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By H. J. Beach, W. C. Goins

The laboratory development and field use of oil well cement compositions* with high resistance to drilling mud contamination are described. Resistance is obtained by adding a I-lb mixture composed of three parts paraformaldehyde to two parts sodium chromate tetra-hydrate for each sack of cement. This mixture neutralizes the cement-retarding properties of quebracho and other tannins, starch, sodium carboxymethylcellu-lose, Ignite, and monovalent salts of lignosulfonic acid. The retarding properties of calcium lignosulfonate are unaffected. The decontaminating mixture may be used in common cement (designated Type I by ASTM specifica-tions,' Class A by API Std. 10A2) or in a slow set slurry prepared from common cement by addition of calcium lignosulfonate. No changes in slurry viscosities or thickening times are caused by the protecting reagents. The method has been used in 185 field jobs where an improved success ratio has been obtained in plug setting. INTRODUCTION Field experience and laboratory investigations have established contamination by drilling mud as a major factor in oil well cement failures. During 1955, 12 attempts were required to set six open-hole cement plugs in the Timbalier Bay field, La. Eighteen to 30 hours elapsed between placing and testing the plugs in preparation for sidetracking operations. Considerations of rig time expense required immediate resetting where soft cement was drilled after a reasonable waiting period. Sea water drilling mud was used in each well and daily additions of thinners, usually lignites, had been required. Sodium carboxymethylcellulose had been added regularly to control fluid loss. The 50 per cent plug failures were attributed primarily to contamination by the mud. Similar experiences can be found in other fields along the Texas and Louisiana coasts where drilling muds normally contain large quantities of organic treating materials. Cement contamination was the subject of a survey by the Mid-Continent District Study Committee on Cementing Practices and Testing of Oil-Well Cements of the API.3 Data collected from member laboratories and released in Sept., 1951, reported the effects of a number of drilling mud treating chemicals on cement. The study revealed that many of the additives, notably the organic materials in relatively small quantities, had marked effects on the properties of cements tested. Severe losses in strength and erratic thickening time resulted from small additions of mud treating chemicals such as quebracho, starch, sodium carboxymethylcellulose, and lignite. The report included no recommendations of methods for overcoming the problem. One investigation of the contamination problem reported the successful use of activated charcoal in setting cement plugs after conventional slurries had failed.4,5 The investigation indicated that an optimum concentration of 5 per cent activated charcoal was effective in combating contamination from 16.7 volume per cent of treated mud. Laboratory and field muds were included in tests and contained varied quantities of ode or more of the following: quebracho, caustic, starch, lime, and calcium lignosulfonate. The function of the charcoal appears to be physical, removing the organic materials by adsorption. The method may be employed in API Class A or Class D (unretarded slow set) cements. The chemical approach presented here is based on

Jan 1, 1958

By J. P. Heller, H. B. Bradley, A. S. Odeh

A potentiometric model technique is presented for determining the areal sweep efficiency of a five-spot well pattern, at and beyond breakthrough. A sharp interface between displaced and displacing fluids is assumed. Although the prototype svstem is referred to as a waterflood operation, obvious changes in the notation and computations will adapt the results to other displacement processes. The results of the study include the following. 1. Areal sweep efficiencies for a five-spot well pattern, at and beyond breakthrough, for mobility ratios (displacing to displaced fluid) of 4:1, 2:1, 1:1 and 1:4. 2. Extension of potentiometric analysis to the investigation of the areal sweep efficiency beyond breakthrough in a five-spot pattern by the application of conformal mapping and conductive-solid models. 3. The use of layers of conductive fabric in representing mobility ratio changes in potentiometric models. 4. The development of a probe mechanism for probing conductive solids. The results obtained by conductive-cloth models agree with earlier areal sweep efficiencies at breakthrough obtained by Aronofsky and Ramey 1 on the potentiometric analyzer using electrolytic-tank models. Results beyond breakthrough differ from those obtained by the X-Ray Shadowgraph technique. Data from this study show that, for mobility ratios greater than one, water cut rises rapidly as fluid is produced after breakthrough. However, for mobility ratios smaller than one, a large increase in area swept resulted with only a small increase in water cut. INTRODUCTION In calculating reservoir performance of waterflood-ing operations and other fluid-injection programs, it is necesssary to estimate the areal sweep efficiency * before and after injected-fluid breakthrough into production wells. Influence of mobility ratio on oil-production history, before and after breakthrough for a five-spot well pattern, has been studied by X-Ray Shadowgraph techniques 2-5 and by gelatin models.6 In none of these investigations was the transition zone controlled experimentally. Steady-state anaiog techniques assume that a vertical and discrete interface exists between the displacing and displaced phase. Thus, when using a potentiometric analysis, it is assumed that no transition zone exists. To determine the areal sweep efficiency beyond breakthrough for a five-spot well pattern using the potentiometric analyzer, four principal problems had to be resolved. These were the following. 1. The laborious method of representing changes in mobility ratio in electrolytic tanks by means of contoured wooden blocks. 2. Vapcrization of the electrolyte solution during the study causing concentration changes and, thereby, variable conductivity. 3. The scale-limitation problem 7 that is accentuated by abrupt eiectrolyte depth changes. 4. A wellbore geometry problem. EXPERIhlENTAL EQUIPMENT AND PROCEDURES CONDUCTIVE-SOLID MODEL The theory, equipment and procedural techniques of the electrolytic-tank potentiometric model have been treaced excellently by Lee8 and by Muskat.9 By the use of a conductive solid to represent the fluid conductivity of the porous media, the need for contouring wooden blocks to represent mobility ratio was eliminated. It was found that a carbon-black coated fabric, Uskon D-16,** could be employed as a fairly uniform conductive media. This material, when stacked in appropriate layers and pressed together, can be used to represent changes in mo-

By J. W. Freeman, D. N. Frey

Fundamental reasons for the improvement in creep resistance of an austenitic alloy by cold working were investigated mainly by X-ray diffraction. The creep resistance was found to be improved by the internal stresses in the lattice of the alloy induced by the cold work. THIS investigation was concerned with the fundamental reasons for improvement in creep resistance of an austenitic alloy as a result of cold working. Also, the investigation was carried out to elucidate the conditions under which cold working could be expected to improve the creep resistance. To achieve these ends, creep resistance and internal structure were correlated for a variety of cold-worked conditions. Since the aim of the investigation was not to obtain specific and extensive information on any one alloy, creep testing was done with a single stress at 1200°F. Structural studies were carried out primarily with X-ray diffraction characteristics. The alloy used, low carbon N-155, was selected on the basis of being representative of at least some of the alloys used in gas turbines. Low carbon N-155 alloy in the form of %-in. sq bar stock was used in this investigation. The chemical composition, in percent, was: C, 0.13; Mn, 1.43; Si, 0.34; Cr, 20.73; Ni, 18.92; Co, 19.65; Mo, 3.05; W, 1.98; Cb, 0.98; N, 0.14; and Fe, balance. The bar stock was produced from a 13-in. sq billet, finished to 7/s in. round cornered square between 2060" and 1910°F. Prior to use in this particular investigation, the bar stock was solution-treated 1 hr at 2200°F and water quenched. This procedure was used in order to put the stock in a condition where effects of prior processing were minimized. Experimental Procedure The specific approach to the problem was twofold. First, the influence of cold working, under various conditions, on the creep rate under a single stress at 1200°F and on the internal structure was in part determined. Second, the effect of annealing at various times and temperatures on the creep rate and internal structure of the cold-worked samples was in part evaluated. The first step was basic to the investigation—creep resistance and structure were to be correlated. The second step was taken to see if the annealed samples showed some internal changes which could also be correlated with changes in creep resistance. This it was felt would facilitate solution of the basic problem. The creep and structural studies were carried out on samples reduced approximately 5, 15, and 40 pct at room temperature and 15 pct at temperatures up to 2200 °F. Annealing of various of the samples was done at 1200°, 1400°, 1600°, and 1800°F for time periods up to 1000 hr. Studies of the annealed samples were concentrated on materials rolled approximately 5, 15, and 40 pct at room temperature and 15 pct at 1400°F. The creep tests were carried out at 1200°F under 40,000 psi, the latter being approximately the 1000 hr rupture stress of the material

Jan 1, 1952

By J. P. Heller, H. B. Bradley, A. S. Odeh

It is an accepted procedure to represent oil field displacement problems in which the pressure is relatively constant by a potentiometric model. Variations in reservoir permeability thickness product are represented in the model by proportional variations in electrolyte depth. It is shown that significant errors are present wherever these variations are of such magnitude that the consequent differences in the electrolyte depth in the model or any regions therein are appreciable in comparison with their respective horizontal dimensions. To demonstrate the order of magnitude of this error, a hypothetical linear oil field in which permeability varies linearly with distance was treated both analytic.ally and by potentiometric model. The results obtained from the model are compared with the exact solution for various configurations of linear geometry. Deviations in flow times up to 11 per cent were observed. It is confirmed that these discrepancies can be reduced by increasing the areal scale and/or decreasing the vertical scale of the model. It is the purpose of this work to assist in the design of potentiometric models by indicating the relationship between this error and the chosen scale factors. INTRODUCTION The fundamental geometrical criterion which determines whether the pressure distribution in an oil or gas reservoir may be simulated in a conventional potentiometric model is the requirement that all reservoir parameters be constant along any vertical line between its upper and lower boundaries. This situation never obtains exactly; nevertheless, it is usually assumed that there is no permeability stratification within the section of interest, that all wells completely penetrate the sand, that there are no gravitational effects, and that variations in thickness of the sand are small compared to the horizontal extent of the field. In these ways the reservoir problem is reduced to two dimensions in which there is no variation of pressure in the vertical direction within the limits of the sand. Variations in sand thickness and/or horizontal pesmeability may be taken into account as described by Muskat, by considering the fluid conductivity of the reservoir in its horizontal plane to be proportional to the product of permeability and sand thickness. If the variations in sand thickness are small compared to the horizontal dimensions of the reservoir, then it is a good approximation to consider the reservoir problem to be essentially two dimensional. The same approximation, however, is made in the simulation of the assumed two-dimensional reservoir by the electrolytic model. The model, if it is to take into account variations of permeability-thickness product, must of necessity be made in three dimensions, that is, with variable depth. Most potentiometric model studies and theoretical treatments reported in the literature to date2,3,4,5,6,7,8 are those in which either an average permeability was used or a constant permeability was assumed. This is understandable since detailed permeability data are not usually available for the majority of reservoirs. Many investigators have recognized that the failure to incorporate permeability variations within a reservoir in model studies leads to serious error in predictions made

Jan 1, 1957

By G. O. Hiers

IN 1948 in the United States, 184,300 tons of lead was fabricated as coverings for electric power and communication cables. Such covering generally is called "sheathing" for the principal lengths of the cables, while the short lead encasements of the joints are called "sleeves." For the purpose of this paper, both lead sheathing and lead sleeving can fittingly be called lead tubing. In the United States in the same year, 34,262 tons of lead was consumed in making extruded lead pipes. Such pipe is employed frequently for water or chemical solution conveyance with gage pressures up to 100 psi. Consequently, the walls are thicker in ratio to diameter than is the case with the cable sheaths. For this discussion, lead pipes can be thought of as tubes or tubing. About 19 centuries ago, the Romans produced metallic lead of about 99.9 pct purity. Evidently this was cast in flat sheets of Y8-in. thickness, for instance. Such sheet of 10-ft lengths was bent around a removable core producing a tube somewhat oval in cross-section and with a typical internal diameter of, say, 3 in. This method of production necessitated a seam or longitudinal joint evidently made by casting the seam metal adherently. The seam metal, as analyzed recently, contains about 1 ½ pct Sn. Blow pipes were said to have been employed when the joint was made. Specimens of such pipe were found both in Italy and in the British Isles. It is believed the pipes conveyed water for drinking purposes and for baths. Numerous specimens are still in existence in a good state of preservation, due to lead's usual inertness in air or water. According to Claude E. Pearson,1 there were various stages in the evolution of lead extrusion presses for making tubes: I. First press by Joseph Bramah, 1797. 2-First successful press by Thomas Burr, 1820. 3-First bridge die press, J. and C. Hanson, 1837. In 1845, Wheatston and Crooke made the first lead sheathed electric cable. Flat lead strip was wound spirally around the insulated conductor. Overlapping edges of lead were soldered. Early cables were also made by pulling insulated conductors into 50-ft lengths of lead tube. Borel in France, and Wesselau are credited with devising the first presses for extruding lead sheaths directly on cables in 1879. In the United States, Eaton, in 188o, and Roberston, in 1885, introduced new presses of improved design. Following Cunningham's original idea of making lead traps and. bends in 1873, the presses apparently were improved and made successfully soon thereafter. Between the years 1930 and 1940, two continuous extrusion presses for lead were developed abroad. One apparently was originated by Dunsheath and made by the Henley Telegraph Works Co. The other was developed by the Pirelli-General Cable Co. CURRENT PRODUCTION In addition to the several descriptive chapters on lead extrusion in Pearson's book, the Metals Handbook2 recently described pipe, sheath, and collapsible tube production. The latter is by impact extrusion.

Jan 1, 1951

By John B. Campbell, George G. Binder, Loren H. Jenks

Conventional methods of producing crude oil generally leave in the depleted reservoir 1 to 3 bbl of oil for every barrel brought to the surface. This paper describes a field test which explores the possibility of using gas-driven liquid propane to improve oil recovery efficiency. Laboratory theoretical and experimental studies leading to the field test indicated that low residual oil values could be obtained using limited amounts of propane driven by gas. The field test involved (I) repressuring the reservoir to the vapor pressure of liquid propane, (2) injecting the liquid propane, and (3) injecting dry natural gas to drive the propane and oil to the producing wells. Considerable preliminary work, including new drilling, work-overs, and a pressure survey was necessary. During the test, oil production rates have averaged about nine times the final primary rates. The field average GOR is still below the pre-test value. Oil recovery to date is 112,000 STB. About one-third of the 143,-000 bbl of propane injected has been produced to date. Results of the C-2 block test are encouraging and larger, more definitive field projects ore indicated. INTRODUCTION The cost of finding new crude oil reservoirs continues to increase. Today the oil industry is drilling more and deeper wells and making fewer big discoveries. Nevertheless, the demand for oil and oil products increases each year. It is natural that oil companies, faced with this situation, concentrate on recovering more of the oil existing in our known crude oil reservoirs. There is room for much improvement. For every barrel of oil brought to the surface by present day methods of producing crude oil, generally 1 to 3 bbl are left behind in the depleted reservoirs. The "unrecoverable" oil in petroleum reservoirs is largely "trapped" by capillarity. Since flushing with a solvent is exceedingly effective in combatting oil loss due to capillarity, much effort in this direction has been made in recent years1,2,3,4,5. Liquefied petroleum gas (LPG) has been suggested as a relatively inexpensive. abundant, easily recoverable solvent for crude. Some operators have observed striking responses in oil recovery at production wells offsetting input wells in LPG storage reservoirs6,7,8. In spite of the low unit cost of LPG, however, it is uneconomic in general to inject a volume of LPG into a reservoir to remove a like volume of oil. A modification of solvent flushing in which a limited quantity of liquid propane is gas driven through a reservoir appears capable of recovering much more than 1 bbl of oil per barrel of propane injected. Also, most of the propane injected should be recoverable for sale or re-use. Since such a process could well have widespread and profitable application, The Carter Oil Co. is making an extensive evaluation of the technique's possibilities. Laboratory development of the gas-driven propane recovery technique was sufficiently encouraging to justify testing in the field. Since 1952, the Production and Research Departments of The Carter Oil Co. have cooperated in a field test in the C-2 Block leases of the

Jan 1, 1958

By S. F. Reiter, You-Chao Liu, W. R. Hibbard

Cyril Stanley Smith in his classic 1948 Institute of Metals Lecture&apos; noted in the case of annealing twins that: "It is well known that approximately the same number of twins per grain and the same general geometry are maintained in large grains as in small ones, a fact that certainly suggests a mechanism such as the above where boundaries and twins grow proportionately together. If this view is correct, a spherical grain should have no mechanism for keeping its twins." Such a constancy of twins per grain would be of particular interest as a tool for the study of the origin of annealing twins. It has been proposed by Mathewson2 and later by Barrett3 that in face-centered cubic metals slip occurs in the {111} Plane by <112> shears which combine in pairs to produce the macroscopically observed <110> movement. This proposal is schematically inviting since <112> slip permits the atoms of one plane to move along the interatomic valleys of its neighbor rather than up the hills across the atom sites. There is strong experimental evidence? that annealing twins result from the growth of nuclei in the form of "twin faults" produced by single <112> shears. It is possible that more twin faults would form at low deformation temperatures than at high ones, because the more rigid lattice may increase the tendency to "freeze" the twin faults and prevent their dissipation in slip. This is suggested by (1) the greater resistance to slip at low temperatures and (2) greater tendency toward mechanical type twinning at low temperatures (a summary of these factors is presented by Seigle and Brick5). These considerations would suggest the following: a. Constant twin/grain ratio for specimens deformed constant amounts at a constant temperature, but annealed at various temperatures above the recrystalliza-tion temperature. b. Larger twin/grain ratios for re-crystallized specimens previously deformed constant amounts at lower temperatures. The purpose of this investigation is to test these considerations. One half in. rods of phosphorous deoxidized electrolytic copper and 70-30 alpha brass (68.36 pct Cu, 0.005 pct Pb, 0.01 pct Fe, 31.62 pct Zn remainder) were rolled to a thickness of 0.350 in., milled to specimens 0.350 X 0.437 X 2 in., and annealed at 700°C to an average grain size of 0.065 and 0.090 mm, respectively. These specimens of each metal were then rolled 50 pct reduction in thickness and annealed one hour under conditions which were all combinations of the following: Rolling Annealing Temperatures. Temperatures. °C °C -70 400 25 500 200 600 Standard metallographic techniques&apos; were used to prepare specimens. By the method of lineal analysis7 using a minimum of ten samples of fifty grains each for each specimen, the ratios of twins* per total grains, twins per twinned grain, twin families* per total grains and twins per twin family were determined. Recrystallized grain size was determined by A.S.T.M. comparison methods.8 All observations were made on the rolling plane. The results are tabulated in Table 1.

Jan 1, 1950

By M. K. Yen, W. R. Hibbard

Previous studies of plastic deformation of metals have emphasized the important role of bending and constraints during strain under relatively pure stresses.1"5 Some new phenomena such as early conjugate slip6 and polygonization7 are intimately concerned with the relief of bending stresses, the former by slip and the latter by a process analogous to re-crystallization. However, few analyses of the bending deformation of single crystals were found in the literature, and those8,9 are sufficiently previous to the modern interpretations of slip to invite further investigation in this area. The transverse bending mode of testing, using the two-point loading method, was selected because the center portion of the specimen may be considered as under a theoretically pure bending stress with a uniform bending moment. Considerable attention was given to both the lattice distortion and flow characteristics of the crystals during deformation. Experimental Proeedare A specimen under the action of equal and opposite couples at both ends is said to undergo pure bending. The shear and moment diagrams of a specimen under the two-point loading method of transverse bending are shown in Fig 1. The moment over the middle-third of the span is equal to PL/6, and the vertical shear is zero. Fig 2 (A) illustrates the stress distribution in the elastic range on a plane across the middle of the specimen. It can be seen that the normal stress has a maximum value at the extreme surfaces on the tension and compression sides, and decreases proportionately to zero as it approaches the neutral plane. However, when the plastic range is reached, the stress distribution is no longer a straight line relation, but changes in a manner which can be best illustrated as shown in Fig 2(B). The following calculation and stress analysis are mainly in accordance with the works reported by Timoshenkol0 and Kochendörfer.9 From the simple beam formula, the maximum normal stress will occur at the surface of the specimen. For a round specimen with a radius r and for a rectangular specimen with a height 2h and width 2b, the maximum normal stress, Sp, will be given by the following formulas: For round specimen: 2PL Sp = 3pr3 [1] For rectangular specimen: Sn = 8bh2 [2] Since it is reasonable to consider that slip takes place under the same conditions as in uniaxial loading, the resolved shear stress S?, along the operative slip direction will be as follows: For round specimen: 2PL sin x cos ? Sp = 3pr3 sin x cos ? [3] For rectangular specimen: PL S8 = 8bh2 sin x cos ? [4] where X is the angle between the specimen axis and the slip direction and X, the angle between the specimen axis and the major axis of the glide ellipse. It was also reported by Kochenclorfer9 that the critical bending moment, that is, the bending moment exerted on the specimen to initiate slip, should be higher than the value given by the equations stated above. Based

Jan 1, 1950

By Jerome F. Kuzmick

Many investigations have been made on the effect of the variables of pressure, sintering temperature and sintering time on the physical and microstructural charactcristics of metal-powder compacts. Severa1 such investigations have indicatcd that pressure is the least important of these three factors in an attempt to secure a dense. strong compact by a simple coltl-pressing and sintering procedure. However, it was felt that a further study of the effect of pressure on pressed and sintered metal powder compacts might prove interesting, for the following reasons: In work done in the past on the effect of pressure, temperature. arid time, the, metal-powder compacts were subjected to long sintering periods, and temperatures right up to the melting point of the metal were applied. It was thought that pressure might exert a more profound effect under short-time simtering and within narrower ranges of temperature. such as normally would be applied in large-scale production of metal-powder parts. 2. It was hoped that something further might be learned of the nature of the bond in pressed and sintered metal-powder compacts. 3. It was thought that interesting infor mation concerning the work-hardening effect of pressure on the crystal structure. of sintered metal-powder compacts would be obtained. Procedure Rectangular bars, 2 by 1/2 by 1/4 in. were molded from the following metal powders: Atomizcd till powder, 325-mesh Atomized aluminum powder, 325-mesh Reduced copper powder, 100-mesh Electrolytic iron powder, 100-mesh Atomized 70-30 brass powder, l00-mesh The, till powder was molded at various pressures up to 40 tolls per sq. in. This was the maximum, because at higher molding pressures there was considerable extrusion of tin into the die wall, jamming the die plungers. The tin specimens were not -in tered, as this phase of the work was- done merely to see how much a very sold metal could be compressed. The aluminum powder was compressed at various pressures up to 50 lons per sq in. Higher pressures could not be used because of extrusion into the die wall The compacts were sintered one hour at 000 in pure dry hydrogen. The copper powder was molded at vari-ous pressures up to 96 tons per sq. in. One set was sintered at 750°C., another at 050 C. for one hour in pure dry hydrogen. The electrolytic iron powder was molded at various pressures up to 00 tons per sq. in. and sintered, one set at Soo°C and one set at 1300°C for one hour in pure dry hydrogen. Extra 325-mesh specimens were also prepared to study the effect of reduced particle size on grain structure. The brass powder was molded at various pressures up to 96 tolls per sq. in. and silltered for one hour. one set at 65o°C. and one set at 800°C, in pure dry hydrogeu.

Jan 1, 1945

By F. Kurata, A. F. Bertuzzi, P. C. Davis, T. L. Gore

The phase and volumetric properties of 10 very volatile mixtures are presented for temperatures from — 200°F to above the critical points. These mixtures consisted of natural gases and of mixtures of natural gases with methane and nitrogen. Existing correlations of compressibility factors have been extended to apply to these mixtures. Existing correlations of critical pressures and temperatures do not apply to these mixtures. Methods have been developed for estimating critical temperatures of these mixtures to ± 4°F and critical pressures to 2 5 per cent. These methods apply to other volatile and very volatile mixtures. The results of this work are particularly applicable to the separation of nitrogen from hydrocarbons by low-temperature distillation. INTRODUCTION Knowledge of the low-temperature phase and volumetric properties of natural gases and of other mixtures of the light hydrocarbons is becoming increasingly important as interest in low-temperature separation processes increases. Low-temperature distillation has been used to separate ethane and ethylene from natural gas and from refinery gases for petrochemical uses. Removal of nitrogen from natural gas by low-temperature distillation has been proposed 7,20 as a means of increasing the capacity of existing gas transmission lines and of improving the marketability of the gas. Further application of low-temperature separation processes has been retarded by lack of data on the phase and volumetric behavior of mixtures at low-temperatures and at high pressures. This paper presents the results of determination of the phase and volumetric properties of 10 very volatile mixtures at temperatures from - 200 °F to above the critical point. These mixtures consisted of natural gases with methane and nitrogen. Generalized methods are presented for estimating the critical temperatures, critical pressures, and the densities of such mixtures. EXPERIMENTAL APPARATUS AND PROCEDURES The apparatus and the experimental procedures have been described in an earlier paper13. The method consists of displacing the mixture from a reservoir which is maintained at constant temperature and pressure into an agitated glass equilibrium cell which is maintained at constant temperature. The liquid level within the glass equilibrium cell was visually observed, and the pressure was measured to within & 3 psi with a calibrated Bourdon gage. COMPOSITIONS OF MIXTURES STUDIED The compositions of the mixtures studied are summarized in Table 1. The measured properties included in Table 1 will be discussed later in this paper. The sources of these gases are described below: Gas "A-1&apos;&apos; was obtained from the Phillips Petroleum Co. Its composition was reported in connection with earlier work." The properties of this gas were reported in an earlier paper.13 Gases "A-2, A-3, A-4" were prepared by mixing nitrogen with gas "A-1." Gas "AB-1" was prepared by mixing methane with gas "A-1." The properties of this gas were reported in an earlier paper.&apos;" Gases "AB-2" and "AB-3" were prepared by mixing nitrogen with gas "AB-1." Gas "B" was obtained by W. W. Bodle of J, F. Pritchard & Co. from the primary separator of a well in western Kansas. Gas "C" was obtained from a Cities Service Co. pipeline at Lawrence, Kans. Gas "D" was prepared by mixing gas "AB" with gas "C."

Jan 1, 1955

By T. P. Papazoglou, N. A. D. Parlee, W. C. Phelps

HE high vapor pressures of metals such as lead, calcium, lithium, bismuth, and magnesium at steel-making temperatures present experimental problems which have thus far rendered it almost impossible to obtain really reliable data for their solubilities in liquid iron. Many investigators have attempted to equilibrate liquid iron in the same crucible with the undissolved liquid phase of such volatile metals. The published results,l-6 although useful, are often questionable on the grounds of not being obtained under true equilibrium conditions. Such information is not always of practical value in any case since the equilibrium vapor pressure is often several atmospheres and steel is not currently made at these pressures. Solubility measurements at lower partial pressures (< 1 atm) appeared to be more practical and easier to make. These data could be used to calculate solubilities at other pressures where Henry&apos;s Law is obeyed, and to estimate solubilities under other conditions of temperature and pressure with useful accuracy. This note outlines the development of a general technique for the measurement of solubilities in systems of this kind. The method involves equilibration of the high-boiling metal at known temperatures with the vapors of a low-boiling metal at known partial pressures. Analyses of quenched samples provide vapor pressure-solubility data and make calculations of alloy thermodynamics possible. The principle involved is similar to the closed-system diffusion-transport method which is difficult to apply with most high-melting liquid metals like iron, due to closure problems. A two-zone horizontal (molybdenum wire element) tube furnace, Fig. 1, provides two constant-temperature zones in a reaction tuve (3/4 in. ID by 1 in. OD by 36 in.). A high-boiling metal sample, 9, introduced in the higher-temperature zone, is maintained at temperature T1, and a volatile metal sample, 7, in the lower-temperature zone, is held at T2. A stream of argon with 10 pct hydrogen is passed via flowmeters, 1, and mixing-drying towers, 2 and 3. through the reaction tube at a favorable flowrate and acts as a carrier gas which entrains vapor from the volatile liquid metal at a specific constant partial pressure. The gas mixture passes through a system of constrictions, 6 and 8, to the higher-temperature zone, establishes intimate contact with the high-boiling liquid sample, 9, and exits through a small condenser tube. The entire system is at (nearly) atmospheric pressure and the volume of carrier gas passed is measured with a wet gas meter. When the high-boiling sample attains equilibrium with the vapor phase, both samples are removed and quenched. Analysis of the high-boiling sample for solute content reveals its solubility for the low-boiling metal at a vapor pressure calculated from carrier-gas volume and either a) weight loss of volatile metal or 6) weight gain of high-boiling sample plus condenser (which collects the undissolved vapors). To test the capabilities of the method, liquid silver at 1403&apos;C was equilibrated with lead vapor at various partial pressures. The relatively simple Pb-Ag system was particularly suitable for uncovering experimental problems and providing the first step toward investigations with more volatile metals and more difficult combinations.

Jan 1, 1965

By V. R. Garfias, R. V. Whetsel

As pointed out in previous studies, estimates of petroleum reserves if they are to be of value must not only presuppose a clear understanding of what is actually meant by reserves but must be subject to constant revision to conform with changes in their component factors. When such estimates are analyzed it must be clear that it is virtually impossible to obtain comparable figures reflecting the same degree of accuracy, to represent the reserves not only in various countries, but at times even of different fields in the same country. Estimates of reserves in the United States, subject to frequent independent checks, are obviously more reliable than those furnished, for instance, by the Soviet Government, as the latter must be accepted at their face value and are open to the suspicion of being made to conform with predetermined programs of propaganda. Any tabulation of the reserves of all producing countries, therefore, gives a total that is misleading, as the component items arc not arrived at on the same basis and therefore are not homogeneous in a true sense. Only a fraction of the petroleum stored underground, usually associated with natural gas, is or can be brought to the surface, and although practically all the natural gas underground can be rccovered, in actual practice in some fields a large part of the gas that reaches the mouth of the well is wasted. It is thus estimated that in the United States only some 25 to 35 per cent of the petroleum underground in proven fields is actually economically recovered. Estimates of reserves, therefore, should make clear the distinction between the known amount of oil underground in producing fields and the portion that actually can be brought to the surface. It cannot be overemphasized that as a result of the operation of the "Law of Capture," which controls subsoil ownership in the United States on comparatively small landholdings that seldom if ever cover the entire producing area, the oil fields are not as economically exploited as some forrign fields, and that as a result (were it not for the easy accessibility of the domestic market, the largest in the world) some American production would now be unprofitable in open competition with foreign oils.

Jan 1, 1939

By Samuel Wyer

F. G. CLAPP, New York, N. Y. (communication to the Secretary*).¬I assume that where this valuable paper states, near its end, that "it is not possible to establish a market price, " the author means that no particular price which will fit all conditions and fields can be given. I am not in agreement with Mr. Wyer, however, that the actual value of natural gas leaseholds is "largely a matter of opinion." I would even be willing to express myself very strongly as believing that if we, as experts, cannot give anything closer than a mere opinion, our testimony or reports are not of great value to our clients. I believe, moreover, that by detailed geological examinations and with our latest knowledge of geological structure, principles of natural gas occurrence, etc., we can approach just as near a certainty in natural gas valuations as we can in oil valuations, and much more so than in the valuation of many metal prospects, in which only the upper few feet of the vein has been opened. In other words, we are getting nearer and nearer every year to bringing geology as applied to oil and gas development into the class of an exact science. Mr. Wyer&apos;s paper gives an excellent outline for methods of leasehold valuation. Being presumably intended as an outline only, it can be expanded indefinitely by a detailed discussion of the methods of valuation for the four different classes of leaseholds which he mentions: (A) "Producing;" (B) "Protective;" (C) "Reserve;" and (D) "Prospective." This classification is probably as good as can be made in practice. In the producing leaseholds in particular it is easy to establish a market price at which these leaseholds should be bought or sold. The question would arise in any case whether or not the leases are connected with a pipe line or the distance from the pipe line. Assuming that a pipe line already taps the property and that gas is already being sold for a certain figure, this price must be multiplied by the number of thousand cubic feet still "in sight" in the ground, from which is to be deducted (a) bonuses, (b) rentals, (c) royalties, (d) cost of drilling, (e) taxes and

Jan 12, 1916

By R. V. Whetsel, V. R. Garfias

As pointed out in previous studies, estimates of petroleum reserves if they are to be of value must not only presuppose a clear understanding of what is actually meant by reserves but must be subject to constant revision to conform with changes in their component factors. When such estimates are analyzed it must be clear that it is virtually impossible to obtain comparable figures reflecting the same degree of accuracy, to represent the reserves not only in various countries, but at times even of different fields in the same country. Estimates of reserves in the United States, subject to frequent independent checks, are obviously more reliable than those furnished, for instance, by the Soviet Government, as the latter must be accepted at their face value and are open to the suspicion of being made to conform with predetermined programs of propaganda. Any tabulation of the reserves of all producing countries, therefore, gives a total that is misleading, as the component items arc not arrived at on the same basis and therefore are not homogeneous in a true sense. Only a fraction of the petroleum stored underground, usually associated with natural gas, is or can be brought to the surface, and although practically all the natural gas underground can be rccovered, in actual practice in some fields a large part of the gas that reaches the mouth of the well is wasted. It is thus estimated that in the United States only some 25 to 35 per cent of the petroleum underground in proven fields is actually economically recovered. Estimates of reserves, therefore, should make clear the distinction between the known amount of oil underground in producing fields and the portion that actually can be brought to the surface. It cannot be overemphasized that as a result of the operation of the "Law of Capture," which controls subsoil ownership in the United States on comparatively small landholdings that seldom if ever cover the entire producing area, the oil fields are not as economically exploited as some forrign fields, and that as a result (were it not for the easy accessibility of the domestic market, the largest in the world) some American production would now be unprofitable in open competition with foreign oils.

Jan 1, 1939

By L. S. Darken

It has been known for sometime that in an ionic lattice, such as that of Ag,S or FeO, the migration velocity of the anion may differ markedly from that of the cation, the cation being usually the more mobile. It has been shown, for example, that during the formation of silver sulphide tarnish on silver, the tarnish layer grows principally by the motion of silver cations through an essentially stationary silver sulphide lattice. Similarly, the growth of wüstite scale on iron proceeds principally by motion of iron ions, this being accomplished with the aid of vacant iron lattice sites into which the iron may readily move. Likewise investigations of solid solutions of various salts show that there is usually considerable difference in the mobility of the different cations. Measurements of the mobility of various metals in liquid mercury indicate that the various metals move at different rates relative to the mercury. In view of the foregoing it seems reasonable to suppose that when any single phase solution is acted upon by a field, the atoms of different elements respond in different ways; in particular, that the force arising from a particular concentration gradient in a binary alloy would cause the atoms of one component to move with a drift velocity which is in general different from that of the atoms of the other component. The recent experiments of Smigelskas and Kirkendall&apos; support this viewpoint, since they found, in essence, that during diffusion in alpha brass zinc moves appreciably faster than copper. This was evidenced by the relative motion of inert molybdenum wires. Such a phenomenon is incompatible with the place interchange theory of diffdsion proposed by several authors, most recently by Bir-chenall and Mehl.2 This theory has, however, also been questioned3v4 for other reasons, principally because of the high energy required for direct atomic interchange. The rather large difference between self-diffusivity, as determined by tracer technique, and mutual diffusivity, as determined with the aid of another element at low concentration, might also be interpreted as favoring the above idea; however. Birchenall and Mehl have pointed out that there is another possible interpretation of this difference; this is discussed later. A rather interesting and pertinent observation was made by Schwartz, who noticed that tungsten lamp filaments, heated by direct current, commonly fail by necking down in the region at the temperature gradient near the positive end, with a concomitant swelling at the corresponding position near the negative end. He introduces considerable auxiliary evidence to show that this phenomenon is occasioned by the motion of tungsten cations which migrate in the high temperature region from the positive end toward the negative end. The mechanism of this migration is not clearly understood. If, however, this experimental evidence be accepted, we are forced to conclude that alloying elements in the tungsten may migrate by the same or a Similar mechanism, whatever it may be, at a greater Or lesser rate, thus giving rise

Jan 1, 1949

By L. S. Darken

It has been known for sometime that in an ionic lattice, such as that of Ag,S or FeO, the migration velocity of the anion may differ markedly from that of the cation, the cation being usually the more mobile. It has been shown, for example, that during the formation of silver sulphide tarnish on silver, the tarnish layer grows principally by the motion of silver cations through an essentially stationary silver sulphide lattice. Similarly, the growth of wüstite scale on iron proceeds principally by motion of iron ions, this being accomplished with the aid of vacant iron lattice sites into which the iron may readily move. Likewise investigations of solid solutions of various salts show that there is usually considerable difference in the mobility of the different cations. Measurements of the mobility of various metals in liquid mercury indicate that the various metals move at different rates relative to the mercury. In view of the foregoing it seems reasonable to suppose that when any single phase solution is acted upon by a field, the atoms of different elements respond in different ways; in particular, that the force arising from a particular concentration gradient in a binary alloy would cause the atoms of one component to move with a drift velocity which is in general different from that of the atoms of the other component. The recent experiments of Smigelskas and Kirkendall&apos; support this viewpoint, since they found, in essence, that during diffusion in alpha brass zinc moves appreciably faster than copper. This was evidenced by the relative motion of inert molybdenum wires. Such a phenomenon is incompatible with the place interchange theory of diffdsion proposed by several authors, most recently by Bir-chenall and Mehl.2 This theory has, however, also been questioned3v4 for other reasons, principally because of the high energy required for direct atomic interchange. The rather large difference between self-diffusivity, as determined by tracer technique, and mutual diffusivity, as determined with the aid of another element at low concentration, might also be interpreted as favoring the above idea; however. Birchenall and Mehl have pointed out that there is another possible interpretation of this difference; this is discussed later. A rather interesting and pertinent observation was made by Schwartz, who noticed that tungsten lamp filaments, heated by direct current, commonly fail by necking down in the region at the temperature gradient near the positive end, with a concomitant swelling at the corresponding position near the negative end. He introduces considerable auxiliary evidence to show that this phenomenon is occasioned by the motion of tungsten cations which migrate in the high temperature region from the positive end toward the negative end. The mechanism of this migration is not clearly understood. If, however, this experimental evidence be accepted, we are forced to conclude that alloying elements in the tungsten may migrate by the same or a Similar mechanism, whatever it may be, at a greater Or lesser rate, thus giving rise

Jan 1, 1949

By C. E. Nelson

The purpose of this discussion is to outline briefly the practices commonly followed in this country for the melting and refining of magnesium and its alloys. The processes used for the various forms of primary magnesium, as far as there are differences in the physical shape or behavior, will be discussed. The refining of general fine scrap or secondary magnesium was presented in an earlier paper.1 Inasmuch as the use of fluxes is an essential part of all the melting and refining processes, the principal aim of this paper will be to deal with these in sufficient detail to point out their unique characteristics, in order to make their use more effective. Types oF Melting Practice All melting and refining processes for magnesium and its alloys require the use of fluxes. These fluxes have a magnesium chloride base and other halide salts or oxides are added to give a density or behavior exactly suited to the particular melting practice. The successful handling of magnesium depends upon the proper use of the correct fluxes. There are four general methods of melting, summarized in the following paragraphs and treated in more detail in the section on Melting and Refining. Open-pot Method The open-pot method makes use of No. 230 flux.2 The flux provides protection during melting and a molten pool of flux into which the solid magnesium melts. It is stirred through the molten metal bath and agglomerates oxide or similar foreign bodies; then on quiet standing separates away, leaving the refined metal ball floating in an encircling layer of molten flux. It forms only a thin fluid film over the surface of the molten metal, which may be &apos; parted for hand-ladling processes and tends to cover the metal again after the ladle is removed. A very light dusting of the pot surface with fresh flux immediately after the ladle is removed is usually desirable. The open-pot method is used generally in the following processes: (I) alloying and secondary smelting in the production of ingot, (2) in sand foundries for premelting and to a smaller extent for the production of small castings requiring hand ladling, (3) in permanent-mold founding for premelting and also direct ladling to castings, (4) for continuous methods of preparing metal in the production of billets or ingots from which wrought products are fabricated, (5) in general scrap recovery. Crucible Process The crucible process makes use of No. 310 flux, which has the property of being thinly fluid at the start, to provide protection and refining qualities, and then drying out or thickening after a time, leaving a protecting crust on the pot surface until the time of casting. At that time it can be readily skimmed off or held back, thus allowing the contents of the crucible to be poured out directly into castings without fear of flux contamination. This flux is not

Jan 1, 1944

By J. B. Pullen

THE United Verde mine is in the north central part of Arizona, on the northeasterly slope of the Black Hills, near the town of Jerome. Ore was first discovered in the district about 1875, and the first mining claims were located by M. A. Ruffner and associates in 1877. In 1888 the late Senator William A. Clark secured control of the property and under his ownership it developed into one of the country&apos;s most important copper producers. The property was sold to the Phelps Dodge Corporation in 1935, and since then has been under this Corporation&apos;s management. Except for shutdowns caused by general world-market conditions, production has been continuous from 189o to date. GEOLOGY The mineralized zone ranges in area from approximately 12 acres to less than 5 acres. All mineralization occurs in the pre-Cambrian intrusives. The first intrusion, according to geologic records, was the quartz porphyry, which later was intruded by augite diorite. Following the diorite intrusion through a series of intrusions of lesser magnitude, a pipelike mass of massive sulphide, quartz and rock was formed. The diorite forms the hanging wall of this mass, and the porphyry the footwall. Between the footwall and the sulphide a band of chlorite schist was formed, probably owing to metamorphic conditions. Commercial ore occurs along the contact of the schist and sulphide extending into the sulphide, sometimes entirely through the schist, and fingering out into the porphyry. The ore deposit was formed by replacement similar to deposits formed in limestone areas. Faulting and deformation occurred in pre-Cambrian times and again in the Tertiary period, removing approximately 2000 ft. from the top of the main United Verde ore body, forming the United Verde Extension ore body, the only other major ore body in the district. Major development work has shown that the sulphide mass extends to the 3300-ft. level, and diamond drilling below this level has indicated that the mass might extend below the 3700-ft. level, but in a diminished quantity. While many copper minerals exist in the mine, the chief commercial mineral is chalcopyrite. A plan and vertical section of the mineralized zone showing the principal geological features is shown in Figs. I and 2. GENERAL DESCRIPTION AND PHYSICAL CONDITION OF MINE After over 50 years of active production, ore still exists on almost every level of the mine. This condition is due to many causes -mine fires, which broke out as early as 1894, caused the abandonment of certain areas; subsidence and ground movements retarded the cleaning up of others. Furthermore, in the early days there was such an abundance of ore that when mining became difficult it was a simple matter to replace the production by going to a deeper level. Several attempts were made to recover the ore in the fire zone, both by glory-holing

Jan 1, 1941

By R. S. Silo

A new process for leaching oxidized copper ore (CuO) is presented. Its principle advantage is that it requires low cost raw materials. For large operations the only materials used are sodium chloride (NaCl) and calcium carbonate (CaCO3). In those operations of medium size, sulfur, which is abundant in the North of Chile, is used. However the process may also be applied to small copper plants provided low cost sulfuric acid is available as a substitute for sulfur. That is, it may be applied to those small capacity plants where large additional installations for the regeneration of the leaching solution are not needed. The method is comprised of six stages, namely: Crushing, Leaching, Washing of the Solution, Precipitation, Regeneration of the Leaching Solution, and Fusion. A flow diagram for this process in a large or medium-sized plant is given. LEACHING This process requires hydrochloric acid as the leaching solution for treating copper ores. This is easily produced from sulfuric acid and sodium chloride as follows: A small excess of NaCl is advisable to avoid the presence of free sulfuric acid. The experiments reported here were performed with 36 grams of HC1 per liter of solution to obtain a free acidity equivalent to 50 gpl of H2SO4 (the usual leaching solution concentration). Hydrochloric acid leaching may be done by either of the usual methods; i.e. percolation or agitation. The method selected depends on the characteristics of the ore. No matter which method is chosen, low pressure air can be used either as an air lift for circulation of the solution, or for agitation of the pulp with "Pachuca" tanks. In either case, there are no problems with respect to oxidation. Leaching by agitation produces good recovery; but at times, the problem of high consumption of leaching solution or the overproduction of grinding slimes which interfere with contact between phases negates this advantage. The percolation method was used in this study. Percolation took place in four 15-liter containers, 11 1/2 in. diam. by 12 in. height, having hemispheric bottoms. Each container was fitted with a wooden bottom having 1/4 in- holes. The air lift was a 3/4 in. plastic tube 10 in. high. Air at 6 psi was supplied from a rotating laboratory compressor. 10 kg of ore were charged to the container and counter-current leaching was used. The leaching solutions were fed through the center pipe in order to use the ascending solutions to reject the air in the charge. The solution circulated through the air lift in order to facilitate the movement according to the increase in density produced by the reaction between the phases present. Specific observations made in this report cannot be generalized because the leaching characteristics are dependent on the nature of the ore used, the method of leaching, and the production of primary or secondary slimes while crushing or leaching.

Jan 1, 1967

By E. T. Stephenson

Wert and Marx1 pointed out that a straight-line relationship exists between the activation energy of a relaxation process and the temperature at which the maximum relaxation occurs. The data available at the time indicated that this relationship held for a number of Snoek peaks, several grain boundary peaks, and pair relaxation in a brass. Theoretical justification for the observed relationship was found in the following equation, which Wert and Marx derived from the theory of interstitial atomic diffusion coefficients:&apos; where AH is activation energy, R is the gas constant, T is the internal friction peak temperature, v is the interstitial atomic frequency, f is the frequency of the applied stress, S is entropy of activation. More accurate internal-friction data on interstitial diffusion in bcc metals have become available since Wert and Marx&apos;s paper. Table I gives activation energies calculated by several authors from a combination of elastic aftereffect data and the peak temperatures at several frequencies of measurement. (In the case of Fe-C and Fe-N, the referenced authors5&apos;7&apos;8&apos;10 also used high-temperature diffusion data.) However, diffusion experiments at 150°C and above1&apos;-13—rather than anelastic techniques—were used to determine the activation energy of hydrogen diffusion in Fe-H. In order to plot this recent data as a AH vs T graph we calculated the peak temperatures of the systems listed in Table I (with the exception of Fe-C, Fe-N, and Fe-H) by using published values3&apos;&apos; of AH and Do. These calculated peak temperatures varied by only a few degrees from experimentally determined peak temperatures. The calculated values were felt to represent the better average. A number of investigators have found the peak temperatures in Fe-C and Fe-N to be 38 to 40°C and 20° to 24°C, respectively. The values of 39" and 22°C (312° and 295°K in Table I) were determined by carefully executed experiments.6&apos;8 The hydrogen peak temperature has been measured at 1 cps,12 20 cps,14 and 35,000 cps.15 All hydrogen peak temperatures were adjusted to 1 cps for Table I using AH = 3000 cal per mole. As Fig. 1 shows, the data of Table I fit a straight line at least as well as the earlier data used by Wert and Marx. Linear-regression analysis was applied to the data in Table I. The Fe-H data was omitted because the activation energy has not been experimentally determined in the temperature range of the peak. The analysis yields the equation: with a standard error of 860 cal per mole. The agreement of the data in Table I with the Wert-Marx equation is excellent. Strict application of Eq. [I] forces the linear regression analysis through the origin. In this case, the analysis gives a slope of 62.1 cal per mole per deg, and a standard error of *890 cal per mole. With this value, it follows from internal-friction theory that Hence, Do varies by only 30 pct among these bcc-interstitial systems. Thus, a concept suggested originally by Wert and Marx1 is confirmed by recently published data. The

Jan 1, 1965