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By John J. Gilman

BECAUSE of their layerlike structure, zinc crystals exhibit strong anisotropies for almost all physical and chemical properties. This should, and indeed does, greatly influence the plasticity of zinc for various crystal orientations. At low temperatures, the investigator of this plastic anisotropy is plagued by the great variety of deformation modes that operate. However, at high temperatures (250° to 419°C) only two deformation modes predominate: basal (0001) and prismatic (1010) glide. Furthermore, since strain hardening is virtually absent at high temperatures, the plasticity for these two modes of deformation can be very simply described by means of two equations of state. It is the purpose of this paper to describe the experimental behavior of basal and prismatic glide in zinc crystals, and to interpret this behavior in terms of other physical properties (in particular, the thermal expansion coefficients and the elastic constants) using the theory of dislocations. Fig. 1 defines the two planes of the zinc structure that will be discussed. Glide occurs very readily on the basal planes at all temperatures, and there is a very large literature on this subject. Much of the literature has been reviewed by Schmid and Boas;' it will not be reviewed here. Kolesnikovl was the first to show that if basal glide is circumvented by stressing a zinc crystal parallel to the basal planes (giving zero shear-stress on the basal planes) then, at temperatures above about 320°C, glide on the first-order prism planes occurs. His results have recently been confirmed by Cahn, Bear, and Bell." These previous workers have established the existence and crystallographic elements of prismatic glide; the present paper is concerned with the stress, strain rate, and temperature relations of prismatic glide as contrasted with basal glide. Experimental Methods The crystals were square ones, 6x6 mm, that had been grown in precision Pyrex tubes by a method that is described in detail elsewhere.' Most of the crystals were 99.999+ pct Zn (New Jersey Zinc Co. CP grade). Some were alloyed with 0.1 -+-0.005 atomic pct Cd, and chemical analysis showed that almost all of the added cadmium persisted through the crystal-growing process. For measurements of nonbasal glide, crystals were oriented with their basal planes parallel to both the rod axis and one of the flat faces of the square cross section. However, the orientation of the close-packed directions [1210] with respect to the rod-axis was variable. For basal glide measurements, the angle between the basal plane and the specimen axis was 35". The orientations were measured by the Gren-inger back-reflection X-ray method. The problem of finding a suitable method of gripping the crystals was the most serious experimental obstacle that arose. Because of the large plastic anisotropy of zinc, the usual gripping methods were unsatisfactory. Some methods that were tried were: high melting-point solder, making heads on the ends by locally melting a crystal, and electroplating nickel on the ends to form enlarged portions. For all these methods, the regions of the grips were weaker than the crystals themselves. Finally, two methods were decided upon: bend tests and direct machining of tensile specimens. In the bend tests, specimens were loaded as simple beams so that gripping was not a problem. The beams were 1 in. long and the axis of bending was parallel to the hexagonal axis of the crystals. For the crystals that were machined into tensile specimens, brass bars with slots in them were used to support the crystals, and thereby minimize the distortions due to machining. The crystals were glued into the brass bars with plastic cement which was later dissolved away with acetone. See Fig. 2, left. No clamps were used near the crystals and the machining was done using a milling machine with a fly-cutter. The tool bit was very sharply pointed to minimize burnishing. The feed was less than 1 mil per cut. The depth of cut was 2 mil for roughing cuts, and % mil for the finishing cuts. This machining method produced surface layers of tiny recrys-tallized grains only 2 to 3 mil deep, and the bodies of the crystals were not measurably disturbed. After the crystals had been machined and removed from the brass holders, they were chemically polished until about 5 mil had been removed from all their surfaces. The polishing reagent consisted of equal parts of concentrated HNO,, 30 pct H3O and ethyl alcohol; it is described in detail elsewhere." A typical crystal is shown in Fig. 2, right. The I-shaped faces are normal to the hexagonal axis of the crystal; otherwise the projections at the ends would simply shear off when the crystal was loaded. The cross section in the 2?-in. gage length is 0.215x0.115 in. It was found that the polished

Jan 1, 1957

By E. Miller, K. Komarek, W. Johnson

The activity of aluminum in solid Cr-A1 alloys has been measured by an isopiestic technique between Cr-A1890' and 1126" and 13 and 80 at. pct Al. The integral free energy of mixing has a minimum value of —5600 cal per g-atom at 59 at. pct Al. The maximum solid solubility of aluminum in chromium was determined to be 43 at. pct Al, and the composition limits of the compounds CrA14, Cr4A19, and Cr5Al, at 1000"~ were found to be 79 to 80, 66 to 70, and 59 to 63 at. pct Al, respectively. The thermodynamic properties of the Cr-A1 system have been investigated as part of a thermodynamic study of aluminum-transition metal systems.172 Little information is available on the equilibrium properties of the Cr-A1 system. The heats of formation of solid Cr-A1 alloys have been determined by Kubaschewski and Haymer at 600" and low-temperature specific heat data have also been obtained.~ More extensive work has been performed on the phase diagram, and a compilation has been provided by Hansen and Anderko,~ their phase diagram at elevated temperatures being essentially based on the work of Bradley and LU.~ The high-temperature portion of the phase diagram shows an intermediate phase CrA14 decomposing peritectically at 1018°C and existing at 82 at. pct A1 at 1000°C. They also identified the compounds with solubility limits of 72 to 75 at. pct A1 at 1000°C, and Cr5A1,, existing at 61 at. pct A1 at 1000°C. The maximum solid solubility of aluminum in chromium at 1000°C was found to be 46 at. pct Al. These elevated-temperature data were obtained by examination of quenched samples and were considered as less precise than the lower-temperature data. Koester, Wachtel, and Grube7 have revised the phase diagram as a result of their magnetic susceptibility and X-ray study. The results of this work differ appreciably from those of Bradley and Lu at temperatures above 800°C. The CrA1, compound is given as existing between 79 and 81 at. pct A1 at 1000°C, and they do not indicate the presence of a CrA13 phase reported by Bradley and Lu. They also report the compound Cr4Alg as having solubility limits of 66 to 70 at. pct A1 at 1000°C, while Bradley and Lu show this compound stable only up to 870°C. Koester et al. state that the high-temperature modification of the compound Cr5A18 is stable down to 1125"C, and not 980°C as stated by Bradley and Lu, and that the low-temperature modification of Cr5Al, has a range of homogeneity of 58 to 63 at. pct A1 at 1000°C. They also report that the maximum solid solubility of aluminum in chromium is 43 at. pct A1 at 1000°C. APPARATUS AND EXPERIMENTAL PROCEDURE An isopiestic method was employed which has been successfully applied to the determination of aluminum activities in solid ~e-All and Ni-Al alloys. Alloy specimens were held at different positions in a temperature gradient and were equilibrated with aluminum vapor from an aluminum reservoir kept at the temperature minimum of an impressed thermal gradient in a closed alumina system. Diffusion of aluminum into the specimens occurred until equilibrium was reached, at which the partial pressure of aluminum in each of the specimens was given by the vapor pressure of the pure aluminum reservoir. The activity of aluminum referred to liquid aluminum as the standard state in a given equilibrated sample at temperature T could therefore be expressed by: vapor pressure of pure aluminum at _ the temperature of the reservoir Vapor pressure of pure liquid aluminum, at specimen temperature T Since both the temperature of the aluminum reservoir and the specimen temperatures were determined experimentally, and the vapor pressure of pure aluminum is known as a function of temperature,' the activity of aluminum in a given aluminum alloy of known composition could be calculated. Initial runs were made with samples consisting of pure chromium chips placed in alumina crucibles. These runs exhibited large inconsistencies, indicating that equilibrium was not attained. High aluminum content Cr-A1 alloy powders were therefore substituted for the pure chromium specimens. The starting composition of the alloys was adjusted through experimentation until the concentration change necessary to attain equilibrium was small. In this manner, consistent results were obtained in reasonable times. SPECIMEN PREPARATION Alloy specimens were prepared from chromium of 99.997 pct minimum metallic purity: with 0.028 to 0.038 pct H, 0.0002 pct N, and 0.27 to 0.46 pct 0 (Aviquipo, Inc.). The aluminum had a purity of 99.99+ pct and the following impurities: 0.003 pct Cu; 0.002 pct S; 0.002 pct Fe; 0.001 pct Pb; 0.001 pct Ga (Aluminum Corp. of America). Alloy powders were prepared from weighed mixtures of chromium and aluminum by double-arc melt-

Jan 1, 1969

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

The factors which control the rate of dissolution of pure gold in cyanide solution were studied both directly and through measurement of solution the current-potential curves for the anodic and cathodic portions of the reaction. The mechanism of dissolution is probably electrochemical the reaction in nature, and the rate is determined by the rate of diffusion of dissolved oxygen or cyanide to the gold surface, depending on their relative concentrations. The significance of the results and the effects of impurities are considered. ALTHOUGH the dissolution of gold in aerated cyanide solutions has been used as an industrial process for treatment of gold ores since the late nineteenth century, the factors which determine the rate of the reaction have never been identified unambiguously. Studies of the rate of dissolution by Maclaurin,1 White,2 Christy,3 Beyers,4 Thompson,6 and others are contradictory in their conclusions; some claiming that diffusion of the reactants to the gold. surface controls the rate, and others that the chemical reaction is inherently slow and related to high activation energy for the reaction. Christy3 and 'Thompson" both suggest that the reaction is electrochemical in nature and that the dissolution of gold proceeds at local anodic regions while the oxygen is reduced at cathodic regions on the gold surface. Although their studies are ingenious and do indicate an electrochemical reaction under the conditions of study, their experiments were of limited nature and failed to identify the rate-controlling process in the system. The importance from an industrial viewpoint of a knowledge of the mechanism and rate-controlling factors in gold dissolution can be illustrated as follows: If the rate is controlled by a slow chemical reaction rather than by diffusion of the reactants, then an increased temperature should have a marked accelerating effect; agitation of the slurry should have no effect on rate: and increased concentration of reactants should cause acceleration of the rate. If the rate is controlled by the diffusion of one or the other of the reactants to the gold surface, then increased agitation should increase the rate; increased temperature will increase the rate, but not as much as for the case of a slow chemical reaction; increased concentration of the reactant which is diffusion limited will increase the rate; and the concentration of other reactants should be without effect on the rate. It may be concluded that for design of a commercial process for gold leaching, the rate-controlling factors of the reaction should be understood so that an intelligent choice of the conditions of agitation, temperature, and reactant concentration may be made. The experiments described here lead to the unambiguous conclusion that in a system of pure gold and a pure aerated cyanide solution the rate of dissolution is controlled either by the rate of diffusion of dissolved oxygen or cyanide to the gold surface, depending on the relative concentrations of each. There is also ample, but not conclusive, evidence that the mechanism of the reaction is identical to that of electrochemical corrosion. The practical significance of these conclusions will be discussed later in the paper. Experimental The experimental method used in this work was to employ an electrolytic cell which performed the overall gold-dissolution reaction, and to study the anodic and cathodic reactions of this cell as to their nature and the rate-controlling factors. Simple experiments on the rate of dissolution and the potential of the dissolving specimen also were performed under conditions of agitation, temperature, and concentration identical to those used in the electrode studies. Analysis of the electrode studies by well established theories of electrochemical corrosion were made, and the results were found to bear a one-to-one relation with actual rate and potential measurements. Electrode Studies: The Anodic Reaction: The gold specimen used for all of the electrode studies and the rate determination consisted of a sheet of 99.99 + pct Au wrapped around a lucite rod and sealed at the edges with plastic cement, thus forming a cylinder of gold of known and constant area (8.0 sq cm). The lucite rod was threaded into a brass spindle which could be rotated at speeds of 100, 300, and 500 rpm. For the electrode studies electrical contact between the gold cylinder and the brass spindle was made by means of a gold strip covered with plastic. The anodic dissolution of gold was studied by immersing the electrode in a solution containing known concentrations of KCN and KAu(CN)2 but free of oxygen, and by passing an anodic current through the gold electrode. The pH of the solution was maintained between 10.5 to 11.0 in these and all other tests by addition of KOH. The pH was measured before and after each test by means of a glass-elec-

Jan 1, 1955

By J Price, M. R. Geer, H. F. Yancey

COAL mine operators recognize coal as an abrasive material, because the wear of drilling, cutting, and conveying equipment is reflected as a cost item for replacement of parts. Similarly, industrial consumers of coal experience abrasive wear on all coal-handling equipment. Operators of pulverized fuel plants are doubtless most keenly aware of the abrasiveness of coal, because under the high contact pressures developed between coal and metal in pulverizers, abrasive wear is increased many fold. Moreover, experience in operating pulverized fuel plants has demonstrated that some coals are much more abrasive than others. Hardgrove' stated that maintenance costs entailed by the wear of grinding elements is often a more important variable than the cost of the power required to pulverize different coals. Craig2 also reports that one coal may cause pulverizer parts to wear several times faster than another. It is apparent, therefore, that those concerned with pulverizing coal could profitably employ a method for estimating the abrasiveness of different coals, just as they utilize standard tests for thermal value, grindability, and ash-fusion temperature to assist in selecting the most suitable and economical coal to use in a particular plant. The objective of this investigation was to develop a test procedure that would be suitable for general use in estimating the abrasiveness of coals. However, few, if any, of the standard tests now used for evaluating the properties of coal are the product of a single investigation or the result of a single investigator's efforts. Rather, in each case, a testing procedure was devised by one investigator, used by others on a wider variety of coals, and finally refined completely as the result of the joint efforts of a number of interested people. Thus, the test procedure for estimating abrasiveness developed in the course of this work may not be refined sufficiently in its present form for general use, but it may serve as the starting point from which an acceptable test procedure can be developed. The method has been used thus far on only about a dozen coals, and there has been no opportunity to attempt a correlation between experimental results and actual plant experience. Only wider use of the procedure by other investigators and correlation with plant experience can determine to what extent the method will have to be modified to render it suitable for general application. Test Method Although the literature contains no record of an attempt to devise a method for estimating the abrasiveness of coal that could be used industrially, several investigators have tested properties of coal that are closely related to its abrasiveness. The abrasiveness of a material generally is considered to be related to its hardness, and hardness tests for coal have been employed by Heywood,' O'Neill," and Mathes. Also, the resistance of coal to abrasion, a property that presumably is related to the abrasiveness of coal, was measured by Heywooda and by Simek, Pulkrabek, and Coufalik.2 11 these investigators tested only individual pieces of coal. Since coal is a heterogeneous material having components of varying properties, tests of this type can yield results having little more than academic interest. Only a test method that utilizes a representative sample of coal can give results that are useful industrially. The abrasion tests used for various other materials have been considered for adaptation to testing the abrasiveness of coal. The tests used for metals,7-9 paving and flooring,'" and rubber," cannot be used because coal is not sufficiently abrasive.~ The present experimental work was begun before World War II and was conducted by three research fellows"'" working under a joint agreement between the University of Washington and the Bureau of Mines. After a great deal of preliminary work with a variety of apparatus and materials, a test procedure was developed which consisted of rotating a test disk 2Yz in. diam in a steel mortar containing the coal sample. The shaft carrying the test disk at the lower end and a 100-lb load on the upper end was free to move vertically. The bed of coal in the mortar was kept fluid by low-pressure air admitted through a port near the bottom of the mortar. Measurable wear on an Armco iron disk could be obtained in this test procedure, but, despite extensive efforts to eliminate them, several major disadvantages remained in this test method. First, with most coals the amount of wear on the iron disk did not exceed a few milligrams. Second, a single type of disk was not applicable for all coals. A smooth iron disk gave satisfactory results with both bituminous and sub-bituminous coals, but hardly any wear with anthracite or coke. A disk having studs or projections gave more satisfactory abrasion losses with anthracite and coke and presented no operating difficulties with free-burning bituminous and sub-bituminous coals. It could not, however, be used with caking coals because these coals formed a

Jan 1, 1952

By E. P. Dahlberg, R. E. Reed-Hill

On the assumption that stress or strain relaxation occurs as the result of a thermally activated process, equations are derived relating to tensile experiments that give the strain as a function of the time under the condition of constant stress, and the stress as a function of the time for constant strain. It is demonstrated that if the strain-rate equation i = previously proPosed by Kuhlmann., is used as a starting point, then the relaxation of strain at constant stress may be expressed by the equation c = (-RT/(Y) 1tz tanh (t + is the strain capable of being relaxed at any given instant. Similarly, it is shown that the relaxation of stress at constant strain may be given by a = (-RT/B) In tanh (t + t0)/27, where a is the instantaneois value of the relaxable stress. The fact that these relationships reduce to well-known empirical equations at both large and small values of the stress Or strain is also shozcn. The present theory is shown to agree well with experimental data obtained from tensile elastic aftereffect experiments on a zirconium specimen prestrained at 77 k as to make it strongly anelastic. It is also demonstrated that elastic aftereffect data obtained using torsional specimens ?,Lay agree reasonably well with the equation derived for the case of tension. RELAXATION experiments are often employed as a means of studying metallic deformation mechanisms.' The simplest and most commonly employed techniques involve stress relaxation at constant strain and strain relaxation at constant stress. In general, however, investigations of this nature have been seriously handicapped in the past by a lack of suitable equations giving the time dependence of the relaxing variable over an interval that extends from small strains up into the region where internal-friction experiments become strain-amplitude dependent. This paper presents a derivation of such a set of equations for the case where the time-dependent part of the strain is anelastic or recoverable and the specimens are loaded in simple tension. The relaxation of strain under the condition of constant stress will be considered first. Let us assume that strain relaxation occurs as the result of a reversible thermally activated process that occurs at a number of relaxation centers lying in an elastic matrix. Then, following Kuhlmann,2 we may express the rate of strain relaxation as follows: where C is the strain rate, AFx the free energy of activation of the process controlling strain relaxation, a, the effective or average resolved stress at the relaxation centers, u an activation volume, R the universal gas constant, T the absolute temperature, > a factor with dimensions of a volume that accounts for the strain contribution of a successful operation of a unit process, N the number of relaxation centers per unit volume, and v the Debye frequency. The first term on the right of Eq. [I] represents a strain rate in the direction favored by the stress, while the second term represents the rate in the opposite direction. It is implied in Eq. [I.] that both F and v are symmetrical with respect to the two basic directions of operation of a relaxation process. Eq. [I] may also be written where and S and Q are the activation entropy and activation energy, respectively, of the relaxation process. In the following, A will be considered a constant. This is compatible with a set of experimental conditions where the relaxation rate is controlled by a single basic reversible process in which it may be assumed that the temperature dependence of the product ?Nv is negligible in comparison with the temperature variation of the exponential term. It is also implied that v, 7, and N do not depend strongly on a, . In deriving a relationship for the strain as a function of the time from her equation, equivalent to Eq. [2], Kuhlmann2 chose to consider only the limiting cases where the time was either very small or very large. It will now be shown that it is possible to integrate Eq. [2] to obtain a single equation valid over a wide range of strains if the concept of relaxable strain is introduced. The use of this quantity, which is the difference between the instantaneous value of the strain and the value of the strain at complete relaxation, represents the primary point of departure of the present theory from that of earlier workers. Let us express the effective stress at the relaxation centers in terms of strain. For this purpose we may use the following equation derived by zener3 for the case of strain relaxation at slip bands: where M? and M are the relaxed and unrelaxed moduli respectively, go the applied constant tensile stress, and m an average orientation factor that takes account of the fact that a,, the effective stress at the relaxation center, may not be a tensile stress (i.e., a

Jan 1, 1967

By Willard C. Lacy

Rather than attempting to present a summary of the many and highly varied papers that have been presented at this symposium on sampling and grade control, I will attempt to extract the general philosophy of analysis and approach, and attempt to identify the trend of future developments. First, the term "sampling" is used with its broadest connotations. A sample consists of a representative portion of a larger mass, and must represent the mass not only in the grade of contained metals or minerals, but also in all other respects in terms of mineralogy and mineral quality (1, 5), deleterious materials, recoverability of economic components, physical behavior, geophysical response (I), and even archaeological and environmental aspects (7, 11). The sample must be taken from a locality and in such a manner and quantity that it is representative of the larger rock mass. This calls for complete and accurate geological control and an understanding of the nature and distribution of the contained chemical and physical elements and a record of the effectiveness of the different sampling methods. Second, value of a given mass of ore material is based upon its profitability - the difference between recoverable value and costs to achieve recovery, beneficiation and sale. There is a strong movement in mining geology control toward more complete analysis in determining cutoff grades and in grade control, as illustrated by the kriging of metallurgical recovery factors as well as grade at the Mercur Mine (8). To achieve a "profit- ability factor" as a guide for economic mining practice requires further integration of: 1) the value of contained metal or mineral, 2) percentage recovery of values, 3) dilution of ore with waste rock, 4) addition to, or loss of value as a consequence of by-product materials or deleterious components, 5) cost of producing a saleable product plus mini- mum profit to justify the effort (cutoff), and 6) cost of land restoration (7, 11). All these parameters vary with the rock type, rock structure, mineralogy, depth, geometry, mining and metallurgical methods, but they must be sampled and analyzed if sampling and grade control are to reflect profitability. A wide variety of deposits has been presented at this symposium; each deposit with its own problems and special solutions. Deposits containing high unit-value components, e.g. precious metals and diamonds, present special problems in the obtaining of accurate samples and generally require statistical analysis control methods or may disregard or modify occasional high or occasional low values, based upon experience (12 ) Grade control may be accurate for the long term but may vary for the short term. Bulk sampling is always essential. Deposits containing metals or minerals with low unit value are very sensitive to transport costs, and they are often very sensitive to small amounts of deleterious components or differences in physical or chemical behavior. Problems of sampling and grade control change with the genetic type of deposit, with the stage of deposit development and with the size of the information base. Precious metal epithermal deposits (2, 6, 8), because of rapid vertical zonation and erratic lateral distribution of values, have always been difficult to evaluate and maintain grade control and ore reserves. On the other hand, evaluation and grade control are relatively easy in bulk-low- grade deposits (4, 13). However, these deposits generally have a low margin of profit and are sensitive to mining and beneficiaton costs, price fluctuations and political costs. Industrial mineral deposits (5) often must be evaluated on the basis of their behavior, rather than by chemical analysis. Environmental impact generally increases with the scale of the operation, but certain elements or minerals have especially high impact effects (7, 11). In the exploration phase there is no production control of sampling procedures and careful geological observations are particularly essential. The greatest number of problems is related to the oxidized outcrop where the chemical environment of the ore body has changed and the contained values may have been enriched, depleted or values left unchanged (2, 6). Present evidence suggests that gold values may be very mobile under certain conditions (2, 6) and stable under others. Everything must be sampled in detail. Principal values and by-product or deleterious elements may vary dependent upon their position within the soil profile. Such factors as geomorphic position, erosion rate, vegetation, climate, etc., may affect the interpretation (1, 3). During the development phase it is equally easy to overtest, to have "paralysis by analysis," as to undertest (3, 6). Bulk samplng and testing are

Jan 1, 1985

By F. E. Pawlek, J. K. Gerlach

The chloridizing roasting of ores is applied when metal sulfides and oxides are to be converted into soluble or volatile compounds. The chlorine required is either obtained from the admixed chlorides of sodium or calcium or added in the gaseous state. In the first part of the investigations the reaction rate of the chlorides of sodium or calcium with gas mixtures of SO,-0, or SO ,-O2 ,-SO , was measured. The rate for reactions with gas mixtures SO2-O2 is ThE chloridizing roasting of ores is applied when metal sulfides and oxides are to be converted into soluble or volatile compounds. At present the process is mainly applied to produce nonferrous metals which occur in pyrite cinders in small concentrations. Thereby the nonferrous metals are converted into water-soluble, acid-soluble, or volatile compounds whereas all the iron remains as insoluble oxide. The chlorine required is either obtained from the admixed chlorides of sodium or calcium or added in the gaseous state. The reactions occurring during the roasting process can be divided into two groups: solid-solid reaction and gas-solid reaction. The reactions between solids proceed by means of solid-state diffusion and are therefore of low velocity. The heterogeneous reactions between solids and gases of the roasting atmosphere5 are high-velocity processes and determine the velocity of the chloridizing roasting. These gas-solid reactions shall be the subject of the paper presented. In order to investigate the still little-known processes which occur during the chloridizing roasting 6-' the complex reaction is split into several partial steps. First the reactions of NaCl and CaCl, with gas mixtures of SO2 and 0, have been investigated at temperatures between 500" and 600°C by measuring the weight increase of the samples. The gas mixtures used in this series of experiments had first variable compositions, then the amount of SO 2 had been increased. Furthermore the influence of Fe 2 O3 admixtures upon these reactions, the behavior of pure Fe 2 O3 with the gaseous reactants, and the chlorination of the sulfides of lead, copper, nickel, and zinc have been investigated. FORMATION OF GASEOUS CHLORINE Pyrite cinders are never completely roasted and therefore contain still a small amount of sulfide sulfur. When heated again in air, this sulfur is converted into SO,. Accordingly the formation of chlorine can first be described by the reactions: dependent on the composition of the gas phase. If more than 1 pct SO 3 is added to the roasting gas, the reaction rate is determined only by the concentrations of the SO,. In the second part the reactions between chlorine and metal sulfides are discussed. The rate of formation of gaseous chlorine is higher by me order of magnitude than is the reaction rate between ZnS and chlorine. The reaction rate of NiS and PbS lies considerably below that of ZnS. The conversion rate of both pure Fe 2 O 3 and Fe 2 O 3 containing NaCl or CaCl2 when reacting with SO2-O2, mixtures with and without SO3 portions was measured at temperatures of 500", 550°, and 600°C. The weight increase of pressings was determined by means of a spiral balanceg and the reaction rate calculated therefrom according to Eqs. [ll to [31 and [5] to [7]. The prepared samples were suspended on a platinum filament in a vertically mounted tube of mullite (ID 4 cm, length 110 cm) which could be heated by a resistance tube furnace. The platinum filament was tied to the lower end of the spiral balance. A supremax glass tube (length 70 cm) was mounted gas-tight on top of the reaction tube. The unit was sealed up at its top by a ground-in stopper which was holding the spiral balance with the sample. The spiral balance therefore hung outside the high-temperature region of the furnace. Fig. 2 shows the experimental arrangement schematically. While lowering the sample into the reaction tube pure nitrogen was flowing through the reaction zone providing a protective atmosphere. After the sample had reached the reaction temperature within approximately 1 min, the protective gas was replaced by the sulfur dioxide-oxygen reaction mixture. It took about 30 sec until the mixture filled the tube homogeneously. A Ni/NiCr thermocouple placed in the center of the furnace where the sample hung during the measure-

Jan 1, 1968

On the Art of Metallography (Howe Memorial Lecture), by F. F. Lucas; Beneficiation of Iron Ore. Abstract of paper by C. E. Williams followed by Round Table Discussion; A Statistical Analysis of Blast-furnace Data, by R. 8. McCaffery and R. G. Stephenson; Air Discharge of Circular Tuyeres, by R. S. McCaffery and D. E. Krause; Open-hearth Steel Process as a Problem in Chemical Kinetics. by E. R. Jette; Carbon-oxygen Equilibrium in Liquid Iron, by H. C. Vacher and E. H. Hamilton; A Thermodynamic Study of the Phasial Equilibria in the Bystem Iron-carbon (Abstract), by Yap, Chu-Phay; Influence of Dissolved Carbide on the Equilibria of the System Iron-carbon (Abstract), by Yap, Chu-Phay; Inclusions and Their Effect on Impact Strength of Steel, I and 11, by A. B. Kinzel and W. Crafts: Method for Electrolytic Extraction of MnO, MnS, FeS and Si02, Inclusions from Plain Carbon Steels, by G. R. Fitterer; Permanent Growth of Gray Cast Iron, by W. E. Remmers; Some Notes on Blue Brittleness, by L. R. van Wert; Austenite-pearlite Transformation and the Transition Constituents, by A. Sauveur; Age-hardening of Austenite, by F. R. Hensel; Transformational Characteristics of Iron-manganese Alloys, by H. Scott; Composition Limits of the Alpha-gamma Loop in the Iron-tungsten System, by W. P. Sykes; Magnetic Properties Versus AUotropic Transformations of Iron Alloys, by T. D. Yensen and N. A. Ziegler; Dilatometric Study of Chrome-nickel-iron Alloys, by V. N. Krivobok and M. Gensamer; Low-carbon Steel, by H. B. Pulsifer; Bright Annealing of Steels in Hydrogen, by F. C. KeUey; Development of Continuous Gas Carburieing, by R. J. Cowan. Transactions, Institute of Metals Division, 1931. 500 pages. Index. Papers and discussions presented before the Division at Chicago, Sept. 22-26, 1930 and New York, Feb. 16-19, 1931. X-ray MetallograpIhy: X-ray Determination of Alloy Equilibrium Diagrams (Annual Lecture), by A. F. Westgren; Suppressed Constitutional Changes in Alloys. by G. Sachs; Texture of Metals after Cold Deformation; by F. Wever. Theoretical Metallurgy: Studies upon the Widmanatitten Structure. I.—Introduction. The Aluminum-eilver System and the Copper-silicon System; by R. F. Mehl and C. S. Barrett; Studies upon the Widmanstatten Structure, 11.—The Beta Copper-einc Alloys and the Beta Copper-alumnum Alloys, by R. F. Mehl and 0. T. Mareke; Application of X-rays in the Manufacture of Telephone Apparatus, by M. Baeyerts; Thermal Conductivity of Copper Alloys. 11.—Copper-tin Alloys; 111.—Copper-phosphorus Alloys, by Cyril Stanley Smith; Thermodynamic Study of the Equilibria of the Systems Antimony-bismuth and Antimony-lead, by Yap, Chu-Phay. Ganeral: Cemented Tungsten Carbide; a Study of the Action of the Cementing Material, by L. L. Wyman and F. C. Kelley; Influence of Casting Practice on Physical Properties of Die Castings, by C. Pack; Fabrication of the Platinum Metals, by C. S. Sivil; Effect of Certain Alloying Elements on Structure and Hardness of Aluminum Bronze, by 9. F. Hermann and F. T. Sisco. The WorkinG oF Metals: Metal Working in Power Presses, by E. V. Crane; Forming Properties of Thin Sheets of Some Nonferrous Metals, by W. A. Straw, M. D. Helfrick and C. R. Fischrupp; Die Pressing of Braas and Copper Alloys, by J. R. Freeman. Jr.; Plasticity of Copper-sina Alloys at Elevated Temperatures. by A. Morris: Directional Properties in Cold-rolled and Annealed Copper, by A. Phillips and E. 9. Bunn; Effect of Combinations of Strain and Heat Treatment on Properties of Some Age-hardening Copper Alloys by W. C. Ellis and E. E. Schumacher; Constituents of Aluminum-iron-silicon Alloys, by W, L. Fink and K. R. Van Horn; Equilibrium Relations in Aluminum-antimony Alloys of High Purity, by E. H. Dix, Jr., F. KeUer and L. A. Willey; Equilibrium Relations in Aluminum-magnesium Silicide Alloys of High Purity, by E. H. Dix. Jr., F. Keller and R. W. Graham; Constitution of High-purity Aluminum-titanium Alloys, by W. L. Fink, K. R. Van Horn and P. M. Budge; Experiments on Retarding the Age-hardening of Duralumin, by E. H. Dix. Jr. and F. KeUer; Aluminum-silicon-magnesium Casting Alloys, by R. S. Archer and L. W. Kempf; Modulurr of Elasticity of Aluminum Alloys, by R. L. Templin and D. A. Paul; Quenching of Alclad Sheet in Oil, by H. C. Knerr.

Jan 1, 1931

By R. R. Vandervoort

The creep behavior of Nb(Cb), Ta, Mo, and W was determined under conditions of constant atomic dif-fzisivity, constant stress to elastic modulus ratio, and nearly equivalent grain size, and the steady-state creep rates obtained from these tests were correlated with calculated stacking fault energies for the metals. These results, in conjunction with similar data for several fccMetals,13 suggest that stacking fault energy may influence the creep strength ofbcc metals. The interrelationship between steady-state creep rate, subgrain size, and stacking fault energy was examined. It was found that the subgrain size for a given creep stress, increased as stacking fault energy increased, but that this relationship did not cormpletely account for the effect of stacking fault energy on creep rate. The crystallography and energetics of stacking fault formation in bcc metals has been discussed by a num-ber of authors,1-5 and impurity stabilized stacking faults on (112) planes have been observed in Nb,6,7 w,8,9 Fe,] and V" by transmission electron microscopy. However, a crucial question is whether or not stack-ing faults influence the mechanical strength of bcc metals. Potentially, stacking faults could increase strength by reducing the mobility of the partial dis-locations bounding the fault, by acting as barriers to slip dislocations, and by retarding the climb of dislo-cations during high-temperature deformation. The objective of this study was to seek a correlation be-tween creep strength and stacking fault energy for several bcc metals; namely, Nb, Ta, Mo, and W. The creep behavior of most polycrystalline metals and alloys at high temperatures and moderate stresses can be described by the following relation:11,12 im=Af(s) where i, = minimum creep rate, A = constant, j(s) = a function involving metallurgical structure, a = applied stress, E = average elastic modulus at the test tempera-ture, w = constant (equal to 5 for most pure metals), D = diffusion coefficient. One factor in the structure function F(s) which sig- R. R. VANDERVOORT, Member AlME is Research Metallurgist, Process and Materials Development Division, Chemistry Department, Lawrence Radiation Laboratory, University of California, Livermore, Calif. Manuscript submitted February 28, 1969. IMD nificantly affects the creep resistance of fcc metals is stacking fault energy, and creep rate has been shown to vary directly with stacking fault energy to the 3.5 power." In the latter investigation, four fcc metals of widely different stacking fault energies (Ag, Cu, Ni, and Al) were creep tested at a constant stress to modulus ratio of 1.21 x 10-4, at a constant diffusivity of 2.7 x 10-12 sq cm per sec, and at nearly equivalent grain sizes of about 0.7 mm. The creep data were then correlated with stacking fault energies. In the present study, a similar procedure was followed. All materials used in this work were consolidated by powder metallurgy techniques. Impurity contents in the as-received materials are listed in Table I. Chemical analyses showed that no measurable contamination of the test specimens occurred during pretest annealing treatments or creep testing. Specimens with a gage section 0.75 by 0.125 by 0.050 in. were creep tested in tension in a vacuum of less than 10-9 torr. Deformation at temperature was measured by tracking fiducial marks on the gage section of the specimen with an optical comparator. Optical deformation measurements also permitted observation of the macroscopic characteristics of the deformation Table I. Typical Specimen Impurity Content, ppm Nb Ta Mo W C 45 10 155 6 O 185 30 4 10 N 30 6 3 2 H 5 I 1 <1 als 3 10 2 15 Ca <5 I3 5 Cr 5 <3 10 <5 Cu 10 50 2 15 Fc 10 10 150 35 Ni 2 150 20 <5 Si <I0 1 3 <10 Ta 100 Ti 10 8 1 Zi 15 50 1 3 Table II. Test Conditions for Constant Stress-Modulus Ratio of 6 X 10.&apos; and Constant Diffusivity of 2.7 X 10-12 sq cm per see, and Grain Size Values for the Given Pretest Annealing Treatments Literature references Pretest Annealing for E and D Treatment Stress, Temperature, ___"&apos;Values__ Grain Tempera-Metal psi "C E D Size, mm ture, .C Time hr Nb 745 1525 14 15 to 17 0.83 1650 I Ta 1220 1770 18 19.20 O.91 1800 I Mo 1975 1630 18 21 0.77 2200 I W 2140 2265 18 22 040 2400 5

Jan 1, 1970

By D. W. Rudd, D. W. Vose, S. Johnson

The permeability of Mo-0.5 pel Ti to hydrogen was investigated over a limited range of temperature and pressuire (709° to 1100°C, 1.i and 2.0 atm). The resulting permeability, p, is found to obey the The experimental data justifies the permeation mechanism as a diffusion contl-olled pnssage of Ilvdrogen atoms through the metal barrier. 1 HE permeability of metals to hydrogen has been investigated by a number of workers and their published results have been tabulated by Barrer&apos; up to 1951. Since most of the work on the permeability has been accomplished prior to this date, the compilation is fairly complete. Mathematical discussion of the permeability process has been reported by Barrer, smithells, and more recently by zener. From these efforts several facts are observed. First, the permeability of metals to diatomic gases involves the passage through the metal of individual atoms of the permeating gas. This is evidenced by the fact that the rate of permeation is directly proportional to the square root of the gas pressure. Second, the gas permeates the lattice of the metal and not along grain boundaries. It was shown by Smithells and Ransley that the rate of permeation through single-crystal iron was the same after the iron had been recrystallized into several smaller crystals. Third, it has been observed that the rate of permeation is inversely proportional to the thickness of the metal membrane. Johnson and Larose5 verified these phenomena by measurirlg the permeation of oxygen through silver foils of various thicknesses. Similar findings were noted by Lombard6 for the system H-Ni and by Lewkonja and Baukloh7 for H-Fe. Finally, it has been determined that for a gas to permeate a metal, activated adsorption of the gas on the metal must take place. Rare gases are not adsorbed by metals, and attempts to measure permeabilities of these gases have proved futile. ~~der&apos; found negative results on the permeability of iron to argon. Also, Baukloh and Kayser found nickel impervious to helium, neon, argon, and krypton. From what was stated above concerning the dependence of the rate on the reciprocal thickness of the metal barrier, it is seen that although adsorption is a very important process, at least in determining whether permeation will or will not ensue, it is not the rate determining process for the common metals. A case in which adsorption is of sufficient inlportance to cause abnormal behavior has been noted in the case of Inconel-hydrogen and various stainless steels.&apos;&apos; APPARATUS The apparatus used in this study is shown in Fig. 1. The membrane is a thin disc (A), but is an integral part of an entire membrane assembly. The entire unit is one piece, being machined from a solid ingot of metal stock. When finished, the membrane assembly is about 5 in. long. Two membrane assemblies were made; the dimensions of the membranes are given in Table I. The wall thickness is large compared to the thickness of the membrane, being on the average in the ratio of 13 to 1. There exists in this design the possibility that some gas may diffuse around the corner section of the membrane where it joins the walls of the membrane assembly, If such an effect is present, it is of a small order of magnitude, as evidenced by the agreement of the values of permeability between the two membranes under the same temperature and pressure. A thermocouple well (B) is drilled to the vicinity of the membrane. The entire membrane assembly is then encased in an Inconel jacket and mounted in a resistance furnace. The interior of the jacket is connected to an auxiliary vacuum pump and is always kept evacuated so that the membrane assembly will suffer no oxidation at the temperatures at which measurements are taken. The advantages of this configuration are: 1) there are no welds about the membrane itself, so that the chance of welding material diffusing into the membrane at elevated temperatures is remote. 2) It is possible to maintain the membrane at a constant temperature. Since the resulting permeation rate is very dependent upon temperature, it is advisable to be as free as possible from all temperature gradients. 3) It is possible to obtain reproducible results using different specimens. The only disadvantage to this configuration is the welds (at C) in the hot zone. The welding of molybdenum to the degree of per-

Jan 1, 1962

By G. F. Leaming

The paper by R.V. Ramani and R.J. Sweigard is a wonderful description of the labyrinthine web that has been spun about the mining industry by energetic bureaucrats and politicians over the past 50 years. The remedy for the problem, however, is not more of the same, but less. That may be difficult for the industry to achieve, for it is not a technical solution but a political one. And the current fervor for more detailed planning at all levels of government and private enterprise has become deeply ingrained. The authors recommend the provision of more information about mining and mineral resources to "macro" (i.e., government) land use planners. They apparently overlook, however, the already strong tendency on the part of most government land use planners to consider themselves omniscient. Thus, giving them more information about the technical problems of mining will only make them want to get more and more involved in the "micro" (private, site specific) mine development and production plans of the individual mining firm. In fact, this has already happened at all levels of jurisdiction from municipal to federal government. Examples are legion. The most effective way to ameliorate the adverse impacts of government land use planning on existing and potential mining operations is to: (1) introduce greater flexibility in the definition of land use zones by local and state governments; (2) adopt realistic and relevant ambient environmental performance standards in governing relationships between mineral land uses and concurrent or subsequent nonmining land uses; (3) allow greater leeway for economic considerations in land use decisions in contrast to the explicit legalistic approach now in vogue; (4) recognize that all minerals are not the same and that sand and gravel mining should not be treated the same as underground metal mining, coal stripping, oil field production, or in situ leaching; and (5) eliminate the notion that mining operators should be responsible for determining in detail the use of land by subsequent owners of mined land. This last bit of conventional ethic really makes no more sense than requiring the builders of every shopping center or government office complex to provide detailed plans for the use of that land when its use for shopping or government is ended. Did the builder of Ebbetts Field plan for Brooklyn after the Dodgers went to Los Angeles? Should the developer of the Bingham Pit plan for suburban Salt Lake City after the copper mining goes to Chile? The nation&apos;s mining industry must address these questions before further bankrupting itself to provide more data to planners and spending thousands of dollars per acre to create land that when reclaimed is worth only a few hundred dollars per acre. ? Reply by R.V. Ramani and R.J. Sweigard We thank Mr. Learning for his valuable contribution. His views on the problems of land use planning and mineral resources are most welcome additions to our paper. As the title indicates, our paper was more concerned with the impacts of land use planning on mineral resource conservation than with the details of the planning process. On the whole, his five recommendations would be helpful for mineral resource conservation. However, we would suggest that the argument he presents for his final recommendation does not address the differences between mining as a land use and commercial or institutional uses. We believe that this difference is the crux of the issue. We share Mr. Learning&apos;s desire to ameliorate the adverse impacts of land use planning. Possibly the most detrimental impact is the loss of mineral resources. Any development, whether mineral or community, that does not give proper consideration to other resources can result in permanent loss or sterilization of resources. With proper planning, some of these losses can be avoided. As our paper indicated, one factor that limits the consideration of mineral resources, and ultimately leads to their sterilization, is the generally inadequate levels of resource characterization and understanding of the unique nature of mineral resources and mining operations. The last point raised by Mr. Learning is also important. In terms of reclamation and land use planning in mining districts, we certainly do not advocate spending more than what the results are worth. The main thrust of the paper was to explore the avenues for conserving the mineral resources so that, at some appropriate time, the issue of mining and reclamation can still be addressed. ?

Jan 1, 1986

By D. J. McAdam

In a series of papers the author and associates have discussed the influence of temperature on the tensile properties of metals.11-18 These papers present much information about the influence of temperature and the stress system on the conventional indices of mechanical properties, with special attention to the fracture stress. A recent study of the data, however, has revealed much additional information about the influence of temperature on the fundamental factors involved in the flow of metals. The present paper presents results of this study. Attention will be confined almost entirely to results derived from tension tests of unnotched cylindrical specimens at strain rates a little slower than those used in ordinary tension tests. According to a concept first presented by Ludwik and elaborated in recent papers by others,8,9,22,23 the mechanical state of a metal depends on the total plastic strain, but not on the temperature during straining, provided that the only structural changes are those essential to plastic deformation. In the summer of 1948, however, the author made the previously mentioned study of results of a general investigation by the author and associates and reached the conclusion that the mechanical state depends not only on the total strain, but also on the temperature during the straining. A number of diagrams were then prepared. These conclusions were presented without diagrams in a discussion last October of a paper by Dorn, Goldberg and Tietz.2 The metals used in the investigation on which this paper is based were Monel and oxygen-free copper. The Monel was supplied by the International Nickel Co. through the courtesy of Dr. W. A. Mudge. The copper was supplied by the Scomet Engineering Co. through the courtesy of Dr. Sidney Rolle. The data to be presented are based on results of tests at temperatures ranging between 165 and — 188°C. Description of the apparatus and methods of test are given in previous papers.1011&apos;1"2 The present paper is the first part of the general discussion of the influence to temperature on the stress-strain-energy relationship for metals. The next paper will deal with metals that are subject to structural changes other than those induced solely by plastic deformation. Influence of Temperature and Plastic Strain on the Flow Stress of Monel and Copper For a study of the influence of temperature on the stress-strain relationship, flow-stress curves obtained with annealed metals at various temperatures will be compared with curves obtained with the same metals after cold drawing or cold rolling at room temperature. Diagrams thus obtained with Monel and copper are shown in Fig 1 to 8. Fig 1 to 7 show the variation of the flow stress with temperature and plastic strain; Fig 8 is a diagram of a different type, derived from Fig 4 to 7. In Fig 1 to 7 strain is expressed in terms of A0/A, in which A0, and A represent the initial and current areas of cross-section. Since values of Ao/A are represented on a logarithmic scale, abscissas are proportional to true strains; moreover, the true strains representing prior plastic deformation and those representing subsequent strain during a tension test are directly additive. Fig 1 shows flow-stress curves obtained with annealed Monel. Five of the curves are based on results of tension tests. Between yield and the maximum load, the flow was under longitudinal tensile stress; between the maximum load and fracture, the local contraction induced transverse radial tensile stress. The portions of curves designated F, therefore, represent flow with increasing radial stress ratio, the ratio of the transverse stress S3 to the longitudinal stress Si. Curve Fo is based on the ultimate stresses of specimens taken from bars that had been cold drawn various amounts.17 Since the tensile stress at the maximum load is unidirectional, curve Fo represents the course that a flow-stress curve would take if the stress during an entire tension test could be kept unidirectional. The flow-stress curve F obtained at room temperature (Fig 1) has been established accurately by numerous measurements of the diameter of the specimen during the extension from yield to fracture.17 At the time of the experiments, however, no apparatus was available for measuring the diameter during tension tests at low temperatures. Nevertheless, curves have been established to represent with sufficient accuracy the flow at low temperatures. Each flow-stress curve must be tangent to a curve U, which starts at a point representing the ultimate stress of annealed metal. Since the ultimate stress is based on the area of

Jan 1, 1950

By S. G. Gibbs

A new method for predicting the behavior of sucker-rod pumping systems is presented. The pumping system is described by a flexible mathematical model which is solved by means of partial diflerence equations with the aid of computers. Polished rod and intermediate-depth dynamometer cards can be calculated for various bottom-hole pump conditions. The technique permits simulation of a wide variety of operating conditions, both normal and abnormal. The data generated with the new technique are useful in refining the criteria for design and operation of sucker-rod systms. INTRODUCTION Sucker-rod pumping systems are used in approximately 90 per cent of artificially lifted wells. In view of this wide application, it behooves the industry to have a fundamental understanding of the sucker-rod pumping process. Oddly enough, our understanding has been rather superficial. This is evidenced by the semi-empirical formulas which have been used as the basis for design and operation of sucker-rod installations. Thoueh- we have realized the limitations of our methods for many years, it has not been computationally feasible to use more refined techniques. With the advent and widespread use of digital computers, it is now possible to handle the mathematical problems associated with sucker-rod pumping. This paper summarizes a computer-oriented method which can provide greater insight into the sucker-rod pumping process. It is hoped that this technique, and techniques which may evolve from it, will prove to be the tool needed by industry to obtain the most efficient use of rod pumping equipment. THE MATHEMATICAL MODEL Prediction of sucker-rod system behavior involves the solution of a boundary value problem. Such a problem includes a differential equation and a set of boundary conditions. For the sucker-rod problem, the wave equation is used, together with boundary conditions which describe the initial stress and velocity of the sucker rods, the motion of the polished rod and the operation of the down-hole pump. Of these items, the wave equation, the polished rod motion condition and the down-hole pump conditions are of primary importance. Discussion of the mathematical model centers about these factors. ROD STRING SIMULATION WITH THE WAVE EQUATION The one-dimensional wave equation with viscous damp- is used in the sucker-rod boundary value problem to simulate the behavior of the rod string. This equation describes the longitudinal vibrations in a long slender rod and, hence, is ideal for the sucker-rod application. Its use incorporates into the mathematical model the phenomenon of force wave reflection, which is an important characteristic of real systems. The viscous damping effect postulated in Eq. 1 yields good solutions, even though nonviscous effects such as coulcomb friction and hysteresis loss in the rod material are present. Fortunately, the nonviscous effects are relatively small, so the viscous damping approximation used in the wave equation is adequate. The coefficient v is a dimensionless damping factor which is found in field measurements to vary over fairly narrow limits. For mathematical convenience the gravity term is omitted in Eq. 1. The effect of gravity on rod load and stretch can be treated separately, as will be noted later. Since Eq. 1 is linear, the legitimacy of this procedure is easy to demonstrate. POLlSHED ROD MOTION SIMULATION The motion of the polished rod is determined by the geometry of the surface pumping unit and the torque-speed characteristics of its prime mover. By determining the motion of the polished rod, we formulate an important boundary condition. From trigonometrical considerations it can be shown that the position of the polished rod vs crank angle 0 is given by (see Fig. 1) These equations are obtained from the general solution of the "four-bar" linkage problem and can be used to describe the kinematics of any modern beam pumping unit.&apos; If prime mover speed variations are disregarded, the angular velocity of the crank is constant, and Eq. 2 can be used to predict the position of the polished rod vs time. However, the constant-speed condition leading to constant crank angular velocity is only approached in practice: hence, it is better to make provisions for prime mover speed variations in the mathematical model. The speed at which the prime mover runs is determined by its torque-speed characteristics and the torque imposed upon it. The torque that the prime mover "feels" is the net torque arising from the polished rod load and the opposing torque from the counterbalance effect. The

ARTICLE I Name and Object Sec. 1. This Division shall be known as the Institute of Metals Division of the American Institute of Mining and Metallurgical Engineers. Sec. 2. The object of the Division shall be to furnish a medium of cooperation between those interested in the field of physical metallurgy; that is, the nature, structure, alloying, fabrication, heat treatment, properties and uses of metals; to represent the AIME insofar as physical metallurgy is concerned, within the rights given in AIME Bylaw, Article XI, Sec. 2, and not inconsistent with the Constitution and Bylaws of the AIME; to hold meetings for the discussion of physical metallurgy; to stimulate the writing, publication, presentation and discussion of papers of high quality on physical metallurgy; to accept or reject papers for presentation before meetings of the Division. ARTICLE II Members Sec. 1. Any member of the AIME of any class and in good standing may become a member of this Division upon registering in writing a desire to do so, but without additional dues. Sec. 2. Any member not in good standing in the AIME shall forfeit his privileges in the Division. ARTICLE III Funds Sec. 1. The expenditure of the funds received by the Division shall be authorized by the Executive Committee of the Division. ARTICLE IV Meetings Sec. 1. The Division shall meet at the same time and place as the annual meeting of the AIME, and at such other times and places as may be determined by the Executive Committee subject to the approval of the Board of Directors of the AIME. Sec. 2. The annual business meeting shall be held within a few days before or after the annual business meeting of the AIME. Sec. 3. At a meeting of the Division, for which notice has been sent to the members of the Division through the regular mail or by publication in the Journal of Metals at least one month in advance, a business meeting may be convened by order of the Executive Committee and any routine business transacted not inconsistent with these Bylaws or with the Constitution or Bylaws of the AIME. Sec. 4. For the transaction of business, the presence of a quorum of not less than 25 members of the Division shall be necessary. ARTICLE V Officers and Government Sec. 1. The officers of the Division shall consist of a Chairman, a Senior Vice-Chairman, a Vice-Chair -man, a Secretary and a Treasurer. The office of Secretary and Treasurer may be combined in one person, if desired by the Executive Committee. Sec. 2. The government of the affairs of the Division shall rest in an Executive Committee, insofar as is consistent with the Bylaws of the Division and the Constitution and Bylaws of the AIME. Sec. 3. The Executive Committee shall consist of the Chairman, Senior Vice-Chairman, Vice-Chairman, past Chairman, Secretary, and nine members, all of whom shall be nominated and elected as provided hereafter in Article VII. Sec. 4. The Chairman, Senior Vice-Chairman and Vice-Chairman shall serve for one year each, or until their successors are elected. Each member of the Executive Committee shall serve three years. The Chairman shall remain a voting member of the Executive Committee for one year after his term as Chairman. Sec. 5. The Treasurer of the Division shall be invited to meet with the Executive Committee, but without ex-officio right to vote. He shall be appointed annually by the Executive Committee, from the membership of the Executive Committee or otherwise. Sec. 6. The annual term of office for officers of the Division shall start at the close of the Annual Meeting of the Institute and shall terminate at the close of the next Annual Meeting. ARTICLE VI Committees Sec. 1. There shall be standing committees as follows: Programs Committee. Finance Committee, Membership Committee, Annual Lecture Committee, Technical Publications Committee, Mathewson Gold Medal Committee, Nominating Committee, Education Committee and such other Committees as the Executive Committee may authorize. Sec. 2. It shall be the duty of the Programs Committee to secure the presentation of papers of appropriate character at meetings of the Division. Sec. 3. It shall be the duty of the Finance Committee to inquire into and examine the financial condition of the Division and to consider proper means of increasing its revenue and limiting its expenses. The Finance Committee shall audit the accounts of the Division and report to the Executive Committee prior to the Annual Meeting of the Division. It shall render a budget to the Executive Committee estimating receipts and expenses for the ensuing year so that action can be taken on same at the first meeting following the Annual Meeting.

Jan 1, 1953

By A. E. Bibb, J. R. Fascia

Single-crystal wafers of zirconium have been exposed to 680°F neutral water. The single crystals were of known orientation and weight-gain data as a function of crystal orientation were obtained. These data show that all the crystal faces studied obeyed a cubic rate law out to the time of transition whereupon the crystals corroded at an approximately linear rate. The time to transition varied from 114 days for (1074) crystals to about 325 days for the (2130) faces. The epitaxial relationship be-tween metal and monoclinic oxide was found to be (0001) H (111) and [1120] 11 [101]. A black tight adherent oxide layer was formed on the crystals in the pretransition range. This black oxide was found to be monocrystalline. The white corrosion product produced after transition was found to be polycrys-talline but highly oriented. X-ray line-broadening studies found that the black oxide was a highly strained structure whereas the white oxide was relatively strain-free. These results indicate a strain-induced re crystallization or fragmentation accompanies the change from protective black oxide to nonprotective white oxide. ZIRCONIUM alloys have been used quite extensively in high-temperature aqueous environments. Alloy additions can be made to commercial sponge zirconium which enhance the corrosion resistance of the zirconium in both water and steam media, which raise the tolerance limit for certain impurities detrimental to corrosion resistance, and which reduce the amount of free hydrogen pickup during corrosion. The development of the corrosion-resistant zirconium alloys has been a long and tedious job involving trial and error methods. This technique has been necessary because of a lack of fundamental data and hence understanding of the corrosion mechanisms. The objective of the work described herein was to provide some fundamental data with respect to the aqueous corrosion of zirconium crystals as a function of the orientation of the exposed surfaces. Hg. The zirconium chunk was then cooled to below the transformation temperature (862°C) and reheated to 1200°C for 8 hr. The ultimate size of the zirconium grains increased with the number of cycles. Rapid or even furnace cooling through the transformation temperature produces a considerable amount of substructure which was intolerable in corrosion experiments as it would be in the study of any crystallographically dependent property. It was found that a high-temperature a-phase anneal for approximately 4 days reduced the substructure below the limits detectable by visual or X-ray means. Crystals so produced were carefully cut from the massive zirconium chunk and oriented by standard back-reflection Laue techniques. The crystals were then mounted in a goniometer head and, by using the three degrees of freedom available, slices on the order of 0.015 to 0.020 in. were cut parallel to any desired crystal plane. These slices were then carefully polished on both sides to produce smooth flat faces, pickled to remove about 0.002 in. per face, annealed for 1/2 hr at &apos;750°C in a vacuum of approximately 10"5 mm Hg, flash pickled, and checked for orientation. The pickling solution was 45-45-10 vol pct HN0,-H20-HF and continuous agitation was provided to eliminate pitting of the slices. Any slice that was not within 2 deg of the desired orientation was discarded, and any evidence of substructure as indicated by the Laue spots was also grounds for discarding the sample. Thin slices were used for the corrosion tests because weight gain per area data could be obtained with only a minimum area exposed to the corrosive media that was not of the desired orientation. The thin single-crystal slices were of irregular shape and as a result the areas were determined by placing a crystal inside an inscribed square of known area, enlarging a picture of this assembly about X5, and tracing both the enlarged square and crystal with a planimeter. The zirconium used to produce these single crystals was crystal-bar grade, a typical analysis of which is given in Table I. An oxygen analysis on prepared crystals gave a concentration of 205 ppm. The hydrogen concentrations are believed to be less than 15 ppm due to the dynamic vacuum anneal given each crystal. Typical nitrogen values for zirconium treated in this manner are about 10 to 20 ppm. RESULTS AND DISCUSSION Single-crystal wafers have been exposed to de-oxygenated, deionized water in static autoclaves.

Jan 1, 1964

By G. H. Wilson

INTRODUCED in 1946 to serve a need in power-plant operation, closed-circuit TV has been used by well over 200 organizations in approximately 25 different industries. Known as industrial television, or simply ITV, it can be described as a private system wherein the television signal is restricted in distribution, usually by confinement within coaxial cable that directly connects the TV camera to one or several monitors, Figs. 1, 2. The picture is continuous and transmission is instantaneous, permitting an observer to see an operation that may be too distant, too inaccessible, or too dangerous to be viewed directly. Destructive testing or the machining of high explosives can now be conducted hundreds of feet away by personnel who still have close control through the eyes of the TV camera. It is also possible for one man to control operations formerly requiring the co-ordinated efforts of several workers. For example, at a large midwestern cement plant conveyance of limestone from primary crusher to raw mill and loading into five storage bins once necessitated the work of two men, one having little to do but prevent spilling of material by manually moving the tripper on the belt conveyor as occasion required. TV cameras mounted on the tripper now provide bin level indication to the conveyor operator at the crusher position so he is able to control the entire loading operation remotely, Fig. 3. By means of a switch, the picture from either camera is alternately available on a single viewer, or monitor, Fig. 4. Each camera is mounted on the tripper by means of a simple adjustable support and looks down into the bin, which is identified by the number of cross members on the vertical rod. Each associated power unit is located on a platform above the camera, Fig. 5. This centralized control by means of TV often has produced superior results, and in many instances saving in operating costs has been sufficient to write off equipment costs within six months to a year. Where a key portion of a process may be enclosed or otherwise inaccessible, TV again reduces the likelihood of mistakes and permits closer control by making available to the operator valuable information he might otherwise never possess. An example of this can be found at a strip mine where the coal seam lies 50 ft or more below the overburden, which is removed by a large wheel shovel. From his centrally located position the shove1 operator was unable to judge accurately to what extent the wheel buckets engaged the earth. His chief indication of efficiency was the amount of overburden on the belt conveyor as it passed his control point 75 ft from the wheel. Now, two television cameras mounted on the tip of the boom permit the operator to view the wheel from each side and provide him with a close-up view of the buckets so that he can take immediate and continuous advantage of their capacity, quickly compensating for ground irregularities and avoiding obstructions, Fig. 6. While the word television conjures up visions of highly complex and intricate apparatus such as that employed in modern TV studios and transmitting stations, the term industrial television should indicate compact, straightforward equipment. Most present-day ITV systems contain fewer than 25 tubes including camera and picture tubes. The average home television receiver alone requires at least that many tubes. Equipment like that illustrated in Fig. 1 contains only 17 tubes, of which 3 are in the camera. It can operate continuously and dependably, without protection, in any temperature from 0" to 150°F. It consumes less current than a toaster and weighs under 140 lb. Camera and monitor may be separated by 1500 to 2000 ft and by greater distance with additional amplification. This equipment is designed to withstand vibrations up to 21/16 in. and will operate successfully under more severe conditions of vibration and heat when suitable enclosures are provided. Any number of cameras may be switched to a single monitor, and any number of monitors, within reason, used simultaneously. Two types of applications in the mining industry have already been described. A third under serious consideration by several organizations will make use of ITV for remote observation of conveyor transfer points at copper concentrating plants so that evidence of belt breakdown and plugging of transfer chutes can be spotted immediately and costly overflow of material avoided. A television camera will soon be installed to view a trough conveyor near the exit of an iron-ore crusher to indicate clogging of the crusher as evidenced by reduction or absence of material on the

Jan 1, 1955

By D. W. Loucks

There is plenty of evidence to indi-cate that at least one of man&apos;s chief interests in life is to make himself as comfortable as possible. If you doubt this, just watch the fellow next to you for the next half hour trying to find the most comfortable position that a hard chair has to offer. Comfort, however, does not always mean an easy chair. To some, it may mean a wealth of money; to another, freedom from worry. But to most of us, it means first of all a comfortable atmosphere in which to live, and to a great many of us it probably also means freedom from that annoying task of firing the furnace. Today more than ever before. automatic heat is one improvement that is placed high on everyone&apos;s list. Perhaps this is because automatic heating is becoming relatively cheaper. Perhaps it is because of a good publicity campaign on the part of the oil and gas men or maybe it is just that we are getting lazier day by day. At any rate, almost every issue of Better Homes and Gardens, House Beautiful, or your other favorite home magazine carries an article extolling the virtues of this or that automatic heating system. If I were to ask you to name the first thing that came to your mind when I said automatic heat, you would prob-ably say either gas furnace or oil burner. Or if you had just been studying heating systems, you might possibly say heat pump. But chances are you would not mention anything about coal, and yet coal is the most common source of the greatest automatic heat of them all. I say this because coal is the fuel used almost universally by the district heating industry in producing and delivering to certain heavily populated areas heat ready to use at the touch of a valve or the click of a thermostat. Although the industry is over a half century old, it has not experienced the widespread development of other utility industries because of certain limitations which I believe you will realize from the next few minutes discussion. District Heating Operations We may define district heating as any operation where two or more buildings are heated from a central heating plant. The method of heat transfer may be hot water or in some cases warm air, but generally the medium of heat transfer is steam. So universally is steam used that the industry is frequently referred to as the district steam industry. The Allegheny County Steam Heating Co. which operates the district heating system in downtown Pittsburgh is a subsidiary of the Du-quesne Light Co. Although organized in 1912 primarily as a means of securing the electric load of downtown buildings, the service has now become so valuable and so popular that it is no longer considered a necessary adjunct to the electric business but rather a separate business standing on its own feet. Fig 1 shows the layout of the plants and distribution system of downtown Pittsburgh. Two generating plants, one known as the Stanwix and the other as Twelfth Street, supply the area. Each has two boilers with capacity totaling 1,350,000 lb per hour. The Stanwix Plant is supplied coal by truck. The coal is pulverized at the plant and burned as powdered fuel. Coal is supplied to the Twelfth Street Plant also by truck but the boilers arc stoker fired. Over 1 1/2 miles of tunnel house a portion of our main lines, but it requires over twelve miles of pipeline, ranging in size from 32 down to 1 in. in diameter, to supply all our customers. The distribution system consists of two systems in a sense, one high and one low pressure with certain interconnections between the two. Our high pressure system supplies steam up to 125 Ib to some but not all customers, while the low pressure system operates in the range of 10 to 20 psi. Note that the two plants are tied together through large steam mains and that the system to some extent is a loop system, making it possible to have a portion of the line shut, down without interrupting service to any customer. Fig 2 conveys a picture of the extent to which steam service is used in the downtown triangle. The black area indicates the buildings which now use district steam. The dotted area indi-

Jan 1, 1950

By N. J. Grant, C. C. Wang

The Ti-Cr-O ternary system has been studied in detail near the titanium-rich corner within the limits of 10 wt pct 0, and 20 wt pct Cr. Studies were extended, but not in detail, to the region beyond 25 wt pct 0, (50 atomic pct) and 62 wt pct Cr (60 atomic pct). Four isothermal sections at 1400°, 1200°, 1000°, and 800°C are presented as well as two vertical sections at 1 and 2 wt pct 02. DURING the last decade much interest has been shown in the development of high strength titanium alloys for high temperature and corrosion resistant applications. Extensive research is being carried out at present, as the current literature indicates, in order to study the properties of titanium and to develop improved alloys. Two of the important alloying elements in commercial titanium alloys are chromium and oxygen and it would be desirable to know their combined influence upon titanium. For this purpose the present work was carried out to investigate the titanium-rich corner of the ternary system TiICr-0. The binary systems Ti-Cr and Ti-0 have been published recently. The Ti-Cr system was studied by several investigators " and their results are in close agreement. The eutectoid decomposition of the B phase has been shown to be extremely sluggish. TiCr, was the only intermetallic compound found in this binary system and was formed at 1350°C by a transformation from the p phase. TiCr? was established as the cubic C 15 (MgCu,) type of structure with 24 atoms per unit cell and was designated as the y phase. This terminology will be adopted in the present work. There was disagreement about the actual composition of this compound among the several investigators, although it is evident from their data that the compound probably has a solubility range of about 2 to 3 pct and is in the vicinity of 65 pct Cr. It has been indicated recently that a high temperature modification of this y phase (TiCr,) existed at a temperature above 1300°C." &apos; This high temperature modification was identified as a hexagonal C 14 (MgZn,) type of structure with 12 atoms per unit cell. The exact transformation temperature from the high temperature phase to the low temperature phase has not been established. A considerable hysteresis was observed and, due to the sluggishness of this transformation, the high temperature phase often co-existed with the low temperature phase at temperatures below 1300°C. A preliminary study of several Ti-0 compounds and the Ti-0 system had been carried out by Ehr-1ich."-"&apos; The most complete binary Ti-0 system was the one reported recently by Bumps, Kessler, and Hansen." The first intermediate phase found in the system was the 8 phase which formed by a peritec-toid reaction of the phases a and Ti0 at temperatures below 925 °C. This reaction is extremely sluggish. The structure of this 8 phase was tentatively identified by these authors as being tetragonal and the lattice constants were found as c,, - 6.645A, a,, = 5.333A and c/a = 1.246A. Experimental Procedure The raw materials used for this investigation were TiO,, electrolytic chromium, iodide titanium, and sponge titanium. The TiO, was in the form of powder of chemically pure grade (99.8 pct pure). The chemical analysis of the electrolytic chromium was: 0, 0.50 pct; Fe, 0.07; Cu, N, and C, 0.01; and Pb, 0.001. The oxygen in the chromium was calculated as part of the final oxygen content of the alloys. The alloys were prepared by the cold crucible method using a tungsten arc. The entire system was evacuated and flushed with purified helium three times and then filled with helium. Each alloy was melted, turned over, and remelted at least four times to insure homogeneity. The total melting time was generally from 6 to 10 min. A master alloy of 25 pct 0,-75 pct Ti was prepared to facilitate alloying by melting compacts of TiOl powder with either iodide or sponge titanium, yielding the compound TiO. It was found necessary to bake the TiO, powder compact at about 150°C to remove adsorbed moisture. This was done to prevent the disintegration and spattering of the compact when the arc was struck. TiO, powder dissolved quite readily into the melt and no other trouble was encountered.

Jan 1, 1955

By L. A. Rapoport, W. J. Leas

The original Burkley-Leverett theory has been extended and a more detailed formulation of the waterflood behavior in linear horizontal systems is presented. Particular consideration has been given to the evaluation of capillary pressure effects and differential equations permitting an explicit evaluation of these effects have been derived. On the basis of the developed theory it is recognized that the flooding behavior is dependent upon the length of the system and the rate of injection. At the same time it has been determined that systems of different lengths yield the same flooding behavior if the injection rates and or the fluid viscosities are properly adjrrsted or "scaled." It has also been found that the sensitivity of the flooding behavior with respect to rate and length decreases as any one of these {actors increases in value and that for sufficiently long systems and high rate.; of water injection the flooding behavior becomes independent of rate and length. or "stabilized." To such stabilized conditions the theory formulated by Buckley and Leverett is applicable. A number of laboratory flooding tests have been made and good agreement Iraq been found between theory and experimental observations. The experimental results are discussed and it is shown that under field conditions the flooding behavior is usually stabilized. As a result of these finding; a procedure is indicated for evaluating field performances either on the basis of tests performed with commonly available core samples or by means of calculations using relative permeability data INTRODUCTION In recent years the development of methods for evaluating oil recovery by waterflooding has been the object of considerable research. A theoretical analysis of the mechanisms involved in the displacement of immiscible fluids was originally established by Buckle!- and Leverettl and experimental investipatio~~s have been made by numerons workers." Many of the experimental results are in mutual agreement and bear out several significant features of the flooding mechanism as predicted by theory. Thus it lias been generally recognized that a flood corresponds to the movement of a steep saturation hank or "front" (primary phase), followed by additional gradual oil displacement (subordinate phase). It has also been found that for any porous medium the flooding behavior is largely dependent upon the oil-water viscosity ratio and that for increasing values of this ratio the relative importance of the primary displacement phase decreases while that of the subordinate phase becomes more pronounced. Although the studies to date have clarified certain aspects of the flooding process. they have given rise to observations of a somewhat contradictory nature that cannot he explained in terms of the original theory. These observations pertain mainly to the effect of injection rate or pressure gradient upon recovery. Some investigators report laboratory tests that indicate incresing oil recoverieq with increasing rates of water injectill, others find the flooding behavior to be independent of and other. mention lower oil recoveries with increased injection rates.3 The conflicting evidence indicated above creates considerable uncertainty with respect to laboratory testing procedures and the utilization of the resulting data for field evaluations. The principal purpose of this paper, then, is to resolve these Uncertainties by means of a comprehensive theoretical and experimental investigation of the flooding meanism. THEORETICAL DEVELOPMENT Derivation of Flooding Equations The mathematical description of transient flow phenomena is based upon the consideration of the various processes occurring during an infinitesimal time interval in an infinitesimal volume element and upon the correlation of these processes with those occurring in the adjacent elements. The volume elements are defined as being infinitesimal in comparison to the overall dimensions of the porous system, yet each sufficiently large so aS to encompass the full range of pore openings encountered throughout the system. If a porous system can arbitrarily be subdivided into an infinite number of volume elements all possessing the same distribution of pore openings and if this distribution is unformly continuous. the system may be said to be homogeneous. Such a homogeneous porous medium is considered in the present studivs. It is furthermore postulatecl that only oil and water are present in the pornu wediu. that they act a- totally incompressible and immiscible fluids. and that gravity effects are negligible. In n linear flow system of unit cross sertional area. as treated here. the infinitesimal volume element.; to he considered are cylindrical ".slices" of thickness dx. oriented perpendicularly to the direction of flow. The equations applicable to any such volume element. at my time. describe the movement. of oil and water across the element:

Jan 1, 1953

By R. S. Wagner, W. C. Ellis

A new mechanism of crystal growth involving oapor, liquid, crnd solid phases explains many observations of the effect of implurities in crystal growth from the vapor. The role of the impuuitq is to form a liquid Solution with the crystalline tnalerial to be grown from the vapor. Since the solution is n prefevred site for deposition firorti the uapor, the liquid becorrles supersaturated. Crystal growth occurs by precipitatzon from the supersaturated liquid crt tlie solid-liquid zntevfnce. A crystalline defect, such as a screw dislocation, is not essetztial for VLS (vapor -liquid-solid) growth. The concept of the VLS mechanism is discussed in detail with reference to tire controlled growth of silicon crystals using gold, platinum, palladium, nickel, silver, or copper as an implurity agent. RECENTLY a short communication&apos; described a new concept of crystal growth from the vapor, the VLS mechanism. In this paper we present a detailed description of the process and its application to the growth of silicon crystals and we discuss its relevance to existing concepts of .&apos;whisker" crystal growth. Crystal growth from the vapor is usually explained by a theory proposed by Frank2 and developed in detail by Burton, Cabrera, and Frank.3 In this theory a screw dislocation terminating at the growth surface provides a self-perpetuating step. Accommodation of atoms at the step is energetically favorable, and is possible of much lower supersatu-ration than required for two-dimensional nucleation. Crystals of a unique form resulting from aniso-tropic growth from the vapor are "whisker" or filamentary ones. Such crystals have a lengthwise dimension orders of magnitude larger than those of the cross section. For most filamentary crystals both the fast-growth direction and directions of lateral growth have small Miller indices. The special growth form for a whisker crystal implies that the tip surface of the crystal must be a preferred growth site. sears4 proposed that, according to the Frank theory. a whisker contains a screw dislocation emergent at the growing tip. Such an axial defect provides a preferred growth site and accounts for unidirectional growth. The hypothesis was extended by Price. Vermilyea. and Webb," still implying the presence of a dislocation at the whisker tip. They postulated that impurities arriving at the fast-growing tip face become buried while those arriving on the surface of slow-growing lateral faces accumulate and thereby hinder growth. These considerations led to a whisker morphology. There is increasing evidence that most whisker crystals grown from the vapor are dislocation-free. Webb and his coworkers6 searched for an Eshelby twist7 in zinc? cadmium, iron. copper, silver, and palladium whisker crystals. They found unequivocal evidence for an axial screw dislocation in only one element, palladium. However, not every palladium crystal examined contained a dislocation. Observations with the electron microscope have failed to show dislocations in whisker crystals of zinc, silicon.9 and one morphology of AlN.10 Since many whiskers are completely free of dislocations, an axial dislocation does not appear to be required for whisker growth of many substances. A significant advance in understanding whisker growth has been a recognition of the need for impurities. This requirement has been clearly demonstrated for copper,11 iron,13 and silicon9-1 whiskers. For silicon, detailed studies proved conclusively that certain impurities, for example, nickel or gold, are essential. Another pertinent phenomenon which has received little attention is the presence of a liquid layer or droplets on the surface of some crystals growing from the vapor. Crystals in which this has been observed include p-toluidine,14 MoO3,15 ferrites,16 and silicon carbide.&apos;" The liquid layers or globules were considered to be metastable phases, molecular complexes, or intermediate polymers originating from condensation of the vapor phase. The possibility has been suggested that the halide being reduced is condensed at the tip18 or adsorbed on the surface11 of a growing metal whisker, for example copper. The literature on whiskers discloses illustrations of rounded terminations at the tips. These appear. for example, on crystals of A12O3,19,20 sic,21 and BeO.22 For BeO, Edwards and Happel suggested that during growth of the whisker the rounded termination consisted of molten beryllium enclosed in a solid shell of BeO. A recent paper9 on the growth of silicon whiskers contains many observations pertinent to an understanding of the mechanisnl of whisker growth. These observations are summarized as follows. 1) Silicon whiskers are dislocation-free. 2) Certain impurities are essential for whisker growth. Without such impurities the silicon deposit is in the form of a film or consists of discrete polyhedral crystals.

Jan 1, 1965