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THIS chapter and Chapter 19 deal with the heat quantities involved in open-hearth steelmaking, including the thermal efficiency of the furnace as a generator of high-temperature heat, the heat storage in the steel and slag produced and in the furnace walls, and the heats of the various chemical reactions involved in combustion, in the formation of slag, and the refining of steel. The fundamental laws to be considered are the first two laws of thermodynamics as applied to problems involving sensible and potential (or latent) heat only: 1. Heat input equals heat outflow plus storage. 2. Heat may be transferred only from a hotter body to a colder one. The first of these laws relates to the various heat quantities or the heat balance of the process. No one has as yet made an open-hearth heat balance that came out almost exactly balanced. The cause probably lies in the difficulties of accurate temperature and flow-rate measurements at the high temperatures involved and the inherent complexities in flow distribution and air leakage present in any real open-hearth furnace system. Some idea of the magnitude of the heat quantities involved can be obtained by a brief, crude outline of the heat balance of a 90-ton heat of steel. We will assume a 60 to 70 per cent hot- metal charge in a fairly fast working and only moderately efficient furnace, burning fuel oil, with a fuel consumption of around 4 million Btu per net ton of ingots produced. The time from start of charge to tap is 9 hr. During this period, the oil burned represents 360 million Btu and the sensible heat in the preheated air at the port ends is 117 million Btu, so that the total heat input at the ports is 477 million Btu. Heat stored in the steel and slag at the end of the heat, plus the various amounts absorbed by certain bath reactions, amounts to a total of 195 million Btu, but 120 million of this is supplied by the heat in the hot metal and by various heat-evolving reactions in the bath,

Jan 1, 1951

By J. O. Glanville, L. H. Haley

Ice frozen from a dilute chemical solution is mechanically weaker than ice frozen from pure water. This phenomenon is the basis of a practical method for reducing the strength of a mass of frozen coal. If a chemical additive is applied to moist coal prior to its shipment during freezing weather, the resulting frozen coal can be more easily broken than in the absence of the chemical additive. This greatly expedites the unloading and handling of coal during winter. There has been considerable research into the nature and mechanical strength of ice frozen from various solutions. In this paper, literature relating to this process as well as literature relating to the chemical treatment of coal and mineral particulates is reviewed. Some important articles are discussed and speculations made about the nature of the ice-weakening process. A laboratory evaluation of the effects of chemical additives on the mechanical strength of ice and frozen coal has been made. An apparatus designed for this purpose is described, and some results obtained with it are discussed.

Jan 1, 1983

By C. H. Li, R. J. Stokes, T. L. Johnston

Dislocation half-loops, artificially introduced by sprinkling with carborundum, were subjected to stress using three-point loading. The different stages of loop expansion and multiplication were then correlated with the macroscopic stress-deflection curve. Loop expansion started at approximately one-third of the "yield stress," defined here as the motivation stress. Above one-half of the "yield stress" simple multiplication commenced while about two-thirds of the yield stress gross multiplication developed short slip-line segments. These values were not affected by the age of surfaces exposed to both dry and wet air. Slip was not detected on unsprinkled crystals below two-thirds of the "yield stress." Thus the stress to activate intrinsic sources, defined here as the activation stress, was approximately twice the motivation stress. This relationship was independent of the strain rate used. It is concluded that lattice resistance takes the form of a viscous drag rather than a static type of force. THE importance of surface condition and environment as one of the more significant factors controlling the mechanical properties of ionic solids has recently received renewed attention.1-4 In some materials, notably the alkali halides, exposing freshly cleaved specimens to the atmosphere results in a progressive hardening and embrittlement of the crystals. This has been attributed to the surface layer becoming "aged," thereby restricting the motion of dislocations in such a way that pileup and eventually fracture results. It is necessary therefore in studying the mechanical properties of ionic crystals to inquire first into the density and distribution of dislocations in the normal cleaved surface and to understand the role these dislocations play in the onset of plastic flow. Knowledge of the effect of environment on this behavior will then assist in understanding the mechanism of embrittlement on aging. In the work reported here a method is described for studying the initiation of plastic flow from dislocation sources in the surface of magnesium oxide crystals. Preliminary results are described of the influence of surface age on this behavior. EXPERIMENTAL TECHNIQUES The magnesium oxide used in this investigation was obtained from the Norton Co. and had a nominal purity of 99.5.pct. Single-crystal specimens, having dimensions typically 1/4 by 1/8 in. cross section and 1 in. in length, were prepared by cleavage over (100) planes from the parent crystal. They were deformed under three-point loading with 3/4 in. spacing between the two end supports and a constant rate of deflection at the center of 0.001 in. per min. The maximum strain rate therefore was 1.5 X 10-5 sec-1. Reasons for choosing this particular form of loading will become apparent in a later section. In addition, a number of confirmatory type tests have been performed at higher loading rates where the maximum strain rate was increased to 1 x 10-3 sec -1. Following deformation the crystals were etched to reveal the dislocation distribution. In a previous paper5 we described a satisfactory etching solution consisting of 5 parts of saturated ammonium chloride, one part of sulfuric acid, and one part distilled water. Immersion of the crystals for 1/4 hr at room temperature developed reproducible conical etch pits at the points where dislocations emerged through the surface. It should be mentioned that dislocations freshly introduced by room temperature deformation gave sharply pointed etch pits which generally distinguished them from the almost flat-bottomed pits obtained on "grown-in" dislocations. The distinction is obvious in the photomicrograph included in Fig. 5(b). Annealing crystals at 1000°C for 12 hr on the other hand gave sharper etch pits on the grown-in dislocations and the distinction was no lower -possible; a similar observation has been reported for lithium fluoride. We have succeeded furthermore in chemically polishing magnesium-oxide crystals. Boiling in fresh 85 pct ortho-phosphoric acid for only 1 min resulted in a microscopically smooth surface which could again be etched to reexamine the dislocation distribution. This boiling time was sufficient to remove the surface damage introduced by cleavage (see next section). SURFACE DISLOCATION SOURCES There are a number of ways by which dislocations may be introduced into cleaved surfaces to act later

Jan 1, 1960

By Paul Queneau

FEW of us who waded ashore on the Norman beaches realized the importance of coal to a successful invasion. General Eisenhower and his staff had been aware of the essential need for coal and an able Solid Fuels Section had been set up under the direction of Colonel Robert P. Koenig, of Indiana. This organization met the requirements of the invading armies on their march to the Rhine. East of the Siegfried Line enemy territory, the Army Engineers were called upon for assistance. When the Engineers were advised that, in addition to their normal duties, they were to occupy and place in operation the coal mines in the Twelfth Army group area, plans were drawn up overnight and action was initiated immediately. The Sixth Engineer Special Brigade, a versatile outfit which made a notable record D-Day on Omaha Beach, was selected to handle the operation. Within 48 hours of the new assignment an advance command post was set up cm the west bank of the Rhine at Homberg, just below German-held Duisburg. The 368th Engineer General Service Regiment was assigned to the Brigade, and the British 44th Pioneer Group, including specialist personnel, was also attached. This large British unit was added because most of the mines would shortly come within the British zone of

Jan 1, 1946

By K. G. Wikle, W. W. Beaver

A general survey of the mechanical properties of commercially pure beryllium fabricated from powder by vacuum hot pressing and other consolidation methods is presented. The effect of fabrication method, grain size, strain rate, and directionality upon both room and elevated temperature tensile properties is reported. BERYLLIUM metal, in spite of its rather restricted use, has been the object of attention for many researchers in the past half century. However, such work was performed on special experimental lots of metal made in small quantities by a variety of reduction methods. Not until 1946 was there a substantial production of beryllium metal, and not until 1950 was there a steady production of a commercially standard beryllium in the United States. This output was both the result of a requirement of the Atomic Energy Commission for a high grade beryllium of consistent quality and the development of a powder metallurgy process, by the Brush Beryllium Co., known originally as Process Q, which yielded a fine grained beryllium suitable for fabrication. Because this powder metallurgy product, known as QMV, superceded other types of metal made previously and represents the great majority of beryllium in use today, it seems worthwhile to present the results of studies on the mechanical properties of this metal as currently made. To the design engineer and the metallurgist, beryllium has extremely interesting properties. It is as light as magnesium alloys while having a stiffness modulus 40 pct greater than steel and a strength-weight ratio superior to titanium and aluminum alloys and aircraft steels. The melting point is high, 1287°C (2348°F), and it has good corrosion resistance both in air and water. Also, it is highly transparent to X-rays and has good heat and electrical conductivity (electric conductivity is greater than 40 pct of Cu). To the atomic energy program beryllium is considered a valuable material because of its low neutron-capture cross section and high neutron-scattering cross section which make it a good moderator and reflector for the lower velocity neutrons. A major technical difficulty limiting the use of beryllium, especially in structural applications, has been its notch sensitivity and consequent room temperature brittleness. Kaufmann, Gordon, and Lillie1 have reported their work on the mechanical properties of beryllium performed from 1946 to 1950. They studied the room and elevated temperature properties of cast and extruded beryllium and extruded electrolytic flake, Table I. Cast and extruded alloys of 85 to 99 pct Be were tested also. They found that extruded metal developed good strength and appreciable ductility in the extrusion direction and that thermal treatment and alloying provided little improvement in mechanical properties. They concluded that preferred orientation and fine grain size were the means of obtaining optimum tensile properties in beryllium. Other investigators have measured and commented on one of the most striking mechanical properties of beryllium, namely, its abnormally low Poisson's ratio.2 Udy, Shaw, and Boulger3 presented the latest published survey on properties of beryllium but their information is based only on published data available before April 1949 and cites little information on metal fabricated by powder metallurgy

Jan 1, 1955

By K. E. Gray, M. S. Seth

Equations of elasticity for transversely isotropic, axisymmetric, homogeneous, porous media exhibiting pore fluid pressure were formulated. Using an analogy between thermal and porous body stresses, it was shown that the solution for a transversely isotropic porous body may be obtained by incorporating body forces and the stresses due to a boundary load into the corresponding solution for the thermal stress problem. Equations of elasticity ad the thermal analogy method were used to determine transient horizontal, tangential, and vertical stresses and radial displacement in a semi-infinite cylindrical region when either a constant pressure or a constant rate of flow is maintained at the wellbore. The vertical and tangential displacements are zero from the conditions of the problem. A numerical analysis was made of the solutions obtained by using a digital computer to determine the relative influence of each system variable. Considering rock as a porous body with internal fluid pressure generally gives results significantly different than considering the rock to be nonporous; the directional character of rocks leads to significant differences as compared to results based upon the common assumption of isotropy. Stress gradients are high near the wellbore but die out away from the well. Radial stresses are compressive or neutral, whereas tangential stresses are tensile, neutral or compressive, depending upon the boundary conditions and physical properties of the system Vertical stresses are compressive for an unbounded system. For constant wellbore injection rate, the vertical stress is proportional to the rate of fluid injection and decreases with time, whereas the radial and tangential stresses increase with time. At a given location, the radial displacement generally is very dependent upon time. INTRODUCTION A realistic appraisal of the state of stress in subsurface rock formations would be of considerable interest and use to the petroleum industry. For example, knowing the state of stress in proximity to a wellbore would be of fundamental importance in designing a fracturing operation or, more important, of clearly understanding the conditions necessary to produce rock failure of desired dimensions and geometry. Understanding conditions necessary for rock failure at the wellbore would also be of utility in a preventive sense. For example, borehole stability is an important consideration for many rock formations, and knowledge of the stress state at and near the wellbore under conditions of substantial pressure gradient due to fluid flow would be of great value. When fluid flows through a porous body which is initially at some uniform stress level, the following forces generate stresses at any point in the body. (1) Forces due to nonuniform pressure distribution. With increasing pressure the elements of a body are compressed. Such compression cannot proceed freely in a continuum when the pressure is not uniform throughout, and thus, stresses due to flow of fluid are set up. (2) Pore fluid pressure. This gives rise to normal stresses whose value at any point is the product of areal porosity and the fluid pressure. Although the fluid exerts uniform pressure, the stresses it creates in an anisotropic body may not be the same in all directions since the areal porosity in an anisotropic porous body is a direction-dependent quantity. This consideration leads to the concept of directional porosity. (3) Body Forces. The flow of the moving fluid imparts a force to the rock matrix, the magnitude of which depends upon the pressure

Jan 1, 1969

By K. D. Hester, A. W. Fletcher

A nickel-copper sulphide concentrate was treated in a pilot plant at Warren Spring Laboratory during 1961, by a hydrometallurgical roast-leach-solvent extraction process devised to cleanly separate the metal values and produce acid sulphate liquors containing the metals. It is shown that 86 pct of the nickel and 95 pct of the copper could be leached from the calcine, after a sulphatizing roast on finely ground flotation concentrate. Iron was removed from the leach liquor by limestone neutralization with a small loss of values. Copper and nickel were separated by solvent extraction with naphthenic acid in kerosene after partial neutralization of the iron-free liquors with ammonium hydroxide. Hydrogen sulphide and chlorine were used to remove zinc (and residual copper) and cobalt impurities respectively. The recovery of pure copper and pure nickel, by electrowinning, from the acidic solvent extract strip liquors finally produced, appears technically feasible. An economic analysis of production costs shows that small, geographically isolated, nickel-copper sulphide deposits cannot usually be worked profitably by established processes. The requirements for profitable operation on a comparatively small scale could possibly be met by a flotation-roast-leach process. Two difficulties, obtaining satisfactory extraction of nickel from a sulphide concentrate and separating the copper and nickel in solution, have prevented the previous use of this method. A solution to the first problem, dissolution of the nickel, was described in a recent paper by Thornhill.1 It was shown in this paper that copper and nickel in a flotation concentrate could be oxidized to water soluble sulphates by roasting in a fluidized bed with added salt cake. Workers at the Warren Spring Laboratory have shown that the separation of copper and nickel can be accomplished by solvent extraction using a relatively inexpensive carboxylic acid, naphthenic acid. Moreover, the mineral acid required to strip values from the loaded solvent could be produced, and the metals recovered, by electrowinning; thus the latter section of the process was regenerative. The removal of iron from the leach liquor and the elimination of impurities such as zinc and cobalt before nickel electrowinning would be necessary to complete the flowsheet. The process under investigation could therefore be summarized (Fig. 1) as follows: 1) Flotation to produce a bulk sulphide concentrate. 2) Fluidized bed roasting to sulphate the nickel and copper minerals. 3) Leaching of roaster calcine to extract soluble nickel and copper. 4) Precipitation of iron from the separated leach liquor by air oxidation after the adjustment of pH and temperature. 5) Recovery of copper from the iron-free Liquor by pH adjustment and liquid-liquid extraction. 6) Purification of the copper raffinate by removing zinc and residual copper as insoluble sulphides and cobalt as cobaltic hydroxide. 7) Recovery of nickel from the purified liquor by pH adjustment and liquid-liquid extraction. Laboratory and pilot plant studies detailed below, were carried out at the Warren Spring Laboratory, to test the feasibility of each one of the unit processes and to obtain preliminary plant design data. FLOTATION The ore was an altered basic rock containing concentrations of magmatic sulphides.

Jan 1, 1964

By C. K. Ferguson, J. A. Klotz

This paper describes experimental investigations conducted at the California Research Corporation's model oil well. The first part describes filter loss from several drilling muds through bore hole walls during mud circulation and drill string rotation. The effect of mud properties and drill string rotation with mud circulation is described. Filtration from a bore hole full of drilling mud, not circulating, but under pressure for extended time periods, is also discussed. The second part describes filter loss to permeable formations from beneath a drilling bit where filter cuke has no opportunity to develop appreciable thickness. If potential flow theory is applied to predict filtrate invasion from this hole bottom, targe invasions arc calculated. But model well experimentation shows that filtrate invasion from the hole bottom is controlled by mud particles that penetrate the formation ahead of the bit. This experimentation provides data to estimate the effect of mud particle penetration on fluid loss to formation. The third part presents an estimate of mud filtration during drilling of a well. INTRODUCTION As oil wells are drilled by the rotary method, drilling mud circulates up the annulus between drill pine and well wall. Drillers adjust mud density so that the pressure at the bottom of the mud column is several hundred psi greater than the pressure of reservoir fluid. As a result of this pressure difference, the liquid part of the mud filters into the rock around the bore and mud solids deposit as a filter cake on the well wall. For many reasons the petrogleum industry, within the past 20 years, has spent much money and energy to determine the volume of mud filtrate that enters rock around the well bore and dedicated much research effort to reduce this volume. Among the reasons for attempts to determine the volume of mud filtrate and to reduce this volume are the following: 1. If filtrate damages the permeability of oil sand, the resultant damage to oil well productivity will depend on the distance that the filtrate invades the oil sand; reduction of filtrate volume may, therefore, increase well productivity. 2. Filtrate that penetrates shale sections may cause the shale to swell and to slough into the well bore. Uncontrolled sloughing may stick drill pipe. Reduction in filtrate volume may reduce drilling trouble. 3. Electric log resistivity curves are changed by invasion of a mud filtrate; the change depends on the depth to which filtrate invades. Knowledge of this depth is necessary before resistivity logs can be interpreted accurately. For these reasons, specifications the place an upper limit to drilling mud filter loss are now written into almost all drilling programs. These specifications are based on APT Recommended practice 29, Standard Field Procedure for Testing Drilling Fluids,' which describes a static filtration test operated at 100 psi filtration pressure and at ambient temperature. Although this test is adequate for mud control, it cannot be used to compare filtration properties of different muds. Schremp and Johnson' showed, for example, that mud with a low API filter loss does not necessarily have low filter loss at bottom hole temperature and pressure. Also, no information has been available about the effect of bottom hole mechanics (mild circulation, drill string rotation, and bit action) on mud filtration. This paper discusses filtration data measured in the California Research Corporation's model oil well, which models closely oil well bottom hole geometry and hydrodynamic conditions. The filtration processes that

Jan 1, 1955

By N. J. Grant, K. M. Zwilsky

A series of copper-alumina dispersion strengthened alloys were prepared using three different copper and two different alumina powder sizes. Improvements in strength of up to ten times that of pure copper were found in room-temperature as well as elevated-temperature stress-rupture tests. Conductivity values remained from 70 to 90 pct that of pure copper. The best alloys were based on the finest metal powder (1 p) and contained from 7.5 to 10-0 vol pet of 0.018 or 0,033 p alumina. DISPERSION strengthening of metals consists of strengthening a metal matrix by the addition of oxides or other refractory constituents, followed by strain hardening, in order to reinforce the base material and extend its temperature range of application. Since the discovery of SAP by lrmannl and Von zeerleder2 in 1949, many investigators have reported data obtained on a variety of metal-inert oxide alloys.3-7 The present work deals with the mechanical mixing of copper and alumina powders. While several techniques of introducing the second phase have been investigated to date, mechanical mixing so far has been recognized as the simplest, least expensive, and most universally applicable technique that can be used to obtain an ultrafine dispersion of inert particles. In the present case, the effects of changing the metal particle size, the oxide particle size and the volume percent of oxide were investigated. This work is an extension of a previous study.6 EXPERIMENTAL PROCEDURE The starting materials were three different grades of copper powder and two different alumina powders. The three metallic powders were -74 µ(- 200 mesh) electrolytic copper powder consisting of irregular equiaxed particles having a normal screen distribution and analyzing 99.5 pct Cu, and two powders having a 5-µ and 1-µ particle size, average, respectively. The latter powders were produced by the hydrogen reduction of purified sulfate solutions at elevated temperature and pressure and were furnished by the Sherritt Gordon Mines, Ltd. The alumina used was obtained from Godfrey L. Cabot Co., under the trade name of Alon C, one batch of powder having a particle size of 0.018 µ, the other a particle size of 0.033 µ. The crystal structure of these alumina powders was found to be cubic gamma. Each batch of powder was mixed in a Waring Blendor for a total of 15 min, followed by a low-temperature reduction in hydrogen and vacuum compacting in cylinders which were hydrostatically pressed at 35,000 psi to give a compact that could be handled conveniently. Six of the compacts were hydrogen sintered at 900°C while the remaining four were sintered at 1000°C. Subsequently, all compacts were hot extruded at 760°C with a reduction of area ratio of approximately 20 to 1. Evaluation of alloys included density and resistivity measurements, room-temperature tensile tests, stress-rupture tests at 450°C plus one other temperature per alloy, hardness tests, microstruc-tural examination, X-ray analysis of the dispersed phase after dissolving the metal phase, and oxidation studies on two of the alloys. A vacuum-melted, wrought copper rod was tested together with these alloys for comparison purposes. RESULTS Table I is a summary of the compositions, sintering temperatures, densities and conductivity values of the ten alloys prepared. All alumina additions are given in volume percent, and will be referred to as

Jan 1, 1962

By R. J. Schilthuis

In 1929, Coleman, Wilde, and Moore1 undertook an investigation of the theoretical decline in reservoir pressure as related to the production of oil and gas. The most important part of this work was presented in an equation defining the relationship between the reservoir pressure, the quantities of oil and gas produced, the oil and gas content of the reservoir, and the properties of the reservoir fluids. With this equation, it appeared that, with sufficient data, it would be possible to calculate the oil content of the reservoir and predict quantitatively the effect of gas-oil ratio on the decline of reservoir pressure. Needless to say, such an expression would be highly important in evaluating fields and in arriving at a choice of production methods to be used. Unfortunately, at the time these investigators published their work, there were not sufficient data available to permit application of the equation. The technique of measuring reservoir pressures had not been developed, gas measurements were uncommon, oil and water production records were in most cases inadequate, and little was known of the properties of the complex hydrocarbon mixtures making up the oil and gas in the reservoirs. For these reasons, little additional work of a similar nature could be done. However, during the past four years many data have been systematically accumulated on reservoir pressures and the properties of oil and gas, and it is now possible to use these data in furthering the studies on the behavior of oil and gas reservoirs. It is the purpose here: first, to present the derivation of a modified form of the equation given by Coleman, Wilde and Moore, which will permit the calculation of what later will be defined as the "active oil" content of a reservoir; second, to derive formulas for calculating the reservoir-energy changes that occur during the course of production, and finally, to discuss the limitations and application of the equations developed.

Jan 1, 1936

By R. J. Schilthuis

In 1929, Coleman, Wilde, and Moore1 undertook an investigation of the theoretical decline in reservoir pressure as related to the production of oil and gas. The most important part of this work was presented in an equation defining the relationship between the reservoir pressure, the quantities of oil and gas produced, the oil and gas content of the reservoir, and the properties of the reservoir fluids. With this equation, it appeared that, with sufficient data, it would be possible to calculate the oil content of the reservoir and predict quantitatively the effect of gas-oil ratio on the decline of reservoir pressure. Needless to say, such an expression would be highly important in evaluating fields and in arriving at a choice of production methods to be used. Unfortunately, at the time these investigators published their work, there were not sufficient data available to permit application of the equation. The technique of measuring reservoir pressures had not been developed, gas measurements were uncommon, oil and water production records were in most cases inadequate, and little was known of the properties of the complex hydrocarbon mixtures making up the oil and gas in the reservoirs. For these reasons, little additional work of a similar nature could be done. However, during the past four years many data have been systematically accumulated on reservoir pressures and the properties of oil and gas, and it is now possible to use these data in furthering the studies on the behavior of oil and gas reservoirs. It is the purpose here: first, to present the derivation of a modified form of the equation given by Coleman, Wilde and Moore, which will permit the calculation of what later will be defined as the "active oil" content of a reservoir; second, to derive formulas for calculating the reservoir-energy changes that occur during the course of production, and finally, to discuss the limitations and application of the equations developed.

Jan 1, 1936

By N. K. Chen, C. H. Mathewson

Single crystals of high purity aluminum of various orientations were carefully documented after plastic extension. Special attention was given to the formation of slip lines, deformation bands, and asterism. An explanation for the geometry and mechanism of formation of deformation bands is considered. WHILE the general process of plastic extension of face-centered cubic metals is well understood,' the accompanying structural changes due to slip and rotation are far more complex than ordinarily assumed. In the case of stretched single crystals of aluminum, the complicated behavior is especially marked by the formation of deformation bands, as first indicated by Collins and Mathewson." Such bands were believed by them and also by others,".'7 who have discussed banded structure in general, to represent one of the important modes of lattice reorientation and to be intimately connected with the recrystallization process. Yet, despite their fundamental importance to the understanding of the mechanism df both plastic deformation and recrystallization, practically no study of the crystallographic features of these bands in their relationship to the conventional slip process has been attempted. This paper describes part of an extensive investigation on the structural behavior during plastic deformation of aluminum single crystals and is especially concerned with the characteristics of deformation bands. The investigation of the subsequent re-crystallization of deformed aluminum single crystals will be discussed in a later publication. Experimental Procedure Single crystal specimens of 99.996+ pct pure aluminum, Yz in. in diam and 5 to 6 in. in length were made both by the Bridgman method5 nd by a modified temperature gradient method.'* Crystals were selected in which the lineage deviation did not exceed 2"; i.e., as determined from the back-reflection Laue X-ray photograms. These crystals were radiographed to insure that no internal porosity was present. The orientations showed good coverage of the whole area of the Taylor and Elam triangle.' Orientations of the crystals were obtained by the back-reflection Laue technique described by Greninger." Crystals so selected were tapered very carefully in a lathe to obtain a linear decrease in diameter from 0.500 to 0.350 in. along a gage length of 3 in. This is considered desirable because it permits a strain gradient to be introduced in a single specimen at one initial orientation. The advantages of tapered crystals for studying the development of slip lines and recrystallized grains have been pointed out by previous investigators." The cold-worked layer resulting from the machining operation was removed by alternate etching in aqua regia and careful polishing with 2/0 emery paper until undistorted Laue back-reflection spots were obtained. A homogenization treatment at 600 °C for 24 hr was then introduced to insure the removal of residual stress. Two of the crystals so prepared were also checked by use of a glancing angle technique. Using a copper target, at 30 kv and 10 microamperes, a monochromatic beam was positioned at right angles to the axis of the crystal about which it rotated. The time of exposure was 24 hr. From these X-ray photograms, it was concluded that the present method of preparation of single crystals is satisfactory. Following this procedure, the crystals were elec-trolytically polished in a 2:l solution of methyl alcohol and concentrated nitric acid. Intermittent

Jan 1, 1952

By E. L. Claridge, K. S. Lee

Areal sweep efficiency of oil displacement by enhanced-viscosity water exhibiting pseudoplastic behavior was measured in a Hele-Shaw model representing one-quarter of a five-spot pattern. The pseudoplasticity of polymer solutions and the velocity distribution in the five-spot pattern produced a condition under which the mobility ratio between the displacing and the displaced fluid could not be assigned a single value. Instead, the movement of the displacement front is governed by local mobility ratios which are also time dependent. The areal sweep at breakthrough with polymer solutions was poorer than the sweep obtained with Newtonian fluids of comparable viscosity. However, the areal sweep at 1 PV throughput was greatly improved as compared to flood water without polymer. It was also demonstrated that, even after the oil-cut had declined to a low value during a regular waterflood, switching to polymer flood efficiently swept out the oil remaining in the model. INTRODUCTION The behavior of fluid displacements in isotropic porous media for various patterns of injection and production wells has been extensively investigated.1-7 These investigations all concerned Newtonian fluids, i.e., the viscosity of each fluid was constant regardless of flow rate. The generally unfavorable influence on areal sweep efficiency of higher mobility of the displacing fluid as compared to the mobility of the displaced fluid has been established for both miscible and immiscible fluids. The principle was also established that a close correspondence exists between miscible and immiscible flood front behavior,2, 3 although oil recovery in a waterflood at unfavorable mobility ratio may be less than that observed in a miscible displacement at the same mobility ratio. This is true even when oil recovery is expressed on the basis of movable oil. The reason is that oil saturation only slowly achieves its final value behind the water-flood front in accordance with the Buckley-Leverett8 simultaneous flow relations. It is convenient to use miscible displacements for laboratory simulation of waterflood frontal advance since the interfacial tension forces which are negligible in proportion to viscous forces on a reservoir scale9 are thus made nonoperative in the laboratory model. For miscible displacements, the Hele-Shaw type of model adequately represents a porous medium so long as the appropriate scaling rules5-10 are observed in its design and operation. During simulation of waterflood front behavior in the laboratory by using miscible displacements, the behavior of connate water may ordinarily be disregarded since it is usually indistinguishable from flood water in this process. However, when the flood water is deliberately thickened to improve the mobility ratio between water and oil. the effect on the sweep efficiency due to generation of a connate water bank during the process must be considered. In a uniform porous medium, such a bank is generated11 and efficiently displaced by injection of thickened water.l2 The oil originally in-place at the start of the waterflood is then displaced by connate water followed by thickened water. If the flood water must be thickened to obtain a favorable mobility ratio, the mobility of the oil phase is appreciably less than that of the connate water. Hence, the oil phase is inefficiently displaced by the connate water bank, and a considerable proportion of the oil comes in contact with and is displaced by the thickened waterflood front' A recent study 12 of five-spot displacements using miscible Newtonian fluids in which connate water banks of various sizes were simulated shows that, for connate water banks as large as 40 percent of 1 PV, major improvements in sweep efficiency resulted from use of a thickened

Jan 1, 1969

By T. D. Yensen, R. K. McGeary

While we have not been primarily interested in the determination of hydrogen in the alloys that we have been dealing with, we arc very glad to cooperate in this symposium on sampling and analysis for hydrogen, as we can never tell when we may find it desirable to perform such analyses. Vacuum-fusion Method Our primary interest has been oxygen and carbon, in the analysis of which we think we have become very proficient. Our oxygen-analyzing apparatus is of the vacuum-fusion type (Fig. I). This employs Dr. Derge's type of graphite cruciblc and slit sleeve, with graphite powder between, for heat insulation (Fig. 2) supported in a clear quartz bulb connected to the Pyrex glass system by means of a carefully made ground joint. The latter is kept cool by means of an air blast from a circular copper tube surrounding the joint. The crucible is heated by high-frequency induction and the 24 one-gram samples successively dropped in from the horizontal tube at the top by means of a magnet. The gases (H², CO, N2) are passed through the CuO catalyst held at 300°C. (converting CO to CO²I, H² to H²O) and the CO² and H2O frozen out in the main liquid air trap, while N2 is evacuated. At the end of the operation, shown by the termocouple vacuum gauge indicating a pressure of 10-4 mm. Hg, the analyzing system is isolated by means of the mercury cutoffs, and the CO² and H2oare determined by transferring first the CO2 and then the HzO to the small trap at the right. This is done by placing liquid air on the small trap, then removing the liquid air from the large trap for one minute, which is sufficient to evaporate the Co2 and transfer it to the small trap. The CO2 is then measured by closing the mercury cutoff at the extreme right, removing the liquid air from the small trap, warming it up to room temperature, adjusting the mercury level to one of the three marks on the glass tube (corresponding to three volumes calibrated so that I mm. Hg of CO² corresponds to 0.001, 0.002 and 0.010 mg., respectively, of oxygen) and finally reading the pressure. Liquid air is now replaced on the large trap, the mercury cutoff at the right opened, transferring the COz back to the large trap. The cutoff to the pumps is then opened, the liquid air removed for one minute, thus evacuating the CO², the pumps again cut off and the H2 O transferred to the small trap as before, except that it is now necessary to warm the large trap with a Bunsen burner in order to evaporate all the H2O. This requires about three minutes, as the inner tube must be heated to at least 100°C. In order to prevent H²O from being adsorbed on the glass walls, the glass tubing beyond the catalyst (i.e., to the right in Figs. I and 3) is kept heated to about 150°C. by means of Nichrome ribbon as shown in Fig. 3. For a I-gram sample the above amounts of oxygen (0.001, 0.002 and 0.010 mg.) 35

Jan 1, 1945

By K. M. Fagin, D. W. Carter

Six new oil fields were discovered in the East and East Central Texas district during 1942. The Coke and Quitman fields, in Wood County, at this time appear to be the two most important oil discoveries for the year. The. four other oil fields discovered were Concord, in Anderson County; Kildare, in Cass County; Weiland (ClubLake), in Hunt County; and Larissa, in Cherokee County. The Rodessa lime in the Chapel Hill field, Smith County, provided the only new oil zone in older fields. The Hawkins field, Wood County, was the most active in drilling operations, 125 new wells being completed during the year. The Chapel Hill field tied the Coke field for second place with 30 completions each. The third most active field was Kildare, with 10 completions. Like the other oil-producing districts of the country, wartime restrictions reduced the number of oil and gas-well completions to 265 in 1942, compared with 964 completions in 1941. This represents a drop of 72 per cent and only a little more than one half enough to replace the 437 producing wells abandoned in the district during the year. Tn addition, the number of producing wells temporarily shut down nearly tripled, far two principal reasons: (I) the rule of the Petroleum Administration for War preventing operators from equipping more than, one well on each 10 surface acres with pumping or artificial-lift equipment, and (2) the Railroad Commission's issuance of various orders permitting the transfer of allowable for wells having high water-oil ratios and high gas-oil ratios to other wells capable of producing the same with less waste of reservoir energy. No changes were made in prices of crude oil in the district during 1942. Production and Probation The district produced 158,928,281 bbl. of oil and distillate during 1942, compared with 163,566,695 bbl. during 1941, which represents a decrease of 3 per cent. The East Texas field produced 120,680,595 bbl. of oil, compared with 130,377,793 during 1941; a reduction of 9,697,198 bbl., or 7.4 per cent. The production of this field represents 75.9 per cent of the district total, compared with the 79.7 per cent that it furnished in 1941. The district had an estimated basic daily oil allowable of 623,242 bbl. on Dec. 31, 1942. Approximately 31.8 per cent of the production in Texas during 1942 was supplied by this district, compared with 33 per cent during 1941- Changes in the annual production of newer and flush fields in this district are attributable either to a difference in the number of wells producing during the year or to changes in basic allowable and number of shutdown days due to shifting market dconditions brought on by the war. All regularly prorated fields in the district were shut down 123 days. Major exceptions were the East Texas field, closed128 days; Hawkiis, shut down 106 days; and Cayuga, Sulphur Bluff, Talco, and Rodessa, which

Jan 1, 1943

By D. W. Carter, K. M. Fagin

Six new oil fields were discovered in the East and East Central Texas district during 1942. The Coke and Quitman fields, in Wood County, at this time appear to be the two most important oil discoveries for the year. The. four other oil fields discovered were Concord, in Anderson County; Kildare, in Cass County; Weiland (ClubLake), in Hunt County; and Larissa, in Cherokee County. The Rodessa lime in the Chapel Hill field, Smith County, provided the only new oil zone in older fields. The Hawkins field, Wood County, was the most active in drilling operations, 125 new wells being completed during the year. The Chapel Hill field tied the Coke field for second place with 30 completions each. The third most active field was Kildare, with 10 completions. Like the other oil-producing districts of the country, wartime restrictions reduced the number of oil and gas-well completions to 265 in 1942, compared with 964 completions in 1941. This represents a drop of 72 per cent and only a little more than one half enough to replace the 437 producing wells abandoned in the district during the year. Tn addition, the number of producing wells temporarily shut down nearly tripled, far two principal reasons: (I) the rule of the Petroleum Administration for War preventing operators from equipping more than, one well on each 10 surface acres with pumping or artificial-lift equipment, and (2) the Railroad Commission's issuance of various orders permitting the transfer of allowable for wells having high water-oil ratios and high gas-oil ratios to other wells capable of producing the same with less waste of reservoir energy. No changes were made in prices of crude oil in the district during 1942. Production and Probation The district produced 158,928,281 bbl. of oil and distillate during 1942, compared with 163,566,695 bbl. during 1941, which represents a decrease of 3 per cent. The East Texas field produced 120,680,595 bbl. of oil, compared with 130,377,793 during 1941; a reduction of 9,697,198 bbl., or 7.4 per cent. The production of this field represents 75.9 per cent of the district total, compared with the 79.7 per cent that it furnished in 1941. The district had an estimated basic daily oil allowable of 623,242 bbl. on Dec. 31, 1942. Approximately 31.8 per cent of the production in Texas during 1942 was supplied by this district, compared with 33 per cent during 1941- Changes in the annual production of newer and flush fields in this district are attributable either to a difference in the number of wells producing during the year or to changes in basic allowable and number of shutdown days due to shifting market dconditions brought on by the war. All regularly prorated fields in the district were shut down 123 days. Major exceptions were the East Texas field, closed128 days; Hawkiis, shut down 106 days; and Cayuga, Sulphur Bluff, Talco, and Rodessa, which

Jan 1, 1943

The opening session of the Institute was held at the rooms of the American Society of Civil Engineers, No. 4 East 23d Street, VicePresident R. W. Raymond in the chair. After a short introductory address by the chairman, the following names were presented by the Council for election as members and associates of the Institute. They were unanimously elected : MEMBERS. Abbott, James W.,.....Lake City, Col. Abbott, J. J., Jr.,...... Lake City, Col. Bartlett, J. C.,.....Cambridge, Mass. Billings, G. H.,.....Boston, Mass. Blake, Frank C.,.....Lafayette College, Easton, Pa. Dewey, Fred. P.,.....Lafayette College, Easton, Pa. Douglass, Samuel T.,. .. . Ann Arbor, Mich. Emmons, 9. F.,.....New York City. Engle, George U.,.....Philadelphia. Harrington, Dr. Bernard J.,. .. Montreal, Canada. Hayden, Wm. B.,.....Columbus, O. Hill, Leslie C.,.....Capelton, Quebec, Canada. Land, W. J.,......Atlanta, Ga. May, Wm. A.,.....Scranton, Pa. Mills, James E.,.....St. Louis, Mo. Moore, Charles W.,.... Montezuma, Ind. Page, William Byrd,.... Lexington, Ky. Putnam, Douglas, Jr.,.... Ashland, Ky. Richards, Henry,.....Dover, N. J. Boberts, Percival, Jr.,. .. . Philadelphia. Sackett, S. G.,......Brooklyn, N. Y. Schley, Wm. S.,.....Atlanta, Ga. Setz, Gustav,......Mine La Motte, Mo. Talhutt, John H.,.....Lexington, Ky. Torrey, Herbert G.,.... U. S. Assay Office, New York City. Wernlitz, Fred. W.,..., Cartersville, Bartow Co., Ga. Wiestling, Geo. B.,.....Mont Alto, Franklin Go., Pa.

By F. Weinberg

Lead single crystals have been deformed in tension over the temperature range of 4.2°K to the melting point. Changes in flow stress resulting from temperature cycling and strain rate cycling have been measured as a function of temperature for crystals of different orientations and purity. It was found that the flow stress ratio, after correcting for the temperature dependence of the shear modulus, decreased progressively with temperature above approximately 0.5Tm. The activation energy calculated from the high-temperature portion of the curve was found to be markedly higher than that of self-diffusion. For single glide crystals, the corrected flow stress showed an increase above 0.5 Tm before decreasitzg with temperature. This increase is attributed to static recovery occurrittg during temperature cycling. THE temperature dependence of the flow stress, based on temperature cycling and strain rate cycling, has been extensively investigated,' and on the basis of these results dislocation models of the work-hardening process have been proposed. In general, the flow stress is divided into two parts, ts, the short-range interaction term, which is only effective at low temperatures and which decreases with increasing temperature, and TG, the long-range stress term, which is independent of temperature after allowing for the temperature dependence of the shear modulus. The observations demonstrating that tG/µ is independent of temperature were generally carried out at low temperatures to minimize recovery effects. Several investigations have been reported on flow stress measurements at high temperatures2"5 which demonstrate that TG/µ does not remain constant at temperatures above 0.5Tm (where Tm is the melting temperature of the material in OK). Specifically, Hirsch and warrington3 carried out temperature cycling tests at two strain rates on single and polycrystalline aluminum up to 0.8 Tm and on polycrystalline copper. For aluminum they found that the flow stress ratio (the flow stress at temperature T2, divided by the flow stress at the reference temperature T1 in one temperature cycle) dropped progressively with increasing temperature above 0.5Tm. From the slopes of the high-temperature portions of the curves, they determined an activation energy for the deformation process of 1.6 ev (at best) which they considered was in agreement with the activation energy of self-diffusion, 1.35 ev. Calculations of the activation volume demonstrated that the deformation was not controlled by dislocation climb. They proposed a mechanism in which the rate-controlling process at high temperatures was due to the rate of move- ment of vacancies away from jogs, i.e., that of self-diffusion. Results of Lucke and Buhler4 on single crystals of aluminum confirmed this conclusion. They measured the critical resolved shear stress of aluminum over a wide range of temperature and strain rates. They found that the temperature dependence of the critical resolved shear stress was similar to that of the flow stress ratio, as determined by Hirsch and Warrington, and from their data calculated an activation energy for high-temperature deformation of 1.35 ev identical to that of self-diffusion. More recently Gallagher5 has carried out a detailed investigation of the temperature dependence of the flow stress ratio of copper, silver, and gold. In all cases, he found that the flow stress ratio, after adjusting for the shear modulus temperature change, drops at high temperatures. The activation energies he determined were found to be appreciably higher than the activation energy of self-diffusion of the material being considered. The flow stress ratio was found to be dependent on the orientation of the material, and, in addition, an anomalous increase in the flow stress ratio for copper, oriented for single glide, was observed above 0.5Tm. The purpose of the present investigation was to measure the critical resolved shear stress, the flow stress ratio, and the strain rate sensitivity of lead, primarily as a function of temperature. The results should indicate whether, following Lucke and Buhler, the critical resolved shear stress of lead has the same temperature dependence as the flow stress, and, following Hirsch and Warrington, whether the activation energy for high-temperature deformation in lead is the same as that of self-diffusion. Lead deforms as a normal fee material,6'7 is available in high-purity form, can readily be grown as single crystals, and, for this investigation, has the very considerable advantage of having a low melting point, 327°C. The observations of the critical resolved shear stress of lead have been published elsewhere.' EXPERIMENTAL PROCEDURE The experimental procedure was essentially the same as that used in the critical resolved shear stress measurements.' Single crystals of 99.999 pct (59) and 99.9999 pct (69) lead were deformed in tension with a table-model Instron in a silicone oil bath above room temperatures and in a cooled methyl alcohol or liquid-nitrogen bath below room temperatures. The test specimens were rectangular in section, 0.65 by 0.33 cm, and had a 5-cm gage length. The specimens were grown as single crystals with tapered ends, which fitted into matched tapered grips for testing. To obtain the flow stress between two temperatures, specimens were first deformed approximately 1.0 pct at the higher temperature. The test was then stopped, the load relaxed, the oil bath removed without disturbing the specimen, the grips and specimen cooled with a fan and then immersed in liquid nitro-

Jan 1, 1969

By Jack Haptonstall

INTRODUCTION The mines of western central Mexico historically contributed a profusion of gold and silver for the treasury of Spain and later provided sources for financing the Mexican War for Independence and the Mexican Revolution. The western coastal and barranca (cliff) tribes were hunters and extremely hostile, and the Spaniards were not able to penetrate many of the rich districts of their rugged homeland until the mid-1700's. This was more than 200 years after Cortez began the Inquisition by defeating the Aztecs and their allies in a decisive battle in the great city of Tenochtitlan (present day Mexico City). The Spaniards had a voracious appetite for silver and gold, and it was inevitable that they would finally subdue the natives and commence mining activities. Described in this paper are some of the precious metal mining activities in the southern half of the State of Sinaloa and the western half of the State of Durango (Figure l), and specifically those mining activities in the area controlled by the company with which the author was associated for 14 years, Minas de San Luis, S. A. de C. V., the parent company of which is now Industrias Luis Min, S. A. GENERAL DESCRIPTION Geography, Logistics and Climate The most spectacular of the physiographic provinces, the western Sierra Madre Occidental is the cliff or "barranca" province, the

Jan 1, 1983

By S. K. Asunmaa, W. D. English, N. A. Tiner, W. A. Cannon

This paper discusses the reaction of metal surfaces with fluorine. Fluorination reactions result in the formation of metal fluoride films which are "passive" toward further reaction of the metal with fluorine. These films are very adherent, and do not easily detach from the substrate metal by mechanical flexing or thermal shock. Exposure of passive films to a humid atmosphere produces hydrated metal fluorides which cause secondary fluorination reactions upon reexpo-sure of the metal surface to fluorine. The surface films formed range from 10 to 30A in thickness and they pow at the expense of surface oxide films. The apparent film formation is completed rapidly in 15 to 30 min on stainless steel and nickel surfaces. On copper and on Monel surfaces, the film at first grows rapidly, then increases slowly over an extended period of time. Passive films are formed at all fluorine pressures in the range from 0.1 to 1.4 atm at room temperature. ALL metals react when exposed to fluorine. These reactions generally produce surface films which consist of metal fluorides. The rate of reaction is largely determined by the extent to which these films are protective. Although there is an extensive literature concerning reactions of oxygen with metals, there are very few investigations reported concerning fluorine-metal reactions. Brown, Crabtree, and ~uncan' investigated the kinetics of the reaction of gaseous fluorine with copper metal which had been freshly reduced in hydrogen. The reaction rate was independent of pressure over the range from 6 to 60 torr. A logarithmic rate law was obeyed in the temperature range from 25" to 300" ~. There was some deviation at higher temperatures which could have been the onset of a parabolic law. The calculated film thicknesses ranged from about two molecular layers, 10A, for 5 hr exposure at room temperature to thirty-five molecular layers for 5 hr exposure at 200" . The authors concluded that no single mechanism could explain all the observations. O7Donnell and spatkowski2 studied the reaction of fluorine with copper at 450°C at pressures from lo to 133 torr. The reaction was found to be pressure -dependent and followed a logarithmic rate law. It was not entirely diffusion-controlled, and fluorine was thought to be the migrating species in the reaction. Miscellaneous metal-fluorine reactions were investigated by Haendler et ~1.~ Reaction products were identified but no rate data were determined. Air Prod- ucts and Chemicals, Inc., have conducted an investigation of reactions between fluorine and various metal powders at room temperature and 85° C. Fluoride film thickness as a function of time of exposure was reported on the assumption that the reaction takes place between fluorine and metal to form the normal metal fluoride. Surface areas of the powders were only estimated so the relative film thicknesses may not be exact. The data showed reaction rates which were generally logarithmic in character, the rate of film growth virtually ceasing after a few hours exposure time for some alloy powders. The effect of moisture on fluoride films was also investigated by measuring additional reaction with fluorine after exposure of passivated powders to atmosperic moisture. The fluorination of iron was studied by 0'~onnell~ at temperatures from 225" to 525" ~ and at pressures ranging from 20 to 200 torr. In all ranges, the reaction followed a logarithmic rate law and was dependent on the square root of the gas pressure. The author concluded that fluorine gas passes through pores in the film. As the film grows, the blocking of pores leads to a rapid decrease in reaction rate; hence a logarithmic rate law is observed. Jarry, Fischer, and Gunther' investigated the mechanism of the reaction of fluorine with nickel at about 600" to 700°C. On the basis of the metallographic examination of fluoride scales growing on the nickel and from separate radioautographic data, it was claimed that fluorine is the migrating species in the reaction. This is in sharp contrast to the growth of oxide films on nickel where it has been shown that nickel ions migrate through the scale to the gas-solid interface to react with oxygen. Few investigations have been reported of the reaction of fluorine with metal oxides. Such investigations should be of great significance for a better understanding of passivation in view of the ubiquitous oxide films on technical alloys. Haendler et al.3 studied the reaction of fluorine with oxides of copper, tin, titanium, zirconium, and vanadium. Copper (I) oxide reacted as follows in the temperature range 150" to 300"~: temperature above 300" ~ was required for the CuO to react to form additional copper fluoride. Ritter and smith7 also investigated the reaction of fluorine with copper (11) oxide. An oxide powder comprised of spherical particles with a fairly high surface area was reacted with fluorine, starting at room temperature and increasing to 100° C over a period of 3 or 4 hr. The initial reaction was slow until the fluoride film thickness reached about to or 15R at which time the reaction rate accelerated, then decreased again. Most of the kinetic data was obtained during this final phase of reaction. The authors conclude that the film grows slowly at first until the stresses developed in the distorted lattice are sufficient to rupture the initial

Jan 1, 1969