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By L. Guttman, C. S. Barrett, J. S. Bowles

THE transformation from the face-centered cubic (Al) to the face-centered tetragonal (A6) structure in certain alloys of the indium-thallium system reported in the preceding paper1 exhibits many interesting crystallographic and metallo-graphic features, most of which presumably are similar to those of other cubic to tetragonal transformation such as, for example, the one which occurs in the chromium-manganese system,2 the one which, judging by microstructures and X-ray pat-terns,3 probably occurs in the copper-manganese system, the ones accompanying ordering in FePt,4 Copt,&apos; and AuCu,5 and the transformation near 115°C in barium titanate.6,7,8 If, as mentioned in ref. 1, the transformation is second order, the phases in equilibrium do not differ in composition, and it is both possible and likely that the mechanism is a diffusionless one. The present paper reports the results of a detailed study of the indium-thallium transformation and presents a theory for the atomic movements of the transformation which accounts for the observations. Experimental Crystallography of Transformation Markings The transformation from cubic to tetragonal in the indium-thallium alloys produces microstruc-tures of the type illustrated in fig. 1. These structures are observable either as relief effects produced on a smooth surface by the transformation, or after polishing and etching. These microstruc-tures are markedly similar to those found in copper-manganese alloys: iron-platinum alloys," and barium titanate,7,8 where it has been demonstrated that the lamellae are parallel to the (101) planes of the original cubic crystal. That the observed lamellae in indium-thallium alloys are also parallel to the (101) planes was proved by the following analyses performed on single grains in polycrystal-line samples containing 20.75 atomic pct T1. A study of the microstructures of a number of specimens revealed the fact that in many specimens the transformation markings continued unchanged in direction across the (111) interfaces of annealing twins. This at once demonstrates that the lamellae are parallel to a plane that is common to both parent and twin orientations, i.e., a plane in the zone <112>. This conclusion is compatible with the lamellae being parallel to (101) planes. To make a more complete determination of the habit plane of the lamellae, two grains were selected in which annealing twins ({Ill) twins) had been present in the high-temperature modification (cubic). The traces of the annealing twins, and of the transformation markings in both parent and twin crystals, were plotted together in stereographic projection, and a parent-twin pair of orientations was found that accounted for all lamellae as (101) planes. The projection of one of these twinned grains is reproduced in fig. 2. In view of these results the probability of there being another solution for the habit plane remote from (101) is very small, but to explore the possibility that the habit plane deviates slightly from (101), a more precise analysis was undertaken. In this, the orientation of a grain in the cubic modification was determined from a Laue back-reflection photograph taken with the sample at 90°C. The traces of the lamellae that formed in this grain on cooling were plotted in the stereographic projection

Jan 1, 1951

By Emmanuel P. Papadakis

Ultrasonic velocity measurements have been made to study the preferred orientation in cube-textured copper. Methods applicable to thin specimens were employed since the specimens were necessarily of sheet material. The measured velocities in various directions in the sheet differed from the corresponding values in single-crystal copper by 1 to 6 pet. The distribution of the deviations indicated that the align-ment of the (001) planes with the rolling plane was better than the alignment of the [100]and [010] directions with the rolling and transverse directions. Ultrasonic pole figures (velocity us orientation) are shown to be useful in the study of preferred orientation. THIS paper describes one set of experiments in a continuing study of preferred orientation in worked metals. This study has been undertaken to investigate the fundamental properties of metals when used as propagation media for ultrasonic waves. Many such materials are of current or potential use in ultrasonic delay lines. Fundamental studies on ultrasonic propagation parameters such as velocity, attenuation, and diffraction (beam spreading) are of importance in the design of delay lines, in the development of nondestructive testing methods, and in the study of materials themselves. Preferred orientation in worked poly-crystalline metals influences all three above-mentioned parameters, and hence is of particular importance. When polycrystalline metals are subjected to mechanical working, they develop textures dependent upon their crystal structure and the symmetry of the working operation.&apos; The texture consists in the alignment of the crystallographic axes of the grains in preferred directions with respect to the symmetry axes of the working operation. Since the grains are elastically anisotropic, the elastic moduli of worked metals are anisotropic. Hence the velocities of elastic waves in worked metals depend on the directions of propagation and polarization. The worked metal may be thought of as taking on the elastic symmetry of a single crystal: so it possesses the same number of independent elastic moduli as the crystal class it simulates. In general, a worked metal does not adopt the crystalline symmetry of its own grains. For instance, most rolled sheet becomes effectively orthorhombic while all bar stock and wire develop hexagonal symmetry. However, certain metals with cubic crystal structure develop a cube texture upon rolling and annealing.= Nearly perfect alignment of [100]-type directions with the rolling direction, transverse direction, and rolling-plane norma1 can be achieved in certain fcc metals and alloys. These cube-textured rolled metals provide an excellent opportunity to test preferred orientation by means of elastic waves, since a worked metal with 100 pct cube texture would have elastic moduli identical to the moduli of its constituent metal. It is the purpose of this paper to present the results of an investigation upon cube-textured copper. Ultrasonic waves were used. The methods of measurement and the experimental results on the effective moduli will be given. The ultrasonic measurements will be shown to complement X-ray pole figures for the determination of preferred orientation in worked metals. EXPERIMENT To study cube - textured material, it was necessary to use thin-sheet material since a severe reduction in gage (95 to 99 pct) is necessary to produce cube texture. Special ultrasonic methods were needed to investigate the thin material at megacycle frequencies. A) Materials. The cube-textured material tested was a copper alloy containing 1 pct Zn. Specimens already measured for Young&apos;s modulus4 by Alers were kindly supplied by him. The specimens were slabs 3.00 by 0.25 in. cut from sheet 0.047 in. thick. The orientations of the long axes of the specimens with respect to the rolling direction were taken in 15-deg steps from 0 to 90 deg. B) Measurements. Two distinct experiments were performed to measure the phase velocity in these specimens. One measured the shear wave velocity for propagation in the 0.25-in. direction and polarization in the 3.00-in. direction. The other measured the velocity of both shear and longitudinal waves propagating in the thickness direction in the sheet. 1) Plate-Mode Measurements. The velocity of the zeroth-order shear mode5 was measured in the 0.25-in. direction in each strip. The specimens were ground thinner over half their length to assure that the first-order shear mode would be cut off below 6 Mc per sec, leaving the zeroth-order nondispersive shear mode as the only propagating mode. Piezoelectric ceramic transducers of 5 Mc per sec resonant frequency poled in their long direction were solder-bonded to the edges of the thin part of the slabs as in Fig. 1 after these edges had been made flat and parallel by fine grinding. These transducers produced waves polarized in the 3.00-in. direction and propa-

Jan 1, 1967

By AIME AIME

Further details of the 97th meeting of the Institute, at Spokane, have been sent to members in the Special Circular of May 8, 1909, and for convenience a summary of the additional information is given later in this announcement. In spite of the present small number who have joined the party, final arrangements have been made to complete the itinerary given in the circular. It is greatly to be desired, both in behalf of the Institute and in recognition of the special courtesies to be extended on the trip, that the party be made larger. Exceptional facilities to visit the many mines and smelters have been freely provided; and members are requested to make all reasonable effort to attend the meeting at Spokane and participate in the excursions. . For those who cannot take the entire trip, it may be possible to provide special Pullman accommodations after leaving the Yellowstone Park. In order to make the necessary arrangements, however, the names of members and guests contemplating this partial trip should be sent at once to Mr. Theodore Dwight, .39 West 39th St., New York, N. Y. A special train of Pullman cars will leave Chicago September 16. This train will be side-tracked at all places visited, and the sleepers will be available for lodging and the dining-car for meals (luring the entire trip, except while taking the tour through the Yellowstone Park. The general cost of the trip per member will be $300, which includes transportation, berth, and meals for the entire trip from Chicago back to Chicago, almost 6,000 miles, and the tour through Yellowstone Park, occupying in all about 30 days. Special accommodations on the train will be furnished at the following rates

Aug 1, 1909

[¦Abad, Leopoldo F., College of Min., Univ. of California Berkeley, Cal. &apos;23 ¦Abarquez, Ramon F., Met., Bureau of Science Manila, P. 1. &apos;24 ¦Abbey, Robert Graham, Student, Case School of Applied Science Cleveland, Ohio. &apos;21 Abbott, A. N., Mines Supt., Mazapil Copper Co., Ltd ...Concepcion del Oro, Zacatecas, Mexico. &apos;23 Abbott, Clarence B., Gen&apos;l Supt., Iron Mines Div., Tenn. Coal, Iron & R. R. Co., 1405 Minnesota Ave., Bessemer, Ala.&apos; &apos;04] [ ]

Jan 1, 1925

By T. V. Falkie, D. R. Mitchell

Many operational problems in mine haulage cannot be solved economically by conventional analytic or trial and error methods. However, a method of probabilistic simulation, which is based on the fundamental assumption that many of the variables governing any physical system are probabilistic, has been adapted to certain areas of operations research in coal mine haulage. This paper attempts to illustrate how simulation can be used in basic haulage research and what kind of results can be expected. Optimization in this case is performed in terms of locomotive and car movement, as well as best utilization of men and equipment, and is approached primarily from the standpoint of scheduling of the main haulage. Many operational problems in mine haulage cannot be solved economically by conventional analytic or trial-error methods. However, a method of probabilistic simulation, which is based on the fundamental assumption that many of the variables governing any physical system are probabilistic, has been adapted to certain areas of operations research in mine haulage. In many physical cases several probability distributions interact with each other in special ways, and it is not possible to solve for their combined effect in a mathematical equation. This is often true in the case of mine haulage, where such variables as number of empties or loads per trip, travel times, and number of cars or tons produced in a given time are probabilistic. By using a simple example of one secondary haulage segment of a large underground haulage system, this paper attempts to illustrate how simulation can be used in basic haulage research and what kind of results can be expected. Optimization in this case is performed in terms of locomotive and car movement, as well as best utilization of men and equipment. This is the type of preliminary research that will be needed as a first phase in any major haulage study, whether it be a relatively simple economic analysis or a plan for complete automation. The problem of optimization has been approached primarily from the standpoint of scheduling of the main haulage. It is evident that the method of proba-

Jan 1, 1963

By W. F. Mullen, C. W. Stickler

WITH few exceptions, unit operations in the Pennsylvania slate industry in 1950 did not differ appreciably from production methods described by Behrel and Bowles2-4 several decades ago. Many traditionally picturesque but relatively inefficient hand operations continued to contribute to high operating costs in an industry in which the margin of profit, for various reasons, was admittedly low. As part of a general program in which the Pennsylvania State College has been assisting the slate industry to solve some of its problems, time and method studies were used in an effort to determine the bottlenecks of production flow. The results are as applicable to other stone industries as they are to slate. A study of the basic elements in the production of roofing slate, structural slate, and slate blackboards among selected slate producers revealed comparatively few refinements. Any marked difference in operating method was characterized largely by the available equipment, a noticeable difference in the working properties of the rock quarried by a particular company, and by either the habit thinking or ingenuity of the individual operators. With the hope that significant economies in manufacture might result, all the unit operations were broken down into elements for study and analysis. The greater part of the study encompassed those operations from the quarry rim to the finished product; however, to obtain a reasonable synthesis of time allotments per operation, several analyses of quarrying from the finish of the wire saw cut are included for reference. The complete study of quarrying made by Bowles several years ago resulted in the introduction of the wire saw into the operation; there appears to be a need for as fundamental a change in the processing of finished slate as the wire saw was in the quarrying process. Fig. 1 illustrates the flowsheet of quarried rock from the parent bed to the quarry rim with the basic elements which contribute to the difficulty of removing slate from the ground. In Pennsylvania roofing slate is produced by one of three procedures, many operations of which are quite similar. In the traditional or classical method the quarried rock is reduced by sculping and auxiliary manual treatment to workable size and then is split and dressed (trimmed to size) in the conventional shanty. Archaic as this method might appear, there are several elements that result in substantial savings over more mechanized operations. In a modified version of this method, the block is reduced by sawing and gouging preparatory to splitting and dressing in indoor stations. This method is particularly adaptable to rock which fractures unevenly by conventional sculping methods. In the third and more modern method, reduced block received from the block maker is diamond-sawed to length and finished on a production line. Fig. 2 illustrates the flow pattern in each case. In the modified and more modern plans, dressing is done on mechanically-operated trimming machines, which appreciably reduce the fatigue factor of the operator. However, it should be noted that it is advantageous for the operator to be able to control the speed of the knife to prevent breakage of certain classes of stock. In the classical plan the splitter and dresser normally act as blockmakers also and carry their eighter slabs (equivalent in thickness to eight shingles) into the shanties themselves, all of which adds to fatigue and reduced efficiency. The extremely low investment and operating expense of the classical method has undoubtedly been of paramount importance in its continuation. Production of Mill Stock The production of mill stock is accomplished by less picturesque methods than enter into the production of roofing slate but it is, in the main, relatively more efficient because of the increased use of machinery for handling and for finishing. Mill stock can be classified into two categories as far as difference in production method is concerned: structural slate and blackboards. The significant difference in operation is caused largely by the nature of the rock used for each product with the best and easiest cleaved rock being reserved for blackboards to permit the splitting of large slabs to as little as 1/2 in. in thickness. Structural stock, on the other hand, is split into panels no thinner than 11/2 in. and

Jan 1, 1952

By J. P. Morris

PREVIOUS investigations1,2 have shown that alloying elements in liquid iron influence the thermodynamic activity of sulphur and thereby affect the partition of sulphur between metal and slag in the desulphurization process. For example, the greater efficiency of desulphurization in the blast furnace as compared to the open hearth can be attributed in part to a higher level of sulphur activity in blast-furnace metal due to the higher concentration of carbon and silicon. In the present investigation, a short study was made of the influence of manganese on the activity of sulphur in liquid iron and iron-carbon alloys. In contrast to carbon and silicon, manganese was found to decrease the activity coefficient of sulphur; and in iron-carbon alloys it counteracts to some extent the influence of carbon. However, at manganese concentrations normally present in the blast furnace or open hearth, the effect of manganese is small. Since manganese sulphide has a limited solubility in iron, manganese can act, under certain conditions as a desulphurizing agent. Considerable data on the manganese-sulphur product in carbon-saturated melts were obtained in the investigation and have been included in this report. The experimental procedure was the same as that used in the earlier investigations on the effect of silicon&apos; and carbon&apos; on sulphur activity. Briefly, the method was as follows: The molten alloy, contained in a graphite or sintered alumina crucible, was brought to equilibrium at a constant temperature with a mixture of hydrogen and hydrogen sulphide of constant composition by bubbling the gas through the metal. Samples of&apos; the melt were taken for analysis at regular intervals by suction through a 2 to 3 mm bore silica tube dipped into the metal. The experiments were run in a graphite spiral resistance furnace with melts weighing 50 to 60 g. The gas bubbling tubes were made of sintered alumina and were 5/16 in. OD, 1/16 in. ID, and 24 in. long. Equilibrium was assumed to have been attained when the sulphur content of the liquid metal reached a constant value. During an experiment there was a rapid loss of manganese from the melt by volatilization. To offset this loss, small additions of manganese were made periodically. The rate of manganese addition needed to maintain a constant manganese concentration was determined in preliminary tests. In all of the experiments, deposits of manganese sulphide formed above the melts in a cooler region of the furnace. Apparently, these deposits resulted from a reaction between manganese vapor and hydrogen sulphide in the gas. To prove that manganese sulphide did not volatilize from the melts to a measurable extent, an experiment was run in which helium was bubbled through liquid iron containing both manganese and sulphur. Although manganese volatilized rapidly in this test, there was no appreciable loss of sulphur. Volatilization of manganese sulphide from a melt would have led to an apparent equilibrium condition in which the sulphur content of the metal was lower than the true equilibrium value. The experimental results are shown in the first seven columns of Table I. The data in the last two columns were obtained from the previous work on the effect of carbon&apos; and show what the results would have been in the absence of manganese but with temperature, gas composition, and carbon content of the metal remaining the same. Comparison of the last four columns show that, in the presence of manganese, the sulphur content of the metal increased at equilibrium and the activity coefficient of sulphur decreased. However, the results show that, for manganese concentrations below 3 pct, the effect of manganese is small. The values for activity coefficient of sulphur given in Table I were calculated from the following relations: S (in liquid metal) + H2 (gas) = H2S (gas) [l] K ph2s/?s X %S X phg = 0.00251 [2] where K is the equilibrium constant for the reaction, PH2S and ph2 are the partial pressures of hydrogen sulphide and hydrogen, respectively, and ?s is the activity coefficient of sulphur. The standard state for sulphur was taken to be a 1 pct solution of sulphur in pure iron. The numerical value for K at 1600°C was determined in the earlier work. For the purpose of showing graphically the results of the tests run at 1600°C, the activity coefficients of sulphur were recalculated so as to correspond to a manganese concentration in the metal of 2 pct in each case. In the calculation it was assumed that the increase in sulphur content of the metal at equilibrium caused by the presence of manganese

Jan 1, 1953

By J. E. Kirby, L. B. Schnitz, H. E. Stamm III

The production history of a gas-cap-drive reservoir was reproduced by calculations, and predictions were made for operations under primary depletion, pressure maintenance by gas injection, and pressure maintenance by water injection. Although the general equations used in this analysis have been available to the industry for a number of years, the procedure has not had extensive use because of the unusually large time requirements for developing numerical results. The use of digital computing equipment for processing the calculation work generally reduced the time usually required for an extensive analysis of this type. Calculation techniques were developed that were equally applicable for solving the gar-cap-drive problem, whether digital computing equipment or desk calculators are used. These techniques are outlined and the procedures are illustrated by the field problem. INTRODUCTION The analysis of a gas-cap-drive res-ervoir requires the simultaneous solution of the volumetric balance1 and displacement2 equations. Equations for the analysis of combination drive reservoirs were presented by Wooddy and Moscrip in a previous paper." These equations permit the evaluation of possible operating processes in order that the optimum method of pro- ducing the reservoir may be determined. Although these equations represent the basic technique known for the detailed analysis of gas-capdrive reservoirs, the calculation processes are quite complex and time consuming; hence, the procedure has not had extensive use. Recently, these equations were satisfactorily applied with the aid of a digital computer to investigate the completion history of a gas-cap-drive reservoir under the following operating methods: primary depletion, depletion under full pressure maintenance by gas injection, and depletion under full pressure maintenance by water injection. The use of digital computing equipment substantially reduced the time necessary for making the computations and permitted a more concise investigation of the reservoir&apos;s depletion history than was possible when the desk calculator was used. This more rigorous investigation also permitted a detailed analysis of the calculation procedures necessary in the solution of the gas-cap-drive problem. This paper outlines the procedure of analyzing a gas-cap-drive reservoir and illustrates the process with an actual field problem. CHARACTERISTICS OF THE RESERVOIR ANALYZED Production in the field under consideration is obtained from a Frio formation of Oligocene age at a depth of approximately 5,740 ft sub-sea. The accumulation, which is bounded on the flanks by strand lines, is semirectangular in shape with gentle narrowing toward the base of the structure as shown by the sand limits and completion map in Fig. 1. The reservoir development indicates an oil column of 319 ft that is defined by gas-oil and oil-water contacts. Basic data relative to the characteristics of the formation and the formation fluids are shown in Table 1. The formation exhibits considerable shaliaess and thinning near the oil-water contact indicating that little or no benefit will be received from natural water influx. This is substantiated by the fact that wells completed near the original oil-water contact have not produced water. A sizeable gas cap is present; however, considerable faulting is in evidence, and it is believed that only a limited portion of the gas cap will aid in oil displacement and pressure maintenance. Although the reservoir was in an initial stage of depletion, it was believed that as soon as the equilibrium gas saturation in the oil zone was exceeded and a number of upstructure wells were invaded by the expanding gas cap, the resulting high gas-oil ratio production would rapidly dissipate the natural drive and lead to limited oil recoveries and inefficient reservoir operation. This analysis evaluated the effectiveness of the primary displacement mechanism and

Jan 1, 1958

By H. L. Stone, A. O. Garder

A numerical method of solving the partial differential equations which describe the one-dimensional displacement of oil by gas has been presented. Possible extension of the method to treat multidimensional flow is discussed, and the limitations of this extension are indicated. Using this method, it is possible to allow for the existence of a gas cap, the presence of any number of gas-injection or oil-production wells and the evolution of dissolved gas from the oil. It is also possible to allow for variation in the cross-sectional area, elevation, porosity and permeability of the reservoir. The influence of relative permeability and the force of gravity in the direction of flow upon the displacement is considered. The influence of capillary pressure upon the flow and the effect of gravity in the direction perpendicular to flow are neglected. The physical properties 01 the fluids are considered to be Junctions of pressure only, and equilibrium between contiguous phases is assumed. The numerical calculations can be readily carried out by the use of a digital computer. Several example analyses have been performed using the IBM 704 computer, and about one-third of an hour of computing time was required per case. Reservoir behavior predicted by use of this numerical method was compared to data obtained by other methods for three cases — complete pressure maintenance, dissolved-gas drive and gas-cap drive. The independent solutions to these problems were obtained by analytical solution, laboratory experiment and field data, respectively. Agreement of the numerical solution with data from these sources was good; this agreement establishes the convergence and accuracy of the numerical method. INTRODUCTION Most petroleum reservoirs can be produced by any one of several alternative programs. When a reservoir is produced by primary methods, production economics can be influenced by controlling the number and location of wells and the flow rate of each well. An even greater influence may be achieved by augmenting the recovery of oil obtainable by primary methods. This can be accomplished by injection of fluids such as water, natural or enriched gas or a bank of light liquid hydrocarbons. Selection of the most desirable operation requires a means of predicting the reservoir behavior which will result from each of the several alternative programs. The purpose of this paper is to present a mathematical method for predicting the behavior of reservoirs produced by gas-cap drive, dissolved-gas drive or pressure maintenance by gas injection. The method described herein takes cognizance of phase changes caused by a decline or an increase (due to gas injection) in reservoir pressure, of the presence of a gas cap and of the effect of gravity on the flow of gas and oil. Relative permeability relationships are used to define the flow properties of the rock. Allowance is made for variation in cross-sectional area, elevation, permeability and porosity of the reservoir. Both the influence of capillary pressure upon the flow and pressure gradients in the gas cap are neglected. Whenever a liquid phase and a gas phase are in contact, they are assumed to be in equilibrium. The physical properties of the fluids are considered to be functions of pressure only. Therefore, if the method is to be used to predict the effects of a gas-injection program, mixtures of the injected gas and formation crude should-have the same physical properties as mixtures of formation gas and crude. The equations to be presented in this paper apply only to a one-dimensional case; therefore, they neglect the influence of gravity in the direction transverse to the flow. As is well known, this gravitational influence may lead to overriding of oil by gas. Consequently, this procedure as presented is most applicable to long, thin reservoirs for which gravity overriding is not important. On the other hand, the equations presented can be generalized to treat multidimensional flow and, hence, to consider gravity overriding, if desired. A word of caution on two points is advisable here, however. First, the authors have not demonstrated the accuracy of the numerical technique for multidimensional flow. Second, and more important, capillary pressure will often be of importance in multidimensional problems. Obviously, in such cases a generalization of the

By R. E. Reed-Hill

The lattice reorientations in (1011) and (1013) twins of pure magnesium have been investigated using polarized light. Both forms (Ire subject 20 almost complete second-order twinning on the (1012) plane of the first-order twin. The observed deviations of composition planes by 6 and 3 deg, respectively, from coherent twinning planes are caused by second-order twinning. The experimental data indicate that (1011) and (1013) are reciprocal twins with a twinning shear 0.136. In a previous paper1 it was shown that the primary fracture mechanism in single crystals of magnesium strained in tension parallel to the basal plane is parting or fracture inside twins. In the temperature interval 25oto286oC, the observed twinning form, dominant in fracture, was a very small twin which formed in bands. Because these twins were very small and appeared in extensively deformed regions they did not lend themselves to X-ray analysis. Lacking Cou-ling and Pearsall&apos;s2 recently reported polarized light technique for magnesium, the twinning plane indices (K1) were originally determined by two surface composition plane measurements. This plane fell in a major zone (axis < 1120>) at an angle of 55.75 deg to the parent crystal basal plane. Because its habit deviated by 6 deg from{l0ll), 61.9 deg, the experimental data per se were not consistent with simple (1011) twinning and, for expedience, the twin was designated with habit plane indices (30341, 54.5 deg, representing the lowest set of indices corresponding to measured angles. Couling, Pashak, and sturkey3 have also found bands of reoriented lattice with a similar habit in polycrystalline specimens of magnesium and certain dilute magnesium alloys. These bands are significant because their formation in large numbers during plastic flow permit specific magnesium alloys to undergo very extensive deformation by cold rolling. Using polarized light2 they showed that the basal plane in the reoriented material was nearly parallel to the band habit and, as a result, proposed a mechanism for band formation involving a double twinning process in which (1011) twins form and then retwin according to (1012). Because of the obvious similarity between the twin bands observed in single crystals and in polycrystalline specimens, it was decided to investigate if the two phenomena were not identical and, if possible, to verify the retwinning hypothesis. The present paper is a report of this investigation and shows that the twins with the (3034) habit correspond closely to retwinned (l011) twins. Evi- dence is also given for an analogous retwinning process in (1013) twins. EXPERIMENTAL PROCEDURE Rectangular single-crystal specimen deformed in tension (stress axis in the basal plane parallel to [1010], as previously described,4 were polished electrolytically by Jacquet&apos;s method5 and etched in acetic picral.2 All twins studied in this investigation belong to a major zone, whose axis, [1210], was perpendicular to both stress axis and two sides of each specimen [(1210) surfaces]. These latter contain the plane of shear of the twins and measurements of the basal plane trace of twins on these surfaces determines the lattice orientations of the twins. The position of the basal plane in each case was determined with a polarizing microscope using a modification of the technique of Couling and Pearsall.2 For each twin the four positions of maximum extinction were measured, the data averaged, and then the pair of extinctions corresponding to the basal plane was determined by rotating the microscope stage and observing the position at which the color changed from orange to blue with a gypsum red, first-order plate inserted between the crossed Nicol prisms. EXPERIMENTAL RESULTS (1013) Twins—In general, especially in speci-mens deformed at 150°C, (1073) twins appear in greater numbers and larger sizes than (1011) twins, and the lattice reorientation inside these twins is therefore easier to study and measure. Fig. 1 shows an area of an unetched and unpolished (1210) crystal surface containing a number of (1073) twins sloping upward to the right at about 29 deg with the basal plane of the original crystal (horizontal direction). Slip line segments may be seen in both the parent crystal (running horizontally) and in the twins (sloping downward to the right at approximately -22 deg with the horizontal). As may be seen in Fig. 2, the slip lines in the twin are not at the proper angle (64 deg from basal plane of the

Jan 1, 1961

By J. E. McDonald, J. G. Eberhart

A model is discussed from which the work of adhcslon .tor liquid transition metals on aluminum oxide surfaces can he calculated, A close-packed (00011 oxygen surface on A12O3 is assumed with two different types of surface sites: one type involving metal-oxygen bonds and the other man der Waals into actions. The work of adhesion is thus expressed as the sum of these two bonsding free energies. Calculated works of adhesion for nickel, titanium, chromium, and zirconium on sapphire agree well with the experimentally determined quantities. The model is extentled to the calculation of the work of adhesion and shear stress required to remove a thin metal film from a sapphire substrate and is in good agreement with experimental values. The obsewed dependence of the work of adhesion on the free energy of oxide formation of the metal is shown to also provide an interpretation of the tittle dependence of thin-film adhesion. THIS paper presents a model for the type of bonding which occurs across a metal-A12O3 interface. The model is used to explain the results of two types of experiments in which such an interface exists: 1) the adhesion of thin metal films on Al2O3 substrates and 2) the wetting of A12O3 by liquid metal drops. The adhesion of thin films to various substrates has been the subject of a variety of investigations.&apos;-&apos; Benjamin and weaver3 and Bowie,6 using the scratch test developed by Heavens,10 studied the adhesion of metallic films to glass substrates. Their observations for noble-metal film adhesion agree well with an adhesion model involving a van der Waals type of bonding between the film and the substrate. For films of metals whose free energy of oxide formation. ?F°f, has a negative value. Benjamin and weaver3 and Bowie6 found a time-dependent adhesion with an initial value that can be interpreted in terms of van der Waals interactions but a larger terminal value which was related to ?F°f, Karnow-sky and Estill7 deposited films on sapphire at elevated temperatures and noticed no time dependence of film adhesion but a similar correlation with ?F°f. Because of the kinetic problems associated with thin-film adhesion it is desirable to examine adhesion in an equilibrium system. The wetting behavior of liquid-metal drops on Al2O3 provides such a system. Systems of this metal-ceramic type have been studied extensively.11 Humenik and Kingeryl2 have measured the wetting of A12O3 (and other substrates) by several metals and have pointed out that the wetting ability of these metals increases with increasing values of -?F°f. It is thus seen that thin-film adhesion and metal wetting on A12O3 are both related to the tendency of the metal to react with the surface oxide ions of the Al2O3 substrate and, because of this, both phenomena should be explainable by an appropriate model for the metal-Al2O3 interfacial bonding. In the sections that follow, wetting and adhesion data on A2O3 are reviewed and a model is presented by which these phenomena can be interpreted. ANALYSIS OF WETTING EXPERIMENTS In an equilibrium system involving a liquid-metal drop on a solid Al2O3 substrate, the work of adhesion, WAD, is defined by the Dupre, equation as WAD = ?s + ?L -?sL [1] where ?s and ?L are the surface free energies of the solid substrate and the liquid drop, respectively, and ?sL is the interfacial free energy. The work of adhesion is the work required to separate a unit area of the solid-liquid interface into two surfaces. The work of adhesion is usually determined from a sessile-drop experiment in which yL and the contact angle, ?, are measured. The Young-Dupr6 equation is then used to calculate WAD Wad = ?L (1+ cos ?) [2] The literature of this subject has been examined and Table I shows work of adhesion data for various liquid metals as measured on A12O3 substrates. The standard free energy of oxide formation of the metal at the temperature of the wetting experiment, ?F°f . is also tabulated in kcal per g-atom of oxygen. The data is grouped according to the gaseous atmos-

Jan 1, 1965

By Blandford C. Burgess

Mica is an orchid among minerals. It is formed in pegmatites, one of the most bizarre of igneous formations, and is exceeded by few other minerals in the perfection it may attain as to size, color, and cleavage. First used for window glazing, as an ornament and article of trade, it has become one of the most essential insulators of electricity, heat, and shock. Most internal combustion engines use mica condensers or capacitors and such machines of war as planes, tanks, and submarines are immobile without it. The original manuscript of this guide was written in April 1943 at the peak of war emergency. It was not used because shortly thereafter a decision was made to buy on a one price basis eliminating differentials for both quality and size. This is now presented with the thought that from the standpoint of preparedness we can only consider another war imminent and every effort should be made to set up in usable form the experience gained during the Second Morld War. Colonial Mica Corp. was set up by Metals Reserve Co. as a wholly owned government agency to encourage production of domestic mica and to purchase it. It soon became the exclusive buyimg agency for such mica. The writer as Southern Manager called on all the private agencies buying mica to assist in formulating buying policies, methods, and prices. A meeting was held for that purpose in Asheville, N. C., July 20, 1942. In the general discussion the first two hours of the meeting it was decided that the following factors should be considered in pricing strategic mica: clearness, flatness, trimming, color, classification (size and quality), free splitting, hardness, and air inclusions. Most of the mica miners have been buying strategic mica, according to the mine, as No. 1, No. 2, or Nos. 1 and 2 combined. In addition to these grades of strategic mica they have been buying three lower grades of mica, electric (vegetable-stained), black-spotted and black-stained. A number of mines were named one by one and the buyers present gave their opinions as to the basis they would use in buying the sheet mica from each. It was suggested that in addition to the prices already published, prices be posted up to 10 pct higher for special quality and preparation and prices be posted 25 pct lower than the published prices for the lowest acceptable grades of strategic mica, giving the buyers authority to make intermediate prices according to the quality and preparation. It was thought desirable at the same time to announce prices for nonstra-tegic mica where such quality is being obtained in mines producing strategic mica and where it would be necessary to take the output in order to get the strategic mica. It was also suggested that the price of electric and black-spotted mica be 50 pct below the price of the lowest grade of strategic mica and the price of black-stained mica be 60 pct below the price of lowest grade strategic mica. The few experienced buyers available were employed but they were inadequate for the job and others had to be trained. All needed a guide or primer of some kind to attain systematic procedure and consistent prices in their respective buying areas. The Mica Buyers Guide was formulated for that purpose based on experience gained in the first six months of buying. The Preface to the original guide was as follows: The purpose of this guide is to serve as a text in training beginners and as a handbook for experienced buyers of the instructions which have been issued up to this time. At the meeting of prospective buyers last summer, it developed that the first essential to attain uniformity must be some kind of check sheet. Our "Mica Buyers Report" was developed for this purpose and forms the backbone of this guide. Price is determined according to size, quality and preparation. Size can be measured, but no system of measurement or machine has been devised which can be substituted for the trained eye of the buyer to deterrnine quality and preparation. Although the "One Price" system was instituted and the "Guide" not used, the buyers were required to continue making out a "Mica Buyers Report" (Fig1) with each lot of mica purchased. The form proved its value and there is no doubt that in another such emergency some similar form should be

Jan 1, 1950

By W. R. Crane

THE effect of mining in the red-ore mines of the Birmingham district has been observed for some time, but, except in a few localities, little difficulty has been experienced from disturbance of cover. Cave-ins near the outcrop and fracturing of the surface at greater distances are the most pronounced manifestations of disturbance, while limited areas at points distant from the outcrop and under greater depth of cover have actually subsided. There is no doubt but that in time, because of failure of pillars, extensive fracturing and widespread settlement of the surface will result, particularly along the slope of Red Mountain, where mining has been under way for many years. Were it not that the orebed is overlain by one or more water-bearing formations, the fracturing or settlement of the surface would not be serious; but because of these formations, fracturing of the top rock may in itself be of sufficient importance to warrant the adoption of protective measures. Until development openings and surface plants are transferred to Shades Valley, protection of the surface will probably not be considered imperative, as the area involved is not of particular value for agricultural or building purposes. Further, the collapse of pillars over a wide area may develop squeezes that, if not controlled, may jeopardize the integrity of the mines and necessitate a change in development, from slopes to vertical shafts, at a much earlier period than is now contemplated. The occurrence of heavy beds of strong tough materials at varying distances above the orebed make it doubtful whether any serious disturbance of the surface will be experienced at any considerable distance from the outcrop, although some settlement will probably take place. It is certain, however, that no great volume of water will enter the mines from fracturing of the Fort Payne chert bed, as this is known to be a compact and practically impervious formation beyond the leached zone. Not so much can be said, however, regarding other possible sources of water, as pervious beds and through faults that may be encountered in future mining operations.

Jan 8, 1925

||Abad, Leopoldo F, College of Min, Univ of California Berkeley, Cal &apos;23 ||Abarquez, Ramon F, Met, Bureau of Science Manila, P I &apos;24 ||Abbey, Robert Graham, Student, Case School of Applied Science Cleveland, Ohio &apos;21 Abbott, A N , Mines Supt , Mazapel Copper Co , Ltd Concepcion del Oro, Zacatecas, Mexico &apos;23 Abbott, Clarence E, Gen&apos;l Supt, Iron Mines Div, Tenn Coal, Iron & R R Co, 1405 Minnesota Ave, Bessemer, Ala &apos;04 Abbott, Louis Benjamin, Chief Engr, Consolidation Coal Co, Elkhorn Div &apos;Jenkins, Ky &apos;15 Abbott, Robert R , Met Engr, Peerless Motor Car Co Cleveland, Ohio &apos;12 ||Abbott, Wells Osborn, Ray Consolidated Copper Co Hayden, Ariz &apos;23 Abeel, George H, Jr, Cons Min Engr 4612 W 17th St, Los Angeles, Cal &apos;18 Abel, Albert E, Asst to Pres, Valley Mould & Iron Corpn Sharpsville, Pa &apos;19 ?Abeloff, Miran S Address Wanted &apos;21 Abernathy, G E, Kansas State Teachers College Pittsburgh, Kans &apos;20 Abey, Hiroshi, Min & Met Engr, Takata & Co, 2 Yeirakucho, Nechome, Kojimachi-ku,

Jan 1, 1923

By J. Handin

Triaxial compression tests with independently applied external confining pressures and internal pore pressures show that the ultimate compressive strengths of representative oil well cements are nearly linear functions of effective pressure — the difference between external and internal pressures on the jacketed cylindrical specimens (to 15,000 psi). The strengths are little affected by the test temperature to 350F (not to be confused with the curing temperature). At an effective pressure of 15,000 psi, strengths are in the rage of 30,000 to 50,000 psi, comparable to those of sedimentary rocks under similar conditions. The cements become very ductile even under low effective pressures; permanent shortenings of 30 per cent or more are attainable without rupture. INTRODUCTION Since the pioneering work of Richart, Brandtzaeg and Brown1 on the failure of cement under combined compressive stresses, it has been recognized that ultimate compressive strength is greatly enhanced by the application of confining pressure. More recently, Mc Henry2 showed that the strength of concrete was a linear function of the effective pressure (the difference between the external confining pressure on a jacketed specimen and the internal fluid pore pressure), at least for a range of 0 to 1,500 psi. The effect of temperature had not been investigated, and no previous systematic triaxial compression testing of naterials used for oilwell cementing seems to have been done. The present work was suggested by the late J. hi. Bugbee3 who stated that "consideration of the common application of high-pressure hydraulic fracturing to the initial completion or recompletion of wells, and the large pressure drawdowns in some producing wells, particularly those in abnormally high-pressure gas-condensate reservoirs, raises the question of what is a suitable cement strength for various completions. The intuitive belief exists that cement strength need be no greater than formation strength. Tests should, however, be conducted at downhole conditions." The ultimate compressive strengths of rocks penetrated by the borehole must rise several fold with increasing depth.4 This marked enhancement of strength is due to the influence of the effective pressure, the total weight per unit area of the overburden less the hydrostatic pore pressure. (The effect of temperature due to the geothermal gradients is relatively small for depths to 30,000 ft.) .A significant comparison of the strengths of rocks and cements at downhole conditions requires knowledge of the confined compressive strengths of cements as well. EXPERIMENTAL PROCEDURES The theory and technique of triaxial compression testing are fully discussed in earlier reports.4-6 Briefly, cylindrical specimens 1-in. long and 0.5-in. in diameter are jacketed in thin copper tubes of negligible strength, placed in the test chamber and subjected to an external confining pressure of kerosene and loaded axially by the piston at a strain rate of 1 per cent per minute. Pore pressures of water (or kerosene) are applied independently through the hollow piston and are maintained constant during the shortening of the specimen, Tests at sensibly 0 pore pressure are arranged so that any free water in the cement can escape to the atmosphere. (If egress of water were denied, pore pressure would rapidly attain the value of the external confining pressure because of reduction of pore space.) The test chamber can be heated for high-temperature experiments. Unless otherwise noted, the cement samples were air dried for about a week. Recorded during a test are pore and confining pressures, shortening and axial differential force (total force less the product of the confining pressure and the area of the piston). True stress-strain curves are constructed by dividing the measured differential force by the actual cross-sectional area of the specimen at a given

Jan 1, 1966

By S. E. Bronisz, R. E. Tate

s-plutonium samples possessing a strong growth texture have been produced by allowing them to transform under pressure from p to a. A fiber texture with [010] parallel to the pressure axis results. The textured samples are expected to be useful in determining the effects of crystallographic orientation on the physical properties of a plutonium, and initial results of measurements of resistivity and mechanical properties are described. THE crystal structure of a plutonium1 is mono-clinic, P21/m, and many of the metal&apos;s properties should reflect the crystallographic anisotropy. Unfortunately, it has not yet been possible to grow useful sizes of single crystals of a plutonium. Therefore, few of plutonium&apos;s orientation-sensitive properties have been determined as a function of crystallographic orientation. One way to gain information about at least some of the orientation-dependent properties is to study a highly textured sample. Such samples have been produced by cold rolling a plutonium,2 but they are necessarily very small in one dimension. We have now successfully used two other techniques to produce highly textured samples, not limited to small thicknesses. METHODS OF PRODUCING PREFERRED ORIENTATION The texture is produced by causing the plutonium to transform from ß to a while under pressure. It was observed by Gardner3 that applying a compres-sive load during the transformation resulted in the formation of columnar grains of a plutonium, and Cramer4 observed a similar structure in some diffusion couples rolled in the P phase. Neither of these workers, however, investigated the subject beyond these observations. The more flexible of the two methods developed is that of compressive loading. The technique is to enclose a sample of plutonium in a die assembly before applying the load. It is possible, of course, to dispense with the die and simply press the sample between two platens. In this case, however, the unrestrained sample deforms during the pressing, making it difficult to maintain the load and to control the final sample thickness. This compressive loading technique has been used on specimens ranging from 1/4 to 3 in. diameter, with height-to-diameter ratios ranging from 5 : l to 1:6. The procedure begins with loading the sample, a right cylinder of a plutonium, into the pressing die. Plastic deformation of the sample while it is being pressed is minimized by machining the sample so that its diameter is nearly the same as that of the die barrel. Then the loaded die assembly is placed in a vacuum pressing can that fits on a hydraulic press. After a vacuum is achieved the die assembly is heated to 180°C and equilibrated. The load is then applied and the specimen and die are allowed to cool to about 40° to 50°C before the pressure is removed. The resulting sample is composed of rod-shaped a -plutonium grains, the rod axes being parallel to the cylinder axis and the pressing direction. Photomicrographs of the oriented structure are shown in Fig. 1. Although most of the specimen is composed of grains whose rod axes are parallel to the cylinder axis, a thin, peripheral layer consists of rod-shaped grains whose rod axes are perpendicular to the cylinder axis. Presumably, the highly plastic nature of p plutonium leads to approximately hydrostatic conditions during the initial stages of the P — a transformation under pressure. At this time, the grains in the peripheral layer would have grown parallel to the local force direction. During the latter stages of the transformation, the accompanying volume contraction would have eliminated the radial forces, leaving only the axial force and resulting in the growth of the observed structure. The growth texture did not form without the application of pressure. Attempts were made to produce the texture by repeating the standard temperature cycle without

Jan 1, 1965

By R. A. Fitch, J. D. Griffith

A performance calculation method was used in conjunction with experimental studies to develop means of predicting and interpreting miscible floods and to explore possible methods. of improving their efficiency. The calculation method is based upon the division of reservoirs into multiple independent zones or strata. Comparison was made with some experimental floods and with a field project to obtain some measure of the applicability of the method. Two aspects of miscible flooding were considered: (I) the displacement of a miscible front through a reservoir, and (2) the distribution and utilization of the solvent volume injected to maintain miscibility. Calculations and experihental observations indicate that alternate gas-water injection behind a miscible front significantly improves miscible flood performance, both within a single stratum and in a multistrata reservoir. Calculations were made on the extent to which miscibiliry is maintained by a given solvent volume in a stratified reservoir. Two alternate criteria for determining the optimum volume of solvent for injection are discussed. The preinjection of a small volume of water ahead of the solvent is suggested as a method of obtaining more efficient utilization of solvent. Calculations and experiments were made to investigate the effects of water preinjection. INTRODUCTION Miscible fluid displacement as a possible means of recovering oil has been the subject of extensive research and numerous field tests over the past several years. This work has brought out both favorable and unfavorable features of the miscible recovery methods. Many tests have shown that a miscible fluid can displace all of the oil contacted, leaving no high residual oil saturation, as is characteristic of immiscible displacements. The miscible methods have proven dificult to control, however, as evidenced by early breakthrough of the displacing fluid and poor sweep efficiency in several field projects. It became apparent early in the investigation of miscible displacement that the development of improved techniques and better methods of control would be required to extend the range of applicability to any significant portion of our petroleum reservoirs. The purpose of this study was to consider the problem of designing miscible floods to obtain better performance. A performance calculation was used in conjunction with experimental studies to develop means of predicting and interpreting miscible floods and to explore possible methods of improving their efficiency. Two aspects of miscible floods were considered separately in this study and the results are presented in two parts. The first part concerns the manner in which the miscible front is displaced through the reservoir. In these calculations the condition of miscibility between the reservoir oil and the displacing fluid is assumed. In the second portion the distribution and utilization of the preinjected solvent in maintaining rniscibility is considered. This portion dealing with solvent utilization applies only to the enriched gas or LPG slug processes. CALCULATION METHOD AND EXPERIMENTAL STUDIES COMPUTATIONAL MODEL The calculations for expected reservoir performance are based upon the multi-strata concept of reservoir properties. The method assumes multiple, independent strata (no crossflow between strata) and explicitly includes variations in patterns, injectivity, areal sweep and displacement efficiency. Lateral variation in permeability within the strata (for example, directional permeability) may be considered in the calculations, provided the variations are similar in all strata. The calculations based on this model furnish the rates of injection and rates of production of both oil and the displacing fluid for the composite system of strata. To carry out calculations on the mathematical model described, information is required on the performance of the displacement process under consideration in a single stratum element of the pattern to be used. In particular, for a given pattern and displacement process, data are required relating injectivity and composition of the produced stream to the volume of fluid injected. Data on the variations in areal sweep must also be available if it is desired to track the areal sweeps in the multi-strata model. These data may be obtained from experimental work such as model studies or other suitable methods. This representation of reservoir properties is, of course, an approximation and may be inappropriate in some cases. But the representation is not an arbitrary one since most oil reservoirs are essentially successive layers of sediment with the net producing pay zone often comprising but a fraction of the gross formation thickness. The fact that permeabilities measured in the vertical direction are frequently but a fraction of the horizontal permeability adds some evidence to the validity of this model. This type cal-

Jan 1, 1965

By N. J. Grant, E. Gregory

The creep rupture properties of wrought aluminum powder products made from five grades of sintered aluminum powder were investigated at temperatures from 400° to 900°F for rupture times up to 1000 hr. The effect of stress concentrations on materials of this type was investigated by means of notched creep rupture tests. A tentative correlation was obtained between the creep rupture properties and the structure as revealed by electron micrographs. SEVERAL papers have been published recently concerning the production and properties of wrought aluminum powder products and their possible high temperature applications. Most of the published work in this field has come from abroad, notably Switzerland, and articles by Irmann and his colleagues were summarized in English recently.&apos;.&apos; Most of the papers published by Dr. Irmann are principally concerned with the retention of properties (by a product which is produced from extremely fine flake powder and is subsequently hot extruded) after heating to high temperature for prolonged times. The powder may be in atomized or flake form, and during hot working the applied pressure is reported to plastically deform the aluminum powder, thus breaking the oxide skin and welding the particles together. Irmann attributes the remarkable properties to the dispersion of oxide inclusions. Specifically, the product described by Irmann is one labeled SAP (Sintered Aluminum Powder) in which the initial flake powder is so fine that at least 50 pct of the flakes have one dimension of 2 microns or less. The composition of the starting aluminum shows in percent, Fe, 0.18; Si, 0.19; Zn, 0.06; Ti, 0.03; Cu, Mn, Mg, all nil; balance Al, approximately 99.5 pct. Aluminum is not the only material that has been found to have increased resistance to deformation at elevated temperatures when produced by powder metallurgy. It has been reported by Middleton, Pf eil, and Rhodes- hat platinum has a higher recrys-tallization temperature when produced by powder metallurgy and exhibits peculiar properties, many of which are similar to those of the aluminum powder products. Difficulties were encountered in explaining the reason for the strengthening in the case of platinum since the existence of the oxide is doubtful. The authors attributed the special properties to "a small amount of suitably dispersed porosity." This theory was supported by von -~eer-leder4 in the discussion to the paper, and the similarity between this method of hardening and that suggested by Rohner in his theory of age hardening was pointed out. R. de Fleury5 attempted to explain some of the properties in terms of the modulus of elasticity and elastic limit of alumina and aluminum while von Zeerleder examined the relationship between the yield strength and the reciprocal of the powder particle size. Boenisch and WiderholtQ dealt mainly with the corrosion resistance of the powder aluminum material and compared it with other aluminum alloys. The diffusion rates of other metals in SAP and pure aluminum have been compared by Seith and Lop-mann.&apos; They showed that the alloying metals diffuse particularly quickly in SAP possibly due to the very fine grain size. The properties of the Alcoa products were given by Lyle.&apos; The creep rupture properties of SAP and two of the Alcoa experimental powder products were compared by Gregory and Grant hnd it was shown that these products are vastly stronger at 900°F than are the best cast and wrought alloys at 600°F. Since the publication of these data, the authors have investigated two further aluminum powder products and it is the object of this paper to show how the high temperature creep rupture properties of the five materials vary with oxide content and with the structure as revealed by electron microscopy. Materials One of the five products, SAP, a sintered aluminum product, was supplied by the Societe Anonyme pourl Industrie de l,Aluminium, Neuhausen a/RHF, Switzerland, through Dr. R. Irmann, while the others, M276, M257, M293, and M255 were supplied by the Aluminum Company of America as experimental powder metallurgical products. M255- and M293 were made from coarse and fine atomized powders, respectively. The other materials were made from flake powders with significant differences in oxide content, the details of the type of powders used in the manufacture of these materials

Jan 1, 1955

By W. W. Stephens, W. J. Kroll, H. P. Holmes

THE only two methods for producing commercial quantities of malleable zirconium, up to now, have been using magnesium reduction of the anhydrous chloride under a neutral gas, and using purification of raw zirconium by the iodide dissociation method on a hot filament. The purity of the metal obtained by the latter process is about the same as that resulting from the chloride reduction, with the exception of the oxygen content, which may be about 0.05 pct lower in the iodide metal. Even traces of oxygen have a strong hardening effect on zirconium. Since, in the iodide process, the impurities, Si, Al, Fe, Ni, and Mg in the raw zirconium used, are carried over, it would appear uneconomical to use this method of refining solely to eliminate the traces of oxygen, unless very soft metal is desired. One important step to improve the iodide method, namely, dissociating pure iodide made from carbide and recycling the iodine, which would change this refining process into a method for extracting zirconium from the ore, has not yet been made. The Bureau of Mines, by using the chloride reduction, wanted to produce quantities of a reasonably pure and malleable metal at low cost for large-scale industrial use. This aim has been achieved, and a pilot plant permitting production of 600 lb of malleable zirconium per week will be described (fig. 1). Briefly, the Bureau of Mines process consists of reducing purified gaseous anhydrous zirconium chloride with fused magnesium under a noble-gas atmosphere. The reaction product, magnesium chloride, and any excess magnesium metal present are removed from the sponge zirconium in the next step by fusion and evaporation in a good vacuum at about 925°C. In this process, care is taken to keep air out of contact with the hot metal, which otherwise would contaminate the product with oxygen and nitrogen. Both these impurities embrittle zirconium even when present in an amount as low as 0.1 pct. A number of previous reports1-3 describe the method and the various improvements that finally led to a workable process. The major steps made were the production of large quantities of carbide, which is the raw material for producing the chloride, its chlorination with reasonable efficiencies, and the elimination of iron trichloride contained in the raw chloride, as well as that of the zirconium oxide which is always present in this product. The physical nature of the anhydrous chloride, which sublimes at 331°C at atmospheric pressure and melts at 420°C under a pressure of 25 atm, made it necessary to provide a special safety device on the purification and reduction vessels in the form of a lead-alloy seal, permitting escape of excess gases if pressure tended to build up. The main difficulties encountered in the reduction and in the following step, salt separation in a vacuum at elevated temperature, were caused by the material from which the reaction pot was constructed—iron. This metal reacts with zirconium at about 940°C with formation of a eutectic. The last step, salt separation by evaporation of the magnesium and magnesium chloride in a vacuum, is quite unconventional and has not been used before on such a scale. It is only due to the improved construction of high-vacuum pumps, especially oil-diffusion pumps, that such a method could be used. The various steps of the Bureau of Mines process, as described in the general outline above, may be summarized as follows: (1) production of the carbide, (2) chlorination of the carbide, (3) purification of the raw chloride, (4) reduction of the pure chloride with fused magnesium, (5) separation of excess magnesium and magnesium chloride in vacuum at elevated temperature, and (6) melting of the sponge obtained. Production of Carbide The arc furnace, described in a previous report,&apos; was improved both to reduce the graphite consumption caused by the burning of the bottom plates and to concentrate the heat in order to obtain better power efficiency. This was achieved by providing the bottom with graphite plates entirely embedded in refractory bricks, the contact with the current being made with three water-cooled copper plugs. Figs. 2 and 3 show the arrangement. The crucible, made

Jan 1, 1951

By Stuart S. Forbes

Changes and additions made to the Canadian Copper Refiners Ltd. electrolytic refinery between 1949 and 1955 are reviewed. The effect of high current density on current efficiency and section work is discussed. OPERATING and physical changes which have been made to the electrolytic tank house of Canadian Copper Refiners Ltd. suggest a review of present conditions. Previous papers1 a have described the general arrangement. Since then, expansion, closer anode spacing, and higher current densities have increased annual cathode capacity from 112,000 to 182,000 tons. A recent extension to the tank house, begun in the spring of 1954 and completed in August 1955, was undertaken to handle the monthly production of about 3,000 tons of anodes from Gasp6 Copper Mines. The anticipation of these additional receipts and large stocks of unrefined copper caused by the increase in custom smelting at Noranda made it necessary to increase production without immediately available additional cell capacity. Accordingly, from December 1954 through March 1955, the tank house was operated successfully at a current density of 24.0 amp per sq ft. Again, as of September 1955, one of the two tank house circuits is being operated at this high density. Although other refineries may operate at current densities higher than 24 amp per sq ft, none is doing so with anodes which contain silver and gold content as high as those being refined at Canadian Copper Refiners Ltd. General Arrangement The original building consisted of two parallel bays, each 660 ft long and 60 ft wide, with a 24 ft pump bay extending along the west side of the building. A previous expansion, completed in 1939, was to the west of the original building and consisted of two 60 ft parallel bays 240 ft long. The length of these two bays was extended in 1954 to 540 ft, adding one stripper and 12 commercial sections to No. 2 electrical circuit. Space is still available for an additional six commercial sections and one stripper section. Construction on these seven sections started in September 1955, and will be completed early in 1956. The tank house capacity will then be 206,000 tons of cathodes per year. In the two tank houses there is a total of 900 cells distributed as follows—commercial, 468; stripper, 36; total, 504 in the No. 1 tank house (No. 1 circuit): commercial, 360; stripper, 36; total, 396 in the No. 2 tank house (No. 2 circuit). Section arrangement consists of nine cells to a tier and two tiers or 18 cells to a section. Anodes, weighing 620 lb each, are cast with a Baltimore groove and are refined by the multiple system. Solution enters each cell through a bottom inlet at one end and overflows at the top of the opposite end. Rate of solution flow through the cells is controlled by valves at each section to 4.5 gpm. Electrical power to the tank house is now provided by nine 675 kw motor generator sets. Each set consists of a 135-12 v 5000 amp dc generator, driven by a 980 hp 2300 v synchronous motor. When No. 1 circuit is operated at 22,000 amp, five sets, at 4400 amp each, are connected in parallel. As the maximum allowable current on No. 2 electrical circuit has recently been set at 18,000 amp, only four sets are connected in parallel on No. 2 circuit. A tenth set, now being installed, will be reserved as a spare, for use in either circuit as required. Recent Changes In 1949, the annual capacity of the tank house was increased from 112,000 to 132,000 tons by closing the

Jan 1, 1957