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By R. F. Nielsen, R. G. Bentsen

Jan 1, 1966

By J. P. Neumann, L. Raymond

At temperatures near 1000°C, only the (112) (111) slip systems are operatire in tungsten. Therefore, the substructure introduced into the billet upon rleforming a single crystal by rolling at 1000 "C can be controlled by proper selection 01. processing ral'iubles. Using a reduction of 10 pct pel- pass, the (001)[110] and the (110)[001] crystals will deform by duplex slip rip to a 50 pet reduction in thickuess. These rolled single-crystal sheels are characlerized by anisotropic hardening, retention of ductility with warm working, lattice bending which is related to the conlacl (angle, and macroscopic dimensional changecs in the length bid not the width of the billet. When several slip systems become operative, a greater degree of work hardening is itztvoducetl into the crystal. This rolling- condition is characlerized by isotropic hardening, loss of ductilily with warm working, complex lattice distortions, and macro-scopic dimensional changes in both the length rind Width of the billel. IN tungsten, the {1 10}(111) slip systems are operative below room temperature,' while above 700°C only the {112{ (111) slip systems are observed.2,3 In the transition region, i.e., room temperature. both systems appear. It is the purpose of this investigation to show that tungsten single crystals deformed by rolling at a temperature where only one slip system is operative generate dislocation substructure which depends on the crystal orientation. For a specific crystal orientation. the resulting dislocation substructure can be further influenced by modifying the rolling procedure. Crystals oriented for multiple slip display less substructural sensi- tivity to modifications in processing techniques than do single crystals oriented for duplex slip. Under simple slip modes of deformation, very little work hardening is introduced into a rolled single-crystal sheet. Mechanical properties such as room-temperature strength. ductility, and hardness are used to confirm the existence of the different work-hardened conditions generated within the crystal by modified warm-rolling techniques. EXPERIMENTAL PROCEDURE Material. Single-crystal billets of four different crystal orientations. grown by the Arc-Verneuil technique. were ground to a size of 0.25 by 0.375 by 3 in. In terms of their rolling plane and rolling direction, the billets had the following orientations: (1101 [001 ] (110) [110] (001) [110] (001) [100] The actual orientation of all crystals was within 5 deg of the ideal orientations. The typical impurity content of the crystals is given in Table I. Polishing and Etching. Polishing was done elec-trolytically in a 20 g per liter aqueous solution of NaOH at approximately 10 v. It was established by the Laue back-reflection X-ray technique that the surface damage due to grinding and cutting operations with a diamond wheel did not exceed 0.001 in. Therefore after each cutting or grinding operation at least 0.002 in. was removed electrolytically from the surface in order to eliminate surface effects. By lowering the voltage to 3 v, subgrain boundaries and individual dislocations are identified in agreement with Berlec 4 where the etch-pit traces on a cubic plane form a square. The etching time was about 5 sec at room temperature. Rolling. Rolling was carried out on a Loma 2-high mill (Model 600). The peripheral velocity of the 6-in.-diameter rolls was 500 in. per min, with the surface temperature of the rolls about 400° to 450° C The billets were heated before each pass for 30 min in argon to 1000 C. Oxidation of the crystals during rolling in air resulted in a thin layer of greenish-yellow WO 3 This oxide was removed after each pass by immersing the crystals for a few minutes in a boiling NaOH solution. Prior to the initial rolling pass, a surface layer of 0.001 in. was removed by polishing. The crystals were then annealed in vacuum (10-4 torr) at 2400 C for 30 min. All crystals were rolled in the same direction; i.e., the same end was always introduced into the rolls. The rolling program was conducted in

Jan 1, 1965

By C. F. Lucks, W. D. Wood, H. W. Deem

Electrical ad thermal-conductivity measurements have been made on titanium and 6 titanium alloys. The following expression was derived for calculating thermal conductivity from electrical conductivity: K = 0.626 s T x 10-8 + 0.00497 where K = thermal conductivity, cal sec-1 cm-2 cm0C-1 s = electrical conductivity, ohm-]cm-1 T = temperature, deg Kelvin This expression gives calculated thermal conductivities that are not in error by more than 10 pct from the experimental values for A-55 titanium and the 6 alloys measured; namely, A-110AT, C-110M, C-130AM, Ti-6A1-4V, Ti-140A, and Ti-155A, which are representative of the presently available commercial a and a-ß titanium alloys. THERMAL conduction in a gas, liquid, or amorphous solid is accomplished by energy diffusion from molecule to molecule, a relatively slow process. For this reason, such materials have a low thermal conductivity. When a material is crystalline, there is in addition a heat transfer by a vibratory motion of the crystal lattice. It is the contribution of this lattice conduction that makes a crystal a much better conductor than a gas, liquid, or amorphous solid. Lattice conduction, however, does not account for the relatively enormous thermal conductivity of a metal. This is explained by the freedom of movement of valence electrons. These valence electrons drift in a metal in a direction toward a drop in electrical potential and, to a lesser degree, in the direction of a temperature drop in the metal. Since both the electrical and thermal conductivities of a metal depend upon the presence of free electrons, there should be some relatively simple relation between the two. Wiedemann and Franz in 1653 first discovered an approximate empirical relation between the electrical and thermal conductivities of metals at the same temperature. This ratio varies appreciably with temperature, and Lorenz later showed that by adding a temperature factor to the Wiedemann-Franz ratio the value of K/(s T) is constant, where K is the thermal conductivity, a the electrical conductivity, and T the absolute temperature. This Lorenz constant shows a greater variation for alloys than it does for pure metals, the ratio increasing slightly as the proportion of alloying elements increases. It has been found that a closer correlation between electrical conductivity and thermal conductivity can be obtained by means of an equation of the form K - A s T + B [1] where A and B are constants. In this equation the term AsT is the contribution of electronic conduction and B is the contribution of lattice conduction to the total thermal conductivity. EXPERIMENTAL MEASUREMENTS Electrical-resistivity and thermal-conductivity measurements on titanium and 6 titanium alloys serve as the basis for determining an equation of the K = AsT + B type for titanium alloys. Specimens—Table I shows nominal compositions of the 7 metals on which electrical and thermal conductivities were measured. The electrical and thermal-conductivity specimens for each alloy were taken from stock of the same heat and usually from adjacent sections of the same bar. All of the metals measured were in a mill-annealed condition. Methods—Electrical-resistivity measurements

Jan 1, 1959

By R. S. Olson

An analysis of the wash thickener-two stage filtration circuit was undertaken to quantitatively describe the circuit performance. On the basis of information developed in this study, the factors of major importance in reducing soluble loss are: filter wash, wash zone size, filter capacity, filter feed pulp dilution, blow back, filter cloth, water to repulp, water to primary wash, water to feed pulp and thickener underflow. The wash thickener-two stage filtration circuit has been used in many hydrometallurgical plants to separate solute from leach solids. As many as 20 to 30 plant operating variables determine the performance of the wash circuit and hence the soluble loss. The complex relationships of these variables, with each other and with soluble loss, make the evaluation of their effect on mill performance difficult. An analysis of this type of circuit was undertaken to quantitatively describe the circuit performance. THE CIRCUIT The diagram in Fig. 1 represents the operation of the wash thickener-two stage filter circuit. This circuit provides for counter current, cross current or for a combination of countercurrent-cross current operation. The feed pulp stream, J, is intended to include any solution or water, other than primary and secondary filtrate, which enters the wash thickener. Except for filter washing, the operations in the circuit are simple mixing operations which can be described by material balance. The concentration of solute in the filtrate and cake solution after application of wash liquor cannot be described by simple material balance. The displacement washing equation, derived by Rhodes1 and extended by Choundhury and Dahlstrom,2 appears to best describe this case of miscible displacement in porous media. In a useful form, it is

Jan 1, 1963

By H. J. de Haan, L. Schenk

Scope for Thermal Recovery in Shell's Heavy Oil Fields in Venezuela The main heavy oil reservoirs on the East coast of Lake Maracaibo (Fig. I), known as "Bolivar Coast", initially contained some 20 billion bbl of oil in place with gravities in the range of 10 to 15° API. The current total production rate is about 400,000 B/D. Since the recovery to date is on an average only 12.5 percent of the initial oil in place, these fields offer a vast potential for secondary recovery methods. The reservoirs are characterized by moderate depth (generally 1,000 to 3,000 ft; maximum 5,000 ft), good formation properties such as net oil sand thickness (50 to 300 ft), high porosity (30 to 40 percent) permeability (1 to 3 darcies) and oil saturation (initially about 80 percent) and high oil viscosity (100 to 10,000 cp in situ), all of which are favorable for the application of thermal recovery processes. Since 1957, steam drive, steam "soak" and underground combustion have been tested or are being tested in this area.1-3 This paper deals with a major steam drive test in the Tia Juana field. The test was commenced in Sept., 1961, on the basis of encouraging results of laboratory experiments and pilot field tests, which will be discussed briefly. Early Laboratory Investigation of the Steam Drive Process In 1956 a series of model experiments was carried out in the Koninklijke/Shell Laboratorium, Amster- dam, to investigate the displacement of heavy oil by steam.' The prototype studied was a horizontal, un-consolidated heavy oil reservoir, subjected to a linear steam drive. The model, representing a slab from this reservoir along the main flow direction, consisted of a steel tube filled with oil-saturated sand, provided with layers of rock at the top and bottom to simulate conductive heat losses to cap and base rock. Lateral heat losses, perpendicular to the main flow direction, were minimized by insulating the sides of the model. Heat flow and viscosity and gravity forces were scaled by taking the steam injection rate and sand permeability inversely proportional to the geometric reduction factor of the model, and using materials (oil, steam, cap rock, etc.) identical with those of the prototype. The main feature of the process was a frontal displacement mechanism that was observed within wide ranges of injection pressure and rate, oil viscosity, initial oil saturation and sand permeability. The high stability of this front can be attributed to the high volumetric steam flow rates, combined with the reduction in oil viscosity. High recoveries were obtained due to the low residual oil saturation of about 15 percent in the zone swept by steam. The latter value pertains to the specific test conditions (heavy oil, uncon-solidated sand) and may be lower for light oil, due to the effects of steam distillation. The applicability of this experimental approach is limited, as it does not take into account the fact that

Jan 1, 1970

By R. W. Parsons

The over-all apparent single-phase permeability of fracture-rock systems was studied using two different two-dimensional models. In a strict sense the results are applicable only to these models, yet may give some insight into real reseruoir behavior. The regular fracture-matrix model can have any number of regular fracture sets. All fractures within each set have the same orientation, width and spacing. The gross behavior is amlytically equivalent to that of an anisotropic permeable medium. In the heterogeneous fracture systems, individual fracture conductivities vary within a two-dinensioml network pattern. A computer program calculates the overall permeability after the conductivities are randomly placed in the network. The calculated permeability depends upon the distribution of these conductivities and the particular fracture pattern into which they are placed. Although detailed information on actual reseruoir fracture systems is not available, this study shows how some of the possible variables may affect obserued gross reservoir characteristics. INTRODUCTION Characteristics of reservoir rocks are determined by direct (core analysis) or indirect (logging and production tests) examination. Both methods, singly and together, are widely used in reservoir evaluations. For fractured reservoirs a problem exists in relating characteristics of cores to the in situ reservoir properties. Knowing fracture characteristics can be of value in determining production mechanisms. Because of the limitations of observation, the intimate details of a fractured rock system will never be known. One approach in analyzing fractures is to study the behavior of some conceptually simple models. The two models analyzed contain features which may be realistic, yet are mathematically tractable. Flow is considered in two dimensions only, with the plane of interest at right angles with the fractures. This concept represents the horizontal flow in a reservoir system with the fractures oriented vertically. Only single-phase, laminar flow is considered. The regular fracture-rock system permeability is calculable from a simple analytical expression. The heterogeneous system requires a computer program for calculating overall permeability.

Jan 1, 1967

By John Nunes, Frank R. Larson

Temperature-dependent functions of various ten-sile flour stress and fracture parameters were investigated on iron and low composition alloys of Fe-C, Fe-Cr, Fe-Mn, and Fe-Ni. Data were obtained over a range of test temperatures from 200" to -196"C at an initial strain rate of 0.01 min". It was found that the strain-hardening exponent, n, for the Fe-Ni alloys increased significantly at very low testing temperatures with increased alloy addition. Also, the stress and strain at fracture followed a predictable transitional type of behavior. The flour stress-temperature dependence was evaluated employing the relation: M where it is shown that composition can strongly influence the constant M. An empirical formula describing this effect is as follows: M = MI (equivalent at. pct Ni)-'" Some preliminay, tests were run on several commercial steels to test the generality of this relationship. One of the phenomenological explanations of the ductile-to-brittle transition encountered in bcc metals is based upon the difference in the temperature dependence of the flow and fracture stresses.' It states simply that the fracture stress is relatively insensitive to temperature and that the yield or flow stress rises rapidly with decreasing temperature so that, when the flow stress reaches the fracture stress, brittle fracture occurs without appreciable plastic deformation. This behavior is illustrated schematically in Fig. 1 where the ductile-to-brittle transition is shown to occur at two possible temperatures. The lowest temperature, TB, represents essentially completely brittle behavior while the higher temperature, TN, represents "notch" brittle behavior. Support for this theory is obtained when it is observed that fcc metals, which do not commonly have a ductile-to-brittle transition, also do not commonly exhibit any strong temperature de- pendence of the yield stress. This relationship of yield or flow stress behavior with the ductile-to-brittle transition has been generally observed for most metals representative of these two crystallo-graphic structures. One exception to this generalization appears in the case of tantalum where no apparent ductile-to-brittle transition has been observed. However, this may simply be an indication that this type of behavior is not directly related to the flow stress and that some other mechanism such as twinning must also be operative. A comparison of the typical temperature dependence of the yield stress of some representative metals is shown in Fig. 2. In the study of the temperature dependence of the strength of metallic materials, considerable ef-

Jan 1, 1963

By J. Geertsma, F. de Klerk

During the hydraulic fracturing treatment of an oil or gas well the liquid pressure in the borehole is increased until tensile stress in the surrounding rock exceeds tensile strength. Once a tensile fracture is initiated, it is penetrated by liquid from the borehole and fracture propagation under continuous hydraulic action takes place. The fracturing liquid carries a propping agent to ensure a highly permeable flow channel after pressure release. Field results range from failure to obtain increased production to outstanding success. In all cases, however, it unfortunately remains uncertain whether the values chosen for the operational parameters, such as injection rate, pumping time and fluid viscosity, were in fact the ideal ones. Though experience provides a lead, a more satisfactory way to predict results would seem to be to subject the fracture propagation process to a theoretical analysis that (1) makes the maximum use of the relevant physical information and (2) so simplifies the resulting calculations that the field engineer gets practical data that he can handle comfortably. We are attempting here to do this in connection with the prediction of fracture width and areal extent before pressure release. What remains of the fracture afterwards depends on the distribution of the propping agent between the fracture walls, and that is a separate story. Idealization of the Problem To keep the problem tractable, a number of simplify- ing assumptions have had to be made: 1. The formation is homogeneous and isotropic as regards those of its properties that influence the fracture-propagation process. 2. The deformations of the formation during fracture propagation can be derived from linear elastic stress-strain relations. 3. The fracturing fluid behaves like a purely viscous liquid; i.e., any peculiar flow behavior due to the addition of gelling agents or other additives is neglected. Moreover, the effect of the propping agent distribution on the distribution of fluid viscosity in the fracture is not taken into account. 4. Fluid flow in the fracture is everywhere laminar. 5. Simple geometric fracture-extension patterns are assumed — either radially symmetrical propagation from a point source (Fig. 1A) or rectilinear propagation originating from a line source (Fig. 1B). In the first case the periphery of the fracture is circular, in the second case it is rectangular. 6. A rectilinear propagation mode can be accomplished only by injection over a large perforated interval, thus forming a line source. Such a rectilinear fracture must therefore be located in the vertical plane. A circular propagation mode might be expected from injection through a narrow band of perforations. This forms a point source. Because gravity effects are excluded from our considerations, the fracture propagation plane may in this case assume any angle with respect to the wellbore as far as the

Jan 1, 1970

By Charles Jones

IN the winter of 1902, while occupying the position of mining and examining engineer for the Mountain Copper Co., Ltd., of Keswick, Cal., I had occasion to discuss with the General Manager, among other things, the question of the enormous waste of sulphur in smelting cupriferous, pyrite ore, and to cast about for means to utilize this waste or to render the fumes innocuous to vegetation. The decreasing rate of production of California farms, the consequent need of fertilizers, and the opportunity thus offered to utilize large quantities of sulphuric acid in the manufacture of superphosphates naturally brought the subject to the practical and commercial side of phosphates. I was informed that the company had made efforts to find phosphates in the West, without success. I advised as a start placing inquiries for phosphate deposits on the Pacific coast in the current mining ,journals. This was done, with the result that in January, 1903, from an advertisement in the Mining and Scientific Press we got track of a deposit in Rich county, Utah, through T.J . Wilson, of the Southern Pacific railroad in San Francisco. As soon as snow in the mountains would permit, in May, 1903, I undertook an examination of the property, with the result of recognizing the importance of the find, in spite of its lack of facilities for transportation at a commercial figure. On June 15, 1903, I concluded my report by saying, "This may be one of the world's deposits of phosphates." On Nov. 17, 1903, I concluded my report for the season in the following words : " I have now no hesitation in saying that I believe the Carboniferous formation so largely developed in the Wasatch mountains of Utah and the mountains of the Great Basin will prove to be one of the greatest storehouses of phosphoric acid in the world."

Jan 10, 1913

By L. R. Raymond

With the trend toward deeper and consequently hotter holes, measurements of drilling mud properties at atmospheric temperatures are becoming increasingly inadequate.' Both the prediction and control of down-hole mud properties depend in part upon our knowledge of temperatures in the wellbore. Consequently, a better understanding of factors that affect temperatures during circulation and trips could improve drilling operations. It was toward the goal of obtaining this understanding that this study was directed. Other investigators2 have studied the response of fluid temperature in the borehole during trips. However, all of these studies have used an assumed formation temperature profile at the conclusion of circulation and have provided no means to calculate this profile directly. In this study, the formation profile during circulation was calculated. Other investiga-tors3-5 have also studied bottom-hole temperature during circulation. However, they have developed neither general techniques for calculating the entire temperature profile in the system nor generalized methods for predicting bottom-hole fluid temperatures during circulation. Such techniques and methods have been developed and are discussed briefly in the following pages. Temperature Behavior During Circulation Circulation of fluid during the drilling operation is represented schematically in Fig. 1. The process of circulation has three distinct phases: (1) fluid enters the drill pipe at the surface and passes down the drill pipe; (2) fluid exits the drill pipe through the bit and enters the annulus at the bottom; and (3) fluid passes up the annulus and exits the annulus at the surface. To simulate the thermal behavior of the fluid in the system, each of the phases of circulation must be described mathematically. In Phase 1, the fluid enters the drill pipe at a specified temperature, TDo. As the fluid passes down the pipe, its temperature is determined by the rate of heat convection down the drill pipe, the rate of heat exchange between the drill pipe and the annulus, and time. Phase 2 of the circulating process merely requires that the fluid temperature at the exit of the drill pipe be the same as the fluid temperature at the entrance of the annulus; i.e., TD(L,t) = TA(L,l). Thus in Phase 3, the fluid enters the annulus at TD(L, t). As the fluid flows up the annulus, its temperature is determined by the rate of heat convection up the annulus, the rate of heat exchange between the annulus and the drill pipe, the rate of heat exchange between the formation adjacent to the annulus and the fluid in the annulus, and time. These rates of heat exchange and the time dependency of mud temperature are described by well known heat-flow equation.6 Consequently, as shown in the Appendix, the temperature profiles in the drill pipe, annulus, and formation can be obtained by solving Eqs. 1 through

Jan 1, 1970

By F. H. Buchella, J. F. Buchanan

The San Manuel copper deposit is located about 45 miles northeast of Tucson. The concentrator, smelter, administration building, and other plant facilities are located about seven miles southeast of the ,nine area at the new town of Sari Manuel as shown on Figure 1 (Sketch).

Jan 1, 1961

By H. S. Price, J. C. Cavendish, R. S. Varga

A numerical formulation of bigh-order accuracy, based on variational methods, is proposed for the solution of multidimensional diffusion-convection-type equations. Accurate solutions are obtained without the difficulties that standard finite difference approximations present. In addition, tests show that accurate solutions of a one-dimensional problem can be obtained in the neighborhood of a sharp front without the need for a large number of calculations for the entire region of interest. Results using these variational methods are compared with several standard finite difference approximations and with a technique based on the method of characteristics. The variational methods are shown to yield higher accuracies in less computer time. Finally, it is indicated how one can use these attractive features of the variational methods for solving miscible displacement problems in two dimensions. INTRODUCTION The problem of finding suitable numerical approximations for equations describing the transport of heat or mass by diffusion and convection simultaneously has been of interest for some time. Equations of this type, which will be called diffusionconvection equations, arise in describing many diverse physical processes. Of particular interest here is the equation describing the process by which one miscible liquid displaces another liquid in a one-dimensional porous medium. The behavior of such a system is described by the following parabolic partial differential equation:

Jan 1, 1969

By A. B. Parsons

Jan 1, 1971

By R. G. Bentsen, D. A. T. Donohue

The cyclic steam injection process has become the most widely applied and most successful thermal recovery technique in use today.1-4 Normally, steam stimulation is repeated several times during the life of a project. The problem is to select the optimum number and size of steam treatments so that the profits realized over the entire life of the project are maximum. Obviously, operating costs rise directly with the frequency and amount of steam injection. Operating efficiency, on the other hand, can be adversely affected if the amount and frequency of stimulation are insufficient. Thus arises a multistage decision problem; that is, a decision must be made at each sub-period (day, for example), as to whether steam should be injected, and, if so, how much. It is desirable that these decisions be made in such a way as to secure maximum net profit before taxes. This can be achieved by dynamic programming. To use dynamic programming, we must be able to predict not only the production rate-time curve resulting from a given stimulation, but also how changes in stimulation policy will affect this curve. In this study, the effect of steam injection on well performance is estimated on the basis of a simple model that takes into account both steady-state and transient flow. Oil production rate is calculated for both types of flow, and the larger of the two values is used. This allows the calculation to change to radial steady-state flow at such time as this mechanism becomes more effective than the transient mechanism. We propose to show how dynamic programming can be used to optimize the steam soak process with respect to net profit. For this, a mathematical representation of the steam soak technique is necessary. A further objective, therefore, is the formulation of a mathematical model capable of realistically simulating the physical process. Oil Production Response Model The advantage of using a mathematical model is its generality and ease of manipulation. However, the model must be an accurate representation of the physical process, for a solution derived from a model can be no better than the model itself. The question now arises as to how well the model should be expected to simulate reality. In general, the simplest model should be tried first, for additional accuracy is apt to require additional cost and time. Also, the search for a high degree of accuracy may yield only greater complexity and difficulty without yielding significantly better results. With this in mind, we kept our model as simple as possible, yet generally representative of the actual physical process. The number of state variables is limited to three, and stochastic variations in the parameters are ignored. As a consequence, use of this model should be restricted to cases in which the underlying assumptions are not severely violated. In

Jan 1, 1970

By Olav Mellgren

Part I. The interaction between potassium ethyl xanthate and lead salts has been studied thermo-chemically. It is shown that ethyl xanthate reacts with lead carbonate, basic carbonate, thiosulfate and sulfate according to principles of simple chemistry, whereas reactions with lead sulfite, metasulfite, basic thiosulfate and hydroxide at high pH are associated with secondary reactions. A new compound "xanthogen thiosulfate" is postulated. Part 11. Adsorption of ethyl xanthate on galena has been studied quantitatively and thennochemi-cally. It is shown that an ion-exchange mechanism governs the adsorption process and that the heat of adsorption of xanthate on galena is equivalent to the heat of reaction of ethyl xanthate with bulk lead salts. It is concluded that the entropy content of the surface "compound" on galena is different from that of a corresponding bulk lead salt. Alkali depression is in part shown to be due to the instability of the xanthate-galena system at high pH and to the formation of basic lead salts. Sulfate and carbonate ions are shown to have a stabilizing effect on the xanthate-galena system. PARTI. THERMOCHEMISTRY OF ETHYL XANTHATE AND OF ITS REACTION WITH LEAD SALTS In the past little attention has been paid to the chemistry of lead xanthate. It is known that xan-thates form slightly soluble compounds with lead and that suspensions of lead xanthates in alkaline solution decompose rather readily.' The solubility of lead ethyl xanthate is of the order of 2.6 x 10-6 moles per 1. At increasing pH the xanthate concentration of a saturated solution contains more xanthate. Thus at pH 11 this xanthate content is about 100-fold larger than at pH 7.1 Xanthates are known to be consumed when added to a suspension of slightly soluble lead salts such as lead sulfate and lead carbonate. It is unknown to what extent this xanthate consumption is due to a simple chemical reaction because, frequently, observations are made which reveal secondary reaction products in such reactions. Thermochemical study of the reaction between xanthate and lead salts offers a means to clarify the significance of these reactions as the enthalpy changes can be accurately predicted from heat of formation of lead salts in pure solution reactions. In the present work the heats of formation of lead ethyl xanthate from potassium ethyl xanthate and lead salts are determined and some thermochemical aspects of xanthate in solution are studied. The results of these investigations are presented in Part I. In Part II the heat of adsorption of ethyl xanthate on galena surfaces is presented. All enthalpy changes were measured directly in a microcalorimeter. Calorimeter: The calorimeter used for measuring enthalpy changes was similar to that used by Redinha and Kitchener2 which was based on a description by Derbyshire and Marshall.3 Other useful references4,5 are listed. A sketch of the calorimeter

Jan 1, 1967

By Francis Foley

INTRODUCTION DURING the summer of 1919, the late Dr. Henry M. Howe, then Chairman of the Division of Engineering of the National Research Council, organized a committee to obtain a better insight into the behavior of carbon steels under the influence of various treatments by a proper control of the time and temperature factors. During part of 1919 and 1920, work in connection with this investigation was carried on at Dr: Howe's laboratory at Bedford Hills, N. Y. During 1921 there was an enforced hiatus in the work, occasioned by the illness which resulted in Dr. Howe's death in 1922. At that time one of the present authors compiled the results of the work which had been done and this was published in 1923.1 Following the publication of this work, it seemed desirable to carry on in the same manner an investigation of steel of C 0.75 per cent., which steel had not been as fully treated as had the other steels of C 0.34 and 0.52 per cent., used in the published work. Furthermore, certain unusual results have been obtained in the treatment of C 0.52 per cent. steel by quenching and drawing, and repetition of this part of the work seemed advisable. This has been done during the past year at the School of Mines and Metallurgy of the University of Missouri at Rolla, Mo., by a cooperative undertaking of the School and the Bureau of Mines, working in conjunction with the Committee on Heat Treatment of Carbon Steels of the National Research Council. The present paper is a report of the results obtained in this work.

Jan 2, 1926

By W. H. Boyer, J. W. Gabelman

The concept of metal zoning has long been recognized (Spurr, 1907, 1923; Emmons, 1924, 1926; Lindgren, 1933; Rateman, 1950), although it has been considered indistinct for most epithermal districts. The geometric relation of barren zones of hydrother-mally altered rock to ore deposits was emphasized in the work of Lovering (1941, 1949, 1950), Sales and Meyer (1948, 1949, 19501, Burbank (1941, 1950), Schwartz (1939, 1950), and Kerr (1947). Lovering (op. cit.) and Sales and Meyer (op. cit.) emphasized the consistent presence of barren alteration envelopes enclosing individual ore bodies, particularly of the vein type. Schwartz (1950) noted a difference between the distribution of alteration zones described by Lovering and by Sales and Meyer, as compared with those associated with the porphyry copper deposits of the Southwest. The disseminated deposits of the Southwest usually occur within large bodies of altered rock whereas most veins do not. In the following discussion the mineralization process is conceived of consisting of two distinct phases: pre-ore nonmetallic alteration and metallization. In the present investigation the position, size, and shape of all known hydro thermally altered areas and the position, size, and metal type of all known ore deposits were plotted on base maps of southwestern and west-central Colorado (Figure 1). The maps indicate a generally consistent geometric relation between altered and metallized areas. The addition of alteration to the pattern of metal deposits establishes a temperature zoning pattern of much greater clarity than that formed by the epithermal metal deposits alone, and allows a more precise definition of mineral belts. The center of strongest mineralization is indicated to be the area of greatest barren alteration, and metal deposits are grouped about it both under structural control and crudely in response to temperature zoning. The combination of an area of strong alteration and associated marginal clusters of metal deposits is defined as a mineral district. The strong similarity in individual deposits, in groups of different types of deposits, and in the alteration-metallization relation in districts throughout the region implies that a single metallogenic province is represented in southwestern and west-central Colorado. The occurrence of deposits in Tertiary voi-canics indicates a late Tertiary metallogenic epoci., although an early Tertiary epoch is known locally as at Ouray. Patterns formed by mineral districts can be

Jan 1, 1961

By Gorr W. W., Wyche E. H, R. Smith

The combination of high strength and corrosion resistance of cold-worked 18 Cr, 8 Ni steel has been advantageously utilized for some time, particularly in aircraft and rail car structures. There are, however, certain limitations on the use of such materials because the high strengths can be obtained only by cold-working, limiting the available products to sheets, strip, wire and tubes. The authors sought to overcome these limitations by resorting to precipitation-hardening, which has been used so successfully in nonferrous metallurgy but only to a limited extent in iron-base alloys. Accomplishment of this objective not only overcame the limitations, but also effected certain improvements in mechanical and other properties. This paper is an account of the development by Carnegie-Illinois Steel Corporation of a precipitation-hardening 18-8 stainless steel (called Stainless W‡ and tentatively identified as type 322). A description is given of its composition and metallurgical characteristics, heat-treatment, physical and mechanical properties and corrosion resistance. Development of the New Steel For a considerable length of time the authors were unable to determine the mechanism of the precipitation-hardening process that had been noted by Ffield18,19 in 18-8 Ti or 18-8 Cb after cold-working and reheating to moderately elevated temperatures. All known variables were exhaustively studied, but with little success. However, results began to indicate that chemical composition was the most important variable, particularly the ratio of austenite-forming to ferrite-forming elements. The investigators then focused their attention upon the composition, and, in particular, upon the element titanium and its mode of alloying in the presence of other elements. A heat was obtained that could not be brought to the softness level of annealed 18-8. The response to cold-straining and aging* was very marked by previous standards, and, more important, cold-straining was found to be entirely unnecessary to produce the precipitation-hardening effect. The chemical composition of this heat was: C, 0.06 per cent; Mn, 0.54; P, 0.016; S, 0.016; Si, 0.58; Ni, 7.28; Cr, 17.60; Ti, 0.90; Al, 0.17. For some time the development work, particularly on composition, was carried

Jan 1, 1947

By J. R. Kyte, L. A. Rapoport

The material balance equation for partiai or complete 1:trter-drivc reser1,oir.s been re-arranged to include a pressure irrferferencr ternr. This pressure interfernce term was ohtained from the theory established hy Morinda. A .successful progranl deissed to solve the resrclritlg c,qrration in a few hours on a nleelitr .sizeti, digital compuier. No prior knowdelge of the properties of the eqrrifer is required in the solution. 7' ri~rl calculations areatle using various assumed con!binuiions of value of the constant expretsing the qquifer properties correspoinds to the best fit ohtained between observed and calculated field history. Details of the method of calculaion are illus trated by an example. INTKCDUCTICN A method 01' calculating the material balance equation for a partial water-drive reservoir completed in an aquifer has been described in the literature." Pressure interference i'rc,m other pools iocated in the same nquiucr is not taken into account in this solution. When present, the pres- sure interference effect must be included in order to make a complete performance analysis. A correction for this effect has been developed using the theory cstahlished by Mor-tada.' Manual calculation of the material balance for water-drive reservoirs is a formidable task. Such manual ca1culation when interference eflects are includcd would be impossible to completc in any reasonable time period. However, a medium-sized stored program, digltal conlputer can he used satisfactorily. The method is described in the following sections. THECKETICAL CONSIDEKATIOhS The material balance equation for a reservoir producing by partial or total water drive, as proposed by Van Everdingen, This relationship is linear for Z/a from which thc slopc, Z, and the intercept, N, can be obtained by the least-squares method from the data points. It is not necessary lo know the aquifer properties to uktain oplimum values tor 2nd IV. Various assumptions are made tor At,,: where 11 is production time, seconds (oilfield between the equal successive time intervals into which the history is divided. t,, h It, times the number of equal time periods from i.e.. the total dimen-sionless time interval from It is noted that the dinlensionless time interval, At,,, involves all the relevant aquifer properties. Accordingly, any assunlption of is an assumption of the combined aquifer properties which pertain to the solution of the equation. Deviations of the data points from a straight line arc calculated for each assumption of and the value of A, correspond ing to the minimunl deviation is chosen as the optimum solution. This method is described in Ref. 1 and 2. Thc material balance solution is usually made with an initial assumption that the reservoir being studied is located in an infinite aquifer from which there are no other withdrawals. Deviation of the points by amounts greater than can be attributed to inaccuracies in field data may be the result of: (1) boundary effects of a limited aquifer, (2) pressure interference from othcr pools completed in the .sarne aquifer, and (3) a combination of these effects. Differentiation of these effects can be made only on the basis of geologic data. Pressure interference from other fields will result in a pressure drop at the original oil-water boundary having an interference component, The measured instantaneous pressure drops at the oil-water

By P. Sanchez-Mejorada

GEOLOGISTS who are acquainted with the mines of northeastern Mexico realize that the most important lead-silver replacement deposits of the province are confined to a single formation. But since the formation is several hundred meters thick, the author has determined the relative position of the lead mantos in the belief that this information will prove useful in the search for new mines. This article describes the stratigraphic location of lead-silver replacement deposits known in several mines situated in a region comprising part of the states of Coahuila and Nuevo Leon. The area studied extends for 200 km* (125 miles) from east to west and 70 km (45 miles) north to south. Metallogenic Province: The most important metallic deposits of the region have the following common characteristics: 1) The orebodies occur as manto replacements of calcareous sediments. 2) The horizons that have contributed large tonnages of ore are in similar positions in the corresponding stratigraphic columns (as it will be shown later on). 3) Lead is the most important metal in the ores. Silver is commonly present in small amounts. Occurrence of zinc is dependent on the degree of oxidation of the primary sulfides. 4) A large proportion of the total production has been in the form of oxidized ores. 5) The deposits are located on anticlines. Rocks of Cretaceous age crop out over large areas of the states of Nuevo Leon and Coahuila. forming part of a belt that extends to the south along the eastern Sierra Madre. The sediments are cut by a small number of intrusive stocks ranging in characteristics from rhyolite to diorite. The most prominent structural feature of the region is a series of folds trending northwest-southeast. Faulting is not conspicuous in the region, although a major fault zone is found farther East.' The physiography closely reflects structural features, with mountains formed by anticlines and valleys conforming with intermediate synclines. Narrow valleys have also been developed along the axes of many anticlines, where solution of limy sedi- ments and erosion have proceeded along axial tension fractures. Stratigraphy: Rocks of the Upper Cretaceous are exposed in only a small percentage of the total area. Generally they have been eroded away from the mountains and are covered by recent talus and alluvium in the valleys. Humphrey' has published an excellent paper describing the Cretaceous formations of the Sierra de los Muertos, a short distance west of Monterrey. A brief summary of these formations is given below to convey an overall picture of the stratigraphic sequence that prevails just south of the area under consideration. Upper Cretaceous Indidura: Essentially thin shaly sediments. Cuesta del Cura: Limestone in thin wavy beds

Jan 1, 1959