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By E. J. Dulis, G. V. Smith

AS reported several years ago,' nitrogen may be taken up from the atmosphere by austenitic Cr-Ni steels during creep or creep-rupture tests. This was indicated by chemical analysis and by the appearance of a new microstructural phase, or phases, tentatively identified as chromium nitride (S), at the surface or at the intergranular cracks associated with fracture. The nitrogen pickup was observed to be dependent on time, temperature, and deformation. In a more recent investigation, a sample was obtained in which there was sufficient of the precipitate to suggest that it could be readily identified by X-ray diffraction. This sample had been taken from a 1/4 in. diam creep-rupture specimen of annealed, type 304L stainless steel of the following initial composition: C, 0.03 pct; Mn, 0.65; P, 0.010; S, 0.019; Si, 0.54; Cr, 19.50; Ni, 12.02; N, 0.031; and Al, 0.005. The specimen had ruptured after 10,470 hr at 1500°F (2000 psi). In this case nitrides were distributed across the whole section of the sample, Fig. 1. The precipitate occurred both at the grain boundaries and within the grains; the latter precipitate had in some cases the appearance of pearl-ite, and in others was distinctly Widmanstatten. Chemical analysis of the sample after test showed 0.64 pct "soluble" nitrogen (soluble in 1:1 hydrochloric acid: water) and 0.18 pct "insoluble7' nitrogen (insoluble in the hydrochloric acid solution but dissolved by fuming sulphuric acid). For identification of the precipitate by X-ray diffraction, the matrix in the surface layer of the specimen was dissolved by prolonged attack in an alcoholic solution of picric and hydrochloric acids. The appearance of the specimen surface after such etching is shown in Fig. 1c. The diffraction pattern of the surface-concentrated precipitate was obtained with a recording spectrometer in both the forward and back-reflection regions (the latter by adapting a special fixture to the conventional X-ray unit). The observed X-ray diffraction lines, Table I, show the presence of Cr,N and CrN; the agreement with interplanar spacings calculated from reported data2,3 is quite good. Since it has been suggested' that CrN dissolves only in concentrated sulphuric acid, whereas Cr2N dissolves in dilute hydrochloric or sulphuric acids, an effort was made to distinguish between the two nitrides. This proved possible, inasmuch as etching in a dilute solution of hydrochloric acid gave a sample in which microscopic examination showed that much of the Widmanstatten-pearlitic precipitate within the grains had been eaten out, leaving the grain boundary precipitate in relief, and which, when examined by X-ray diffrac-

Jan 1, 1953

By William A. Johnson

IT was pointed out in an earlier paper1 that our understanding of the atomic mechanism by which diffusion occurs in metallic alloys is scarcely in an advanced state. This unsatisfactory condition is the result not of any lack of interest, but of the difficulty of designing experiments that will yield suitable data. The diffusion coefficient of an alloy, measured in the usual way, is simply a number specifying the rate of homogenization of a nonhomogeneous metal; this number, of itself, can furnish neither the rate at which the individual atoms move nor information as to the mechanism by which they move. It does not necessarily follow, however, that such information cannot he obtained, even if the path to be followed is still not clear. Much success has been attained in the study of diffusion in ionic crystals. A number of experiments, for which there are few counterparts in connection with metals, yields information often indicating a detailed mechanism by which diffusion probably occurs. From such work, quite acceptable theories of lattice imperfections have been developed by Wagner, Schottky, Frenkel, Jost and others.2 It is postulated that real crystals of stoichiometric composition contain, in equilibrium, certain imperfections of which the most important types are: (I) vacant cation sites, with an equal number of interstitial ions; (2) vacant anion sites, with an equal number of interstitial ions; (3) equal numbers of anions and cations in interstitial positions; (4) equal numbers of vacant anion and cation sites. The classification of a particular crystal according to this scheme then follows from studies of the variation of electrical conductivity with pressure of the electronegative component surrounding the crystal, with ion size, and with temperature; other physical phenomena, such as the Hall effect, have aided in establishing the classification. The relative mobility of the anion and cation may be determined by chemical analysis of the salt at the electrodes following electrolysis. With such information, and knowing that one ion never occupies the lattice site normally belonging to an ion of opposite sign, it is usually possible to ascertain the diffusion mechanism. It is clear that the same experiments are not applicable to metal crystals, and substitute experiments that yield as much information have not yet been devised. Much can be learned, however, about the mobilities of the two* kinds of atoms in alloys by the use of radioactive metals as indicators. Only one such experiment has been performed in the past. In 1933, Seith and Keil,3 in an effort to explain the great difference between the rate of diffusion of gold in lead and of lead in lead, measured the rate of diffusion of radioactive lead in a gold-lead

Jan 1, 1942

By AIME AIME

TWO technical sessions, an excursion through the Midwest refinery and a smoker, marked the first day of the meeting of the Petroleum Division at Casper, Wyo., on Aug. 28. Ninety-nine members and guests registered and there was an excellent attendance at 'all functions. The -local committee under the general chairmanship of J. C. Lindsay, general manager of the Western Pipe Line Co., had made every possible arrangement for the convenience and comfort of the visiting members and the Program Committee under E. L. Estabrook, vice-chairman of the Petroleum Division, had brought together a most interesting series of technical, papers. The meeting centered mainly on the various features of the Salt Creek field but there were also contributions from the technology of production in California, the Mid-Continent, and the Texas fields. The opening session was called to order by Mr. Estabrook at the Townsend Hotel on Friday morning. The members and visitors were welcomed appropriately by Ex-Governor B. B. Brooks, president of the "Rocky Mountain Oil and Gas Association, who recalled the changes that had taken place as Casper, a frontier cow town, became a thriving oil metropolis. F. Julius Fobs, chairman 'of the Petroleum Division, responded and then took the chair. He introduced H. Foster Bain, Secretary of the Institute, who expressed the regret of those members members who found it impossible to stop over en route to Salt Lake City and his own pleasure at meeting with the Division in the field. Following these introductory ceremonies the technical session began with a "Sketch of the Geological Formations of Central Wyoming," presented by J. G. Bartram of the Midwest staff. It was brief and to the point and contributed greatly to the easy under¬standing of the succeeding papers by those unfamiliar with the region. The talk was illustrated by a large scale columnar section -and a copy of the excellent, geological map of the State recently issued by the U. S. Geological Survey.

Jan 1, 1925

Jan 1, 1885

E.T. CONNER;. Scranton;. Pa-I had the honor of being associated with Mid. Griffith in an investigation of the Scranton mine cave problem several years ago; in the course of which we investigated rather carefully the bearing strength of various materials that might be utilized for, the support of over We found that there were no reliable data as to the resisting strength, for instance, of gob pillars or timber cogs or cribs, nor as to the amount of compression that might be expected under a given burden. We made a series of tests at the Fritz engineering laboratory of Lehigh University, from which we, reduced certain conclusions, subject, however, to further test before they could be definitely recommended. Onr study of the subject was later checked by a commission appointed by the Governor of the State of Pennsylvania, to investigate the same subject the subsidence of the surface, and the danger entailed thereby. The State, commission made a series of tests on a much more ambitious scale at Pittsburgh, in the laboratory of the U. S. Bureau of Mines, and their tests agreed quite closely with those that Mr. Griffith and I had made. As the result of our study, we determined that the most elastic support is the ordinary timber cog or crib, while the most rigid support is a

Jan 1, 1918

United Engineering Society WALTER H ALDRIDGE J VIPOND DAVIES I V N DORR Engineering Societies Library Board SYDNEY H BALL ALEXANDER C HUMPHREYS GEORGE C SLONE JOHN H JANEWVAY Engineering Foundation Board H M BOYLSTON J VIPOND DAVIES GALEN H CLEVENGER Society for Promotion of Engineering Education WILLIAM KELLY ALLEN B ROGERS American Engineering Standards Committee GRAHAM BRIGHT GEORGE C STONE GEORGE E THACKRAY Alternates-RICHARD L LLOYD and HARLOWE HARDINGE

Jan 1, 1923

By AIME AIME

THE ninth International Petroleum Exposition held at Tulsa, May 16-23, broke all size, sales, and attendance records of previous shows. More than $12,500,000 worth of equipment was on the grounds. There were 546 companies exhibiting and every available inch of the fifteen acres allotted to exhibit was taken. Drake Drive, the main street of the exposition, was literally "supply row" with National Supply, Frick-Reid, Continental Supply, Oil Well, Bridgeport, International Derrick and Equipment, and Parkersburg Rig and Reel companies occupying the entire space. The exhibitors were a cross section of American industry, with such firms, besides the strictly oil equipment firms, as the United States Steel Corp. and others allied to the oil industry, exhibiting. Between $10,000,000 and $15,000,000 of equipment is estimated to have been sold on the grounds during the exposition. Valuable contacts were made by the exhibitors with key oil men. Attendance passed the 175,000 mark for paid admissions in contrast with 154,000 for the eighth exposition in 1934. Visitors registered from Venezuela, Soviet Russia, India, Germany, Spain, Mexico, England, Canada, France, Colombia, Greece, West Indies, and Rumania. Hotels were overflowed and a housing bureau found rooms in private homes for thousands. Oil companies set up a schedule of shifts in order that as many of their field men might attend as possible. It is said that the companies want a two-weeks' show in 1938 so that more time will be avail-

Jan 1, 1936

By John J. Strohl, Henry J. Schwellenbach

This paper relates the results obtained by decreasing the size of feed to a rod mill screen circuit. As would be expected, added production was gained and a finer grind with no tonnage loss was made possible.

Jan 12, 1950

By O. Jantti, Erkki Laurila, R. T. Hukki

INVESTIGATION of the methods of analyses for magnetite and ilmenite in the Otanmaki iron-titanium ore and respective mill products has resulted in certain improvements in the methods conventionally employed. The outcome of the investigations is summarized as follows: 1—Development of a diamond-drill core analyser for the determination of magnetic susceptibility of drill cores containing magnetic minerals. 2—Development of a magnetite-ilmenite analyser for pulverized products. 3—Development of a potentiometric method of chemical analysis for the determination of iron, vanadium, and titanium in succeeding steps from one test sample. 4—Proposal for a continuous and automatic magnetite assay method. Diamond-Drill Core Analyser The conventional method of assaying diamond-drill cores consists of splitting the cores, pulverizing them and running chemical analyses on representative samples. The physical properties of magnetic minerals, however, offer an entirely different approach to obtain similar final result by the measurement of respective magnetic susceptibilities in a properly designed instrument. This instrument is shown in Fig. 1. Essentially it consists of a magnetic unit, A, and of a meter unit, B. On top of A is a slot where a piece of diamond-drill core C is visible. The magnitude of disturbance in the original magnetic field caused by the magnetic minerals in the drill core can be observed from the microammeter. This reading is a function of the combined susceptibilities of all magnetic grains in the magnetic field. The magnetic unit is built of E-sheets of a shell transformer, as shown in Fig. 2. The primary coil and two identical secondary coils are wound around the central leg and end legs, respectively. The drill core under examination is placed into one of the air gaps as shown in Fig. 2. The number of ampere-turns of primary coil excited by 50 or 60-cycle ac give a maximum induction of about 600 gauss in the air gaps. The secondary coils are connected in series in the opposite direction. Thus their voltages compensate each other if no drill core exists in the air gap or if the susceptibility of the drill core is equal to zero. As soon as the susceptibility becomes greater than zero, the balance of the magnetic circuit is disturbed, resulting in increased voltage in the terminals of coil 1 and in a respective decrease of voltage in the terminals of coil 2. The voltage difference thus produced is a function of the effective susceptibility of the drill core. If the magnetic grains in the drill core are unevenly distributed, the voltage difference varies as the core is rotated around its own axis. The voltage difference is measured with a Bren-tan0 tube voltmeter. If extreme sensitiveness is desired, the established symmetry of the magnetic circuit does not allow reduction of the 0-voltage difference far enough. Therefore a compensatory voltage of a correct phase taken from the terminals

Jan 1, 1952

By Paul F. Fulton, Robert K. Estes

INTRODUCTION Relative permeabilities are factual data necessary to any prediction of reservoir production behavior. One important problem in determining relative permeabilities of porous media to gas is the effect of gas slippage on these determinations. Since certain aspects of the slippage phenomenon still remain unknown, this study is particularly concerned with that problem. The validity of the theory of gas slippage as it is applied to the flow of gas through porous media has been well established. 1,2,3 Therefore, in determining the permeabilities of porous media to gas by ordinary laboratory procedure, i.e., at atmospheric pressure, the slippage correction should be considered. Rose3 performed experiments on gas relative permeabilities which indicated that the effect of gas slippage on the measured effective gas permeabilities at various liquid saturations decreased with an increase in liquid saturation. Following Rose, it was substantiated experimentally' that the effective gas permeabilities at the various liquid saturations extrapolated to infinite mean pressure were the same as the non-wetting liquid permeabilities at the same saturations. This same paper also presented data which showed that the magnitude of the slippage between those values of gas effective permeability determined at atmospheric pressure and those found by extrapolation to infinite mean pressure decreased with an increase in liquid saturation. However, these experiments were not performed at liquid saturations above 30 per cent. Therefore, the purpose of this experimental work was to determine the effect of gas slippage on permeability measurements at liquid saturations in excesh of 30 per cent. APPARATUS Five core samples were used In this work: two synthetic Alundum samples (A-1, and A-2). a Nichols Buff sandstone sample (NB-13), and two samples from producing formations, a Soso sandstone (S-1), and a vugu-lar dolomitic limestone (R-7). The core samples ranged in permeability from 32 to 663 md. These cores were chosen because they represented a fairly wide range of permeabilities and probably a considerable difference in pore size and pore size distribution. Fig. 1 is a schematic diagram of the apparatus which consists of an air dehydration filter A, two Moore null-matic sub-pressure regulators B and C, the differential oil manometer D, the core holder E, the flowmeter F, the soap reservoir G, and a mercury manometer H measuring the downstream pressure. The interesting features of the apparatus are the two Moore vacuum-pressure regulators. The regulators permit the rapid establishment and easy control during flow at sub-atmospheric pressures of both the differential and downstream pressures, and prevent the surging action of the vacuum pump from disturbing the system during flow. Provided there are no leaks in the system, these regulators will maintain without measurable change selected downstream and differential pressure. Specifically, regulator B controls the downstream pressure and regulator C controls the differential pressure. In opera-

Jan 1, 1957

By Carl Allen

INTRODUCTION IN any discussion of mining one is repeatedly confronted with the difficulty of dealing with so many variable conditions. It is not an exact science and in the choice of a method each varying factor has a certain weight, which, in many cases, experience alone can determine. In mathematical terms, it is a function of many variables. A discussion of mining also loses much of its value unless, costs are considered, because the expectation of profit is the only excuse for carrying on mining at all. As conditions vary they cause fluctuations in cost and there are few operations to which a definite cost can be assigned. The character of the ore may make it difficult to drill, yet because of the ease with which it breaks the total cost of drilling and blasting may be low. In preparing this article the attempt has been, not to cover the whole field of mining, but to describe the different methods of stoping and mining which have distinct principles. In addition to this an effort has been made to show the advantage of dissecting the methods into their detailed operations and applying to these a mathematical study as an aid to the judgment in determining which is the best method to adopt, or in attempting to reduce the cost of a method already in use. Methods of mining include stoping, caving, and various methods of working large deposits which, in addition to the method of actually breaking the ore, require elaborate and definite plans of, development of the orebody. The ordinary methods of stoping are too familiar to all for any elaborate discussion, but it has seemed advisable to review the subject and give the principal advantages' and disadvantages of the different methods.

Jan 8, 1914

By Charles L. Mantell, B. G. Shah

SINCE the beginning of the industry, commercial electrolytic manganese has followed the Shelton patent' among others, which called for the addition of sulfur dioxide in controlled amounts, to a purified manganese sulfate-ammonium sulfate at a controlled pH. Every attempt to eliminate sulfur dioxide additions has resulted in operating difficulties, chiefly solution of the deposited metal and lowered current efficiencies. Many replacements for sulfur dioxide have been proposed and studied, chiefly sulfur compounds, urea, thiourea, and proteins similar to those employed successfully in copper refining. It has been suggested that sulfur dioxide is a re-ductant for higher-valence manganese compounds, or that it is reduced by manganese metal in the deposit to hyposulfites or its compounds, and that these might affect the cathode film or the deposition potential, or the overvoltage of manganese. The additives were studied following the method of Mantel1 and Ferment2 who determined the feasibility of current-potential curves as an analytical tool for monitoring manganese elec trowinning solutions for metallic impurities: nickel, cobalt, silver, copper, zinc, molybdenum, cadmium, magnesium, and sodium. The individual effect of each on the standard polarization was determined for a range of concentrations. Not all affected the polarization curve; cadmium, magnesium, and sodium had no effect. Nickel, cobalt, silver, copper, and zinc yielded a correlation between transition current and concentration of impurity.

Jan 1, 1968

By R. G. Mallon, A. E. Lewis, R. L. Braun, C. J. Sisemore

Large ore-bodies, too deep to mine economically by underground methods, may be mined using nuclear explosives and a high pressure leaching technology. Breaking of a hypothetical ore-body with a series of nuclear explosives is described. The leaching would be accomplished by pumping oxygen into the flooded rubble under the normal hydrostatic pressure. The injection of oxygen gas into the bottom of the rubble chimney induces a circulation of the solutions which carries dissolved oxygen to all parts of the chimney. Copper and other metals would be recovered from the solutions by solvent extraction as they are circulated through a surface plant in a closed system. This provides for control of pH as well as containment of radioactivity. Radioactivity levels in the solution are low, and no radioactive impurities are expected in the copper. This technology will allow production from deposits too deep to be of interest with present technology and will reduce or eliminate some environmental effects of conventional mining, such as open pits, mine dumps, tailings ponds, and SO2 effluent. Close proximity of cities and towns is a limitation because of seismic damage. The technology requires further development for commercial application, and exploration targets must be enlarged to include deeper deposits, before the technology can be applied on a large scale.

Jan 1, 1974

By I. N. Zavarine

Austenite is often defined as a solid solution of carbon or carbide in a nonmagnetic form of iron. Conversely, magnetic measurements are often used by investigators for the purpose of detecting the degree of austenite decomposition after an iron alloy has been subjected to certain thermal or mechanical treatments. Association of the magnetic state with the gamma-phase decomposition is often extended to the alloys of iron with elements other than carbon. Definition of austenite as a nonmagnetic solid solution cannot be accepted in the light of available information without certain reservations. The relation of magnetic transformations with the gamma-phase decomposition in the complex alloys of iron has never been rigorously proved. The present investigation deals primarily with the magnetic transformation that occurs in carbon steels during the quenching process. The work was further limited to a study of magnetic transformation in carbon steels quenched at such rates as are necessary to retain the product of austenite decomposition in a martensitic state. Peevious Work Considerable information has accumulated in the literature with respect to the magnetic transformation in alloys of iron, but nearly all of it relates to transformations under the conditions of equilibrium between the phases of the alloy. Earlier studies of Hopkinson,$(') Curie,(2) and Honda'~) are well known. Investigations of the magnetic

Jan 1, 1934

By Henry B. Fernald

THE Federal income tax treatment of expenditures for exploration and development for mines and other natural deposits (other than oil and gas) was materially changed by special provisions of the 1951 Act that are continued in the present 1954 Code." These present provisions for mines in stance they are the same as the 1951 amendments to the 1939 Code, Secs. 23 (cc) and (ff), respectively, except that for exploration the allowable annual deduction is increased to $100,000 (from $75,000) and minor changes in case of property transfers are made with respect to the four-year limitation. Before 1951 the statutes made no specific pro- visions regarding development and exploration for mines, but the rules were prescribed by Treasury regulations: 1) Before the mine entered the production stage, all development and exploration expenditures for mines, less net receipts, were to be capitalized recoverable through depletion or written off as losses when determined worthless. 2) After a mine entered the production stage, development expenditures were deductible as expenses-currently if ordinary expenses, but on a deferred basis if extraordinary in scope. This recognized the two separate periods, one before and the other after beginning of the production stage. There was no distinction between an exploration and a development period, but exploration was included as part of development.

Jan 1, 1958

By J. M. Donkers, R. de Groot

The various objectives of dredging at sea require different methods and radically different equipment for their optimum fulfillment. In the majority of cases, sea dredging is done by means of dredging equipment connected to a pontoon or ship floating at the surface. As the supporting hull is subject to the influence of waves, swells, currents and wind, the connecting point of the dredging equipment to the hull will generally move relative to the sea bottom with 6° of freedom. The more important hull motions are surge, heave, pitch and roll. Depending on the actual sea and weather conditions and the size of the hull, some of these motions can be so large that dredging equipment of rigid construction (normal or inland dredges) cannot be used. In those cases where mechanical disintegration of the bottom is necessary and where accurate dredging is required, the designer must find a solution for this problem. For cases where the bottom consists of soils that can be handled by plain suction, highly sophisticated dredging equipment such as the trailing suction hopper dredge permit dredging under all but the most severe sea state conditions. This type of dredge picks up the soil from the sea bottom while slowly underway. The drag suction head is fitted on a suction pipe of such flexibility that the supporting ship can carry out all six movements in relation to the draghead (heave, pitch, roll, sway, yaw and surge), while the draghead remains in firm contact with the bottom. The suction pipe is fitted with flexible hoses, a universal hinge, a horizontal hinge, axial turning gland and sliding turning gland with horizontal axis and is suspended flexibly from the ship incorporating swell compensating buffer gear, keeping the wires taut and the draghead bottom contact pressure fairly constant while the dredge moves up and down. Due to the fact that the draghead has a low bottom contact pressure and has little tendency to sink into the bottom, this compensation is not difficult to realize.

Jan 4, 1974

By T. S. Fuller

VARIOUS phases of the embrittlement of solid copper containing oxygen by the action of reducing gases at high temperatures through the work of many experimenters are familiar to readers of metallurgical literature. In 1900, Heyn1 recorded observations of copper being heated in hydrogen with the development of fine cracks, the result of the formation of steam within the metal through the action of hydrogen on the copper oxide usually found in copper. Archbutt,2 in 1905, published the results of experiments, showing that all oxygen can be removed from copper by heating to redness, for several hours, in hydrogen. Intercrystalline cracks and extreme brittleness developed. Archbutt attributed the brittleness to the reduction of oxides present in the copper. Bengough and Hill,3 in 1910, encountered the now well-known embrittlement at the outset of their investigation and stated in their paper: It soon became evident that the effect of any heat treatment depended largely on the presence or absence of reducing gases in the atmosphere of the furnace, as well as on its temperature. Hence it became necessary to adopt a somewhat elaborate scheme of heat treatment. The authors found embrittlement in separate experiments due to both hydrogen and carbon monoxide and concluded that: "The gases ruin the alloys after being heated to about 650° C. in their presence."

Jan 2, 1926

By David Scott

WHEN mining operations were first instituted in the mines of the Miami Copper Co., at Miami, Ariz., the relatively hard character of the ground in the western section of the property made it seem advisable to use a wide shrinkage stope and pillar system. The system as finally evolved was applied to the mining of 2,300,000 tons of ore by the use of stopes and pillars each 50 ft. in width. Development, mining and extraction of this reserve has been continuously in progress since 1910, and the final stages of extraction are now reached. A complete survey of all phases of this system can therefore be made. Modification in working methods was obviously necessary, and the system to be described is believed to be typical of the best features. DEVELOPMENT The preliminary work had three main objectives: The opening of a haulage level, the construction of a drawing-off level, and the driving of sublevels for use in stoping. In addition to these, some extra sublevel drifting was necessary to determine exactly the boundaries of the orebody, the general outline having been determined by churn drilling. This development was based on the requirements of stopes 50 ft. wide, with pillars 50 ft. wide between each stope. The length of these units varied from 200 to 500 ft.

Jan 6, 1916

By N. Arbiter, C. C. Harris

In 1961, a research program started at Columbia into the mechanical aspects of flotation,* and certain ends are now in view. The purpose of this note is to explain these tentative conclusions in the hope of stimulating discussion and eliciting new data, especially industrial data, with which to test the views expressed. The variables presently under consideration are impeller rotational speed, N, volumetric air rate, Q, and impeller diameter, D, the latter being the parameter chosen to designate cell size. The most favorable *The latest work 1 references all previous publications. chemical environment is not under discussion since the procedures for establishing it are better understood than those for optimizing N and Q by virtue of a longer history of more intensive investigation. THE GRADE AND RECOVERY SURFACES With a given ore, chemical treatment, and flotation machine, both grade, G, and recovery, R, are functions of N and Q. The GNQ and RNQ relationships are best viewed in terms of three-dimensional surfaces (Fig. 1) which are experimentally determinate.2 TO maintain grade at an acceptably high level, it is necessary for N and Q to lie within certain limits, and similarly with recovery. However, the ranges of N and Q for grade on the one hand and recovery on the other are rarely the same. Selecting the single N

Jan 1, 1970

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