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By H. C. Chang, N. J. Grant, A. R. Chaudhuri

During the creep of coarse-grained polycrystalline magnesium at elevated temperatures, a nonbasal type of slip was found to play an important role in the deformation processes. The nonbasal slip traces were examined metallographically in eight specimens (13 grains) and the observed glide plane located stereographically for each grain. The tests were run at 500&apos; and 700°F at stresses of 148 to 786 psi. Based on these measurements and theoretical calculations, the crystallographic elements for nonbasal slip were determined. WHEN a metal deforms by slip, the conventional appearance of the slip bands on the surface of a specimen is that of straight lines. Such is the behavior of the face-centered-cubic metals, as for example, aluminum. The particular slip system on which slip occurs in these metals is governed by the criterion of resolved shear stress. Work on the body-centered-cubic metals a-iron,&apos;. &apos; molybdenum, and columbium4 has shown that the process of slip is somewhat more complicated than the simple gliding of one close-packed plane of atoms over another in a close-packed direction and that it results in the formation of wavy and irregular slip traces on the surface. The recent reviews and experiments of Vogel and Brick and Chen and Mad-din3 show that, for the body-centered-cubic metals, the resolved shear stresses along the planes and the degree of close-packing do not necessarily determine the slip system. Theirs and other investigations indicate that a complete understanding of the slip process in the body-centered-cubic metals is not yet possible. However, one behavior displayed by all these metals is that the slip direction is invariably one of the close-packed directions <11l>. The wavy nature of the slip-band traces has been explained on the basis of cooperative slip by planes sharing this same slip direction.1&apos;3l&apos; It is generally acknowledged that, when the hexagonal-close-packed metal magnesium (axial ratio c/a = 1.624) deforms by slip at room temperature, it does so by basal slip in the close-packed direction <1I%>. This type of slip has the conventional appearance of straight lines and is governed by the critical shear-stress law. Schmid and coworkers" showed that basal slip was operative in the temperature range of —185" to 300°C (—300" to 572°F). Work by Servi, Norton, and Grant6 has shown that, during the creep of coarse-grained aluminum at high temperatures, new slip systems come into operation. The existence of a new high temperature slip system at temperatures greater than 225 °C (437°F) for magnesium was suggested also by Schmid. This was later indicated by Bakarian and Mathewson&apos; to be slip along the pyramidal planes (10i1) in the close-packed direction <11%>.* They * Mention will be made in the text of pyramidal planes and prismatic planes. The pyramidal planes referred to are the type I. order 1 of the form {10il); and the prismatic planes of the type 1 of the form (10i0). For the sake of brevity, they are termed in the teat as pyramidal (10il: and prismatic (10i0) planes, respectively. Where reference is made to the pyramidal plane type 1, order 2 of the form {10i2), they are referred to as the pyramidal planes of the type (10i2:. observed that this kind of slip resulted in irregular markings on the specimen surface. According to them, a possible cause for the appearance of the markings was due to "limited accessory slip on the pyramidal {10i2) planes." Burke and Hibbard," on deforming a single crystal of magnesium at room temperature, found evidence of slip on a pyramidal plane {1011). They explained it as being due to the effect of grip restraints. It is pertinent to note at this point that, although basal slip has received a fair amount of attention, only two specimens have been investigated, that of Bakarian and Mathewson and of Burke and Hibbard, to establish the elements of nonbasal slip in magnesium. During the study of the deformation mechanisms

Jan 1, 1956

By Gerhard Derge, Harold Markus

The first paper1 of this series described a technique of careful surface preparation by means of which reproducible results may be obtained from potential measurements of the behavior of tin in carbonate solutions with a pH range from 8.4 to 11.2. It then went on to establish the behavior of pure tin electrodes under these conditions and showed that the metal remains active at all times, though the steady potential attained after several hours decreases from 1.12† volts at a pH of 12.6 to 0.6 volts at a pH of 8.4. This behavior may serve as a norm with which all other data can be compared. In the second paper,2 small amounts of other anions were added to the carbonate solutions and the conclusion was reached that the common impurities encountered in alkaline materials packaged in tin do not increase corrosion. In fact, in some cases these anions may actually promote the formation of protective films. The present paper rounds out this survey by presenting data on the influence of cations added to the carbonate solutions, as well as the effect of alloy additions to the tin. In many cases the potential data are supplemented with weight-loss measurements. Information is also presented on the effects of some additional anions, the influence of gases above the electrolyte, the behavior of high-purity tin, and the effect of atmospheric oxidation on the corrosion resistance of the above-named alloys. Analysis of the entire body of data discloses some general rules applicable to corrosion in carbonate solutions. The experimental methods used are the same as those previously described. Experimental Data Cations.—The carbonates of the cations K+, Li+, NH4+, which are soluble, were studied in the same way as the anions, by adding 0.01 mol of the metal carbonate to one liter of 0.1 M sodium carbonate solution, pH 11.2, or to 0.1 M sodium bicarbonate, pH 8.4. The other metallic carbonates are only slightly soluble, of the order of 10-3 mols per liter or less, and the sodium carbonate solutions were saturated by adding excess reagent several days before the experiment, shaking frequently, and filtering just before use. The chemicals were c.p. grade in each case except the indium salt. This salt was prepared by solution of the metal in hydrochloric acid and precipitation by addition of Na2CO3. These cations may be divided into two classes, according to their effect on the potential behavior of the tin: (I) normal, (2) passive. To offer a basis of comparison, curves I of Figs. I and 2 are given to illustrate the behavior of tin in carbonate solutions saturated with CaCO3. These curves are the

Jan 1, 1941

By Harold Markus, Gerhard Derge

The first paper1 of this series described a technique of careful surface preparation by means of which reproducible results may be obtained from potential measurements of the behavior of tin in carbonate solutions with a pH range from 8.4 to 11.2. It then went on to establish the behavior of pure tin electrodes under these conditions and showed that the metal remains active at all times, though the steady potential attained after several hours decreases from 1.12† volts at a pH of 12.6 to 0.6 volts at a pH of 8.4. This behavior may serve as a norm with which all other data can be compared. In the second paper,2 small amounts of other anions were added to the carbonate solutions and the conclusion was reached that the common impurities encountered in alkaline materials packaged in tin do not increase corrosion. In fact, in some cases these anions may actually promote the formation of protective films. The present paper rounds out this survey by presenting data on the influence of cations added to the carbonate solutions, as well as the effect of alloy additions to the tin. In many cases the potential data are supplemented with weight-loss measurements. Information is also presented on the effects of some additional anions, the influence of gases above the electrolyte, the behavior of high-purity tin, and the effect of atmospheric oxidation on the corrosion resistance of the above-named alloys. Analysis of the entire body of data discloses some general rules applicable to corrosion in carbonate solutions. The experimental methods used are the same as those previously described. Experimental Data Cations.—The carbonates of the cations K+, Li+, NH4+, which are soluble, were studied in the same way as the anions, by adding 0.01 mol of the metal carbonate to one liter of 0.1 M sodium carbonate solution, pH 11.2, or to 0.1 M sodium bicarbonate, pH 8.4. The other metallic carbonates are only slightly soluble, of the order of 10-3 mols per liter or less, and the sodium carbonate solutions were saturated by adding excess reagent several days before the experiment, shaking frequently, and filtering just before use. The chemicals were c.p. grade in each case except the indium salt. This salt was prepared by solution of the metal in hydrochloric acid and precipitation by addition of Na2CO3. These cations may be divided into two classes, according to their effect on the potential behavior of the tin: (I) normal, (2) passive. To offer a basis of comparison, curves I of Figs. I and 2 are given to illustrate the behavior of tin in carbonate solutions saturated with CaCO3. These curves are the

Jan 1, 1941

By H. H. Reamer, B. H. Sage

Attempts have been made to predict the volumetric and phase behavior of naturally occurring hydrocarbon mix-turesl-6 but these methods have not been extended to the higher pressures and tem-peratures that are currently encountered in some producing formations. Furthermore, the methods of prediction at present avail-able have not been tested in a sufficient number of cases to ensure their applica-bility to all naturally occurring hydrocar-bon mixtures, even at the lower pressures and temperatures. For these reasons the behavior of a number of hydrocarbon mix-tures from a field in which the subsurface pressures are above 4500 lb. per sq. in.t and the temperatures are in the neighbor-hood of 250°F. was investigated. Method The objective of this program was to determine the volumetric behavior of ma-terial as it existed in the reservoir as a function of pressure, temperature and com-position. Strictly speaking, this cannot be accomplished in any simple fashion. How- ever, the variations in composition that are encountered within a producing reservoir may be approximated roughly by means of mixtures made up of two arbitrarily chosen constituents. Experience indicates that the liquid and gas phases from a high-pressure gas trap afford a simple source of material for this purpose. Throughout this discus-sion the samples of the gas phase and liquid phase from the production trap will be called the "trap-gas sample" and the "trap-liquid sample," respectively. The volumetric behavior of both of the trap samples was determined throughout the temperature interval between 100" and 250°F. at pressures up to 5000 lb. per sq. in. In addition, the behavior of eight different mixtures containing varying proportions of the two trap samples was studied throughout the same temperature and pressure intervals. The experimental results yielded information concerning the specific volume of the material as a function of pressure, temperature and the relative quantity of the trap samples. The relative amount of each of the paraffin hydrocarbons of lower molecular weight than n-hexane was determined for each of the trap samples. In addition, the specific weight, viscosity and average molecular weight of the hexanes-and-heavier fraction of the trap-liquid sample were determined as well as similar information for each of five fractions separated from this material by distillation. From these data the weight fractions of each of the components from methane through pentane were determined for the trap samples and eight systematically chosen mixtures. Materials The gas and liquid samples were obtained from the production trap of a well in the Rio Bravo field in California during the fall of 1939. Information concerning the condi- 70

Jan 1, 1941

By H. H. Reamer, B. H. Sage

Attempts have been made to predict the volumetric and phase behavior of naturally occurring hydrocarbon mix-turesl-6 but these methods have not been extended to the higher pressures and tem-peratures that are currently encountered in some producing formations. Furthermore, the methods of prediction at present avail-able have not been tested in a sufficient number of cases to ensure their applica-bility to all naturally occurring hydrocar-bon mixtures, even at the lower pressures and temperatures. For these reasons the behavior of a number of hydrocarbon mix-tures from a field in which the subsurface pressures are above 4500 lb. per sq. in.t and the temperatures are in the neighbor-hood of 250°F. was investigated. Method The objective of this program was to determine the volumetric behavior of ma-terial as it existed in the reservoir as a function of pressure, temperature and com-position. Strictly speaking, this cannot be accomplished in any simple fashion. How- ever, the variations in composition that are encountered within a producing reservoir may be approximated roughly by means of mixtures made up of two arbitrarily chosen constituents. Experience indicates that the liquid and gas phases from a high-pressure gas trap afford a simple source of material for this purpose. Throughout this discus-sion the samples of the gas phase and liquid phase from the production trap will be called the "trap-gas sample" and the "trap-liquid sample," respectively. The volumetric behavior of both of the trap samples was determined throughout the temperature interval between 100" and 250°F. at pressures up to 5000 lb. per sq. in. In addition, the behavior of eight different mixtures containing varying proportions of the two trap samples was studied throughout the same temperature and pressure intervals. The experimental results yielded information concerning the specific volume of the material as a function of pressure, temperature and the relative quantity of the trap samples. The relative amount of each of the paraffin hydrocarbons of lower molecular weight than n-hexane was determined for each of the trap samples. In addition, the specific weight, viscosity and average molecular weight of the hexanes-and-heavier fraction of the trap-liquid sample were determined as well as similar information for each of five fractions separated from this material by distillation. From these data the weight fractions of each of the components from methane through pentane were determined for the trap samples and eight systematically chosen mixtures. Materials The gas and liquid samples were obtained from the production trap of a well in the Rio Bravo field in California during the fall of 1939. Information concerning the condi- 70

Jan 1, 1941

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&apos;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 L. Luini, E. Lee

An exploratory survey of the heat treatment response of commercial titanium alloys (Ti-150A, RC-130B, and MST 3AI-5Cr al-loys) shows a wide range of possible hardness and microstructural characteristics. The hardening is primarily dependent on the solid state transformation of the phase. An age hardening reaction which apparently is associated with ß decomposition and precipitation has been shown. Brittleness and notch sensitivity appear to be characteristic of age hardening to high hardness. Ductility, tensile strengths, and elongations are given. A NUMBER of commercially produced titanium-base alloys have been made available by the titanium metals industry. These alloys were developed to combine the light weight of titanium with increased strength through alloy additions. Usually the properties of these alloys are reported for material in the hot rolled and annealed condition. Since the production of commercial titanium has preceded the investigation of titanium-base alloy systems, the potential of these alloys is not well known. Although heat treatability has been indicated for these alloys, data on the response to heat treatment are quite limited. The heat treatability of titanium is based on the allotropic transformation of the high temperature, body-centered cubic ß structure to the low temperature, hexagonal close-packed a structure at approximately 1625 °F. This transformation in the pure metal is of little practical significance in heat treatment since the high temperature phase is not amenable to controlled transformation. Alloy additions serve to alter the transformation kinetics and permit control of the transformation by heat treatment variables. The effects of different alloys on the allotropic transformation in titanium classify them in two general categories,1 a stabilizing and ß stabilizing elements. The a stabilizers, represented by aluminum and oxygen, raise the temperature limits of the low temperature phase and introduce a two-phase a + ß temperature range. The ß stabilizers, represented by molybdenum and columbium, lower the equilibrium temperature of ß and give rise to an extended temperature range where both a and ß phases are stable. Another type of ß stabilizer, represented by iron, chromium, and manganese, introduces a eutectoid reaction. Some commercial titanium alloys belong to complex multiple element systems. Based upon the phase diagrams of the binary systems, the general effect of commercial compositions is to vary the stability of the high temperature phase and significantly alter its transformation characteristics. Therefore it is expected that the characteristics of alloyed titanium can be altered by heat treatment. The present investigation was undertaken to survey the variations in hardness, microstructure, and mechanical properties as affected by heat treatment variables. Commercial Alloys lnvestigated The commercially available titanium-base alloys selected for this investigation and obtained as 3/4 in. diameter hot rolled and annealed bars are listed in Table I. The producer did not determine the chemical composition of the Ti-150A heats X1052 and L685. The early heats of Ti-150A, prefixed with the letter X, were melted with tungsten-tipped electrodes and cast in approximately 500 lb ingots 12 in. in diameter. The heats prefixed with the letter L were melted under a revised melting practice yielding approximately 1300 lb ingots 16 in. in diameter. The final annealing treatment was at 1200" to 1250°F for 1 hr. The MST-3A1-5Cr alloy was melted in an induction furnace and cast in 7 in. diameter ingots. This practice produces high carbon material and some variation in the amount of carbides was found in different sections of the same bar. The RC-130B alloy was melted with a carbon arc. This alloy showed approximately 2 pct carbides. No large segregation effects were observed.

Jan 1, 1955

By Hsun Hu, B. B. Ruth

The rates of migration of high-angle boundaries in zone-refined aluminum crystals rolled 20 to 70 pct in the (110)[i12/ orientation were studied. Following a recovery anneal at an appropriate temperature to stabilize the polygonized structure, boundary migration rates of artificially nucleated grains were measwed isothermally at several temperatures. Results indicate that the rate of boundary migration depends strongly on the amount of deformation and on the cell size of the polygonized matrix, and is related to the driving free energy by a power function. The degree of anisotropy in growth 0.f the re crystallized grains nn&apos;th preferred mientation is independent of deformation; the migration rates of the fast-moving and the slow-moping boundary segments of a gowing grain differ by as much as one order of magnitude. The actir\ation energy fm a grain boundary migration, although nearly the same for both the fast-moving and the slow-moving boundaries for a given deformalion, decreases from 45 to 30 kcal per mole with an increase in deformation from 20 to 70 pct reduction. Re crstallization by the growth of the artificially nucleated grains results in preferred orientation. The Percentuge of&apos; grains favorably oriented for growth increases with increasing deformation. None of these grains corresponds to the ideal Kronberg-Wilson orientation relationship. The observed growth aniso-tropy is discussed in terms of boundary structure. The boundary velocity as a function of the cell inter -facial area, or the driving free energy, is discussed in the light of current theories of boundary migration. It is well established that recrystallization with re-orientation occurs by the migration of high-angle boundaries of strain-free grains. The driving force for this process is provided by the free energy stored in the metal during deformation. A quantitative study of the effect of varying driving force on grain boundary migration in deformed metals has not been possible heretofore, primarily because of: 1) concurrent recovery steadily decreasing the available driving free energy for boundary migration, &apos;-3 and 2) in-homogeneity of strain in the deformed metal.4 Aust and Rutter3 studied grain boundary migration in striated single crystals of zone-refined lead. Although the driving free energy in such crystals remains unaltered during annealing, this method does not provide a range of driving free energies over which measurements of grain boundary migration can be made. In the present investigation, the rates of migration of high-angle boundaries in deformed aluminum zone- refined single crystals were studied at various temperatures, after deformation ranging from 20 to 70 pct reduction by rolling at -78°C in the (ll0)[i12] orientation. The boundary migration rates along different crystallographic directions were determined under steady-state conditions, i.e., in the absence of competing recovery processes or impingement of recrystallized grains growing into the deformed single crystal matrix. Simultaneous recovery was eliminated by suitable anneals prior to the boundary migration measurements. The recrystallized grains, which grew a ni so tropically into the homogeneously polygonized matrix, developed flat boundary segments during early stages of growth. These boundary segments subsequently migrated along a direction approximately normal to the boundary plane into the matrix rystal. Increasing deformation over the range employed was estimated to increase the driving free energy for boundary migration by about five times. The kinetics of the boundary migration process, examined under these conditions, indicate that the boundary velocity is greatly affected by a small change of the driving free energy in the matrix crystals. These results were examined in the light of the current theories of grain boundary migration. EXPERIMENTAL PROCEDURES Single crystal strips (9 by 1 by 0.125 in.) of zone-refined aluminum, were seed-grown by the Bridgman method in a high-purity graphite mold (<lo ppm ash) at 1 in. per hr. Precautions were taken to minimize contamination of the metal during crystal preparation and subsequent handling. Spectrographic analysis of the metallic impurities in the grown crystals is Qven in Table I. The crystals were rolled in the (110)[112] orientation at -78°C to various reductions in thickness, ranging from 20 to 70 pct, in 10 pct increments. The desired reduction was achieved by many rolling passes, each being no more than 0.002 in. To minimize surface friction, the crystal was rolled between two thin layers of teflon. For those crystals rolled more than 40 pct, it was necessary to remove the disturbed surface layers by electropolishing at -5" to -10°C at an intermediate stage of rolling. The edges of deformed crystals were removed by a jeweler&apos;s saw while submerged in alcohol at -78° C to obtain samples of about ? by i in. The distorted metal at the cut edges and the surface layers were then removed by electropolishing, with removal of a minimum of 0.004 in. from each surface. The thickness of the crystals prior to rolling was chosen so that the final thickness was 0.025 in. for all samples. These deformed single crystals were each prean-nealed for 1 hr at an appropriate temperature in the range of 130" to 280°C, depending upon the amount of deformation. The purpose of this preannealing was to

Jan 1, 1970

By Frank C. Aplleyard

The two calcium sulfate minerals-gypsum and anhydrite-occur in many parts of the world, and gypsum has long been of economic importance in the family of industrial minerals. Gypsum, the dihydrate form of calcium sulfate (CaSO4•2H2O) and anhydrite, the anhydrous form (CaSO4) are frequently found in close association, and it is seldom that a calcium sulfate deposit will consist exclusively of one mineral or the other. Although known gypsum deposits are extensive, anhydrite makes up the largest part of total calcium sulfate reserves. However, it has very minor economic use, and most of the following discussion will be devoted to gypsum. Calcium sulfate is one of the principal constituents of evaporite deposits, and when pure, has the following composition: [Sulfur Combined Lime Trioxide Water (CaO) (SO,) (H2O) Gypsum 32.6% 46.5% 20.9% Anhydrite 41.2% 58.8% -] Deposits of pure gypsum or of pure anhydrite which are large enough to be considered commercial have never been found because of both the metastable relationship between the two minerals, and the presence of impurities such as calcium or magnesium carbonates, chlorides, other sulfate minerals, clay minerals, or silica. As a result most mine production of gypsum will range between 85 and 95% pure. Often it is used as mined, although in certain cases, one or more forms of mineral beneficiation are employed to upgrade the product. End Uses The largest use for gypsum is based upon the unique property which calcium sulfate has of readily giving up, or taking on, water of crystallization. With the application of a moderate amount of heat in a process known as calcining, gypsum is converted to plaster of paris (the hemihydrate of calcium sulfate, CaSO4 ½ H2O) which when mixed with water will set or harden as the calcium sulfate returns to the dihydrate form. This semifinished product, usually called stucco, is then manufactured into a large variety of plasters, wallboard, and block for construction use, or into plasters for industrial applications. About 75% of the gypsum used in the United States is calcined for these purposes. Uncalcined uses of gypsum are principally as a retarder for portland cement, as a soil conditioner, as a mineral filler, and other minor industrial applications. About 25% of the gypsum mined in the United States goes into these markets; however, in less developed countries where construction and other industrial uses may be quite limited, the use of uncalcined gypsum for portland cement retarder may well be the dominant-if not the only-market for the mineral. It has often been noted that calcium sulfate constitutes the world&apos;s largest reserve of sulfur, and minor use of both anhydrite and gypsum has been made to produce sulfuric acid or other sulfur compounds such as ammonium sulfate. However, because sulfur is readily available at lower cost from other sources, use of calcium sulfate has been limited to only a few locations where it could compete economically. No such use is reported in the United States at this time. Mineralogy Anhydrite, CaSO4 because of its geologically rapid conversion to gypsum, and relatively high solubility (about 0.2 g per 100 g H2O) is not often found outcropping in climates wet enough to support abundant vegetation except on steeply dipping slopes or other places where hydrated material is continuously removed. Anhydrite rock is most often light to bluish gray in color, and under the microscope, varies

Jan 1, 1983

By J. B. Cheatham

Applications of the mathematical theory of plasticity promises to lead to the solution of many drilling and rock mechanics problems. ,Because of mathematical considerations, the inelastic behavior of rock has frequently been represented by a perfectly plastic model in conjunction with a yield criteria of the Coulomb or Mohr type. The totality of all stress states for which a solid ceases to behave elastically can be represented as a limit surface in stress space. ,Probing of such limit surfaces indicates details of strain hardening which are not provided by the standard triaxial testing procedure. Probing tests of the limit surfaces have been performed on Cardova Cream limestone to provide data for extending plasticity theory to cover situations in which consolidation and strain hardening are present. Test results indicate that this highly porous limestone undergoes a permanent volume decrease when it is subjected to hydrostatic pressures in excess of 3,500 psi. A virgin sample tested under a confining pressure of 1,500 psi has a yield strength of 1,700 psi; however, if the sample is subjected to a consolidation pressure of 5,000 psi, before testing at 1,500 psi, the yield strength is raised to 2,300 psi. Thus, both consolidation and strain hardening are important considerations in describing the mechanical behavior of this limestone. Tests conducted with the axis of the core having different orientations indicate that this rock is also anisotropic. Portions of the initial and subsequent limit surfaces are determined for samples loaded either perpendicular or parallel to the bedding planes. INTRODUCTION Previous experimental work in rock mechanics indicates that no mathematically tractable constitutive theory is inclusive enough to describe the mechanical behavior exhibited by all types of rocks under all conditions of stress and temperature. Indeed, the type of deformation encountered in a single type of rock is known to depend upon the stress and temperature conditions in the rock during deformation.l-5 Certain rocks and minerals, notably those minerals composed of ionic salts, have been shown to exhibit plastic deformation when tested under conditions of high confining pressure.2 Since the mathematical theory of plasticity provides simplifications over the theory of elasticity in certain types of problems, such as those in which limit analysis can be applied, it is of interest to know under what conditions plasticity theory may be applied to rock mechanics problems. The following factors determine the nature of the deformation a particular specimen will undergo: (1) the microscopic structure of the rock, i.e., the structure visible under an optical microscope, including number of phases, porosity, distribution of phases, (2) the mineralogical structure of the solid phases, (3) the conditions of stress and the rate of change of stress and (4) the temperature. Extensive experiments on Yule marble, Carthage marble, Solenhofen limestone and other calcerous rocks indicate that these relatively nonporous rocks deform plastically under certain conditions of loading, and creep under other conditions of loading.l-3 This study is concerned with the behavior of Cordova Cream limestone (Austin chalk) which is also composed almost entirely of calcite and thus has the same mineralogical composition but, because of a rather large porosity, it possesses a different microscopic structure. This investigation was undertaken to learn if Cordova Cream limestone deforms plastically despite the embrittling effect of the pore spaces, and to provide data which can be used to determine whether the mathematical theory of plasticity can describe the mechanical behavior of Cordova Cream limestone. A brief discussion is given of some of the underlying principles of plasticity theory concerning stress space and limit surfaces. Strain hardening is defined and a discussion is given of how the mechanical behavior of a material can depend on the previous history of the loading. This is followed by a description of the experimental procedures

By J. P. Nielsen

When two grains in a polycrystalline specimen meet at a point in the course of grain-boundary movements, and the new boundary created at the point is one of relatively low specific free energy, a nonequilibrium boundary condition occurs. The nonequilibrium is enhanced if the other grain boundaries involved at the point of meeting are relatively high in specific free energy. The nonequilibrium results in a correction by growth of the complex grain (two subgrains) to a large size, sufficient in many cases for it to become a self-propagating unit, i.e., a recrystallization grain. This mechanism, herein called "geometrical coalescence," is proposed as a logical origin for recrystallization nuclei, particularly for secondary recrystallization. RECENT publications1-&apos; indicate that considerable progress has been made toward a complete understanding of the three microstructural processes in metals: recovery, recrystallization, and grain growth. However, a major problem persists, namely, the origin of recrystallization nuclei. It is generally accepted that once a recrystallization nucleus, a secondary recrystallization nucleus particularly, has reached a certain size, it will continue to grow at the expense of its neighbors, simply as a consequence of grain-boundary free-energy considerations. What has remained obscure, however, is the mechanism whereby such a nucleus comes into being and grows to the self-propagating size. Recrystallization Nucleation in a Two-Dimensional Grain-Boundary System In the left portion of Fig. 1 is shown schematically the meeting of grains 1 and 4 on disappearance of boundary 2-3, i.e., the boundary that existed between grains 2 and 3, as might happen in the course of normal grain-boundary migration. If, by chance —and the probability is not necessarily small— grains 1 and 4 are close together in their mutual orientations, or in some other special way mutually oriented so that the new common boundary has relatively a very low specific free energy (hereinafter referred to by s), then the grain boundary arrangement as depicted in the figure is highly unstable. This is particularly so if boundaries 1-3, 3-4, 4-2, and 2-1 are high in their s values. Assuming, for the sake of argument, that boundary 1-4 has a s equal to zero, and the s&apos;s of all the other boundaries present are equal to each other and constant, then the boundary arrangement on the right in Fig. 1 will be

Jan 1, 1955

By C. K. Leith

QUOTING from Dr. Richard T. Ely:1 "Conservation, narrowly and strictly considered, means the preservation in unimpaired efficiency of the resources of the earth; or in a condition so nearly unimpaired as the nature of the case, or Wise exhaustion, admits. And broadly considered, it means more than the word itself implies, for it naturally includes an examination of methods Whereby the natural inheritance of the human race may be improved; and still more broadly considered, and as used in popular discussion, it includes a treatment of the effects of productive conservation methods upon distribution. "Conservation means a sacrifice of the present generation to the future generations Whenever it is carried too far. There is a sharp limit to the economic sacrifice that we may reasonably ask the private person to make for even the present Welfare, and the limit is still sharper when we come to consider the interests of future generations." In a paper on the iron ores of America, presented to the Pan-American Scientific Congress at Washington, I have emphasized the fact that the reserves of iron ores in the two Americas are enormously in excess of the requirements of the present generation, in fact, so large that no shortage is to be anticipated for many generations in the future; that a large part of the value of iron ores is put into them by man&apos;s efforts to make them available. This fact is fundamental for the intelligent consideration of- policies of conservation as applied to iron ore. As I interpret it, this fact makes it practically unnecessary that the present generation should make any especial sacrifice for future generations in the way of conservation of its iron-ore resources. Even if we were disposed to look forward to a period of 100 or 200 years, with a view to insuring the welfare of the people living at that time, it is doubtful whether any procedure we could now formulate would materially help them in the matter of iron ores, so large are the reserves available. In order that an appeal for conservation may be effective it must obviously favor the welfare of the present or immediately following generations; it must promise benefits to general and individual welfare during a period within the range of comprehension of the average man.

Jan 2, 1916

By E. T. Dumble

Discussion of the paper of E. T. DUMBLE, presented at the San Francisco meeting, September, 1915, and printed in Bulletin No. 104, August, 1915, pp. .1623 to 1638. E. L. DEGOLYER, Norman, Okla. (communIcatIon to the Secretary*).-Referring to Mr. Dumble&apos;s description of the stratigraphy of eastern Mexico, I should like to question the classification of the ?Papagallos? or ?Mendez? shales as being of Cretaceous age and the so-called overlapping of the Papagallos or Mendez shales by the Alazan shales; the classification of the San Felipe series as Cretaceous, and the correlation of the San Felipe series with the San Juan limestones. Mr. Durable apparently recognizes the continuity of the great shale formation by his use of the terms "Papagallos" and "Mendez," as equivalent and interchangeable, since the Papagallos Hills in the State of Nuevo Leon and Mendez Station in Northern Vera Cruz, localities at which the shale formation outcrops, and from which the formation names are taken, are approximately 250 miles apart and on opposite sides of the Tamaulipas barrier. The Papagallos shales (evidently referring here to the northern extension only) are said to be non-fossiliferous and no reason for .their Cretaceous classification is given, though in a previous article&apos; they are classified as Cretaceous because at their northernmost outcrop they "have the same relation toward the overlying Tertiary that the Escondido (Cretaceous) has through its whole extent." The Alazan fossil locality was found by me and the first collections from it were sent to Dr. Dall; about 17 species of marine invertebrates were recognized by him, the fauna noted as having a distinct Pacific tincture, and the age of the formation from which they cause pronounced lower Eocene. The outcrop of the shale formation has been traced continuously from this point by me and my assistants into the Panuco River region, where Eocene fossils are reported at a depth of 1,810 ft. in a well at Topila.2 From Topila the formation has been traced continuously north to the Padilla-Jiminez region in Central Tamaulipas. Lithologically, the formation is fairly constant and though I am only generally acquainted with it north of the Padilla-Jiminez region, until definite evidence of the Cretaceous age of the Papagallos shale in its type localities, or of an overlap, is available, it seems to me more logical to consider the shale formation a single stratigraphic unit of Eocene age.

Jan 12, 1915

By HORACE V. WlNCHELL

Location. THE St. Helens mining-district, indicated in sketch-map, Fig. 1, is chiefly in Townships 9 and 10 North, Ranges 5 and 6 East, of the Willamette meridian, in Skamania county, Wash. There is no railroad or even a wagon-road at present connecting it with any base of supplies; access is usually by wagon-road for FIG. I.-SKETCH-MAP OF THE STATE OF WASHINGTON. about 50 miles from the town of Castle Rock to Spirit lake, and from that point by pony-trail from 6 to 10 miles farther. History. Nearly 20 years ago two German farmers, totally inexperienced in prospecting, penetrated this region upon a hunting and fishing-trip. Their attention was drawn to numerous joints and crevices filled with black, glistening tourmaline, and con-

Oct 1, 1912

By Clyde Wyman

THERE has always been a question as to the extent to which oxidizable alloys might he recovered from charged scrap in the, acid electric furnace. While qualitative information was not lacking, the quantities that might be recovered and the conditions best suited for such recovery were not clearly defined. The present investigation was carried out to determine the efficiency of alloy recovery from residuals contained in the bath, especially in regard to the recovery of vanadium. A series of 24 heats was produced at the Burnside Steel Foundry Co., including medium manganese-molybdenum-vanadium, manganese-chromium, and grade B steels, in which vanadium recoveries from the residual vanadium were investigated. Recoveries of other alloys were also studied from the accumulated data. These heats were produced in a 5-ton acid-lined electric furnace. The analysis of metal and slag samples and the micrographs were prepared by the Research Laboratories of the Vanadium Corporation of America. In addition to the vanadium contained in the scrap charge, ferrovanadium was added to the charge and to the molten bath to bring the residuals up to the desired level. Vanadium pentoxide (V2O5) in one series of heats was added to the bath after meltdown, for the same reason. In addition to the general furnace practice, the slags of these various heats were treated with coke breeze, Ferrocarbo-S (silicon carbide), and aluminum dross to determine the effects of different reducing agents upon the alloy recoveries and upon the final product.

Jan 1, 1947

By E. Escobar Pallares

Footnotes to column heads and explanation of symbols are given on page 239. H.C.T. means the deep zone for High Cold Test crude oil. L.C.T. means the shallow zone for Low Cold Test crude oil. They occur in the same area. In the same area there are many shallow pits and some wells. In the column showing total oil production to the end of 1939 are included 355,997 bbl. from shallow pits before 1939. During the last year there was no production from shallow pita.

Jan 1, 1940

By E. Escobar Pallares

Footnotes to column heads and explanation of symbols are given on page 239. H.C.T. means the deep zone for High Cold Test crude oil. L.C.T. means the shallow zone for Low Cold Test crude oil. They occur in the same area. In the same area there are many shallow pits and some wells. In the column showing total oil production to the end of 1939 are included 355,997 bbl. from shallow pits before 1939. During the last year there was no production from shallow pita.

Jan 1, 1940

By J. S. Kasper, R. M. Waterstrat, B. F. Decker

THE large difference in the X-ray scattering factors for molybdenum and manganese makes the o- phase in the Mn-Mo system an interesting one to study with respect to ordering of the atoms. Such a study has been carried out using data obtained from a powder sample, and the resulting evidence for ordering in this compound is presented here. It is not possible, of course, to obtain all the details of structure for a u phase from powder data only. Most difficult of all would be the determination of precise atomic parameters. There is reason to believe, however, that the atomic parameters do not vary greatly in the different s&apos;S and that the precise values obtained from one s structure would then allow decisions as to the ordering of atoms to be made when there is a large difference in scattering factors. In particular, the powder intensities for Mn-Mo s are for the most part in good agreement with those observed for Co-Cr, for which single crystal studies have been made by the authors.&apos; There are a few marked discrepancies in the intensity comparison of the two s&apos;s, and these cannot be removed by adjustment of the parameters. They are interpreted as resulting from a more pronounced effect of ordering of the atoms. Accordingly, the parameters of Co-Cr s&apos; have been used for the calculations of the Mn-Mo intensities. For Co-Cr, the space group is D4h14-P4/mnm with atoms in the following positions: 1—2 in (b); 11—4 in (f), with x=0.1031; 111—8 in (i), with x= 0.3713 and y=0.0370; IV—8 in (i), with x=0.5662 and y=0.2396; and V—8 in (j), with x=0.3160Y and y — -0.250. The unit cell is tetragonal, with an==9.10A and cn=4.74A for the Mn-Mo u phase studied here.

Jan 1, 1955

By Z. Moser, W. Ptak

The experiments were carried out by the method of measuring the electromotive force of concentration cells having zinc as a reference electrode, the second electrode being the liquid alloy Zn-Sn-Cd-Pb. The electrolyte consisted of liquid chlorides and had zinc ions. The measurements were made for seventy -five alloys of different mole fractions within the temperature range of 714° to 877°K. The experimental results enabled the calculation of the activity of zinc in tested solutions. The activities of zinc were calculated by means of Krupkowski&apos;s formulas.3 In addition, the formulas for coefficients of activity of zinc, tin, cadmium. and lead as the function of composition and temperature were given. Activity of zinc was compared with the values obtained from experimental results, and good agreement has been observed. On this basis it can be stated that the theoretical formulas are suitable for determining the thermodynamic properties of liquid quaternary metal solutions. IN the metallurgical processes being carried out at present multicomponent liquid metal solutions take part. For the thermodynamic analysis of these processes it is necessary to know the thermodynamic properties of these solutions. Therefore, many experimental and theoretical papers deal with this problem. The theoretical papers are generally based on the assumption that the structure of liquid metals is similar to their structure in the solid state. In this manner the model of liquid solution, consequently described by means of statistical thermodynamics, has been accepted. This method is being lately developed, especially for solid solutions. Statistical thermodynamics was applied among others by Guggenheim 1 for describing the thermodynamic properties. Unfortunately, the formulas of statistical thermodynamics are often not suitable for the interpretation of experimental results. Attention should be drawn to the relations obtained by means of formulas of phenomenological thermodynamics which always have constants derived with the aid of experimental methods. In the case of the multi-component solutions which contain some additions of impurities besides the basic metal, wagner2 introduced interaction parameters. Equations for the relationship between the activity coefficients and composition were also given by Krupkowski." he application of these formulas requires a good knowledge of the thermodynamic properties of the corresponding binary systems. In these formulas, as in Wagner&apos;s, there appear constants which should be determined from ex- perimental data. Nowadays, different experimental methods are applied for evaluating the thermodynamic functions of solutions, for instance: vapor pressure measurements, calorimetric methods, and the measurements of electromotive force of concentration cells. In the present paper this last method for evaluating the thermodynamic properties of four-component systems, Zn-Sn-Cd-Pb, was applied. For instance in the case of Zn-Sn solutions Alabyshev and Landratov, 4 Fiorani and Valenti, 5 and ptak6 performed the investigations. The Zn-Pb system was worked out by Kleppa 7 and Cd-Pb and Cd-Sn by Elliot and chipman.&apos; This method was also applied for determining the activity of zinc in ternary solutions. 1) EXPERIMENTAL METHOD The experimental arrangement with detailed description is given in Fig. 1. It consists of resistance furnaces, one serving for melting samples and the other containing the flat-bottomed, measuring quartz tube with the liquid electrolyte. Liquid metals and alloys are in glass supremax tubes, which have an opening in their lower part above the metal level. This opening allows the filling of the tubes by the electrolyte. In these tubes tungsten wires are placed which by means of suitable conductors are connected with a potentiometer. It is assumed that tungsten dissolves Fig. 1—Schematic diagram of the experimental arrangement for the investigation of the thermodynamic properties of liquid metal solutions: 1, resistance furnaces; 2, autotransfor-mers; 3, galvanometers; 4, regulator of temperature; 5, gas purifier with concentrated H2SOP; 6, U-tube with P2O5; 7, thermostats; 8, steel block for thermostating; 9, supremax tubes for alloys; 10, tungsten electrodes; 11, inlet and outlet of argon; 12, measuring quartz tube; 13, tube for melting samples; 14, tube for thermocouple; 15, cover of quartz tube; 16, rubber seal; 17, bottom cover; 18, outlet of electrodes to potentiometer; 19, outlet of thermocouples to potentiometer; 20, upper view of the quartz tube cover; 21, orifices for cover screws; 22, orifice for argon inlet; 23, orifice for thermocouple; 24, orifices for tubes containing liquid metals; 25, inlet for water-cooling system.

Jan 1, 1969

By William L. Boyd, Eugene L. McCarthy, Laurance S. Reid

Proper control of the moisture content of natural gas is essential to reliable operation of gas transmission and distribution facilities serving northern markets. The moisture content of natural gas is usually determined by dew point measurement at the existing pressure. For any gas of constant moistrire content. the dew Point varies with the pressure. A correlation of the data of several investigators is prezented in graphical form by the authors. These data were correlated by the authors and F. M. Townsend, C. C. Tsao. M. I). Rogers. Jr.. and J. A. Porter. graduate students in chemi(.a1 engineering at the University of Oklahoma. Of articular interest are the hitherto unpublished low temperature data observed by Wickliffe Skinner. Jr., which are included in this correlation. PRESENTATION OF DATA The problem of interpreting water dew points, or saturation temperatures. of natural gas in terms of specific moisture con-tent has increased in importance during the past decade bec.arl.;e of extensive development.; in the transmission and petro-chemical phases of the natural gas industry. Virtually all gas transported to northern and eastern markets must be dehydrated to a low water vapor content to prevent hydrate formation in transmission and distribution lines and resultant interruption.; in gas deliveries. Complete dehydration is required in certain phases of tile petro-chemical industry involving low-temperature operations. It is a well-known fact that the water vapor content of pure hydrocarbon vapors and their mixtures at superatmospheric pressures cannot be predicted with accuracy by assuming validity of the ideal gas laws." Earlier interest in the general problem was concentrated on the water vapor content of pure hydrocarhons and hydrocarbon mixtures in the pressure and temperature ranges common to gas and oil producing reservoirs in order to obtain fundamental data for the improvement of production techniques and the furtherance of reservoir studies. Excellent data are published for pressures ranging from atmospheric to 10,000 psig and for temperatures ranging from 100° to 460° F4,9,10,11 and are found to be in close agreement. However, experimental data at high pressures and temperatures below 100°F are comparatively limited in scope. Experimental data in the lower temperature range have been reported by Laulhere and Briscoe.8 Deaton, et al,2,3 Hammerscllmidt,5,6 and wade," In general, the pressures employed in these investigations ranged from atmospheric to 1.000 psig while temperatures ranged from 32° to 120°F; i.e., the usual conditions encountered in gas transmission line operations, Additional data were reported by Russell, et al,12 at pressures as high as 2.000 psig and covering a rather narrow atmospheric temperature range. In 1947, Hammerschmidt published a correlation of all available data,&apos; in which the water vapor content of gases at saturation. under high pressure and low temperature. was predicted by extrapolation. In 1948, Wickliffe Skinner. Jr.. presented data on the moisture content of a low nitrogen content gas at low temperature and at pressures ranging upward to 1.500 psia.1-3 Comparison of Skinner&apos;s experimental data with the extrapolated data of Hammerscllmidt revealed an appreciable variation in the lower temperature range. emphasizing the need for a new correlation which would rely on Skinner&apos;s data at lower temperatures. Careful scrutiny of available data suggested that presence of an appreciable quantity of nitrogen in a gas mixture may affect its saturated moisture content so that data obtained from gases with more than three per cent nitrogen were not used in this correlation. CORRELATION OF DATA Data employed in this correlation are presented in Table I. The data of Dodson and Standing.4 McKetta and Katz,9 and Olds, Sage and Lacey10 were compared and found to be in close agreement so that the data of Olds. et al, re-plotted in a more convenient form by the Humble Oil and Refining Co.,&apos; were used for temperatures of 100°F and above. Skinner&apos;s data were used for temperatures below 40°F. Between these intermediate temperature limits, the data of Hammerschmidt.7 Wade" and extrapolated data of Olds. et al.1 were tabulated

Jan 1, 1950