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By Robert E. Bush, E. S. Mardock

The object of this paper is to report recent developments in the quantitative interpretation of radioactivity logs. The use of reference lines is described in the application of the new zero radioactivity reference line for the determination of neutron derived porosities is discussed. Illustrated examples are shown of logs from the reef limestone of the North Snyder Field and from the Lansing-Kansas City limestone of central Kansas. A method of using an interrelation factor calculated from the neutron and gamma ray curves, called the neutron Productivity number, for the estimation of productivity from sandstone formations is discussed. When used in a relative manner the neutron productivity number has aided in Predicting whether a given zone will produce gas or liquid or whether it is too shaly to produce. Examples of logs from wells in the Freites District, Venezuela, and in East Texas are shown to illustrate the application of the neutron productivitv number. INTRODUCTION The petroleum industry was introduced to some of the preliminary results of investigations into the quantitative interpretation of radioactivity logs in October, 1949." It was stated at that time that the methods presented were entirely relative because they involved the use of reference points obtained from the radioactivity log, i.e., shale reference lines, dense zone reference lines, or a combination of both shale and dense zone reference lines. These relative methods offered many advantages to the industry in interpreting radioactivity logs in terms of porosity with particular application to limestone and dolomite reservoirs. However, these relative methods did not offer the wide range of applicability desired because the esta1)lishment of reliable reference points from shale in some areas were difficult. It was recognized that a more reliable mean; of establishing reference lines was vitally needed. Such a method is now available through the introduction of an instrumeutal zero device. It is the purpose of this paper to discuss the application of this new zero reference to the quantitative interpretation of radioactivity logs. Previously all applications of quantitative interpretations of radioactivity logs have been made in limestone reservoirs with little or no emphasis placed on sandstone reservoirs. A brief resumé of investigations into the quantitative interpretation of radioactivity logs in sandstone reservoirs is presented here. This discussion deals primarily with the interrelation of the gamma ray and neutron curves and the response of the latter to the density of the fluids filling the pore space in relatively homogeneous sandstones of uniform porosity. The authors believe that the methods presented herein are only applicable locally to specific fields and reservoirs, and that they probably do not offer a wide range of applicability. However, tile authors believe that the wider use of the new instrumental zero references in sand areas will reveal more information about the specific response of the gamma ray and neutron curves to changes in lithology and saturation. Two applications of quantitative interpretation using the new instrumental zero references are presented. Examples are given which show the comparison of logs and porosity in the limestones and dolomites of West Texas and Kansas. Logs of wells in 'Venezuela and East Texas are compared with the drill stem test data, production data, etc.. to illurtrate the interrelation of the gamma ray and neutron curve: and the rise of methods involving these interrelations to determine certain saturation variables. THE QUANTITATIVE APPLICATION OF RADIOACTIVITY LOGS TO LIMESTONE AND DOLOMITE RESERVOIRS Tile theoretical basis for the gamma ray and neutron curves has been discussed elsewhere.9 he method of recording the logs and apparatus involved has also been thoroughly covered and will not be discussed here.'."".'" It has been shown that the neutron curve responds exponentially to liquid filled porosity over the 1 1/2 to 35 per cent

Jan 1, 1951

By Kenneth A. Moon

An exact statistical treatment of a one-dimensional model is used as a basis for evoluating the reliability of certain simplified expressions for the activity of the solute in interstitial solutions, including one obtained from the exact expression by setting the repulsive interaction equal to infinity. The latter approximation is found to be satisfactory at low and moderate concentration if the repulsive interaction is large, even though not infinite. A similar expression (identical if the co-odination number is two) is derived from the quasichemical expression of Lacher, and is recommended as the best available expression for the excess configurational entropy of interstitial solutions with excluded sites. Some reasonable models are discussed, and the nature of the saturated solutions is determined by inspection. Some of the models reduce to the one -dimensional case. An analysis is given of the excess partial entropy of hydrogen in V-H; Nb-H; and To-H solutions. MOST treatments of the statistical thermodynamics of interstitial solid solutions have followed the classic paper1 of Lacher in making the simplifying assumption that the configurational entropy of the solution is ideal. However, it is becoming increasingly apparent that there are many interstitial solutions with very large so lute-solute repulsions, and for these the assumption of ideal entropy is not valid or useful. It is important to realize that with substitutional solutions large repulsions between the component atoms must lead to phase separation, whereas in interstitial solutions the free energy of the solution is not drastically increased by large solute-solute repulsions until intrinsic saturation is reached at the concentration where further solute would be forced to enter a site in which it would experience the repulsive effect of one or more solute atoms already present. In the limiting case of an infinitely large repulsive interaction, the excess free energy would be attributable entirely to excess entropy, the enthalpy of mixing being zero. AS will be shown below, even if the repulsions are less than infinite, a treatment based on an assumption of infinite repulsions may be very satisfactory up to moderately high concentrations of the interstitial component. Often in solutions where large repulsive interactions exist, there are also small interactions — often attractive—between solute atoms in configurations other than that corresponding to the large repulsion. In such cases the excess free energy will consist of an excess entropy term attributable to the large repulsive interactions, and an enthalpy term corresponding to the other small interactions. Nomenclature to differentiate succinctly between important cases would be a convenience. In this paper the nomenclature shown in Table I will be used. In Table I, and in the preceeding discussion, excess quantities are defined in terms of standard states which are pure solid solvent and pure (possibly hypothetical) solid saturated phase of the structure in question. In practice, it is more convenient to choose the interstitial element as a component, and its conventional standard state. This will add a composition-independent term to the excess entropy and the enthalpy. The earliest paper known to the present author which treats the thermodynamics of athermal interstitial solutions was given by schei12 in 1951, but the statistical derivations in that paper are open to criticism. Speiser and Spretnak were the first to give a correct statistical treatment,3 limited, however, to concentrations sufficiently low that the number of empty sites excluded from occupancy by more than one filled site is negligible. The purpose of the present paper is to extend the statistical treatment to more concentrated solutions, and to examine the magnitude of the errors introduced by assuming that the repulsive interactions are infinite when in fact they must be finite. THE QUASICHEMICAL APPROXIMATION Fortunately, a standard method already exists for taking into account the effect of large interactions upon the entropy of mixing. This is the quasi-chemical method, in which the probability of existence of a given pair of solute atoms in a certain proximate configuration is assumed to be proportional to exp(-w/kT), where w is the energy increase of the solution when the two atoms are moved from isolated locations in the solution to the configuration in question. A quasichemical treatment of interstitial solutions was given in 1937 in a widely neglected paper by Lacher.4 The result comes out

Jan 1, 1963

By T. H. Alden

T. H. Alden (General Electric Research Laboratory)—This paper as well as earlier ones of Dr. Wood represent an important contribution to the experimental description of fatigue fracture. The mechanism of fracture proposed by the authors, however, is not established by this data nor supported by other data existing in the literature. Although taper section metallography provides a rather detailed picture of fatigue crack geometry, photographs so obtained must be interpreted with care. The narrow bands revealed by etching, frequently associated with surface notches, are labeled by the authors "fissures". Measurement shows, taking into account the 20 to 1 taper magnification, that the depth of these structures is at most 2 to 3 times the width. This distinction is important in the conception of a mechanism of crack formation. It is difficult, for example, to imagine a deep, narrow fissure arising from a "ratchet slip" model. A surface notch, on the other hand, may form easily by this mechanism. The notches observed in the present work are the subsurface evidence of the surface slip bands or striations in which fatigue cracks are known to originate.4-6 It is clear that an understanding of the structure of these slip bands is of key importance in understanding the mechanism of fracture. The evidence presented shows that these regions etch preferentially, possibly because they contain a high density of lattice defects, or as the authors state equivalently, because they are "abnormally distorted." However, it is not possible to conclude that the distortion consists of a high density of vacant lattice sites. The fact of a high total shear strain in itself does not assure a predominance of point defects as opposed to other defects, for example, dislocations. Other evidence in the literature which suggests unusual densities of point defects formed by fatigue7-' refers not to the striations or fissures, but to the material between fissures (the "matrix"). If a choice must be made, the preferential etching would seem to be evidence for a high dislocation density, since dislocations are known to encourage chemical attack in copper;g no such effect is known for the case of point defects. A third alternative is that the slip bands are actually cracked, but that near its tip the crack is too narrow to be detected by the authors' metal-lographic technique. In this case the rapid etching can be readily understood in terms of the increased chemical activity of surface atoms. Unless a vacancy mechanism is operative, the motion of dislocations to-and-fro on single slip planes will not lead to crack growth. Point defect or dislocation loop generation are the principal non-reversible effects predicted by this model. In any case, the nonuniform roughening of the surface in a slip band6 requires a flexibility of dislocation motion which is not a part of the to-and-fro fine slip idea. The same is probably true of crack growth by a shear mechanism. Either some dislocations must change their slip planes near the end of the band and return on different planes,'0 or dislocations of opposite sign annihilate." The mechanism by which these processes occur in copper at room temperature or below is that of cross slip. Thus cross slip appears to be essential to fatigue crack growth.6'10"12 The fact that a tensile stress opens the slip bands into broad cracks does not indicate the structure of the bands or the mechanism by which cracks form. The charactersitic concentration of slip into bands during fatigue shows a low resistance to shear strain in these regions. (This fact in itself may be inconsistent with a high concentration of vacancies.) The authors contend also that continuing shear produces an additional mechanical weakening so that the bands fracture easily (are pulled apart) under the influence of the superimposed tensile stress. It is equally possible that the only weakness is a weakness in shear, that the crack propagates by a shear mechanism, and that subsequently the tensile stress pulls the crack apart. Even the direct observation of bands opened by a tensile stress would not be conclusive since, as argued above, they may be fine cracks. The same argument applies to internal cracks, their existence in the presence of a tensile stress not indicating the mechanism of formation. Internal cracks originating in regions of heavy shear have also been seen following tensile deformation of OFHC copper,13 so that this mode of fracture is not unique to combined tensile and fatigue straining. The authors point out in their companion report14 that 90 pct of the cracks formed during pure tor-sional strain were within 8 deg of the normal to the specimen axis. If the tensile stress were an important factor in crack propagation, it is surprising that the cracks cluster about the plane in which the normal stress vanishes. Similarly, a study of zinc single crystals showed that for various orientations the life correlated well with the resolved shear stress on the basal plane,'= and was not dependent on the normal stress across this plane. W. A. Wood and H. M. Bendler (Authors' reply) -Dr. Alden's discussion emphasizes the essential point in the relation of slip band structure to

Jan 1, 1963

By R.K. Matheson

The Nivloc mine is 9 miles west of Silver Peak, Esmeralda County, Nevada. It has been operated by Desert Silver, Inc., since the summer of 1937. The cyanide mill treats 190 tons of silver-gold ore per day. In March of this year the main operations were about 2000 ft. west of the main shaft, which served as the downcast air passage for the mine. The mechanical blowers in use were sufficient to ventilate the west end at that time, but it was foreseen that as the mining area was extended ventilation would be an increasingly difficult problem, especially during the summer months. It was decided, therefore, to continue a raise from a point 100 ft. above the highest mining level (440-ft. level) to the surface; a distance of 443 ft. at approximately 65°. From this point 40 ft. of drifting would be necessary to connect with a shallow shaft on the surface. (Fig. I.) All the raise was serviced from the 440-ft. level; costs and progress obtained in the initial 100 ft. are included in the following pages. Choice of Raise A raise in this locality would have four objects: (I) to provide an ample supply of fresh air to the working places; (2) to explore the vein from the highest mining level to the surface; (3) to provide waste fill for stopes in the area, and possibly provide a transfer for waste from the surface; (4) to provide an emergency exit in the west end of the mine. Before the mining of an ore shoot in the eastern part of the mine, a similar raise had been driven for purposes of ventilation and exploration. This raise and subsequent mining showed the vein to be noncommercial for a distance of about 250 ft. below the surface. However, in the area under operation, old surface workings showed occasional values. Thus from a development standpoint the raise was an excellent prospect. The raise chosen was a three-compartment, stulled raise having two chutes and a manway. The manway inside timber measured 4 ft. 8 in. by 4 ft. 6 in.; it carried air and water pipes, a ladderway and a slide for a timber skip. The two chutes would be used for drawing off the muck and the cleaning of the bulkhead, as well as for ore and waste passes, which would be especially useful for lateral exploration from the raise. The fairly large cross section of the raise (6 by 15 ft.) would provide a large quantity of waste for backfilling, and more could be obtained from a glory hole on the surface. Time Schedule As speed in completing the raise was the main requisite, three shifts were considered, but two shifts were decided upon when it was found that three would necessitate considerably larger fans than those available for clearing the raise. The main diffi-

Jan 1, 1943

By R. K. Matheson

The Nivloc mine is 9 miles west of Silver Peak, Esmeralda County, Nevada. It has been operated by Desert Silver, Inc., since the summer of 1937. The cyanide mill treats 190 tons of silver-gold ore per day. In March of this year the main operations were about 2000 ft. west of the main shaft, which served as the downcast air passage for the mine. The mechanical blowers in use were sufficient to ventilate the west end at that time, but it was foreseen that as the mining area was extended ventilation would be an increasingly difficult problem, especially during the summer months. It was decided, therefore, to continue a raise from a point 100 ft. above the highest mining level (440-ft. level) to the surface; a distance of 443 ft. at approximately 65°. From this point 40 ft. of drifting would be necessary to connect with a shallow shaft on the surface. (Fig. I.) All the raise was serviced from the 440-ft. level; costs and progress obtained in the initial 100 ft. are included in the following pages. Choice of Raise A raise in this locality would have four objects: (I) to provide an ample supply of fresh air to the working places; (2) to explore the vein from the highest mining level to the surface; (3) to provide waste fill for stopes in the area, and possibly provide a transfer for waste from the surface; (4) to provide an emergency exit in the west end of the mine. Before the mining of an ore shoot in the eastern part of the mine, a similar raise had been driven for purposes of ventilation and exploration. This raise and subsequent mining showed the vein to be noncommercial for a distance of about 250 ft. below the surface. However, in the area under operation, old surface workings showed occasional values. Thus from a development standpoint the raise was an excellent prospect. The raise chosen was a three-compartment, stulled raise having two chutes and a manway. The manway inside timber measured 4 ft. 8 in. by 4 ft. 6 in.; it carried air and water pipes, a ladderway and a slide for a timber skip. The two chutes would be used for drawing off the muck and the cleaning of the bulkhead, as well as for ore and waste passes, which would be especially useful for lateral exploration from the raise. The fairly large cross section of the raise (6 by 15 ft.) would provide a large quantity of waste for backfilling, and more could be obtained from a glory hole on the surface. Time Schedule As speed in completing the raise was the main requisite, three shifts were considered, but two shifts were decided upon when it was found that three would necessitate considerably larger fans than those available for clearing the raise. The main diffi-

Jan 1, 1943

By R. W. Raymond

This name is applied to the present mining law, as enacted in 1872 and since, to indicate its leading characteristic—in which it differs from all previous mining laws of this or any other country. The earlier act, passed in 1866, was practically the first attempt of Congress to deal with the question of mining titles upon the public domain. It was framed after nearly twenty years of acquiescence on the part of the Government in the self-constituted tribunals, officials, rules, and customs of the mining districts. In its recognition of these, and in several other particulars, the act of 1866 was open to serious criticisms. It is the purpose of this paper, not to trace the history of legislation on this subject, or show in detail what were the faults of the earlier law, but rather, by a discussion of certain aspects of the present law, to point out how great a revoluition it has effected in the rights of mining locators, and to indicate some of the difficulties attending its application. In the attempt to correct the vagueness of the act of 1866 an entirely new elernent was introduced into the law, bringing with it a new set of difficulties. Under the act of 1866 and the miners' customs which it followed, the lode was the thing claimed and subsequently acquired by patent. And the claim to a given number of feet on the longitudinal course of the lode was rooted in 'a discovery of any part of the lode in any part of the claim. ("Extensions" could in many districts—perhaps universally—be located and claimed on the strength of the discovery in the principal claim to which they referred; but this is a point not essential to the present discussion.) It was not necessary to find the outcrop or the upper edge of a lode in order to lay a valid location upon it. An explorer, sinking a shaft and intersecting a lode not already discovered and claimed by another, could claim by that discovery the number of feet along that lode which the local laws might permit (not exceeding the maximum set by the United States statute) whether his sur-

Jan 1, 1884

By H. W. Mathews, J. D. Wheeler

AS predicted by Messrs. Fuqua and Thompson, in last year's paper on West Texas1, 1935 saw a marked increase in activity in this area over recent years. Both major and independent operators shared in the increased wildcatting operations, which resulted in the discovery of eight and probably nine new fields in this area. During 1935 there were 700 wells completed as compared with 468 in 1934 and only 236 in 1933. Of these completions 579 were producers with a total 24-hr. potential of over 700,000 bbl. It is estimated that the new fields discovered during 1935 added from 200,000,000 to 400,000,000 bbl. to the known oil reserve in West Texas. In addition to these new fields, many of the older producing areas scored marked extensions during the year. New Fields Goldsmith.—-The Goldsmith field, in west central Ector County, gives promise of being the year's outstanding discovery in this area. The discovery well was completed by the Gulf Production Co. in June at a depth of 4177 ft.; it gaged 275 bbl. of 36° gravity oil in 3 hr. through 85/8-in. casing on its first production test. The field has been extended to the east by wells drilled by Phillips and Pure on their Cowden block. Present indications are that the field may contain 10,000 productive acres, and this, together with the large flush production from only a small penetration into the pay, leads to the belief that Gulf-Goldsmith No. 1 was the outstanding Permian lime discovery of 1935. It is quite probable that production will prove to be continuous to the Landreth-Scarborough No. 1, 33/4 miles to the northwest, which was completed for a small producer late in 1934. Sand Hills (Ordovician).—From the standpoint of creating excitement, the outstanding West Texas test of the year was no doubt Gulf-Waddell No. 1, on the northwest nose of the Sand Hills structure. This test was started late in 1934 as a deep test to the Ordovician. Thc Ordovician was topped above 6000 ft,., considerably higher than expected. Oil shows in the Simpson were passed and the well was drilled down to the

Jan 1, 1936

By J. D. Wheeler, H. W. Mathews

AS predicted by Messrs. Fuqua and Thompson, in last year's paper on West Texas1, 1935 saw a marked increase in activity in this area over recent years. Both major and independent operators shared in the increased wildcatting operations, which resulted in the discovery of eight and probably nine new fields in this area. During 1935 there were 700 wells completed as compared with 468 in 1934 and only 236 in 1933. Of these completions 579 were producers with a total 24-hr. potential of over 700,000 bbl. It is estimated that the new fields discovered during 1935 added from 200,000,000 to 400,000,000 bbl. to the known oil reserve in West Texas. In addition to these new fields, many of the older producing areas scored marked extensions during the year. New Fields Goldsmith.—-The Goldsmith field, in west central Ector County, gives promise of being the year's outstanding discovery in this area. The discovery well was completed by the Gulf Production Co. in June at a depth of 4177 ft.; it gaged 275 bbl. of 36° gravity oil in 3 hr. through 85/8-in. casing on its first production test. The field has been extended to the east by wells drilled by Phillips and Pure on their Cowden block. Present indications are that the field may contain 10,000 productive acres, and this, together with the large flush production from only a small penetration into the pay, leads to the belief that Gulf-Goldsmith No. 1 was the outstanding Permian lime discovery of 1935. It is quite probable that production will prove to be continuous to the Landreth-Scarborough No. 1, 33/4 miles to the northwest, which was completed for a small producer late in 1934. Sand Hills (Ordovician).—From the standpoint of creating excitement, the outstanding West Texas test of the year was no doubt Gulf-Waddell No. 1, on the northwest nose of the Sand Hills structure. This test was started late in 1934 as a deep test to the Ordovician. Thc Ordovician was topped above 6000 ft,., considerably higher than expected. Oil shows in the Simpson were passed and the well was drilled down to the

Jan 1, 1936

By R. K. Matheson

THE Nivloc mine is 9 miles west of Silver Peak, Esmeralda County, Nevada. It has been operated by Desert Silver, Inc., since the summer of 1937. The cyanide mill treats 19o tons of silver-gold ore per day. In March of this year the main operations were about 2000 ft. west of the main shaft, which served as the downcast air passage for the mine. The mechanical blowers in use were sufficient to ventilate the west end at that time, but it was foreseen that as the mining area was extended ventilation would be an increasingly difficult problem, especially during the summer months. It was decided, therefore, to continue a raise from a point 100 ft. above the highest mining level (440-ft. level) to the surface; a distance of 443 ft. at approximately 65° From this point 40 ft. of drifting would be necessary to connect with a shallow shaft on the surface. (Fig. I.) All the raise was serviced from the 440-ft. level; costs and progress obtained in the initial 100 ft. are included in the following pages. CHOICE OF RAISE A raise in this locality would have four objects: (I) to provide an ample supply of fresh air to the working places; (2) to explore the vein from the highest mining level to the surface; (3) to provide waste fill for stopes in the area, and possibly provide a transfer for waste from the surface; (4) to provide an emergency exit in the west end of the mine. Before the mining of an ore shoot in the eastern part of the mine, a similar raise had been driven for purposes of ventilation and exploration. This raise and subsequent mining showed the vein to be noncommercial for a distance of about 250 ft. below the surface. However, in the area under operation, old surface workings showed occasional values. Thus from a development standpoint the raise was an excellent prospect. The raise chosen was a three-compartment, stulled raise having two chutes and a manway. The manway inside timber measured 4 ft. 8 in. by 4 ft. 6 in.; it carried air and water pipes, a ladderway and a slide for a timber skip. The two chutes would be used for drawing off the muck and the cleaning of the bulkhead, as well as for ore and waste passes, which would be especially useful for lateral exploration from the raise. The fairly large cross section of the raise (6 by 15 ft.) would provide a large quantity of waste for backfilling, and more could be obtained from a glory hole on the surface. TIME SCHEDULE As speed in completing the raise was the main requisite, three shifts were considered, but two shifts were decided upon when it was found that three would necessitate considerably larger fans than those available for clearing the raise. The main diffi-

Jan 1, 1942

By L. Yarborough, L. R. Smith

This paper presents results of a laboratory study of retrograde condensate recovery by revaporization into dry injection gas. Flow tests were performed in 10.6-ft long sand packs at 100F and 1,500 psi. In three runs methane revaporized the liquid from a n-pentane-methane mixture in the presence of immobile water. TWO of these tests were water-wet, and the third was totally oil-wet. In the three runs n-pentane recovery was complete after 2.5 hydrocarbon PV of injection. There was no significant performance difference between the two wettability extremes. In a fourth experiment, a methane-hydrogen sulfide mixture revaporized a synthetic light, sour condensate. No water saturation was present. Equilibrium compositions and volumetric data were obtained for the four-component condensate. The heavy component, n-beptane, was removed after 6 PV production. Comparison of the effluent fluid compositions with known equilibrium data shows that the flowing fluid was equilibrium vapor and that the mixing zone between equilibrium vapor and dry injection gas was short. Data indicated that complete recovery of retrograde liquid occurred after it was contacted by a sufficient quantity of dry gas. INTRODUCTION When pressure declines below the fluid dew point in a gas condensate reservoir, a liquid phase forms. In this process, referred to as retrograde condensation, the quantity of liquid formed is frequently small enough that the liquid is not a flowing phase. To prevent loss of valuable retrograde liquids, the process of dry gas cycling has been employed for several years as a more or less standard practice. In this procedure the reservoir pressure is maintained above the fluid dew point so that the liquid components may be produced as vapor and then separated at the surface. Although full pressure maintenance by gas cycling seems ideal in terms of preventing liquids loss, several factors can reduce the atuactiveness of such an operation. From a study of a condensate reservoir in Alberta, Canada, Havlena et a1.1 con-cluded that cycling under conditions of declining pressure leads to economic advantages and to a high recovery of hydrocarbon liquids. This study considered effects of volumetric sweep efficiency, retrograde behavior of the original wet gas and revaporization characteristics of the retrograde liquid when contacted by dry gas. The first major work concerning revaporization of liquid in a gas condensate system is that of Standing et a1.2 Calculations based upon the PVT behavior of a recombined gas condensate fluid indicated that all retrograde liquid can be recovered if it is contacted by a sufficient quantity of dry gas. The paper considered the effect of variable permeability upon the recovery of retrograde liquid. Standing et al. concluded that recovery of heavier components in the retrograde liquid is greatest if reservoir pressure is allowed to decline below the dew point prior to dry gas injection. Since the work of Standing et al., several laboratory studies have been reported which show that recovery of hydrocarbon liquids by vaporization into dry injected gas can contribute to increased recovery above that obtained by ordinary production practices. Vaporization from retrograde condensate,3 conventional oil4-7 and volatile oil8 reservoirs has been considered. There is little work that deals with revaporization recovery from condensate reservoirs. This study demonstrates that vapor-liquid equilibrium exists when a dry gas is injected into a porous medium containing retrograde condensate; investigates the effect of wettability on revaporization of retrograde condensate; and provides an indication of the amount of dry gas necessary to

Jan 1, 1969

By E. W. Newman

DURING 1943 and 1944, there was an urgent need for certain grades of optical calcite (Iceland spar) for instruments for military uses. To find a supply of this material, prospecting was carried out in Montana, California and Colorado. Although some production was obtained by the work in California, the best results were from prospecting the large calcite veins of south central Montana. The bulk of the optical calcite mined during World War II has come from that area. The Bureau of Mines took an active part in the search for optical calcite in Montana. It examined most of the known calcite veins in the 70-mile distance between Wilsall, on the Shields River, and Absarokee, on the Stillwater River, and conducted exploration on several of the deposits. The Geological Survey also took an active part by mapping many of the veins. Actual mining of the calcite was performed at first by Calcite Operators, Inc., and later by the Metals Reserve Co., through an agent. A sorting plant was established at Clyde Park, where custom material could be sold. These activities stimulated mining by private operators. To be suitable for military uses, the calcite mined had to meet rigid specifications as to both size and quality. Individual crystals had to be clear and transparent and if in the form of rhombs had to measure at least 7/8 in. on each edge. Some color and a few inclusions in the calcite were allowable, but material with incipient or developed cleavages, or showing twinning other than parallel to the base, was unacceptable. HISTORY OF DEPOSITS The existence of large veins of calcite in south central Montana has long been known, and for many years the farmers of this region have used the common vein calcite for producing grit for chicken feed. According to reports, the first optical calcite produced from Montana came from the Cartwright deposit near Greycliff,1 but until recently the mining of optical calcite in Montana has been limited to spasmodic searching for small crystals suitable for making nicol prisms for saccharimeters and microscopes, or for mineral specimens. The possible need of substantial amounts of optical calcite for military uses began to appear late in 1942 and early in 1943, therefore the Polaroid company began searching for a source of supply in Montana and California. Work on the Wade property near Clyde Park was started on a small scale in the fall of 1942, by A. H. Hansen, of Clyde Park. During the winter and spring of 1943, a modest quantity of optical calcite was mined and shipped to the Polaroid Corporation, Cambridge, Mass. Most of this was produced from the "Hansen vug," which was found close to the surface. Early in the summer of 1943, mining on the Wade property was undertaken by Calcite Operators, Inc., a company organized for mining optical calcite from the Montana and California deposits. This com-

Jan 1, 1945

By Franklin H. Sharp

The operation of the Magmont Concentrator located on the New Lead Belt of Southeast Missouri is described. Ore characteristics affecting lead-copper-zinc separation are enumerated, and the cur- rent methods of separation are detailed.

Jan 1, 1976

By A. H. Heim

A method and apparatus for measuring gas porosities of rocks are described. The apparatus can be assembled from commercially available components. In principle, measurements are made by volume substitution at constant pressure. The maximum error is not more than 0.3 porosity per cent. Typical results are given. INTRODUCTION Determining the porosity of rock samples is one of the most important and yet most varied types of measurement in core analysis. Among the many techniques devised are the so-called "gas porosity" methods. An old and well known example is the Washburn-Bunting method.' The U. S. Bureau of Mines2-' described and later improved the apparatus for a now widely used method generally known as the "Boyle's law" method. In the present form of the Washburn-Bunting method,' the volume of air in the pores of a rock sample at atmospheric pressure is extracted and then collected in a graduated burette at atmospheric pressure. The volume of air is read directly as the pore volume of the sample. The absolute error in reading the collected volume of gas is independent of the total volume; thus, the relative error is larger when the volume is small, as it is for rocks of low porosity. In addition, the sample after measurement contains mercury, which limits its use for other analyses. The Bureau of Mines (or Boyle's law) method measures directly the solids volume of a sample from which the pore volume and porosity are derived, using a separate measurement of the bulk volume. Gas at a few atmospheres pressure is introduced into a sample chamber of known volume containing the rock sample. The pressure is accurately measured. Following, the gas is expanded into a burette at 1 atm, and the gas volume is read directly. From the initial pressure p, and the final pressure p2 and volume v,, the initial gas volume v1 is calculated using Boyle's law; that is, p1v1 = p2v2. Volume v, minus the volume of the empty sample chamber is the solids volume of the sample. The accuracy of the method is limited, unless corrections are made, by deviations of the gas from the "ideal" gas-law behavior assumed in the simple form of Boyle's law. The purpose of the present paper is to describe a method for measuring the gas porosity of a rock which avoids many of these difficulties. Gas volumes are measured directly with the same accuracy as the bulk volumes. Pressures of at least an order of magnitude larger than those of previous methods are employed to insure rapid penetration of the gas into the sample. While special equipment may be built to apply the method, the porosimeter may be constructed as well from commercially available components. For simplicity, the apparatus described will be referred to as the "Constant-Pressure gas porosimeter". THE CONSTANT-PRESSURE METHOD Fig. 1 shows schematically the arrangement of components comprising the present Constant-Pressure porosimeter. Briefly, the method is one of volume substitution and may be considered a null measurement. Omitting (for the present) some of the operational details, the method of measurement consists of the following three steps. 1. After evacuation, the volume of the measuring system (a ballast chamber, a manifold, two gauges and their connections) up to the sample chamber is filled with gas to a high pressure (- 1,000 psi). A sample of the gas at this pressure is trapped in one side of a sensitive differential pressure gauge to serve as the reference pressure for subsequent steps. 2. The evacuated sample chamber containing the rock sample is opened to the measuring system. As the gas expands into the chamber, the resulting decrease in pressure unbalances the differential pressure gauge. 3. The pressure is restored by means of a mercury volumetric pump. The volume of mercury injected exactly equals the free or void volume of the sample chamber (volume of empty chamber minus the solids volume of the rock within). From the injected volume and the known empty chamber volume, the solids volume is obtained and the porosity calculated. The pressure and the volume occupied by the gas are the same before and after opening the sample chamber. Expansion and compression of the gas are incidental operations and do not enter into the calculation of porosity. By the pressure balancing or nulling, the free volume of the sample chamber is merely substituted by an equal and measured volume of mercury. Since the measurements are at constant pressure, there are no compressibility corrections necessary for the sample chamber.

By C. S. Land

Relative permeability functions are developed for both two- and three-phase systems with the saturation changes in the imbibition direction. An empirical relation between residual nonwetting-phase saturation after water imbibition and initial nonwetting-phase saturations is found from published data. From this empirical relation, expressions are obtained for trapped and mobile nonwetting-phase saturations which are used in connection with established theory relating relative permeability to pore-size distribution. The resulting equations yield relative permeability as a function of saturation having characteristics believed to be representative of real systems. The relative permeability of water - wet rocks for both two- and three - phase systems, with the saturation change in the imbibition direction, may be obtained by this method after properly selecting two rock properties: the residual nonwetting-phase saturation after the complete imbibition cycle, and the capillary pressure curve. INTRODUCTION Relative permeability is a function of saturation history as well as of saturation. This fact was first pointed out for two-phase flow by Geffen et al. 1 and by Osaba et a1.2 Hysteresis in the relative permeability-saturation relation also has been reported for three-phase systems.3 Since saturations may change simultaneously in two directions in a three-phase system, four possible relationships arise between relative permeability and saturation for a water-wet system. The four saturation histories of this system were given by snel14 as 11, ID, DI and DD. I and D refer to the direction of saturation change (imbibition and drainage), with the first letter of the symbol indicating the direction of change of the water phase. As used in this paper, the second letter of the symbol refers to the direction of saturation change of the gas phase, i.e., D and I indicate an increase and decrease, respectively, in gas saturation. Only a few three-phase relative permeability curves have been published. Leverett and Lewis5 published three-phase curves for unconsolidated sand, and Snell4 reported results of several English authors for both drairrage and imbibition three-phase relative permeability of unconsolidated sands. Three-phase relative permeability curves for a consolidated sand were published by Caudle et a1.3 for increasing water and gas saturations (ID). Corey et a1.6 reported drainage (DD) three-phase relative permeability for consolidated sands. Recently, Donaldson and Dean7 and Sarem8 calculated three-phase relative permeability curves from displacement data on consolidated sands, also for saturation changes in the drainage direction. The only published three-phase relative permeability curves for consolidated sands with saturation changes in the imbibition direction (11) are those of Naar and Wygal.9 These curves are based on a theoretical study of the model of Wyllie and Gardner 10 as modified by Naar and Henderson.11 Interest in three-phase relative permeability has increased recently due to the introduction of new recovery methods and refinements in calculation procedures brought about by the use of large-scale digital computers. The scarcity of empirical relations for three-phase flow, and the experimental difficulty encountered in obtaining such data, have made the theoretical approach to this problem attractive. RELATIVE PERMEABILITY AS A FUNCTION OF PORE-SIZE DISTRIBUTION Purcell used pore sizes obtained from mercury-injection capillary pressure data to calculate the permeability of porous solids.12 Burdine extended the theory by developing a relative permeability-pore size distribution relation containing the correct tortuosity term.13 The works of Purcell and Burdine were combined by Corey14 into a form that has

Jan 1, 1969

By J. G. Richardson, J. W. Graham

The purpose of this paper is to present the results of theoretical and experimental studies of water imbibition. The imbibition processes are involved in recovery of oil from stratified and fractured-matrix formations in natural water drives and water flooding. An understanding of the role of inhibition in implementing the recovery of oil from such formations is deemed essential to proper control of these reservoirs to achieve maximum recovery. The theoretical studies involved development of the differential equations which describe the spontaneous imbibition of water by an oil-saturated rock. The dependence of the rate of water intake by the rock on the permeability, interfacial tension, contact angles, fluid viscosities and fluid saturatiorls is discussed. A few experiments were performed using core samples to determine the effects of core length and presence of a free gas suturation. The role of water imbibition in recovery of oil from a fractured-matrix reservoir by water flooding was investigated by use of a laboratory model. This model was scaled to represent one element of a frac-tured-matrix formation. Water floods were made at various rates with several fracture widths. Interpretations were made of the behavior expected in a system containing many matrix blocks. The presence of a free gas sntu.ration was found to reduce the rate of water imbibition. In the reservoir prototype of the fractured-matrix model, water imbibition rather than direct displacement by water was the dominant mechanism in the recovery of oil at low rates. INTRODUCTION Imbibition may be defined as the spontaneous taking up of a liquid by a porous solid. The spontaneous process of imbibition occurs when the fuid-filled solid is immersed or brought in contact with another fluid which preferentially wets the solid. In the process of wetting and flowing into the solid, the imbibing fluid displaces the non-wetting resident fluid. Common examples of this phenomenon are dry bricks soaking up water and expelling air, a blotter soaking up ink and expelling air and reservoir rock soaking up water and expelling oil. As increasingly better lithological descriptions have been made of the characteristics of petroleum-bearing formations, it has become obvious that imbibition phenomena which were once considered laboratory curiosities are of practical importance. For instance, in reservoirs composed of water-wet sand strata of different permeability in intimate contact, the tendency of water to channel through the more permeable stratum is offset by the tendency for water to imbibe into the tight sand and expel oil into the coarse sand. Also, in fractured-matrix formations the tendency of water to channel through the fractures is offset by water-wet matrix blocks. As some imbibition of the water into the of the largest fields in the world are fractured-matrix reservoirs, it has become increasingly important to understand all the factors involved in the imbibition process. Examples of fractured-matrix reservoirs are the Spraberry field in West Texas which produces from a fractured sandstone', the giant Kirkuk field in Iran', the Dukhan field in Qatar, Persian Gulf2, and the Masjid-I-Sula-main and the Haft-Kel fields in Southwestern Iran, which produce from fissured limestone3. Research into recovery of oil from fractured-matrix formations was stimulated by the rapid decline of oil productivity of wells in the Spraberry formation. One result of this research was the water imbibition process developed by the Atlantic Refining Co.4 Another idea was that much of the Spraberry oil could be recovered by conventional water-flooding procedures5. Subsequently, pilot floods were conducted in this field to test the feasibility of these ideas. It was felt that an understanding of the role played by imbibition processes in displacement of oil from a fractured-matrix reservoir could not be obtained from field data alone because of the many complicating factors and uncertainties involved. Therefore, theoretical and laboratory studies were undertaken to provide this understanding. Study of the equations which describe the linear, countercurrent imbibition process provided an insight into the role of various factors in the process, such as the permeability of rock and inter-facial tension. In addition to the theoretical studies, imbibition experiments were conducted with core samples to determine the effect on the rate of imbibition of such variables as core length and free gas saturation. The principal experimental studies were conducted by water flooding a scaled model of an clement of a frac-tu red-matrix reservoir to evaluate

By C. Y Garber

Interest in the sink-float plant operated by the Bunker Hill and Sullivan Mining and Concentrating Co. at Kellogg, Idaho, has recently been largely confined to the preparation and reconditioning of the galena medium. The ease and simplicity of these operations in a concentrating mill producing a flotation lead concentrate has occasioned enough comment to possibly justify a brief description. The subject is treated from an operator's viewpoint only; no effort is made to discuss it in a theoretical or technical manner. Plant at Bunker Hill The sink-float plant was first operated in December 1941. It was built for the purpose of quickly increasing mill capacity with a minimum of equipment. It is the Huntington-Heberlein sink and float process using galena medium and is operated under license from the Sink and Float Corporation, New York city. Lead-zinc ore from the Bunker Hill mine is crushed to pass a 1¼ in, screen and is then washed and separated on vibrating screens having 4½-mm. round-hole punched plates. The screen under-size, amounting to 33 per cent of the mill feed, is dewatered and sent to the ball-mill feed bins. The screen oversize goes to the sink-float plant, where 50 per cent of the oversize, or 33 per cent of the mill feed, is float, which is washed free of medium and disposed of as a tailing. The remaining 33 per cent is sink, which, after washing, is crushed to pass 36 in. and joins the under-size in the ball-mill feed bins. The normal plant capacity is 1700 tons per 24 hr. About 1.7 per cent of the total lead and 3.3 per cent of the total zinc in the feed is lost with the sink-float tailings (Table I). More complete descriptions of the H. H. process and Bunker Hill sink-float plant are given in several recent articles, listed at the end of the paper. Preparation OF Medium at Bunker Hill New medium is made intermittently as needed, usually 12 hr. in each 6 days. A small portion of the current mill flotation concentrate is diverted from the lead cleaner cells to a I-in. vertical sand pump and pumped to a two-cell 36-in. Agitair flotation machine, where NaCn and ZnSO4 are added and the grade of concentrate is improved as shown in Table 2. Tailing from this operation is returned by gravity

Jan 1, 1947

By C. Y. Garber

Interest in the sink-float plant operated by the Bunker Hill and Sullivan Mining and Concentrating Co. at Kellogg, Idaho, has recently been largely confined to the preparation and reconditioning of the galena medium. The ease and simplicity of these operations in a concentrating mill producing a flotation lead concentrate has occasioned enough comment to possibly justify a brief description. The subject is treated from an operator's viewpoint only; no effort is made to discuss it in a theoretical or technical manner. Plant at Bunker Hill The sink-float plant was first operated in December 1941. It was built for the purpose of quickly increasing mill capacity with a minimum of equipment. It is the Huntington-Heberlein sink and float process using galena medium and is operated under license from the Sink and Float Corporation, New York city. Lead-zinc ore from the Bunker Hill mine is crushed to pass a 1¼ in, screen and is then washed and separated on vibrating screens having 4½-mm. round-hole punched plates. The screen under-size, amounting to 33 per cent of the mill feed, is dewatered and sent to the ball-mill feed bins. The screen oversize goes to the sink-float plant, where 50 per cent of the oversize, or 33 per cent of the mill feed, is float, which is washed free of medium and disposed of as a tailing. The remaining 33 per cent is sink, which, after washing, is crushed to pass 36 in. and joins the under-size in the ball-mill feed bins. The normal plant capacity is 1700 tons per 24 hr. About 1.7 per cent of the total lead and 3.3 per cent of the total zinc in the feed is lost with the sink-float tailings (Table I). More complete descriptions of the H. H. process and Bunker Hill sink-float plant are given in several recent articles, listed at the end of the paper. Preparation OF Medium at Bunker Hill New medium is made intermittently as needed, usually 12 hr. in each 6 days. A small portion of the current mill flotation concentrate is diverted from the lead cleaner cells to a I-in. vertical sand pump and pumped to a two-cell 36-in. Agitair flotation machine, where NaCn and ZnSO4 are added and the grade of concentrate is improved as shown in Table 2. Tailing from this operation is returned by gravity

Jan 1, 1947

By C. R. Van Hise

[Concluding Contribution of Prof. Van Hise to the Discussion of his Paper, and Others on the Same General Subject, presented at the Washington Meeting, February, 1900 (see Ram., xxx., 27, 177, 323, 424, 578) ; also of the contributions of Vogt, De Launay, Beck, Lindgren, Kemp, Rickard, Bain, Keyes, Collins and Adams, presented at the Richmond Meeting, February, 1901, and to be printed in the present volume.] In June, 1900, shortly after my paper was published in the Fransactions, I made a briefer statement* before the Western Society of Engineers covering the same ground, which, in certain respects, is somewhat of an improvement. For instance, instead of using the terms descending and ascending &th reference to the waters resulting in the two concentrations, my modified statement is as follows: " The first concentration of many ore-deposits is the work of a relatively deep water-circulation, while the reconcentration is the result of reactions upon an earlier concentration through the agency of a relatively shallow water-circulation. Commonly the deep water-circulation is lacking in free oxygen, and contains reducing agents, and the shallow water contains free oxygen. The deep water is therefore a reducing, and the shallow water an oxidizing agent."† Of the papers upon ore-deposits which, in vol. xxx. of the Fransactions, follow my own, or which were presented at the Richmond meeting, a considerable number are wholly con-

Jan 1, 1902

By JOHN R. SUMAN

TONIGHT I want to speak of the current problems and the postwar difficulties facing American industry. American industry has done an outstanding job in adjusting its operations to wartime necessity. The national income for 1942 was nearly $120,000,090,000 and of this outlay approximately $55,000,000,000 went for war material. The enormity of the expenditures for war material is indicated by the fact that the expenditures for war purposes alone were greater than the annual gross national income in the period 1931-34. This tremendous production job in turning out a record output of war products was accomplished by industry in spite of a large number of restraining and hampering influences, and I want to mention several of the more important problems.

Jan 1, 1943

By N. E. Brown, F. L. Versnyder

THE apparent dependency of the electrical characteristics of hexagonal crystalline selenium on microstructure has aroused much interest in microscopical studies of selenium. Microscopic observations on the crystallization of selenium have been made by Escoffery and Halperin,' P. H. Keck,' and other investigators. It is the purpose of this paper to discuss the microstructural changes observed on polished cross-sections of single layers of selenium after various heat treatments. Observations were also made on crystallization of the free-surface layer of these deposits. In general, all of the transformations studied were either transformations of the vitreous selenium to hexagonal selenium or micro-structural transformation of the hexagonal selenium itself. Procedure The selenium used in this work was obtained from the American Smelting and Refining Co. and was approximately 99.96 pct pure. An intentional impurity of 1 part per 2,000 of bromine was added to the material prior to evaporation. A thickness of approximately 0.002 in. of this selenium was vapor deposited on an aluminum base plate. The maximum plate temperature during the vacuum vapor deposition was 140°C. Mounting of the cross-sectional specimens for metallographic study could not be done in plastic mounting media, as is customary, since temperatures in excess of 50°C would cause unwanted transformations. Consequently, a simple clamp-type device was used to mount the specimens for preparation. All grinding operations were then done carefully by hand in order that the specimen not become heated during this operation. Wet polishing was done on the conventional metallographic polishing laps, using successively finer grinding powders. An extremely careful polish is necessary, since observation and micrography of the specimens are done in the unetched condition under polarized light. The two observations of crystallization made on the free surface of vitreous selenium deposits (Figs. 4 and 5) were made on surfaces which were perpendicular to the cross-sections studied. These free-surface layers were examined directly, i.e., no pre- vious metallographic preparation, as obtained from the vacuum vapor deposition. Microscopic Observations A study was made of polished cross-sections of the vitreous selenium as-deposited. It was noted that in all cases there was columnar crystallization adjacent to the base plate, which appeared to occur during the vacuum deposition process. This observation has also been made by Keck? It also was observed that vagrant spherulitic crystallization occurred in the vitreous selenium. The term "vagrant" is used, since these spherulitic grains appear to crystallize at random throughout the vitreous selenium during the vacuum deposition process. Columnar crystallization at the A1-Se interface and a typical spherulite observed in a polished cross-section of "as-deposited" vitreous selenium may be seen in Fig. 1. Cross-sectional samples of vitreous selenium studied after heat treating individual samples for 20 min in 10" steps from 80" to 220°C revealed that crystallization—in this case, columnar crystal growth —proceeds from the aluminum base plate to the surface of the specimen (Fig. 2). Crystallization was microscopically observed to be complete after the 130°C heat treatment. Visual examination of the free surface of the specimen after the 130 °C heat treatment revealed the readily recognizable grey appearance of the completely crystallized selenium, in corroboration of the microstructural observations. No microstructural transformations then appeared to take place between 130" and 190°C. At 190°C the beginning of recrystallization appeared and proceeded until the columnar grain structure had been completely transformed to equiaxed grains between 210" and 220°C (Fig. 3). Naturally, the grain size of the recrystallized grains at the lower temperatures (190" to 210°C) was smaller than is illustrated in Fig. 3. In addition, polished cross-sections of deposits heat treated at 140°C for 10 min to cause complete crystallization and, subsequently, heat treated in 10" steps from 80" to 220°C for 20 min were studied. As expected, no microstructural transformations took place until the beginning of recrystallization was observed at 190°C. A comparison with the previously studied specimens revealed that recrystallization proceeded almost identically in the two experiments although in the first case the deposits were vitreous prior to the series of heat treatments and in the second case they had been crystallized by a previous heat treatment. By heat treating for longer times (180 min) at lower temperatures, the

Jan 1, 1956