer acting as an ultrasonic energy emitter or generator and the other acting as an ultrasonic energy receiver or motor. The P-wave energy emitted from the piezoelectric crystal in the generator transducer is converted into pure S-wave energy at the Drakeol-aluminum

By R. R. Boucher, O. J. C. Runnalls

A pronounced thermal effect has been observed on heating or cooling a1wninum-rich Al-U and Al-Pu alloys. From microscopic and X-ray diffractionstudies, the effectl has been attributed to trnsfor)nations in the inlemetallic phases UAl, and PuAl , involuing rearrangement or cluslering of vacancies The transformation obsrved in Al-20 wi oct U alloys occurred near the a Al-UAl4 eutectic tem-perature of 646°C making it difjicult to detect from heating curves. When cooling, howeoer, thermal mad X-ray analyses indicnted that the high-temperati~re phase labeled p UAL, precipitated initially during euitectic solidification. As solidification continued and after an induction period o-f 5 lo 20 tnin the nu-cleatiorz and growth of the low- twmperature phase, a UAl4 produced an euolution of energy which raised the observed alloy temperature by 1° to 2°C. in Al-Pu alloys the transformation occurred at 645°C, 5 deg below the eutectic solidification temperccture. The eslimated latent heat of transformation was 25 +5 cnl per g PuAl,. The high-tetnpevcl-ture forms of UAl, and PuAl, were easily 9-etccined by chill casting Al-U and Al-Pu alloys and on reheating the alloys the trcltzsforrnation to the a phase was sluggish even above 600°C. Separated single cryslals o-f UAl4, joy example, showed no evidence Of transformalion after heating for 16 hr at 620°C. The transformation rates increased yapidly enough with increasing temperature, however, that a a spontaneous liberation of energy lens observed on occasion when bealing cast Al-20 wt pet U to neal- the RECENT phase studies on A1-Pu alloys have indicated that earlier reported equilibrium diagrams should be modified to take account of several poly- morphic transformations in the intermetallic compound PuAl,.' During the course of the latter work an unexpected heat evolution was observed while cooling a solid alloy consisting of a mixture of a aluminum and PuA1,. The evolution occurred at 645°C, y below the a A1-Pu A1, eutectic solidification temperature. Subsequent thermal-analysis experiments with A1-U alloys showed that heat was evolved there also at a temperature nearly coincident with the a A1-UA1, eutectic solidification temperature of 646°. A search of the literature revealed that similar thermal effects had been observed before for both A1-U and A1-Pu but had never been fully explained.2,3 The purpose of the present paper is to describe thermal-analysis and X-ray diffraction experiments which have led to the conclusion that the thermal effects are due to transformations which involve the rearrangement of vacancies in the intermetallic compounds UA1, and PuA1,. EXPERIMENTAL PROCEDURE The A1-U alloys were prepared by heating super-pure aluminum (99.99 pct +) obtained from the Aluminum Co. of Canada in a graphite crucible surrounded by an induction coil. At 1000°C high-purity uranium metal produced by the Eldorado Mining and Refining Co., Ltd. was dropped into the liquid aluminum and was dissolved completely within 15 min. The impurities in the uranium were A1—4 ppm, Ca-4, C-70, Cr-3, Cu-6, Fe-30, Mg-2, Mn-10, Ni-25, Si-25, and Zn-2. The A1-Pu alloys were prepared by reacting plutonium dioxide with liquid aluminum under cryolite (3 NaF . AlF,) for 10 min at 1100°C in graphite crucibles exposed to the air. The plutonium was 99.8 pct pure, containing trace impurities of Ca, Cu, Fe, Pb, Si, and Zn. The liquid alloys were usually poured into water-cooled molds to provide castings of uniform composition from which samples could be cut for heat treatment and thermal-analysis experiments.

Jan 1, 1965

By D. R. Wieland, H. T. Kennedy

The object of the work reported here was to determine the content of elemental sulfur in gaseous methane, carbon dioxide, hydrogen sulfide, and in mixtures of these gases, at pressures and temperatwes encountered in natural gas reservoirs. Sulfur content at equilibrium is reported for pure methane, carbon dioxide, hydrogen sulfide, and on three binary mixtures of each of the three pairs of gases at pressures of 1,000, 2,000, 3,000, 4,000, 5,000 and 6,000 psia and at temperatures of 150°, 200° and 250°F. In addition, the sulfur content of three ternary mixtures at the same temperatures and pressures are reported. The results indicate that the sulfur content is higher in the gases at higher temperatures and pressures. The content is highest in hydrogen sulfide, intermediate in carbon dioxide and lowest in methane. INTRODUCTION At ordinary pressures and temperatures, the concentration of a nonvolatile material, such as sulfur in a gas at equilibrium, is a function of the vapor pressure of the material and is independent of the nature of the gas. As the pressure and temperature increase, the gas assumes some of the properties of liquids, including the power to dissolve other liquids and solids, to an extent dependent on the nature of both the gas and the material dissolved. At equilibrium, the content of sulfur in the several gases considered here may thus be considered as solubilities which are fixed for a given composition of gas, temperature and pressure. The study of the solubility of elemental sulfur in gases is of interest because sulfur is sometimes present in reservoirs producing natural gas and must be present in the vapor phase. Upon reduction of pressure and temperature, the sulfur precipitates from solution in the reservoir and in the tubing and fittings. Due to the fact that the greatest pressure drop in the reservoir is around the wellbore, the volume of sulfur precipitated will be greatest in this locality and can cause a substantial reduction in the permeability of the formation in this area. As the natural gas flows up the tubing string, the pressure and temperature are further decreased, causing further sulfur precipitation. If the volume of free sulfur is large and remedial measures are not taken, complete plugging of the tubing can occur. Knowledge of the content of sulfur as a function of composition, temperature and pressure will enable the operator to determine what changes in pressure and/or temperature are necessary to keep the sulfur in solution. If the sulfur solubility is large and can be controlled, the operator may desire to produce the well at a high wellhead pressure and temperature and reclaim the sulfur at the surface. The high solubility of sulfur in hydrogen sulfide (5.6 per cent by weight at 5,000 psi and 200°F) suggests the feasibility of recovering sulfur by injecting this gas into sulfur-bearing reservoirs and expanding the produced gas to precipitate out the sulfur. The present project was designed to measure the solubility of sulfur in carbon dioxide, methane, hydrogen sulfide and mixtures of these three gases at various temperatures and pressures. These gases were the major constituents of the gas well where plugging by sulfur was encountered. A study of the published literature shows no data on the solubility of sulfur in any gas, although Hannay and Hogarth,' in 1880 reported that it was soluble in carbon disdlide above the critical temperature of carbon disulfide. EQUIPMENT AND PROCEDURE Fig. 1 shows the layout of equipment employed to bring gases to equilibrium with sulfur and to isolate the quantity of sulfur contained in a known volume of gas. Pure gases were measured in the charging bomb at known temperatures and pressures and displaced into the reservoir bomb to make up the desired mixtures. When equilibrium was achieved

By John Wulff, David A. Stevenson

The solubility of iron and cobalt in liquid lead, the solubility of chromium in liquid tin, and nickel in liquid silver were determined up to 1300°C in an atmosphere of hydrogen. Liquid samples were taken at different temperatures and analyzed. The data obtained were plotted to show the relationship between log mole fraction of solute and the inverse of the absolute temperature. Resulting values for the differential heat of solution (AH) and the excesspartial molar entropy (S)are: for the iron-lead system = _24,200 cal per mole and AT = 5.0 e.u. for the a phase, and AH = 18,300 and S = -0.1 e.u. for the y phase; for the cobalt-lead system AH = 16,500 cal per mole and AS =0.7 e.u.; for the chromium-tin system AH = 15,600 cal per mole and AS = 8.5 e.u.; for the nickel-silver system AH =18,000 cal per mole and AS = 4.0 e.u. RECENT developments in coating, brazing, and heat transfer have focused attention on specific cases of solid-liquid interaction in metal systems, particularly those involving dilute liquid solutions. One fundamental quantity of interest in such systems is the equilibrium phase distribution between solid and liquid phases. In any effort to fully understand such interactions, one must be able to describe the equilibrium state precisely. Furthermore, in order to develop genera! relations for such systems, one must know the equilibrium state in a number of different cases. This investigation was devoted to a study of the equilibrium phase distribution in four binary systems: solid iron-liquid lead; solid cobalt-liquid lead; solid chromium-liquid tin; solid nickel-liquid silver. The iron-lead system was previously studied by Shepard and parkman' and later by Fleischer and Elliott2 with differing results. Both investigations were carried out by sampling the saturated liquid, and analyzing it chemically. The cobalt-lead system was previously reported by Pelzel,3 who noticed no discontinuity near the transformation. A limited investigation of the chromium-tin system was made by Wlodek and wulff4 using a weight loss method. This work was done in conjunction with the development of a process for coating molybdenum with chromium from tin solutions. To more fully under- stand the kinetics of the process, a more accurate determination of a solubility was desirable. No significant data were found in the literature on the nickel-silver system. Data on the latter system were, however, relevant to the investigation of the corrosion kinetics of copper-nickel alloys in liquid silver as carried out by Harrison and wagner,5 EXPERIMENTAL APPARATUS AND PROCEDURE Of the techniques available for the study of such systems the most effective appears to be that of liquid sampling,2,6,7 which is the method used in the present investigation. A schematic diagram of the sampling furnace is given in Fig. 1. Large pieces of solute metal, in excess of saturation solubility, were added to 200 g of the solvent metal, and the entire charge placed in an alundum crucible. Analytical reagent or materials of chemically pure grade were used in all investigations. The crucible was contained in a zircon muffle tube positioned vertically in the uniform hot zone of a Globar resistance furnace. The tube was provided with a number of ports which permitted sampling at temperature and in controlled atmospheres or vacuum; the ports were also useful for evacuation and introduction of gases as well as for thermocouple measurements. A chromel-alumel thermocouple Sheated in a porcelain tube was used for temperature measurements. A purified hydrogen atmosphere was employed in all experiments reported in this paper. The hydrogen was purified by passing it first over hot copper gauze to remove oxygen and then through a molecular sieve immersed in

Jan 1, 1962

By J. Lohrenz, R. J. Francis, G. C. Clark

Compositional material balance methods have been extended to solution gas-gas cap-water drive reservoirs. Partial or complete pressure maintenance as well as reservoir repressuring by gas and/or water injection may be considered. Increrments of reservoir withdrawals and injections equivalent to a given time increment are used as the basic iterative step to allow the extension. An example field study shows how the reservoir volumes. extent of the water drive, and relative permeability ratio function may be estimated. Knowing these, the methods can be used to predict reservoir behavior. INTRODUCTION The compositional material balance is similar to conventional material balances in many aspects. The assumption of a pressure-homogenous reservoir with no transients is common to all conventional material balances1-1 although numerical methods are different. The compositional material balance also contains this assumption. Inclusion of phase equilibria directly in reservoir calculations is the key difference and improvement in the compositional material balance. A continuous account of the compositions of the reservoir fluids and effluents is determined. Calculations of fluid phases and properties can be based on these compositions. Excepting fluid phases and properties determined in this manner, the compositional material balance uses procedures exactly analogous to conventional methods. Brinkman and Weinaug5 and Jacoby and Berry6 have given compositional material balances for simple solution gas drive reservoirs; subsequently Jacoby and Berry' extended their procedure to include pressure maintenance by gas injection at constant reservoir pressure. This paper extends compositional material balance techniques to a more general combination drive reservoir with various types of pressure maintenance operations. The procedure for this extended compositional material balance and an example of its field application are presented. PROCEDURE The numerical calculations of this compositional mate- rial balance are performed on a high-speed digital computer. The most comprehensive case the present compositional material balance program can handle is a solution gas-gas cap-water drive reservoir with (1) water production, (2) water influx, (3) separate or commingled production from the oil and gas zones, (4) any surface processing arrangement including LPG and gasoline production, and (5) gas injection into the gas and/or oil zones." This description of the procedure applies to this most comprehensive case. Appropriate deletions in the procedure can be made for more simple mechanisms. ASSUMPTIONS In common with conventional material balances, the compositional material balance makes the following assumptions: (1) the total reservoir is at a uniform pressure at a given time; (2) the volumetric ratio of gas to liquid withdrawal at reservoir conditions is directly proportional to their mobilities; and (3) instead of assuming a pressure-dependent total gas-oil equilibrium, the cornpbsitional material balance makes a sianificantly different and more rigorous assumption as follows. Thermodynamic equilibrium exists for each component in the liquid-gas mixtures in the reservoir and in surface processing. These three assumptions are fundamental in the compositional material balance procedure. Other assumptions involve arbitrary simplifications of the reservoir mechanisms. This compositional material balance uses the following simplifying assumptions: (1) no bulk mixing occurs between the gas and oil zone; (2) total mixing occurs between any injected gas and the contents of the injection zone; (3) no in situ hydrocarbon liquid is produced from the gas zone; (4) no reservoir gas is retained behind any net bottom-water influx; (5) the residual saturation of hydrocarbon liquid at reservoir conditions behind any net bottom-water influx is constant; and (6) fluids retained behind any net bottom-water influx exert no further influence on the reservoir. These six assumptions are not fundamental. Modifications of the present procedure can be made for different assumptions of the reservoir mechanisms. THE TIME INCREMENT Previous compositional material balances have used a pressure increment for simple solution gas drive reservoirs"" and an increment of injected gas for pressure maintenance.' These increments are suitable for these simple cases. They are, however, inadequate for reservoirs with time dependent drive mechanisms including water drive. A time increment removes this inadequacy and is

By R. I. Jaffee, C. M. Craighead, G. A. Lenning

THERE has been considerable discussion among A metallurgists and others interested in the development of titanium alloys as to the nature of the fine line markings which appear in the microstruc-tures of unalloyed titanium and a titanium alloys. These markings have been variously called x phase, etching pits, and twins. Figs. 1 to 3 show typical examples of the line markings as they appear, respectively, in high purity iodide titanium, commercial purity titanium rod, and a high purity a alloy containing 0.2 pct N. The commercial purity titanium sample, shown in Fig. 2, contains both line markings and some spheroidal retained-ß phase. The ß phase seen in this micrograph should not be confused with the line marking, since it originates from the iron present as an impurity in the sponge metal. It will be noted that the line markings seem to have a definite orientation pattern with respect to the grains and in titanium noticeably resemble the precipitation occurring in artificially aged high purity Al-Cu alloys. This similarity led to the hypothesis that the line markings observed in titanium and a titanium alloys resulted from precipitation of some unknown phase. With the work of Hägg1 and McQuillan2 as background, there was little reason to suspect hydrogen of being responsible for the line markings. Hagg reported that up to 33 atomic pct H was soluble in a titanium, and McQuillan reported an a solubility of up to 8 atomic pct. Furthermore, McQuillan examined metallographically a 5.1 atomic pct H alloy quenched from 300°C and stated that the structure appeared to be a single-phase a solid solution. Line markings have been observed frequently and were first noted by Jaffee and Campbell3 in 1949. They did not observe them in vacuum-annealed titanium and a Ti-O and Ti-N alloys, but did observe them in Ti-H alloys containing 0.25, 0.5, and 1 atomic pct H. They stated that it was doubtful that the markings were a second phase based on hydrogen, because 1 atomic pct was far from the accepted solid solubility of hydrogen in titanium. Finlay, Resketo, and Vordahl,4 in 1950, concluded that the markings were a true second phase as a result of observations on their etching characteristics. Anderson5 Commenting on these markings in titanium was inclined to associate them with hydrogen, but was loath to call them titanium hydride, because of the reported high solubility of hydrogen. Work at Battelle Memorial Institute for the Navy Bureau of Aeronautics," done concurrently with the work described in this paper, provided information on the experiment converse to that described by Jaffee and Campbell in 1949. This work showed that the amount of line markings in unalloyed titanium could be decreased by vacuum annealing at elevated temperature. It was suggested that this was the result of removal of hydrogen; previously, the data of Jaffee and Campbell9 howed that the markings appeared when hydrogen was added. Recent work at Battelle for the Ordnance Corps, Department of the Army, which is described here, now establishes the identity of the markings as a titanium hydride phase. A sample of high-purity titanium rod 1/4 in. diam, 0.009±0.001 wt pct H (0.43 atomic pct), Fig. 1, was resistance heated in a 0.05 micron vacuum for 41/2 hr at 1500°C. During the early states of heating, the pressure increased to 150 microns, indicating that gases were being evolved. After cooling in vacuum, the iodide titanium rod was analyzed for hydrogen. Vacuum-fusion analysis showed 0.0006 ±0.0003 wt pct H (0.03 atomic pct) to be present.* Metallographic examination of the vacuum-annealed rod showed only a transformed ß structure. There was no evidence of fine line markings, Fig. 4. A section of this vacuum-annealed rod was cold rolled to 0.040 in. thick sheet and annealed for 1 hr

Jan 1, 1953

By H. A. Fisch, A. J. Opinsky, J. L. Bartos

Fort?-six- two-grain bounduries were studied in doped tungsten 1amp wire that had been heated to 3450°K very vapidly. Back-reflection Laue photograms were taken of the grain boundary partners and solved, using a computer. The resulting distribution of large-grain orientations was analyzed. Rotational axes were calculatedfor each grain boundary pair. The axes of least rotation show an anisotropy of rolalional angle. WhILE the orientations of large grains in straight doped tungsten wire have been studied extensively, little has been done to characterize the boundary that separates them. Rosi.1 upon seeing the jagged interlocking boundary in doped tungsten wire. inferred that the grains should have a preferred orientation, and proved it. He interprets his data as indicative of a single ideal orientation—(531)— being parallel to the wire axis. Rieck2, 3 and Mannerkoski' have essentially confirmed this finding. Opinsky, Orehotsky, and Siegle argue that the data suggest that (211)—a plane-is parallel to the wire axis instead. This (211 ) contains the (531). and hence would appear to be a more general case.5 Ahlborn and wasserman6 report that their orientation data stretch from (110) through (531) to (311). This path is the locus of {211 Recently. Opinsky has suggested that the data can be interpreted as a series of ideal orientations that can be related by coincidence relationships to the (110) fiber texture. All these investigators have determined the orientations of the large grains by the back-reflection Laue technique, and they have all obtained similar results. Only Rieck5 as methodically looked at the large grains along a wire. He was apparently not concerned with the relationships of the large grains across their common boundary, but only with their individual orientations. This research was undertaken to fill this gap in the under standing of the mechanical properties of tungsten wire. Only the crystallographic aspects of the problem will be reported here. In addition, the large number of large-grain orientations, which was accumulated in this study. will also be analyzed. EXPERIMENTAL MATERIAL AND TECHNIQUES All of the data were obtained from four pieces of the same 7-mil-diam General Electric tungsten lamp wire. Twelve-inch lengths of the cleaned wire were heated in vacuum by the flick of a switch to 90 pct of the amperes necessary for fusion (a temperature of approximately 3450°K) and held for 1 min. On the basis of other data. it is estimated that the rise time is of the order of 0.5 sec. The four pieces of wire could have come from anywhere within about 18 ft of wire. Consecutive segments of each piece of wire were mounted in bakelite and polished metallographically The polishing procedure followed that described by woods. "nly boundaries between two grains that each occupied the entire cross section of the wire were photographed and X-rayed. The metallographic sample was mounted accurately with respect to the X-ray unit. Steps were taken to read the films as accurately as possible with the conventional Greninger net. The data were then entered into computer programs that solve the Laue film by precisely the same techniques that are used in the solution of the film by means of the stereographic projection. The use of the computer has probably shifted the main source of error from the stereographic plot to the reading of the film. On the basis of several experiments, it is thought that the error associated with the entire process, from mounting the sample through the computer solution, is of the order of about one-half degree. The output of the computer is the direction cosines of the fiducial direction (the wire axis) and the locations of the three cube axes. The former data were used to calculate the differences in orientation between the two grain boundary partners, and the latter were used in the calculation of the rotational axes that could bring the two grains

Jan 1, 1970

By A. S. Yue

Small-angle tilt boundaries have been observed in a lamellar eutectic structure. These boundaries are morphologically similar to a theoretical till boundary originally proposed by Burgers. The production of a small-angle tilt boundary in the lamellar eutectic structure is attributed to the formation of an indentation on a planar solid-liquid interface during growth. Constitutional supercooling due to the accumulation of impurity atoms ahead of the interface is primarily responsible for the generation of an indentation. The distance between two faults of like sign, designated as lamellar fault distance, is calculated by the Burgers equation for small-angle boundaries. It was found that the lamellar fault distance decreases exponentially and the tilt angle increases exponentially with freezing rate. SMALL-ANGLE tilt boundaries have been observed in many crystals in the as-grown states by etching techniques. However, a detailed substantial proof for revealing the presence of dislocations in the form of etch-pits was recently accomplished by Vogel. These boundaries are described as an array of dislocations of like sign. The angle of tilt associated with a boundary is treated theoretically by Burgers3 and is given by 0 = b/D for small tilt-angle where b is the Burgers vector of the dislocations and D is their average spacing. During the course of experimentation on the solidi fication of the lamellar Mg-32 wt pct Al eutectic a microstructure which was strikingly similar to a dislocation tilt boundary was observed. An example of the type of microstructure is given in Fig. 1, which shows a combination of transverse and top sections of the lamellar eutectic structure. The lamellae of the top section on one side of the apparent tilt angle are not parallel with those on the other side. Consequently, some lamellae must be terminated somewhere. Fig. 1 shows that the termination of lamellae is analogous to a dislocation tilt boundary in a crystal lattice originally proposed by Burgers. This work represents a closer look at such structures. The factors governing the production of the small-angle tilt boundary are discussed in terms of the freezing condition and impurity distribution in the melt. The effect of freezing rate on the distance between two faults, designated as lamellar fault distance, and the tilt angle is also described. In addition, the lamellar fault distance is determined by means of the Burgers equation for small-angle tilt boundary. EXPERIMENTAL PROCEDURE The slightly impure Mg-32 wt pct Al eutectic rods, 5/8 in. in diam and 12 in. long, were made from 99.99 wt pct Al and 99.98 wt pct Mg and were cast in a high-purity graphite mold. Some of these rods were purified by zone-refining the eutectic using direct-radiation helical-coil furnaces5 A molten zone about 2 in. long was passed through the cast rods at a speed of 5.3 x 104 cm per sec for ten passes of the molten zone. Before the freezing experiment was begun, 2-1/2 in. of the material from the head and tail ends of the zone-refined eutectic were removed from the rod to eliminate any impurity. The freezing experiments were carried out under controlled conditions,8 using a protective atmosphere of purified argon. At the end of each run, observation of the tilt boundary was made throughout the entire length of the rod with a light microscope on the top, longitudinal, and transverse sections (three mutually perpendicular sections) of the lamellar eutectic solid. The experimental data used for the determination of interlamellar spacing and tilt angle were taken from the middle portion of

Jan 1, 1964

By Wallace W. Wilson

This DaoerAA calls to attention for the first time, to the writer's knowledge, a purported recovery of oil by substantially horizontal gas cycling that is considerably in excess of 50 per cent of the oil originally in place. The average angle of dip along the path of travel of the gas is less than one degree of arc. The best recovery by gas cycling previously brought to the writer's attention1 occurred in the case of the Mile Six Field in Peru, where about 68 per cent of the original oil in place has so far been recovered. In this case, however. the recovery was greatly aided 1)y the high dip angle of about 17.5". An approximate estimate of recovery was made by the method developed by the writer' for the case of the Cook Ranch Field, using an average relative permeability ratio function dictated by past experience with a number of good quality sandstones. A result of about 40 per cent recovery of the original oil in place wa* obtained after the 8.5 pore volumes of cumulative gas cycling undergone by the Cook Ranch Field. Tile writer desires to emphasize what appears to him as the sound engineering practiced at Cook Ranch, and also the care attending the taking of data and the high quality of the calculations made. It is impossible to take issue on factual grounds with any of the conclusions drawn in the paper. It is, however, desired to point out the difficulty of explaining the unexpectedly favorable oil recovery on ordinary theoretical grounds. It would be of interest to know whether relative permeability ratios have been measured on the Cook sand. The operator is inclined to attribute some of the excess benefit to settling of the oil across the bedding planes into the lower part of the sand. It is difficult for the writer to appreciate the importance of such an effect, inasmuch as the concomitant opening of excessive vacated pore space in the upper part of the sand would he expected to cause excessive bypassing of the gas. REFERENCE 1. Welge. H. J.: "A Simplified Method for Computing Oil Recovery by (Gas or Water Drive." Trans. AIME, (1952), 195, 91. AUTHOR'S REPLY TO MR. WELGE Welge has poined out clearly the difficulty of applying material-balance procedures in calculating the Performance of low-pressure, dispersed gas injection operations. There can be no argument that even with the most favorable assumptions of K,/K,, and with cumulative gas cycling in excess of normal expectations, the calculated oil recovery will be considerably less than the 72.5 per cent recovery realized from this project to Jan. 1, 1951. There probably are at least two reasons for the unusually high recovery from this reservoir, the effects of which would be difficult or impossible to calculate by known methods: 1. The operator did not use the same injection wells for the entire operation, and exercised considerable control over producing GOR by changing the locations of injection wells whenever well performance indicated excessive bypassing. Fifty-six wells were used for injection, not over 29 of which were in use simultaneously. This procedure resulted in frequent shifting of the fluid movement patterns in the reservoir and undoubtedly increased the ultimate recovery. The writer knows of no satisfactory procedure for calculating the effect of this practice. 2. Vertical movement of oil across the bedding planes of the reservoir rock hy gravity drainage tended to maintain a relatively high oil saturation, and hence a favorable K,/K, ratio, in the lower sections of the reservoir. As pointed out by Welge, this condition has aggravated the tendency for high producing GOR, but at the same time it has resulted in increased oil recovery. As may be seen from the performance charts for the various battery areas, operating (GOR'S have been quite high for the last several years of reported history.

Jan 1, 1952

By L. Adler

Any design of a mine roof in bedded deposits which ignores differential deflections at the supports can quickly lead to dangerous overstressing. As illustrated by the typical case presented on page 1029, if one support deflects only 0.1 in. more than its neighbor, stresses 50 pct higher than anticipated will result. Previous studies1-3 have assumed that the mine roof acts like a beam clamped at both ends, with no deflection or slope' at the supports (Fig. 1). Essentially this assumes:5* ?A = ?, = ?b and dA = dB = 0. However, a host of conditions can cause differential sag or deflection at one support, and even an apparently trivial deviation can have major consequences in the beam: variations in spacing, size, and material of supports; local settlement due to floor heaving or lower mine openings; non-uniformity in wedging or bolt tensioning.8 In one particular instance concrete pillars, poured in place, shrank away from the roof upon setting.' When understood and controlled, differential sag becomes a definite advantage, permitting the transfer of loads from one support to another. Where one support is a bolt or prop and the other a pillar or rib, the load on the former can be reduced while the load on the pillar or rib is increased. This means two things: 1) savings can be effected by using smaller artificial supports such as props and bolts and 2) loads can be increased in the rib to induce eventual failure for longwall caving. In this last respect, another factor underlying coal bumps becomes understandable. The design of a mine roof by beam theory assumes that when a bedded formation is homogeneous, iso-tropic, and elastic, it will act like a uniformly loaded beam, fixed or clamped at both ends,6 s in Fig. 1.'" These are important assumptions. The uniform load is the weight of the beam itself or its body load. For a beam of unit width, this load becomes per foot: w = yhb. w = uniform load y = specific weight, lb per ft3 h = depth or thickness of beam, ft b = width of beam, ft Since b = 1, w - yh [ 1 ] A beam fixed at both supports is statically indeterminate to the second degree, that is, two equations in addition to those for static equilibrium are required to determine the reactions at the supports. These equations result from the geometry. From statistics: ^F,= 0;RA + RB — wL = 0 [2] wU S,M0 = 0 ; MB H------------MA — RBL = 0 [3] it Using superposition in which the left support is kept intact and the right one resolved into an active force and moment, we obtain from Fig. 2:" ?b = ?m + ? b2 + ?B3 = 0 dB = dB1 + dB2 + dB3 / wU Ma RBL \ V d°=(-r+-2—r)-zr [5] Where: Subscripts refer to position on axis of beam R = force, lb M = moment, ft-lb w = uniformly distributed load, lb per ft L = span, ft 0 = slope, radians d = deflection, ft E = Young's Modulus, lb per ft" 1 = Moment of inertia about the neutral axis, ft4 Solving Eqs. 2 through 5 for the four unknown reactions, we obtain: 2 L3 Fig. 3 is obtained by plotting MA and M, vs d, and then plotting RA and R, vs d, and adjusting their scales to coincide with MA and M, vs d,. It should be noted in Eqs. 6 and 7 that as dB increases, MA increases the same amount that Mn decreases. Eqs. 8 and 9 show a similar relationship between RA and R,. Proof that MA is the maximum absolute moment occurring in the beam is as follows: where M, = moment at x wx-When where M,., = maximum positive moment Eqs. 6 and 8 into above: For small dn: MA> M,,,

Jan 1, 1960

By Herman Dykstra, Irving Fatt

Relative wetting phase permeabilities calculated from capillary pressure-saturation data are compared with measured relative permeability data. The equation relating relative permeability to capillary pressure-saturation data is derived by assuming that a porous medium is analogous to a bundle of capillary tubes. The equation includes a term to correct for the difference between fluid path length and length of core. Relative oil permeability data in the water-oil-gas system are presented, and it is shown that if the water is considered part of he rock matrix, the relative oil permeability curve is typical of a wetting phase relative permeability curve. Apparatus for measuring two and three-phase relative permeabilities are described. INTRODUCTION The difficulty in measuring relative permeability of cores has made it desirable to have a correlation between relative permeability and some more easily measured property of porous media. Such an easily measured property is the capillary preisure-saturation relation. In the past there has been a tendency to separate the capillary pressure concept from the very complex pore geometry and to consider that the capillary pressure-saturation curve give? only some characteristic distribution of interfacial curvature between two fluids.' Recently, however, it has been realized that if capillary pressure data are to yield information concerning pore size distribution2 and fluid flow in porous media. the pore must be assumed to have a simple shape such as a cylinder or a sphere. Childs and George' showed that relative water permeability could be calculated from the capillary pressure-water saturation curve by assuming that the pores are cylinders in which the fluid flowing obeys Poiseuille's Law, and that the capillary preisure curve indicated the size and number of pores. Purcell5 derived an equation relating the permeability of a porous medium to the capillary pressure curve by assuming the porous medium to he analogous to a bundle of capillary tubes. Gates and Lietz6 calculated relative permeability by an equa-tion derived from Purcell's equation. In this paper an equation is derived giving the relative water permeability as a function of water saturation by as-sulning that the core sample can be represented by a bundle of capillary tubes in which the fluid path length is not the same as the bulk length, and in which the fluid path length varies with saturation. THEORY For a bundle of N capillary tubes the flow through dN tubes will be dQ = qav dN ..........(1) where Q is the total flow rate through all the tubes and q., is the aberage flow rate through the tubes in the interval dN. If the interval dN is made small the average flow rate through a tube in the interval dN is given by Poiseuille's Law, 8 nl where ?P is the pressure drop across the tube of length 1 and radius r, and µ is the viscosity of the fluid. Substituting for qav in Equation (1), dQ =pr4 ? P/8µl dN.........(3) Darcy's Law for linear flow of an incompressible fluid in a porous medium is Q = KA?P/µL...........(4) where K is the permeability and ?P is the pressure drop across a bundle of tubes which has replaced the porous medium of length L and cross-sectional area A. Differentiating Darcy's Law with A, ?P, µ, and L constant, dQ = A?P/µL dK.........(5) Equating (3) and (5) gives dK------------dN.........(6) 8Al If the pores are assumed to be cylinders dV =pr2ldN..........(7) where V is the volume of flowing fluid in the pores. Substituting for dN in Equation (6) gives dK = —dV..........(8) 8AI' By definition the saturation, S, of the core is v v S =V/Vp..........(9) Vv -PAL

Jan 1, 1951

By Irving Fatt, Herman Dykstra

Relative wetting phase permeabilities calculated from capillary pressure-saturation data are compared with measured relative permeability data. The equation relating relative permeability to capillary pressure-saturation data is derived by assuming that a porous medium is analogous to a bundle of capillary tubes. The equation includes a term to correct for the difference between fluid path length and length of core. Relative oil permeability data in the water-oil-gas system are presented, and it is shown that if the water is considered part of he rock matrix, the relative oil permeability curve is typical of a wetting phase relative permeability curve. Apparatus for measuring two and three-phase relative permeabilities are described. INTRODUCTION The difficulty in measuring relative permeability of cores has made it desirable to have a correlation between relative permeability and some more easily measured property of porous media. Such an easily measured property is the capillary preisure-saturation relation. In the past there has been a tendency to separate the capillary pressure concept from the very complex pore geometry and to consider that the capillary pressure-saturation curve give? only some characteristic distribution of interfacial curvature between two fluids.' Recently, however, it has been realized that if capillary pressure data are to yield information concerning pore size distribution2 and fluid flow in porous media. the pore must be assumed to have a simple shape such as a cylinder or a sphere. Childs and George' showed that relative water permeability could be calculated from the capillary pressure-water saturation curve by assuming that the pores are cylinders in which the fluid flowing obeys Poiseuille's Law, and that the capillary preisure curve indicated the size and number of pores. Purcell5 derived an equation relating the permeability of a porous medium to the capillary pressure curve by assuming the porous medium to he analogous to a bundle of capillary tubes. Gates and Lietz6 calculated relative permeability by an equa-tion derived from Purcell's equation. In this paper an equation is derived giving the relative water permeability as a function of water saturation by as-sulning that the core sample can be represented by a bundle of capillary tubes in which the fluid path length is not the same as the bulk length, and in which the fluid path length varies with saturation. THEORY For a bundle of N capillary tubes the flow through dN tubes will be dQ = qav dN ..........(1) where Q is the total flow rate through all the tubes and q., is the aberage flow rate through the tubes in the interval dN. If the interval dN is made small the average flow rate through a tube in the interval dN is given by Poiseuille's Law, 8 nl where ?P is the pressure drop across the tube of length 1 and radius r, and µ is the viscosity of the fluid. Substituting for qav in Equation (1), dQ =pr4 ? P/8µl dN.........(3) Darcy's Law for linear flow of an incompressible fluid in a porous medium is Q = KA?P/µL...........(4) where K is the permeability and ?P is the pressure drop across a bundle of tubes which has replaced the porous medium of length L and cross-sectional area A. Differentiating Darcy's Law with A, ?P, µ, and L constant, dQ = A?P/µL dK.........(5) Equating (3) and (5) gives dK------------dN.........(6) 8Al If the pores are assumed to be cylinders dV =pr2ldN..........(7) where V is the volume of flowing fluid in the pores. Substituting for dN in Equation (6) gives dK = —dV..........(8) 8AI' By definition the saturation, S, of the core is v v S =V/Vp..........(9) Vv -PAL

Jan 1, 1951