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By W. C. Hazen, A. V. Henrickson

URANIUM plant operations of the Kerr-McGee Oil Industries at Shiprock, N. M., began in December 1954. As originally designed, the plant treated Plateau carnotite ores by the acid cure process, which dissolved both uranium and vanadium minerals. After 16 hr of acid curing, the ore was conveyed to an agitator and leached for 2 hr in acid liquor at a pH of 1.0. The leach pulp was then separated at 100 mesh in a classifier, the sands continuing through a washing classifier circuit and the slimes going to a countercurrent decantation system of four thickeners.

Jan 9, 1957

WALTER P. JENNEY, Rapid City, S. Dak.: This paper is the first publication, I believe, of the fact that traces, up to two or three ounces to the ton, of tellurium have been found in the gold ores of the Black Hills occurring in the Potsdam formation. There are two great classes of ore-deposits in the Black Hills. First, the gold-ores in the Archæan, of which the great Homestake lode, extending from Lead City to Central, in the northwest section of the Hills, may be taken as a type; second, the refractory gold-ores found in the Potsdam sandstone over a

Jan 1, 1897

By Donald A. Brobst

The minerals barite (BaSO4 barium sulfate) and witherite (BaCO3 barium carbonate) are the chief commercial sources of the element barium and its compounds whose many uses are nearly hidden among the technical complexities of modern industrial processes and products. Barite, the major ore mineral, is extremely vital to the petroleum industry which in 1973 consumed at least 80% of the world's produc¬tion of 4.4 million tons as a major ingredient of the heavy fluid, called mud, that is circulated in rotary drilling of oil and gas wells. The re¬maining 20% of the barite production was consumed chiefly in the manufacture of barium chemicals and glass and as a pigment, filler, and extender. Barite occurs throughout much of the world and is available from three major geologic types of deposits-vein and cavity fill¬ing, residual, and bedded-in sufficient quantity at competitive prices to meet current demands. The world's demand for barite is expected to increase, and geologic circumstances are favor¬able for the discovery of new deposits of com¬mercial value. Witherite is much less common and abun¬dant than barite, although it is more desirable in many ways as a raw material for the pro¬duction of barium chemicals. The United States has not produced witherite since about 1950; England is currently the chief producer of witherite. End Uses Most of the world's barite production since 1926 has been used as a weighting agent for the muds circulated in rotary drilling of oil and gas wells. The muds fundamentally are mixtures of water, clay, and barite in different proportions that vary according to local reservoir condi¬tions. Muds with a specific gravity as great as 2.5 are used. The mud is pumped down the hollow drill stem, passes through the bit at the bottom of the hole, and rises to the surface in the space between the drill stem and the wall of the hole. In the course of this circulation the drill bit is cooled, cuttings are removed, the drill stem is lubricated, the walls of the hole are sealed, and the hydrostatic head of the column of weighted fluid helps to confine high oil and gas pressures. The latter feature aids in prevention of gushers, thus reducing both environmental pollution and waste of oil and gas resources as well as conserving the natural reservoir pressure for greater production and rate of recovery of the products contained in the rocks. Barite is particularly well suited for drilling mud because it is clean, easy to handle, soft (nonabrasive), heavy, virtually inert chemi¬cally, and relatively inexpensive compared to many other available heavy materials. Barite is used in the manufacture of glass in continuous tanks. The addition of barite ho¬mogenizes the melt and gives greater brilliance and clarity to the finished glass. Ground barite, both unbleached and bleached by sulfuric acid, is a common industrial filler, extender, and weighting agent. The rubber in¬dustry is a major consumer of barite as a filler. Barite also is added to bristolboard, heavy printing paper, playing cards, rope finishes, brake linings, clutch facings, plastics, and li¬noleum, to name but a few uses. Bleached barite has long been an extender in white lead paint because of its weight. The low index of refraction of barite, however, makes its ability to cover marks poorer than some other sub¬stances, but its low capacity for absorption of oil is a good feature. Off-color or unbleached barite can be used as a filler in colored paints. In the construction industry, some lump barite is used in concrete aggregate to weight down pipelines buried in marshy areas and to shield nuclear reactors. Because barite absorbs gamma radiation well, its use reduces the amount of expensive lead shielding otherwise

Jan 1, 1975

By E. J. MCOAUSTLAND

THE behavior of steel after overstrain and at moderate temperatures is fairly well known. It has been made the subject of much investigation, and our knowledge is clear and definite on many points. The ultimate raising of the elastic limit, after moderate overstrain, and the consequent lowering of the ductility, seem to be well established. It is also well understood that the immediate effect of overstrain is to lower the elastic limit, possibly to zero, but that if not interfered with, this limit will subsequently rise higher than before. The "tests after moderate temperature," reported in this paper, were undertaken to verify the above statements for the particular steel under investigation, and also to determine, if possible, the total time required for complete recovery from this state of overstrain. The behavior of overstrained steel at temperatures at or below 32° F. is not so well known. Tests made by Prof E. G. Coker, at McGill University,' show that steel, overstrained and subjected to cold, will remain in a state of overstrain for an indefinite period. I am not aware of any other published results of tests along this particular line. The effect of time and temperature on the recovery of steel from overstrain was made in 1902-3 the subject of sortie investigation in the laboratories of the College of Civil Engineering of Cornell University. A general plan was outlined in connection with the regular courses of instruction in testing of materials; but the press of routine work and the demands of the schedules on the time of the students were so great as to presage long delay in the completion of the work. Not much had been accomplished up to 1904-05, when Messrs. E. C.

May 1, 1906

By R. P. Rothwell

THE first difficulty mentioned is that in some instances two or more beds of coal separated by sandstone or slate rocks of considerable thickness in one part of a basin, are found running together in another part. Of course, we may happen to strike first the part of the basin where there is but a single seam, and in this case the bed would appear to divide into two or more branches within a short distance. Such cases are not rare in the anthracite coal-fields. I would suggest as an explanation of this phenomenon the gradual sinking of the peat-marsh-the embryo coal-bed-on one side, and the moving forward of the marsh, so that on one part of the bed the formation of peat would still be progressing, while another part, being under water, would be covered with mud and sand. Thus we have different portions of the same bed of different ages. Now if the sinking of the marsh be stopped for a time, the bed will become thicker in the portions left exposed, and if the sinking now changes in direction, so that the part that had previously gone down com¬mences to rise, we should have the phenomenon of a bed, continuous throughout, with one portion overlying another, and separated from it by rock strata. These are exactly the conditions observed in splitting beds. While one side of the lake is sinking, and the peat-marsh moving on in that direction, the other side may be rising,

Jan 1, 1873

By Clyde E. Williams

IN planning a postwar program for manufactured products, it is essential that the bases for the plans be wisely chosen. First we must make certain assumptions as to the war's ending. Let us assume: (1) complete victory by the United Nations, (2) peace terms that will ensure the direction of the economy of all nations of the world toward peaceful pursuits, and (3) an early ending of the war, that is, before the nations of the world, excluding the enemy, are near the point of physical and spiritual exhaustion. Thus, our manufacturing plants and transportation facilities will still be in good shape. The plants and transportation facilities, as well as the cities of a large part of Europe, however, will be badly crippled. The rich mineral and other raw material resources of the world, little of which was under control. of the Axis powers before the war or will be after the war, will not be used up. Control of these raw materials, or at least an important part of them, will remain in the hands of the strong peaceful nations.

Jan 1, 1943

By Hiland G. Batcheller

HISTORY shows that the nation which makes the most steel is the most likely to win wars. Today the course of war shows that the nations which get there first with the most steel of the right kind will be the ones to win. Not only the most steel, mind you, but the right kind. Adequate production, which was enough for victory before the days of totally mechanized warfare of 1943, must now be accompanied by still better quality as well as more effective distribution. Further, both production and distribution must be flexible enough to permit rapid shifts from one weapon to another for use in varying elements in varying geographical areas. Thus the problem of making enough steel of the right kind at the right time in the face of changing requirements dictated by experience has been and will remain highly complex. This does riot permit us to ease our restrictions on nonessential use. War is a complex business, like the job of making steel for war. Each time we solve one problem, another pops its head up. Yet we are making some progress.

Jan 1, 1943

By Lloyd B. Underwood

Dr. Gardener, in Chapter 2, has presented a comprehensive state-of-the- art review of site investigations For tunneling. Nearly all of the techniques he discussed will also be required for future site investigations. Therefore, this chapter will be devoted to a few rather new exploration techniques plus ideas for improving some of the present-day methods. In March 1962, the first symposium on "Remote Sensing of Environment" was held at the University of Michigan.l Since that time, four additional symposiums have been held at the same University. Also, the technical Literature has recently included a number of articles on remote sensing techniques. A recent one appeared in the February 1968 issue of Materials Research and Standards.Vt was entitled "Developments in Remote Sensing Applicable to Airborne Engineering Surveys of Soils and Rocks," and was written by Dana C. Parker. Mr. Parker predicts that aerial reconnaissance will someday supplant soil augers, rock drills, surface reconnaissance, and geophysical surveys as the engineer's primary means of obtaining information about soils and rocks. He states, "The engineer wishing to survey a route or a site or to locate rock and soils suitable for construction projects will be able to push some buttons in an airplane and record all the data required for determining the relevant conditions. In a short time after he returns to earth with his rolls of film and charts, he will be able to reduce and analyze the data by partially computerized techniques and to compile a concise and comprehensive engineering report that gives all the relevant information about rocks, soil, water, and vegetation in the area he surveyed. Most important he will feel as confident with his recommendations, derived primarily from image characteristics and spectral power distributions, as his predecessors did with recommendations based on more tangible evidence obtained from drill cores and surface reconnaissance." The airborne sensors for engineering surveys of soils and rocks are those that sample some electromagnetic property of the materials that com- prise the terrain and cover its surface. In addition to cameras, these include

Jan 1, 1970

By Thomas Read

AMONG the large number of deep mines in the world there are several which do not differ much in depth. The St. John del Rey mine, in Brazil, has reached a vertical depth of 6726 ft. below the top of its shaft; miners enter it, however, through an adit which intersects the shaft 324 ft. below its top, wherefore it might be said that the mine is really only 6400 ft. deep. In the Kolar gold field of India there are a number of deep shafts, one of which reaches to a vertical depth of 6140 ft. below surface. In South Africa also there are a number of deep shafts, the Village Deep being 6100 ft. early in 1921. The City Deep, Ltd., proposes to sink to a depth of 7000 ft. but pre-sumably by the time it does so the St. John del Rey will be deeper than that, since it has been increasing in depth at an average rate of about 150 ft. per year. The deepest shaft in the United States, the Tamarack No. 5, although it is only 5308 ft. deep, actually approaches nearer to the center of the earth (4100 ft. below sea level, as against 3958 ft. , at St. John del Rey). The deepest workings in the Calumet & Hecla go down to 4600 ft. below sea level. The St. John del Rey is not only the deepest, mine in the world, but it also is worked by the oldest registered English mining company, which was organ-ized in 1830 to work a mine at a considerable dis-tance from this one. That mine proved unprofitable, and in 1837 operations were transferred to the. deposit now under discussion, where operations have been prac-tically continuous ever since.

Jan 6, 1923

By Verne E. Hooker, Robert M. Becker

The evaluation of in-situ rock stresses from measurements of the change in diameter of a borehole that is stress-relieved by overcoring has become a common practice. Generally the stress evaluation has been based on isotropic relations whereas rock in varying degrees is aniso tropic. A plane elasticity solution fora circular hole along one axis of an orthotropic medium has been adapted to evaluation of in situ stress. The necessary elastic parameters for this evaluation may conveniently be obtained from static tests on the overcore in conjunction with a consistent orthotropic thick-wall cylinder solution. The method and equations for the laboratory and field evaluations are summarized and illustrated. The determination of in-situ rock stresses from boreholc deformation measurements has gained widespread acceptance. Hastl measured the change in diameter of a borehole that was stress-relieved by drilling a larger concentric core; this overcoring method has produced a major portion of the field data for recent stress evaluations in rock. These evaluations are based on the elastic properties of the rock, which are conveniently determined by testing the overcore.6-8 The stress evaluation and the overcore testing procedures generally assume isotropic relations whereas rock is anisotropic in varying degrees. Recently, an anisotropic plane stress solution was adapted for evaluation of in-situ stress9 and a related plane strain solution was developed for the testing of stress-relief core. 10 The present paper unifies the stress evaluation and overcore testing procedures for a general class of anisotropic rock. Equations are presented for calculating the state of stress in a plane normal to the borehole, and a consistent thick-wall cylinder solution is given for determining the necessary elastic properties. In addition, a complete example of stress evaluation from laboratory and field data is presented, and the order of error in computing the state of stress from isotropic relations is illustrated. Several limitations of the results should be emphasized. All results assume small linearly elastic deformations of a homogeneous medium. Rock characterized by orthotropic, transversely isotropic, and isotropic elasticity is considered; however, the anisotropic results assume a special relation among certain elastic constants in addition to geometric orientation with respect to a plane of elastic symmetry. For some stress determinations in rock, these may be severe limitations. On the other hand, the anisotropic evaluation procedure involves little additional effort and is much more flexible than the corresponding isotropic evaluation procedure. The collection of field data is identical. The laboratory determination of elastic parameters is no more difficult and time-consuming for the anisotropic than for the isotropic model. Only the calculations require some additional effort for the anisotropic evaluation, and this additional effort is eliminated by use of a small computer. The flexibility of the anisotropic procedure is greater because more than two independent elastic constants are available in fitting rock data. For the special relationship assumed among orthotropic constants, five independent elastic constants are available for the determination of in-situ secondary principal stresses as compared with two independent elastic constants for the isotropic model. Much of the material presented is either directly from the literature or adapted from the literature through superposition or the usual transformations. Consequently, only enough detail for clarity of presentation is included. RELATIONS FROM ANISOTROPIC ELASTICITY Materials that have three mutually orthogonal planes of elastic symmetry are called orthotropic. By directing the axes of the coordinates perpendicular to these planes, Hooke's law for an orthotropic solid 11 is

Jan 1, 1970

By C. D. Stahl, S. M. Farouq Ali

This investigation attempts to describe and simulate the alcohol displacement process by means of a cell model, as employed in chemical engineering practice. The proposed model is more simple than previously proposed models. and utilizes parameters chosen on a theoretical basis. The model successfully reproduced the formation of the stabilized bank and the breakthrough of alcohol, the latter depending on one of the model parameters, which may be correlated with the length of the porous medium. Moreover, the effects of the phase behavior of the liquid system involved, as observed in experimental studies, were reproduced. Several variations of the basic model were devised and tested on a digital computer. These included the cases in which: (1) the actual value of fractional flow was used in cell-to-cell computations; (2) the number of cells was varied within the same run; and (3) incomplete rather than complete phase equilibrium was assumed within each cell. The proposed cell model clarifies the basic mechanism of the process. Detailed concentration profiles obtained for each cell, for instance, showed the mechanism of bank formation in relation to the phase behavior characteristics. The results obtained indicated a varying degree of phase equilibrium concommitant with changes in the velocities of the phases in an actual alcohol displacement. This condition was approximated by changing the number of cells during the simulation. Interesting information was obtained on the influence of path length on the efficiency of alcohol displacement, which has been the subject of some controversy. Certain limitations preclude the use of the proposed model as a substitute for experimental studies. The results obtained were, nevertheless, of value in interpreting the experimental results. INTRODUCTION During recent years considerable effort has been directed toward an understanding of alcohol displacement, the process whereby oil and water are recovered from a porous medium by the continuous injection of a solvent. The complex nature of the physical process involved has so far defied a complete mathematical treatment. Other methods of approach, amounting to an overall material balance, have been proposed, yielding useful information on certain aspects of the process.1-3 Taber et al, in particular, defined the displacement mechanism in terms of the phase behavior of the alcohol-oil-brine system invoIved.2 Wachmann reported a mathematical treatment of alcohol displacement subject to certain simplifying assumptions? Donohue proposed the use of a "cell model" for simulating alcohol disPlacement.5 The nature of the assumptions involved limited the utility of the model. The present work attempts to examine the variables involved in the simulation of alcohol displacement and discusses several possible versions of the basic cell model. Under certain conditions the model results are similar to the experimental results. In particular, the spontaneous formation of of the stabilized bank and the effects of the system phase behavior were successfully reproduced. PREVIOUS WORK ON CELL MODELS Cell models and the theoretical plate concept are often used in solving chemical engineering problems in which an explicit mathematical solution may be difficult or impossible to obtain. Examples of such applications occur in distillation, gas-liquid chroma tography,6 reactor technology, absorption, etc. In petroleum engineering, such a model was used by Attra7 to describe non-equilibrium gas drive, and by Higgins and Leigh ton8 to calculate sweep efficiency in water flooding. Aris and Amundsen pointed out the equivalence between the diffusion model and perfectly mixed cells connected in series.9 Deans proposed a three-parameter cell model to simulate two-component

Jan 1, 1966

By R. E. Miner, J. K. Jackson, D. F. Gibbons

Internal-friction measurements were made during isothermal aging treatments of 18 pct Ni maraging-steel wires between 420° and 612°C. A sharp initial drop in the internal-friction level was interpreted in terms of a rapid dislocation recovery reaction. The rate of the recovery was found to be independent of temperature. Truncation of the recovery reaction was apparent in those systems that exhibited the rapid age-hardening characteristics of the maraging steels. It is proposed that this initial hardening response is the result of a low activation energy preprecipitation reaction involving molybdenum. A gradual rise in the internal-friction level at longer aging times was associated with the precipitation of a molybdenum-containing precipitate. CONSIDERABLE research effort has recently been devoted to the mechanisms responsible for the high strength and toughness of 18 pct Ni maraging steels. These bcc martensitic alloys are found to harden during aging at temperatures between 400° and 600°C. The aging response is very rapid with more than half the total hardness increase occurring within the first few minutes of aging, Fig. 1. Precipitate particles have been observed in the later stages of aging by a number of investigators.'-' While the identity of the precipitates remains the subject of some controversy, one or more of the intermetallic compounds, Ni3Mo, Ni3Ti, and Fe2Mo, are almost certainly involved. Heterogeneous nucleation of precipitates at dislocations has been noted8 and cobalt is believed to enhance the formation of fine, homogeneously distributed particles by lowering the solubility of the alloying elements in the martensitic matrix.3,7 Transmission electron microscopy studies of the initial hardening behavior have not been fruitful. Strengthening mechanisms based on atomic ordering have not been generally supported by X-ray and neutron-diffraction experiments.9 In the present investigation, the aging reaction was studied using isothermal-aging internal-friction measurements. The marked sensitivity of internal friction to short-range diffusion and precipitation processes has provided a convenient tool for the elucidation of the strengthening mechanisms operative in the maraging steels. EXPERIMENTAL PROCEDURE An upright torsion pendulum was used to measure the internal friction of several maraging steels during isothermal aging. The pendulum was placed in an atmosphere of helium at a pressure slightly less than atmospheric. To permit measurement of internal friction during the first minutes of aging, the specimens were rapidly heated by passing a current through them in a manner similar to that described by Ang and Wert.10 Thermal gradients in the specimen were largely eliminated by using specially designed specimen grips11 which produced temperature variations of less than 1 pct over 90 pct of the specimen length and less than 3 pct over the entire length at aging temperatures up to 620°C. A proportioning strip-chart program controller was employed to maintain constant specimen temperature during treatments of up to 36 hr duration. A number of vacuum-melted laboratory heats having compositions near that of a typical commercial 18Ni-7Co-5Mo-0.4Ti alloy were investigated. The amount of cobalt was varied from 0 to 7 wt pct in five of the heats. Either molybdenum or titanium was omitted in the remaining two heats. The alloy desig-

Jan 1, 1967

By L. R. Duncan, O. M. Wicken

Magnesium, the eighth most abundant element in the earth's crust, is found widely distributed in a variety of minerals. Among the more commercially important ones are magnesite (MgCO3), brucite (Mg[OH]2), dolomite (CaMg[C03]2), and the salts magnesium sulfate and chloride often found in natural brines. Among other commercially important magnesium-containing minerals are olivine ([MgFe]2Si04), talc (H2Mg3[Si03]4), and serpentine (H4Mg3Si2O9). These are valuable because of desirable characteristics given them by the magnesium content and its placement in the particular crystal structure. These minerals are the raw materials for a host of products including magnesium metal and several grades of magnesia or magnesia-containing materials for refractories, fluxes, fillers, insulation, cements, decolorants, fertilizers, and chemicals. Considering only those minerals valued for their magnesia or magnesium content, over 85% of the material tonnages are processed to be used as refractories. Dolomite, which is used in enormous tonnages for its physical properties in construction, has an important use as a refractory raw material in its own right and, after calcination, as a precipitant for magnesium hydroxide, which is an intermediate for the production of magnesia or magnesium metal. Magnesia from the reaction of calcined dolomite (or limestone) with seawater or magnesium-containing brines has supplanted much of the production of magnesia from mined magnesite, particularly in the United States. The best known of the minerals directly and widely exploited for magnesia content is magnesite, one of the calcite group of rhombohedral carbonates which includes calcite (CaC03), siderite (FeCO3), and rhodochrosite (MnCO3) among others. The members of this group enter into a wide range of substitutional solid solutions when the positive ions have similar radii. The radii of magnesium and iron ions are within 6% of each other; hence, magnesite and siderite form a complete series of which breunnerite (ferroan magnesite) is a well-known end member. However, the radius of calcium ion is 36% larger than that of magnesium ion, and only limited substitution exists at each end of the MgCO3-CaCO3 series. Dolomite is not a member of the calcite group, but results when calcium and magnesium ions alternate in equal number in an ordered structure among carbonate ions. The result of these relationships is that calcite and dolomite, often found intermixed with magnesite, occur commonly as identifiable crystal entities which can often be separated to a varying degree from the magnesite by various beneficiation techniques. Magnesite, when pure, contains 47.8% MgO and 52.2% CO.. The pure mineral is sometimes, but rarely, found as transparent crystals resembling calcite, but, preponderantly, magnesite contains variable amounts of the carbonates, oxides, and silicates of iron, calcium, manganese, and aluminum. Magnesite may be either crystalline or amorphous (cryptocrystalline). The crystalline form has a hardness of 3.5 to 4.0. The color may range from white to black with shades of yellow, blue, red, or gray. The color is not a fundamentally significant indicator of purity, but in a given deposit, an experienced person can often roughly grade magnesite by assessing color and crystallinity. The crystalline form of magnesite occurs in

Jan 1, 1983

By William E. Ford, Edward Salisbury Dana

430. The more important of the special properties of a mineral species with respect to heat include the following: Fusibility; conductivity and expansion, especially in their relation to crystalline structure; change in optical characters with change of temperature; specific heat; also diathermancy, or the power of transmitting heat radiation. The full discussion of these and other related subjects lies outside of the range of the present text-book. A few brief remarks are made upon them, and beyond these reference must be made to text-books on Physics ant1 to special memoirs, some of which are mentioned in the literature (p. 305).

Jan 1, 1922

By Arnulf Muan, Carlos Landolt

Equilibria involving Cu-Pt alloys, copper oxides, and atmospheres of known ox2gen pressures have been determined at 1000' and 1200 C. The data obtained have been used to calculate activity-composition relations in the alloys. A moderate negative deviation from ideality is found. At high copper concentrations, the results of the present study are in good agreement with those of previous investigators, whereas at low copper concentrations the activities obtained in this investigation are slightly higher than those reported previously. The present study is part of a research program dealing with the determination of phase relations and thermodynamic properties of copper-containing systems at high temperatures. The information available for such systems is very scanty, particularly for copper oxides and their combinations with other oxide components. Platinum is commonly used as a container in studies of oxide equilibria. To evaluate quantitatively the extent of reaction between the oxide and the container, a knowledge of activity-composition relations in Cu-Pt alloys is necessary. Such data are not available for Cu-Pt alloys in the temperature range of particular interest in the present research program, and particularly for alloys low in copper. Studies of various aspects of the systems Cu-Pt and Cu-0 have been reported in previous literature. The system Cu-Pt is known1 to form a continuous solid-solution series above 812.C, whereas ordered phases are present in certain composition ranges at lower temperatures. Thermodynamic data for the system have been reviewed by Hultgren et al.,' who presented free energies of mixing at 65Oo C, mainly derived from electromotive force cell measurements by Weibke and Matthes.3 Enthalpies of mixing at 640°C have been obtained by Oriani and Murphy4 with liquid tin calorime-try. Their results differ considerably from those derived from the temperature dependence of the data of Weibke and Matthes. Thermodynamic data for the disordered alloys have been obtained by Assayag,5 and more recently by Schmahl and Minzl,6 by Myles and Darby,7 and by McCormack, Myers, and Saxer.8 The two latter sets of data7'' became available after the present study was completed. In the system Cu-0+ two oxides are stable at high temperatures, CuO and CuzO+ each having only minor deviations from stoichiometry. Equilibria in the liquidus temperature region of the system Cu2O-CuO have been studied by Roberts and systemsmyth,9'10CuzO-CuO by Vogel and ocher,I1 by Osterwald,12 and recently the the present authors.13 The system is of the eutectic type with a eutectic temperature of 1083.C The composition of the eutectic liquid corresponds to Xcu0 = °.44, and the oxygen pressure of the coexisting gas phase is Po2 = 0.55 atm.13 Equilibrium oxygen pressures for coexistence of solid CuO and solid Cu2O have been determined by Schmahl and Muller,l4 by Gadalla, Ford, and white,l5 by Bidwell,16 and recently by the present authors.13 There is reasonably good agreement among the various sets of data. Free energies of formation of Cu2O(s) from the elements have been derived by Tretyakov,17 by Bidwell,16 by Kiukkola and wagner,18 by Pal'guev and Neuimin," and by Steele and Alcock,20 There is particularly good agreement among the latter three1'-20 sets of data. THEORETICAL BASIS Consider a subsolidus isothermal section of the system Cu-Pt-0, as shown in Fig. 1. Two phase as-

Jan 1, 1970

By Jack L. Taylor

Single crystals of tungsten grown from powder -metallurgy swaged rod by high-temperative annealing were deformed in tetzsion at temperatures from 2500 to 5000 OF. Orientation of specittzen tensile axis, strained ratrix, and defortnation bands was determined optically by reflections from {110} etch pits. Slip traces meve analyzed and slip directiorz determined. Results indicate that {110}(111) , {112){111}. and {123}{111} type slip occur in tungsten over the terpe,atuve rutge investigated. Slip is orientation-dependent occuvring on tCuzt cowzbitzation oj slip plane and direction which has the highest critical resolved shear stvess. Overshooting appears to be a general occurrence between 2500' and 5000°F. Dejornatiotz bands show rotation in a directiorz opposite to the yotation of tire tensile axis. DEFORMATION in bcc metals has been reviewed by Maddin and Chen,' Keh and eissman,' and most recently by Nabarro, Basinski, and olt. From these reviews it is apparent that some disagreement exists concerning the crystallography of plastic deformation in bcc metals. There is evidence of noncrystallo-graphic slip, the crystal slipping on or near a noncrys-tallographic plane in the (111) zone for which the resolved shear stress is greatest. There is also evidence to indicate that crystallographic slip occurs in the planes of the same zone. On the other hand, there is agreement that the close-packed direction ( 111) is the slip direction in bcc metals. Further, in pure bcc metals4 and alloys the operative crystallographic slip systems are strongly dependent on temperature. Both crystallographic and noncrystallographic slip have been reportede8 in tungsten, a group VIA bcc metal. The number of slip families which operate in the case of crystallographic slip, however, has been in question. The earliest study by oucher' of single-crystal tungsten tested at temperatures of 1800 to 5000°F led to the conclusion that only {112)( 111) type slip operated. Raymond and eumann recently reached the same conclusion studying deformation by rolling of plasma-flame single crystals at 1800°F; however, only [loo] and [110] orientations were studied. Work at high temperatures by Leber and Pughs on tungsten and Chen and Maddin9 on molybdenum suggests that conjugate slip on nonparallel (110) planes may account for the slip on (112) and (123) planes found by others working with bcc metals. The present paper presents evidence of three families or modes of slip in tungsten in the temperature EXPERIMENTAL PROCEDURE Material. Standard microtensile specimens, 0.160 in. diam by 0.640 in. gage length, were ground from commercial powder-metallurgy swaged tungsten rod, type MK. Specimens were heated for 10 min at 5150°F or 6 hr at 5400°F in vacuum of 1 x 105 Torr or less to produce single crystals. At the lower temperature an average of two out of seven specimens heated in a group developed single crystals throughout the specimen length as shown in Fig. 1, the rest remaining wholly poly crystalline. At the higher temperature, three or four out of seven specimens became single crystal. Other than to note that Laue X-ray photographs generally showed sharp, well-defined spots, no attempt was made to assess crystal perfection or measure dislocation density. Two tungsten single crystals grown from the melt by the plasma-arc process were also used for this study.

Jan 1, 1967

By K. E. Starling

Phase equilibria data were used to develop an equation-of-state correlation for complex hydrocarbon mixtures, thereby circumventing difficulties associated with use of pressure-volume-temperature data. Equilibrium phase data for two condensate reservoir fluids were used to determine equation-of-state parameters for hydrocarbons as heavy as C22H46 in a modified form of the Benedict-Webb-Rubin equation of state. Comparative tests of K-values from the resultant correlation were made with data for condensate reservoir, separator and gas plant absorber mixtures. Generally, for temperatures above OF and computed liquid densities below 0.55 Ib-mole/cu ft, the modified BIVR equation predicted K-values in close agreement with the experimental data. INTRODUCTION Accurate predictions of thermodynamic behavior for complex hydrocarbon mixtures are necessary for many calculations in the petroleum industry. Because of the relatively high cost of extensive experimental data, many correlations for prediction of phase behavior have been developed. Some of these, such as the correlation of K-values presented in the NGAA Equilibrium Ratio Data Book, are totally empirical.l Others, such as the Benedict-Webb-Rubin (BWR) equation-of-state method, are semitheoretical.2-4 Unfortunately, published correlation methods often do not accurately predict the phase behavior of complex hydrocarbon mixtures, principally because of inadequate representation of the effects of components heavier than decane. This paper presents a new approach to this problem in which basic equation-of-state relations including heavy hydrocarbon effects are applied. Equilibrium phase data for two condensate reservoir fluids containing hydrocarbons as heavy as C22H46 are used to correlate component K-values. The BWR equation was chosen as the prototype equation of state for this study because of its proven capability for accurately predicting phase behavior and thermodynamic properties of light - hydrocarbon mixtures? Research was directed toward development of BWR parameters for the heavy hydrocarbons and modifications of the mathematical form of the BWR equation for application to complex hydrocarbon mixtures. The new equation-of-state approach presented differs considerably from previous methods in that phase equilibria rather than PVT data are used for determination of equation-of-state parameters. It is an explicit approach since the parameters are determined directly from mixture data. As such, it does not encounter problems inherent in the implicit method used by Benedict, Webb and Rubin 2-4 and numerous other investigators—one in which mixture parameters were postulated to be functions of the pure component parameters. The pure component BWR parameters, in turn, were determined from experimental PVT data. This method has been limited to mixtures containing components lighter than decane because of lack of vapor phase PVT data. Studies have been reported in which BWR parameters have been determined explicitly from PVT data for binary mixtures.6-8 However, since small concentrations of heavier components have only a minor effect on PVT behavior, it is doubtful that these explicit methods would yield useful results for condensate systems. Ellington and Eakin9 have shown that the accuracy of K-values predicted by an equation of state developed from mixture PVT data probably would be more than an order of magnitude lower than the accuracy of the PVT data. On the other hand, an equation of state utilizing parameters developed from phase equilibria data should predict K-values with accuracy comparable to the accuracy of the experimental phase compositions. This work applies this explicit approach with the objective of improving hydrocarbon mixture phase behavior predictions. Results are evaluated by comparing predicted and experimental K-values at reservoir, separator and gas plant

Jan 1, 1967

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 R. A. Morse, W. W. Owens, D. R. Parrish, T. M. Geffen

Laboratory studies of several factors affecting measurements of relative permeability were made using the three-section plastic-covered core technique. Results show that the core assembly, properly constructed, will perform as a single unit, and that the testing technique will, under suitable conditions of pressure gradient, gas expansion, and migration of partial water saturation, permit measurement of flow characteristics not affected by technique. Wettability equilibrium is readily established in cores exhibiting strong wetting preference to water or oil when initially saturated with water. Laboratory tests must be conducted so that saturation changes represent those that occur in the reservoir. Immediate implications of saturation history are (1:) that the possibility exists of increasing the displacement efficiency of solution gas drive reservoirs over the natural process, and (2) residual gas saturations following water flooding in gas or gas condensate reservoirs will be 15 to 50 per cent pore space rather than 1 to 11 per cent as generally believed. INTRODUCTION Solutions of petroleum reservoir problems pertaining to production performance require the use of true relative permeability characteristics. 'This relationship of fluid conductivity and saturation has been obtained by reservoir engineers in four ways, namely: 1. From past gross reservoir performance and the extrapolation of this data based on experience,1,2 2. By using published fluid flow relationships obtained in laboratory studies on general type porous materials,3, 4, 5 3. By attempting a mathematical derivation of flow behavior," using some experimentally obtained characteristics of reservoir rocks, and 4. By laboratory flow tests using representative rock samples of a reservoir. The first three methods listed above have shortcomings which make their use limited or questionable. Production characteristics of only certain processes are obtained from field data and these are not available at the beginning of a reservoir's producing life, at which time they are desirable. It is fortuitous if general fluid flow characteristics obtained experimentally have accurate application to specific field problems. Also, it is felt that at this time there is not sufficient knowledge of the flow behavior of oil, water, and gas in porous materials to enable applicable analytical description of this to be made based on other measured rock characteristics. Measurement of relative permeability in the laboratory offers the only direct method subject to adequate checking for determination of flow characteristics applicable to field problems. Primarily, this paper deals with laboratory experiments to establish the effects of several factors on the measurement of relative permeability and the practical significance of this knowledge. Laboratory flow tests are essentially model studies; the gross reservoir being represented by a small rock sample. It is necessary to simulate in experiments all the factors of importance which influence flow in the reservoir, as well a.; to eliminate effects peculiar to the model studied to assure measurement of valid flow behavior. Factors which affect the measurement and behavior of fluid flow in porous materials have been studied by other investigators.3,7,8,9,10,11 This analysis is not intended to evaluate fully all factors involved, but to establish first the validity of measurements by the technique used and then study flow behavior under various conditions. The studies reported are as follows: 1. Effects of pressure gradient, 2. Effects of gas expansion in tests conducted at near atmospheric pressure, 3. Effects of migration of a partial water saturation in oil-gas-water systems, 4. Effects If wettability characteristics of the system. and 5. Effects of the fluid saturation history. The first three are important only in laboratory measure-

Jan 1, 1951

By D. R. Parrish, T. M. Geffen, R. A. Morse, W. W. Owens

Laboratory studies of several factors affecting measurements of relative permeability were made using the three-section plastic-covered core technique. Results show that the core assembly, properly constructed, will perform as a single unit, and that the testing technique will, under suitable conditions of pressure gradient, gas expansion, and migration of partial water saturation, permit measurement of flow characteristics not affected by technique. Wettability equilibrium is readily established in cores exhibiting strong wetting preference to water or oil when initially saturated with water. Laboratory tests must be conducted so that saturation changes represent those that occur in the reservoir. Immediate implications of saturation history are (1:) that the possibility exists of increasing the displacement efficiency of solution gas drive reservoirs over the natural process, and (2) residual gas saturations following water flooding in gas or gas condensate reservoirs will be 15 to 50 per cent pore space rather than 1 to 11 per cent as generally believed. INTRODUCTION Solutions of petroleum reservoir problems pertaining to production performance require the use of true relative permeability characteristics. 'This relationship of fluid conductivity and saturation has been obtained by reservoir engineers in four ways, namely: 1. From past gross reservoir performance and the extrapolation of this data based on experience,1,2 2. By using published fluid flow relationships obtained in laboratory studies on general type porous materials,3, 4, 5 3. By attempting a mathematical derivation of flow behavior," using some experimentally obtained characteristics of reservoir rocks, and 4. By laboratory flow tests using representative rock samples of a reservoir. The first three methods listed above have shortcomings which make their use limited or questionable. Production characteristics of only certain processes are obtained from field data and these are not available at the beginning of a reservoir's producing life, at which time they are desirable. It is fortuitous if general fluid flow characteristics obtained experimentally have accurate application to specific field problems. Also, it is felt that at this time there is not sufficient knowledge of the flow behavior of oil, water, and gas in porous materials to enable applicable analytical description of this to be made based on other measured rock characteristics. Measurement of relative permeability in the laboratory offers the only direct method subject to adequate checking for determination of flow characteristics applicable to field problems. Primarily, this paper deals with laboratory experiments to establish the effects of several factors on the measurement of relative permeability and the practical significance of this knowledge. Laboratory flow tests are essentially model studies; the gross reservoir being represented by a small rock sample. It is necessary to simulate in experiments all the factors of importance which influence flow in the reservoir, as well a.; to eliminate effects peculiar to the model studied to assure measurement of valid flow behavior. Factors which affect the measurement and behavior of fluid flow in porous materials have been studied by other investigators.3,7,8,9,10,11 This analysis is not intended to evaluate fully all factors involved, but to establish first the validity of measurements by the technique used and then study flow behavior under various conditions. The studies reported are as follows: 1. Effects of pressure gradient, 2. Effects of gas expansion in tests conducted at near atmospheric pressure, 3. Effects of migration of a partial water saturation in oil-gas-water systems, 4. Effects If wettability characteristics of the system. and 5. Effects of the fluid saturation history. The first three are important only in laboratory measure-

Jan 1, 1951