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By R. H. Jacoby, V. J. Berry

Future depletion performance and ultimate oil recovery from reservoirs producing under volumetric control are often predicted with the aid of a material balance equation. When the reservoir fluid is very volatile, however, certain assumptions implicit in the use of the conventional methods are no longer valid. This is became laboratory differential vaporization test procedures do not adequately represent the reservoir depletion process and the performance of surface separation facilities. In such cases recovery of stock tank oil per unit of pressure decline can be predicted only from a detailed knowledge of the separator conditions and the over-all composition of the fluid entering the wellbore at each stage of depletion. Surface recovery is not simply related to the total quantity of liquid flowing into the well under reservoir conditions. In order to improve predictions for reservoirs which produce volatile oils, a step wise method of calculation has been developed. This method uses relative permeability data and multicomponent flash calculations to predict oil and gas production as a function of reservoir pressure. Calculations are presented for a reservoir containing a volatile crude oil, and predicted tank oil recovery by primary depletion is more than twice that predicted by conventional methods which are known to be adequate for ordinary black crude oils. Calculated maximum produced gas-oil ratio is less than one-fourth of the conventional prediction. Wellstream compositions have also been used to determine variation in stock tank oil composition and liquid content of the separator gas. This information is of particular importance for crude stabilization calculations and for design of gasoline plant facilities to recover LPG and natural gasoline. INTRODUCTION The estimation of oil reserves and the prediction of future recovery performance of petroleum reservoirs is a frequent task of the petroleum engineer. If the reservoir produces under volumetric control, performance calculations for primary depletion are made by combining oil and gas material balances with the gas-oil flow characteristics of the reservoir rock. For black oil reservoirs, the Schilthuis1 type material balance is commonly employed. For gas or gas-condensate reservoirs, where only one phase is flowing under bottom-hole conditions, a more simplified material balance is used. In the period in which these material balance methods were conceived and put into practice, it was common to classify reservoirs according to the type of fluid produced as (1) black oil reservoirs, or (2) gas or gas-condensate reservoirs. Recently, however, deeper drilling and more extensive studies of reservoir fluid properties have led to the recognition of reservoir fluids with phase characteristics between those of ordinary black oils, and gases or gas-condensate fluids. These intermediate fluids contain relatively large amounts of the hydrocarbons ethane through decane and are found in deep, high temperature (250°F) reservoirs. Such fluids are often referred to as high shrinkage crudes or "volatile oils." They are usually characterized by tank oil gravities above 45° API. high solution gas/oil ratios,

Jan 1, 1958

By Will Coghill

As the title indicates, this paper treats of the degree of liberation of minerals after grinding. To obtain the supporting data a "tool" not commonly used by metallurgists has been employed. It is the "heavy solution." The advantages gained through its use are shown. Actual ores were employed in order to make the study concrete. The selection was somewhat incidental and happened to embrace the red iron ores of Alabama. So, any reader interested in these ores will find some of their properties described. The red ores constituted the material examined and a somewhat new adaptation of heavy solutions was the tool of examination. If either the ores or the tool interest the reader these notes may be of some value. The writer's chief interest was in the rate of liberation of locked grains. Ores are generally ground preparatory to concentration and as long as the concentrators make suitable products the effectiveness of the grinding is likely to be unquestioned. But when suitable products are difficult to make, an investigation becomes imperative. In such a case a dissection of the ore might be made to find the cause of the trouble. Such a condition of unsuitable products exists in the low-grade red iron ores of Alabama. They are difficult to concentrate. To be sure it might be said that the concentration of iron ores is a new thing and that the ore-dressing methods are undeveloped, but a glance at the industry reveals an abundance of methods and devices for almost all imaginable conditions. Concentrating machinery has not taken a part in this investigation; the use of it would have been only machinery testing, and should never precede the ore testing which consists of such methods as herein outlined. When the properties of the ores have been gleaned the machinery may be used more effectively.

Jan 12, 1926

By W. F. Holbrook, T. L. Joseph

The problem of sulfur control is important in all blast-furnace operations but particularly for certain grades of steel because of the rigorous specifications. During the past decade the tendency has been to produce pig iron and hot metal of lower sulfur content. As most of the sulfur in the iron originates in the fuel, the use of high-sulfur coke demands modifications in practice to meet sulfur specifications. While it is generally known that high temperatures and more basic slags favor desulfurization, operators as a rule produce the most acid slag that will permit proper desulfurization. The viscosity of blastfurnace slag has been thought to be related to desulfurization and has been investigated by Feild and Roysterl, also McCaffery and his associates*, but apparently no systematic effort has been made to determine the relative desulfurizing powers of slags over the range of composition encountered in practice. Development of Testing Method Because slag and metallic iron are immiscible, the desulfurization reaction is heterogeneous, occurring only at the interfaces between slag and metal bodies. In the blast furnace the newly reduced iron, containing FeS, descends through the slag bath probably either as small drops or streams, at the interfaces of which desulfurization occurs. After its descent through the slag the iron collects to form a bath of metal, at the top surface of which desulfurization reaction probably occurs. These two steps have been thought to account for all desulfurization in the blast furnace. Kinney3 found that metal removed from the blast furnace just above the tuyeres contained three to four times as much sulfur as the iron at cast. Herty and Gaines4 conclude that most of the sulfur is removed while the metal is passing through the slag. Mund, Stoecker

Jan 1, 1936

By William M. Newton, John E. Sherborne

The relation between the properties of electric logs and the fluid used in drilling a well is briefly discussed in this paper, and the fact that the resistivity of the drilling mud and its filtrate can appreciably affect such logs is shown. Apparatus was designed and a procedure established to determine the effect of various factors on the resistivity of drilling mud. Five muds commonly employed in California were tested and the following observations were made: I. The effect of raising the temperature from 80°F. to 180°F. is to decrease the resis-tiviiy of the mud or filtrate approximately 50 per cent. 2. The resistivity of the mud in most cases closely approximates that of its filtrate. 3, The change in the resistivities of muds caused by the addition of chemical is not the same function of the amount of chemical added for each mud. 4. The effect produced by increased sodium chloride content is to reduce markedly the resistivity of the mud and its filtrate. 5. Weighting materials, such as Baroid and limestone, tend to increase the resistivity of drilling mud. 6, Cement and counteracting reagents reduce mud resistivity. Introduction During recent years, the practice of "electrically logging9' a geologic formation by means of a system of electrodes lowered in a well bore has provided data of inestimable value concerning the nature of the sediments penetrated. Thus, it is generally possible, by means of electric logs, to distinguish readily the differences between shales, sandstones, cherts, limestones, and other rock forms. The distinguishing characteristics recorded in this manner have made possible long-range and closely detailed mapping and visualization of deeply buried structures1-5 to a degree not to be obtained with a reasonable expenditure of money by any other means at present in use. Besides being of value in correlation work, electric logs have been found, in some instances, to be useful in estimating the nature of fluid contained within the pores of a rock. In special cases, even the relative permeabilities at different horizons have been determined.6 That electric logs should reflect in some measure such physical properties of rocks as porosity and permeability and, in addition, give rise to data pertaining to the fluid content of rock interstices, becomes evident when the conditions giving rise to the electrical phenomena measured are known. However, it is not the purpose of this paper to review the present status of electric logging; rather, the reader is referred to the papers cited on page 220 for the principles and practice involved. Importance of Drilling FLuid in Electric Logging Because the drilling fluid must be the medium through which the electric logging device is made to traverse the formations penetrated by a borehole, and since, in general, the drilling mud completely surrounds

Jan 1, 1942

By H. B. Pulsifer

The unprecedented high price of zinc ore prevailing through the early months of 1915 caused great activity in the Joplin district of Missouri. The Media mill is conspicuous as one of the first of the new "big mills" of the district. The mill was built over a mine previously worked but abandoned in 1912 because of the leanness of the ore and the large quantity of water encountered. The ore prices prevailing—$100 a ton in June, 1915, as against $50 in 1912-—favored the new undertaking. The mill was designed for good recovery so that it might operate in times of depression. In design and equipment, the mill is exclusively local in conception and construction. Former Exploitation The tract of land is a part of the large Guinn holdings; 70 acres are comprised in this particular lot, which is situated just a mile north of the center of Webb City on the Alba line of the Southwest Missouri Electric Railway. The ore lies 242 ft. below the surface at the top of the knoll which is surrounded by the well known properties: Black Cat, Ground Floor, Florence, Hurry-Up, Electrical, and Mercantile. Since the abandonment, in 1913, of the Yellow Dog a bit farther to the north, the Black Cat, Ground Floor, and Florence workings had been flooded. However, as there was no cut through from this side into the area it was proposed to exploit, it was thought that moderate pumping facilities would take care of the water. Three shafts had already been sunk to the ore horizon during the previous operations; the ground was connected by wide drifts and possibly 10 acres mined out, principally about the two southerly shafts which at surface are 8 and 13 ft. lower, respectively, than the collar of the shaft at which the new mill was built. The former mill on the lease was known as the Bohemian Girl. This mill, built in 1910, was removed after some 3 years' work. A head frame and hopper still existed at the middle shaft, sometimes known as the lower Hold Out shaft, but at the most northerly

Jan 1, 1918

By H. Margolin, A. Coucoulas

Fused alumina or silica crucibles were used as the containing vessel. X-ray powder photographs were taken with CrKcll radiation and the use of Straumanis type Norelco cameras of 114.6 mm diam. Crystallographic data for these compounds are shown in Table I. These results are in agreement with others of this series reported previousiy by Wernick and Geller.l The abnormally large atomic volume of Eu and Yb metal3 is manifested in EuAl2, and YbAl2, when one compares them with the compounds reported in Ref. 1. However, the behavior of Yb in the Ni compound is the same as that observed in Ni5Yb having the Cu5Ca structure.4 Thus, it appears that Yb has a valence closer to 3 only in the Ni compounds; i.e.. the 2s and Id electrons are lost to the conduction band.1,4 Europium in EuAl2 appears to have a valence closer to 2. In previous work.' X-ray patterns of ingots of NdCo2 indicated a multiphase material with faint indication of the presence of a phase having the MgCu2 structure. It was thought that NdCo2 formed peri-tectically from the melt, resulting in a multiphase system when cooled under nonequilibrium conditions. An X-ray pattern of a sample from a melt cooled more slowly than in past work showed that the major phase was NdCo2. The lattice constant, Table 1, is in excellent agreement with the value one can predict from the data of Ref. 1. One of the other phases was identified as Co5Nd. The author wishes to thank J. H. Wernick for his guidance in this work, and D. Dorsi for the preparation of these compounds. 'J. H. Wernick and S. Geller: AIME Trans., in press. 'J. H. Wernick and S. E. Haszko: to be published. 'F. H. Spedding and A. II. Daane: Progress in Nuclear Energy, Series 5, Eds.: H. M. Finniston and J. P. Howe, McGraw-Hill Book Co., 1956. 'S. E. Haszko: to be published. 'J. H. Wernick and S. Geller: unpublished work. 6J. 11. Wernick and S. Geller: Acia Cryst., 1959, vol. 12, p. '162. A reinvestigation of the lattice parameters of Ti-Sn alloys by the present authors has revealed consistently hiher c and a values than those obtained by Worrier. The difference is most pronounced in the c-parameters which are, therefore, used as a basis of comparison. This discrepancy was not due to air contamination, since precautions were taken to exclude this possibility. Specimens for Debye-Scherrer photograms were prepared by arc-melting 15-g buttons of Bureau of Mines titanium and 99.99 pct Sn, with compositions of 6, 8, 10, and 12 at. pct Sn. These buttons were forged under an oxygen-acetylene torch to 1/8-in. sq rods to produce relatively fine grained material. Scale and some surface were ground off, and the rods, after wrapping in molybdenum and titanium sheet, were vacuum annealed 15 min at 800 °C to remove hydrogen. Heat treatment of one of the samples at 875°C to produce ß and reveal a at the surface showed no surface contamination. Following the vacuum treatment, the specimens were wrapped in molybdenum and annealed for 1 week at 800°C under two atmospheres of argon. After water-quenching, the rods were ground so that the thickness tapered to 0.1 mm at the tips. The ground specimens were then recapsuled as previously and reannealed 1 hr at 800°C to remove cold work. The

Jan 1, 1961

By W. F. Holbrook, T. L. Joseph

The problem of sulfur control is important in all blast-furnace operations but particularly for certain grades of steel because of the rigorous specifications. During the past decade the tendency has been to produce pig iron and hot metal of lower sulfur content. As most of the sulfur in the iron originates in the fuel, the use of high-sulfur coke demands modifications in practice to meet sulfur specifications. While it is generally known that high temperatures and more basic slags favor desulfurization, operators as a rule produce the most acid slag that will permit proper desulfurization. The viscosity of blastfurnace slag has been thought to be related to desulfurization and has been investigated by Feild and Roysterl, also McCaffery and his associates*, but apparently no systematic effort has been made to determine the relative desulfurizing powers of slags over the range of composition encountered in practice. Development of Testing Method Because slag and metallic iron are immiscible, the desulfurization reaction is heterogeneous, occurring only at the interfaces between slag and metal bodies. In the blast furnace the newly reduced iron, containing FeS, descends through the slag bath probably either as small drops or streams, at the interfaces of which desulfurization occurs. After its descent through the slag the iron collects to form a bath of metal, at the top surface of which desulfurization reaction probably occurs. These two steps have been thought to account for all desulfurization in the blast furnace. Kinney3 found that metal removed from the blast furnace just above the tuyeres contained three to four times as much sulfur as the iron at cast. Herty and Gaines4 conclude that most of the sulfur is removed while the metal is passing through the slag. Mund, Stoecker

Jan 1, 1936

By Nicholas J. Grant, Rolf Nordheim, Thomas B. King

Constant-load creep-rupture tests were conducted in an argon atmosphere at temperatures of 1600 to 2200°F on two heats of iron containing about 0.06 and 0.09 pct P in solid solution. The tests were conducted in the as-cast condition. Stresses were selected to give strain rates approaching those encountered in the hot working of steel, and within the limits of the creep-rupture test apparatus, namely. from about 0.001 to 50 pct per sec. FOR generations, rolling and forging practices have been developed largely by empirical methods, based on prior experience. While largely successful, difficulties are frequently encountered when new or different alloy compositions are tried for the first time. There is need to know the relationships which exist among temperature, strain rate, composition, and other variables on the deformation and fracture characteristics of steels. It has been shown for aluminum and several high-temperature alloys that the deformation and fracture characteristics follow rather well-defined laws and patterns which are closely related to the effects of strain rate, temperature, and composition.1"3 As the melting temperature of aluminum or its alloys was approached, it was possible to study the interplay of work-hardening factors and recovery or recrystal-lization, the latter resulting in improved ductility and increased resistance to intercrystalline fracture. In particular, the effects of composition are very poorly known. Within the meaning of "composition" should be included impurity elements, such as sulfur, phosphorous, lead, copper, and many others, as well as those elements which are added for alloying purposes in iron. The role of multiphase structures, in contrast to solid solutions, should also be studied in much greater detail. high strain rate creep-rupture tests would provide information regarding the deformation and fracture characteristics of metals at hot-working temperatures. It was also desired to establish the stresses which are necessary to accomplish the desired deformation, and to relate these to the strain rate and temperature. Secondly, it was the purpose of this particular study to determine the effects of phosphorus, within solid solution limits, on the deformation and fracture characteristics of iron at hot-working temperatures. EXPERIMENTAL PROCEDURE Two phosphorus levels were selected, one corresponding to the upper limit normally found for commercial steels, and one substantially higher than this, but within the region of solid solubility at the test temperatures chosen for this investigation. Twenty-pound heats were prepared by induction melting electrolytic iron in air in a magnesia lined furnace. After deoxidation with about 0.2 pct Al, ferro-phosphorus was added, and the heats were then poured into prefired silica molds. The purpose of using silica molds was to obtain a slow cooling rate during solidification to produce a relatively coarse grain size, producing a structure subject to some segregation and therefore more nearly characteristic of ingot structures. The major part of the casting assembly provided a large shrinkage head in order to produce sound castings and to promote slow cooling of the specimens. The primary austenitic grain size varied from ASTM No. 2 to No. 00. The composition of the heats, including a low phorphorus melt, used for comparison purposes, is shown in Table I. It will be noted that the oxygen content of the phosphorus containing heats is relatively high, in spite of the deoxidation practice, a condition which is difficult to control in small melts. Creep-rupture tests were nevertheless undertaken when it was noted that this quantity of oxygen did not appear to give results any different from those from a heat containing 0.01 pct 0, low phosphorus and comparable carbon Content;4 see Table 11.

Jan 1, 1961

By William M. Bowron

Thirty years ago, when I stood on the cliff of red fossil iron-ore, on Red mountain, Jefferson county, Ala., I asked what were the geological relations of this remarkable deposit. In reply I was told that it was a limestone, colored and saturated by some unknown but wholly external influences, and that at a reasonable distance from the surface the color would disappear. I could find no satisfactory explanation, either of the nature of this wonderful external permeating influence, or of the cause of such a ferrous impregnation selecting this one particular bed of limestone, to the exclusion of the higher and lower beds of the same material which are not even stained. I. The Present Theory. Referring to this subject, Dana says :' "The clays, clayey sandstones and limestones of the Clinton epoch, through New York and the Appalachians, show that the mud-flats and sand-banks, and hence the shallow seas of the coast region, still continued.... The beds of argillaceous iron-ore, which spread so widely through New York and some of the other States, west and south, could not have been formed in an open sea; for clayey iron-deposits do not accumulate under such circumstances. They are proof of extensive marshes, and, therefore, of land near the sea-level. The fragments of crinoids and shells found in these beds are evidence that they were, in part at least, salt-water marshes, and that the tides sometimes reached them." At first, this explanation seemed satisfactory, but the more I studied the ore the less satisfying the explanation became. 1. In the ore itself, I found associated with the small particles of rounded matter (now consisting of iron oxide in which organic structure, if ever present, has become lost, though the

Jan 1, 1906

By H. D. Attra

The effects of phase behavior on reservoir economics is a function of both fluid composition and flow properties of the reservoir rock. In some operations such as gas injection into volatile crude-oil resertoirs, the stock-tank recovery derived from vaporization of the reservoir oil by the displacing gas can approach the recovery derived from the displacement mechanism. In other cases of gas-cycling reservoirs, the dry injected gas can effectively vaporize a retrograde liquid phase, allowing a substantial reduction in cycling pressure with no appreciable loss in recoverable liquids. Because of these effects, it is essential that phase behavior be considered in developing the economics of any secondary recovery program in which gas is the injected fluid. The inclusion of phase behavior in conventional calculation procedures has been retarded because of the complexity of the calculation and the large volume of laboratory data required. However, by applying high-speed computers and new laboratory techniques, the phase-behavior displacement calculation has been developed to economically include this basic fundamental of gas displacement. The calculation is performed by reducing the reservoir to a series of one-dimensional segments. Phase changes, saturation distributions and changing fluid properties are evaluated for each segment as a function of time. The relative volumes of equilibrium liquid and gas displaced from each segment are determined by a trial-and-error procedure to meet the requirements of phase equilibrium and two-phase flow. The produced fluids are flashed through conditions of surface separation approximating those in the field to obtain actual values for stock-tank liquid recovery and producing gas-oil ratios. Based on the results of successful field studies, the technique appears to have application to reservoirs producing under a nonmiscible gas-displacement mechanism and should substantially increase the reliability of this type of analysis when phase behavior is an important factor. Predicting reservoir performance under gas-injection operations involves three basic principles of reservoir engineering. First, a material balance exists between the displacing gas and the displaced reservoir fluid. Second, the oil and gas flow in relationship with the two-phase flow property of the reservoir rock; and third, phase equilibrium exists between the displacing gas and the native reservoir fluid. To illustrate these three principles, consider the one-dimensional reservoir shown in Fig. 1. The reservoir is divided into a series of segments representing a one-dimensional cross section between an injection area and a producing area. So represents the oil saturation, Cw represents the connate-water saturation and Sg represents the displacing gas saturation. The gas is moving into Segment 1 and the reservoir oil is being produced out of Segment N. Consider the case when gas has just moved into Segment 1 and the displacing gas-oil contact is at position a-a The volume of oil pushed out of Segment 1 is a function only of mobility and the two-phase flow properties of the reservoir rock, that is, Kg/Ko and µo/µg. Behind the front if the injected gas is foreign to the reservoir oil (a nonequilibrium gas), there will either be vaporization of the oil into the gas or condensation of the gas into the oil. In either case the net result is a mass transfer and a re-distribution of composition and liquid and gas saturation. If the displacement is at constant pressure and is continued, the gas moves into new segments, proceeding succesively into Segment 2, 3, etc. The total volume of oil produced from the reservoir

By John E. Sherborne, William M. Newton

The relation between the properties of electric logs and the fluid used in drilling a well is briefly discussed in this paper, and the fact that the resistivity of the drilling mud and its filtrate can appreciably affect such logs is shown. Apparatus was designed and a procedure established to determine the effect of various factors on the resistivity of drilling mud. Five muds commonly employed in California were tested and the following observations were made: I. The effect of raising the temperature from 80°F. to 180°F. is to decrease the resis-tiviiy of the mud or filtrate approximately 50 per cent. 2. The resistivity of the mud in most cases closely approximates that of its filtrate. 3, The change in the resistivities of muds caused by the addition of chemical is not the same function of the amount of chemical added for each mud. 4. The effect produced by increased sodium chloride content is to reduce markedly the resistivity of the mud and its filtrate. 5. Weighting materials, such as Baroid and limestone, tend to increase the resistivity of drilling mud. 6, Cement and counteracting reagents reduce mud resistivity. Introduction During recent years, the practice of "electrically logging9' a geologic formation by means of a system of electrodes lowered in a well bore has provided data of inestimable value concerning the nature of the sediments penetrated. Thus, it is generally possible, by means of electric logs, to distinguish readily the differences between shales, sandstones, cherts, limestones, and other rock forms. The distinguishing characteristics recorded in this manner have made possible long-range and closely detailed mapping and visualization of deeply buried structures1-5 to a degree not to be obtained with a reasonable expenditure of money by any other means at present in use. Besides being of value in correlation work, electric logs have been found, in some instances, to be useful in estimating the nature of fluid contained within the pores of a rock. In special cases, even the relative permeabilities at different horizons have been determined.6 That electric logs should reflect in some measure such physical properties of rocks as porosity and permeability and, in addition, give rise to data pertaining to the fluid content of rock interstices, becomes evident when the conditions giving rise to the electrical phenomena measured are known. However, it is not the purpose of this paper to review the present status of electric logging; rather, the reader is referred to the papers cited on page 220 for the principles and practice involved. Importance of Drilling FLuid in Electric Logging Because the drilling fluid must be the medium through which the electric logging device is made to traverse the formations penetrated by a borehole, and since, in general, the drilling mud completely surrounds

Jan 1, 1942

By Walter R. Hibbard, Harold Margolin

The effect of ten ternary additions on the aging of a Cu-Ag alloy was measured by X ray, microstructure and hardness. A supersaturated copper-rich transition structure was found. The effect of the ternary element was related to differences between transition and precipitate lattice parameters and analogies with solution and strain hardening. IN addition to the prerequisite of diminishing solid solubility with falling temperature, the theory of coherency hardening1 proposes that the principal source of hardening during precipitation is strain caused by coherency between the matrix and precipitate. For a given system greater coherency hardening would result from lengthening the period of coherent growth and/or increasing the number of nuclei, other things remaining equal. However, the hardness change during aging is a function of a number of phenomena in addition to coherency hardening, such as dispersion hardening, loss of coherency, solute depletion, matrix recovery or recrystal-lization, coalescence, and their relative time sequences. The present investigation was undertaken to study the effect of ternary additions on the age-hardening of Cu-Ag alloy. For this purpose a series of alloys were made containing as ternary constituents Mg, Al, Si, P, Mn, Ni, Zn, As, In, and Sb. These elements were added to a master 5 wt pct Ag in Cu alloy in such amounts as to obtain alloys listed in Table II containing the following approximate atomic percentages: 96 pct Cu, 3 pct Ag, 1 pct ternary addition. A 97 atomic pct Cu, 3 atomic pct Ag alloy was used as a comparison standard. There have been numerous investigations of age-hardening in Cu-Ag alloys2-lo but few of ternary Cu-Ag alloys. Pfister and Weist" found that 1 wt pct Ni reduced the solubility of Ag in Cu above 600 °C and that the rate of precipitation was slower than in polycrystalline Cu-Ag alloys of similar silver content. More recently Hodge, Jaffee, Dunleavy, and Ogden12 investigated the effect of ternary additions of Mg, Li, P, Cd, Zn, Zr and Be on strength properties of Cu-Ag alloys. Mg, Cd, and P were found to increase strength in the aged and cold-worked condition. Experimental Procedure Charges weighing 7.5 lb were melted in a closed carbon crucible under a reducing atmosphere* of nitrogen and hydrogen. A Durville-type casting procedure with a hot-top arrangement was used to obtain a sound casting, 2x2x43/4 in. Prior to rolling and annealing of the ingots, a trial solution anneal of rolled sections of the hot-top portions indicated that at 780°C melting was avoided except for the Cu-Ag-Sb alloy. This alloy could not be produced as a single phase within the limits of temperature control. i 3" to 5oC, since melting occurred at 64O °C, and below this temperature precipitation was

Jan 1, 1952

William P. Blake, TUCSON, Ariz. (communication to the Secretary): As one who in youth, now nearly half a century ago, had the privilege of participating in the initial explorations which have alreacly resulted, within a single lifetime, in the establishment and Development of a vast continental empire, so well described by Dr. Douglas, I may be permitted to supplement with some additional details the comprehensive sketch given in his paper. Before the War Department, in 1853, sent out the Pacific railroad exploring parties, Fremont had already made his memorable expeditions, exploring the Great Basin and the passes into California; Sitgreaves had traversed, from east to west, the Zuni and Moqui country; and, still later, Emory had examined the region along the boundary-line between the United States and Mexico. The services of these pioneers deserve to be mentioned in even an outline of the history of continental development. Concerning the five practicable railroad-routes, suggested in the Reports of Explorations aid Surveys," etc., as published

Jan 1, 1900

By J. Szekely, Robert G. Lee

Calculations are presented for the prediction of the combined radiative-convective heat loss from molten steel held in a ladle, covered by initially molten slag. A mathematical formulation is given and numerical solutions are presented of the resultant partial differential equation. It is shown that a slag layer of about 2 to 3 in. thick would prevent any significant heat loss from the top metal surface for Periods of up to 1 hr. For thinner slag layers (or in the absence of the protective slag) appreciable heat losses would occur; plots given in the paper allow the quantitative evaluation of the fall in the metal temperature due to this heat loss. The ironmaking-steel processing operation involves several intermediate steps where the molten metal is held or transfered in ladles. The quantitative assessment of the heat losses occurring under these conditions is of considerable importance in process design considerations since the temperature of the metal may have to meet rigid specifications in any given part of the processing sequence. While the metal is held in a ladle, heat is lost by two mechanisms: i) by conduction into the ladle walls; ii) by radiation and convection from the top surface. Calculations relating to the conductive heat loss, are readily made and information may be found in the literature both on data pertaining to metallurgical situations and on the techniques that are available for performing additional computations.'-3 The evaluation of the combined convective-radiative heat loss is less straightforward, especially when there exists a protective slag layer covering the metal. In this latter case, as the top slag surface loses heat partial solidification may occur and the latent heat thus given up by the slag may represent an effective barrier to the heat loss from the metal. A semiquantitative assessment of the role played by the slag in preventing heat loss from the metal has been made in a previous paper,4 where it was shown that a slag layer 6 in. thick would act as a near-perfect insulator for periods of up to 2 hr. However, this first paper reported on an essentially preliminary investigation that considered only one slag layer thickness; furthermore, the boundary conditions used for the calculations were somewhat restrictive since no allowance was made for changes in the metal temperature. The purpose of this second paper is to extend the scope of the preliminary investigation previously reported by: i) considering several slag layer thicknesses; ii) allowing for variations in the metal temperature; and finally iii) by performing calculations on the net loss from the metal rather than from the slag surface. FORMULATION Consider a slag phase extending from y = 0 to y = L1, covering a metal phase that occupies the region extending from y = Ll to y = L, as illustrated in Fig. 1. Denote the slag and metal temperatures by TS and Tm and assume that initially both slag and metal are molten, having a uniform temperature Ti. At time = zero the surface represented by the y = 0 plane (top slag surface) is brought into contact with cold air, the temperature of which is given as T Thus for time > zero, heat will be transfered from the slag to the air by natural convection and thermal radiation; as a result of this heat loss the slag temperature will fall and after some time a solid phase is formed and a solidification boundary (more realistically described as a zone) will move progressively from y = 0 toward y = L1. Once the region of temperature gradients, moving ahead of the solidification zone, reach the slag-metal interface (y = L1) there will be a net transfer of heat from the metal through the slag to the cold air, across the y = 0 plane. In the formulation of moving boundary problems, involving phase changes that require computer solution, it is convenient to represent both phases by a single equation, making allowance for the latent heat of solidification by assigning an appropriate temperature dependence to the specific heat content. Thus the energy equation for the whole of the slag may be written as follows:

Jan 1, 1969

By H. K. Najarian

This paper describes recent development work on the Wheaton-Najarian Vacuum Condenser for Zinc at Josephtown Zinc Smelter, wherein, to dissipate the heat of condensation, the "airlift" action of gases bubbling through the molten zinc in the condenser is utilized to circulate the zinc through an outside "cooling well" and cooling it continuously. AN earlier paper1 gave an account of initial development of the Wheaton-Najarian Vacuum Zinc Condenser at the Josephtown Zinc Smelter of the author's company. This paper is a progress report of further development work over the years directed toward improving the efficiency and increasing the capacity of the condenser. In this type of zinc condenser, zinc vapor with accompanying noncondensable gases from electro-thermic zinc smelting furnaces is passed upwardly through a mass of molten zinc confined in a refractory-lined U-tube. The zinc vapor condenses in the molten zinc and the noncondensable gases are drawn out of the condenser by suction applied over the surface of the molten zinc. The heat of condensation of zinc, amounting roughly to 1000 Btu per lb of zinc condensed, is absorbed by the molten zinc and, in turn, is dissipated continuously to keep the temperature of molten zinc in a range to permit effective condensation. At the time of publication of our first paper, we had at Josephtown Smelter five units of 69-in.-bore metal furnaces and one larger metal furnace having 96-in. bore. Each 69-in. metal furnace had a condenser with 22-ft overall length. The 96-in.-bore furnace had a condenser with overall length of 31 ft. Condensers were of circular cross section, with corrugated steel outer shell and carborundum lining. Diameter of these condensers was 32 in. inside the refractory lining. Molten metal in the con- denser was kept cool by spraying cold water on the outside of the condenser shell. Under good operating conditions, 22-ft condensers produced some 12 tons of metal per day; and the 31-ft condenser, about 22 tons. When the furnaces produced zinc vapor at higher rates, invariably the condenser temperature would rise to levels where excessive blue powder would form and accumulation of accretions in the condenser would be accelerated. We found that, with the system of cooling in use, we had to provide heat-exchange surface of some 150 sq ft to condense 1000 lb of metal per hr with reasonable efficiency. The wall of the condensers was made up of 5/8-in.-thick corrugated-steel shell having next to it several layers of mica and inner refractory lining of special carborundum shapes to fit the corrugation in the steel shell, and having a minimum thickness of about 2 in. Relatively low rate of heat transfer through the thick condenser wall and slow internal circulation of the molten zinc limited the rate of heat exchange between hot metal within the condenser and the cold water flowing over the outer steel shell. The thickness of the condenser wall was about minimum that we considered suitable for continuous operation. As we learned to operate the electrothermic furnaces with higher power input, producing zinc vapor at higher rates, it became apparent that we needed condensers having larger heat-exchange surfaces. Our 96-in.-bore furnace had 6 single-phase power circuits with transformers rated at 500 kva each and normally good for power input of 3000 kw.

Jan 1, 1959

By Pablo Hadzeriga

Great Salt Lake brine was subjected, in laboratory scale, to conditions simulating solar evaporation. Solid phases and the variation in composition of the liquid phase throughout the potassium salts crystallization zone are presented. These experimental results are discussed and compare with stable equilibrium data of the quinary system Cl-, SO4, Na+, K+, Mg + + and H2O. The Great Salt Lake brine in Utah is a vast reserve of several potential chemicals which has attracted much attention in the recent past. From the standpoint of an ore reserve, it may be said that the lake contains a low grade ore which has to be concentrated by evaporation of water. Because of the fairly favorable weather conditions in the Great Salt Lake area, it seems reasonable to consider solar evaporation as an economical means of concentration. From the view of phase chemistry, the main constituents of Great Salt Lake brine make it belong to the five component system: C1-, SO4=, Na+, K+, Mg++ and H2O. Because of their low concentration, the presence of other elements may be regarded as having little effect on the equilibrium of the five main components. Equilibrium data for the quinary system of our interest has been available for many years. Using these data, it is possible to calculate how the brine of the lake will concentrate when subjected to solar evaporation. In practicing solar evaporation, the weather factor and supersaturation conditions cannot be ignored, but their introduction into calculations using equilibrium diagrams is almost an impossible task. With the experimental work presented in this paper, an attempt is made to compare the stable equilibrium data of the quinary system as applied to the case of the Great Salt Lake brine and the dynamic equilibrium when that brine is subjected to continuous solar evaporation. Sea water brine belongs to this quinary system when only the major constituents are considered. The study of this system has been carried on since the last decades of the nineteenth century. The reason for these intensive studies was to give a geological explanation to the underground potash deposits. AS a result, many theories were presented trying to relate the equilibrium data with the geological formation, paragenesis and metamorphism of these deposits. Two main approaches were followed for the equilibrium studies of this quinary system. One of them, and the best known to us, was the school started in Germany in the last century by J. H. Van't Hoff. The other one, which started about the same time, was the school of N. S. Kurnakov in Russia. Both approaches were different and as a consequence generated opposite theories about the geological formation of potash deposits. The Van't Hoff school studied the quinary system of sea water under careful laboratory control, resulting in stable phase diagrams. During these studies, Van't Hoff recognized the difficulties in crystallizing some double salts.' ". . . . we unexpectedly found that some compounds whose formation in the solutions under investigation was possible at 25°C, nevertheless totally failed to put in an appearance. These, not to mention the calcium salts, were leonite, MgSO4 . K2SO4 4 H2O; kainite, KC1-MgSO4 . 3 H2O; and kieserite, MgSO4 .H2O. Even exceedingly slow crystallization with the addition of the compounds themselves did not remove the condition of supersaturation in the case of these bodies." However, those salts (leonite, kainite, and kieserite) were included in the stable phase diagram at 25°C as shown in Fig. 1 using D'Ans data.3 The figure also shows the sequence of crystallization of the Great Salt Lake brine according to the stable diagram. In later studies by the Van't Hoff school, especially by D'Ans,3 Karsten,4 Autenrieth,5,6 attention

Jan 1, 1968

By V. M. Dobrynin

Experimental data demonstrate that physical properties of porous rocks change under pressure. In this paper an assumption is made and proved that under pressure the changes of physical properties such as porosity, density, permeability, resistivity and velocity of elastic waves are controlled to a large extent by the pore compressibility of rocks. It is also shown that the pore compressibility of rocks can be determined, within the range of pressures from 0 to 20,000 psi, by knowing the maximum pore compressibility and the magnitude of the pressure. Mathematical equations were developed which permit one to define changes in physical properties of porous rocks under pressure. These equations were verified by experimental data obtained from the study of sandstones. INTRODUCTION In studying the behavior of porous rocks under pressure in the field of petroleum technology, the most interesting aspect is the observation of those properties which characterize the rocks as possible reservoirs — for example, porosity, permeability, resistivity, density and the velocity of elastic waves. The literature dealing with this problem mainly contains data concerning the study of only one or at most two of these parameters, but not of the group as a whole. An attempt is made in this paper to find general equations involving each of these parameters, which will permit the study of the behavior of rocks under pressure. All experimental data used here were obtained from the investigation of consolidated sandstones. EXPERIMENTAL In addition to the use of published experimental data, an experiment was carried out which studied the main physical properties of sandstones under pressure. Two homogeneous quartz sandstones were chosen for this purpose: (1) the Torpedo sandstone from Kansas, and (2) the Medina sandstone from Ohio. The porosity of the Torpedo sandstone was 20.2 per cent, and that of the Medina 8.7 per cent. Permeabilities were 45 md and less than 1 md, respectively. Each sandstone contained about 5 per cent clay minerals, consisting mostly of kaolinite and chlorite, which were distributed quite evenly throughout the samples. One cylindrical sample 2 in. in diameter and 5 in. in length was cut from each sandstone and then saturated in a vacuum with a 3N solution of NaC1. This high concentration was used in order to obtain true formation factors and to decrease the swelling of the clay minerals. The methods of mounting the samples and measuring the changes in porosity and resistivity were practically the same as those described by Fatt and Mann.1,2 Changes of resistivity under pressure were studied for sandstones with 100 per cent water saturation, and for sandstones with the irreducible water saturation. The irreducible saturation was obtained by enclosing the saturated rock samples in relatively fine silicate powder so as to remove the water by capillary action. This procedure is described by Orkin and Kuchinski.3 Changes of permeability with pressure were determined at room temperature using nitrogen as the flowing medium. In studying the effects of pressure, one series of measurements was made using an internal pore pressure Pi equal to the atmospheric pressure, while the overburden pressure Pe ranged from 0 to 20,000 psi. A second series of measurements was used over the same range of overburden pressure, but with an internal pore pressure of 1,800 psi. When the results were compared on the basis of net overburden pressure (Pe — 0.85 Pi ), there was practically no difference for these two sandstones. The origin of the factor 0.85 in the expression for net overburden pressure is given by Brandt,4 Fatt5 and Geertsma.6 The relatively large bulk volumes of the sample (about 15 cu in.) made it possible to observe a

By E. F. Bradley, R. I. Jaffee, H. R. Ogden, E. S. Bartlett, D. N. Williams

The mechanical properties of solid-solution-strengthened columbium alloys have been assessed as a function of alloying additions. Studies included the effects of tungsten, tantalum, molybdenum, and vanadium. Elevated temperature fabrication was required at alloying levels above about 15 pct W or 10 pct Mo. Tungsten, molybdenum, and vanadium additions increase tensile strength at room temperature and 2200°F, but tantalum additions exert little strengthening. Similarly, tungsten, molybdenum, and probably vanadium additions increase the ductile-to-brittle transition temperature, and tantalum additions decrease this parameter. The 2200°F stress-rupture strength is increased by tungsten and molybdenum additions; with 20 to 25 at. pct additions, 100-hr rupture strengths of 30,000 psi are obtainable. Small vanadium additions exhibit mild stress-rupture strengthening, and tantalum additions are innocuous. At 2500°F, tungsten additions retain stress-rutpure strengthening capability, but molybdenum additions are much less effective. Tantalum additions augment the stress-rupture strengthening of tungsten plus molybdenum additions at 2500°F. Of the refractory metals, columbium possesses specific potential for structural use in the temperature range from 2000" to about 2500°F. Desirable features of columbium are its good low-temperature ductility, ease of fabrication, oxidation mechanics (lack of a volatile oxide at moderate temperatures), good availability and reserves, and relatively low density. However, alloying is required to provide attractive strength at elevated temperatures. Published information concerning alloying be- havior of columbium relative to mechanical properties is sketchy, particularly in consideration for long-time applications at temperatures in excess of 2000°F. Only a few stress-rupture data at temperatures from 2000" to 2500°F have been reported;'-' these are too meager to allow rationalization of the effects of various alloying additions on creep or stress-rupture properties. Additional published data do, however, give some insight toward understanding of systematic alloying behavior for columbium relative to low-temperature strength4-' and ductility,' and elevated temperature tensile behavior.4,6 This paper is intended to augment previous knowledge, and to promote understanding of the alloying behavior of columbium for long-time structural service at elevated temperature. BASIC CONSIDERATIONS Solid-solution strengthening is recognized to be of prime importance in improving strength in columbium-base alloys. Other strengthening mechanisms may be (and are, in current alloys) used to augment solid-solution strengthening. As strengthening results primarily from lattice distortion, the strengthening effectiveness per atom depends upon atomic size mismatch between solvent and solute. Another factor in this regard is conformance to ideal solution behavior in the solid solution. Thus, for example, despite appreciable differences in the degree of mismatch between tungsten (5 pct), molybdenum (5 1/2 pct), and vanadium (7 1/2 pct) in solution in columbium, all are about equally effective in straining the columbium lattice at room temperature.'-' Similarly, tantalum additions do not strain the columbium lattice, and little strengthening is expected. Size effects being equal, maximum solution strengthening at high temperatures is anticipated to result from the addition of elements that increase the melting temperature of columbium. This expectation is based on an increase in the electronic bonding forces exhibited in the transition metal series as electronic structures approach those of the Group Vl metals. Of the metals that exhibit ex-

Jan 1, 1963

By M. R. J. Wyllie, H. W. Patnode

In the quantitative interpretation of electric log data it is essential to know the formation factor, defined as the ratio of the resistivity of the formation 100 per cent saturated with brine to the resistivity of the brine.' This concept implies that the formation factor for any given rock is constant irrespective of the resistivity of the brine or solution with which it is saturated. It is apparent that this can be true only when the rock matrix is wholly non-conductive. As reservoir rocks may contain clay or shale having an appreciable conductance one may expect these constituents to influence the determination of true formation factor. The formation factor may be theoretically derived from log data by dividing the resistivity of the mud filtrate invaded formation by the resistivity of the mud filtrate. Such a method of calculntion has implicit in it the assumption that the fluids in the invaded formation are wholly replaced by mud filtrate. that the solid matrix is non-conducting, and that the formation factor of the invaded zone is identical with the formation factor of the uninvaded zone. Since the validity of the first two basic assumptions regarding the insulating character of porous matrices and the displacement of the interstitial fluids in porous media do not appear to be fully established, the formation factors of a number of cores and clay slurries have been measured under conditions suitable for verifying the assumptions and the extent of any errors inherent in them. CORE STUDIES Apparatus and Procedure Resistivity measurements were made on short cylindrical permeable cores which had been previously mounted in lucite.2 The cores were clamped by means of insulated bolts between brass plates about 5 cm square and 1 cm in thickness. The plates were provided with a ring seal to prevent leakage between them and the core mount, and had a centrally located orifice so that fluids could be flowed through the mounted core. The brass mounting plates were used as electrodes and any current flow between them necessarily passed only through the constituents of the intervening core. Fluid saturation of the core, and fluid flow through the core, were effected by a centrifugal pump connected to the outflow end of the core, thus providing a differential pressure across the core of approximately one atmosphere. The procedure used was first to evacuate each core by means of the pump and then to saturate the core with an aqueous sodium chloride solution of known resistivity. The resistance of the core was measured and flow of the solution through the core continued for sufficient time to establish a constant resistance reading. After equilibrium had been reached with one solution, another sodium chloride solution of a different resistivity was flowed through the core and the flow continued until a constant resistance reading was again obtained. This procedure was continued until resistance measurements of the core had been made with a series of solutions within a salinity range from 1.0N NaCl to distilled water. The data obtained enabled the apparent formation factor of given porous rocks when saturated with fluids of different resistivity to be computed and also provided information regarding the ability of an invading fluid to displace interstitial water from a core. Results Berea Sandstone — The first core examined was a specimen of Berea sandstone." This core had been cut essentially parallel to the bedding for permeability studies. The core was clamped in the core holder and saturated with 1.0N NaCl solution and the resistance determined. It was subsequently flushed and the resistance measured when saturated in turn with 0.1N, 0.025N, 0.01N, .005N sodium chloride solutions and finally with distilled water. In flushing the core with each

Jan 1, 1950

Edward S. Simpson, Perth, Western Australia (communication to the Secretary): In 1896 the East Coolgardie gold-field was divided into three fields, viz. : Area, square miles. Officia1 Centers. (1) East Coolgardie,. . 634 Kalgoorlie. (2) Broad Arrow,. , 588 Kurawa. (3) Northeast Coolgardie,. 22,960 Kanowna. The whole of the area embraced by the eastern gold-fields is covered with late Tertiary sands and gravel, with occasional beds of clay shales. These mostly overlay granite which occasionally shows through in small round hills. At Coolgardie, Kalgoorlie and other mining centers, belts of diorite, serpentine and highly metamorphosed sedimentary rocks appear on the surface. The rainfall at Kalgoorlie in 1897 was 4.75 inches. That the climate has not always been so arid is evidenced by the recent discovery at Coolgardie (only twenty-five miles away) in the late Tertiary formations of a thick bed of brown coal, containing numerous fossil fern-leaves. As assayer and mineralogist to the Government of Western Australia I have had occasion to examine a large amount of the Kalgoorlie ores, both in Perth and at the mines at Boulder itself. The only tellurides I have been able to determine are

Jan 1, 1899