Search Documents

By J. W. Powell, F. H. Spedding

A complete review of the use of chelating agents in the sepa ration of rare earths by ion-exchange is given as well as a concise description of the recent pilot-plant operations of the Ames Laboratory. The two chelating agents which show the greatest promise are ethylenediamine-N,N,N',N'-tetraacetic acid and N'-(2-hydroxyethyl)ethylenediarnine-N,N,N '-triacetic acid. The first successful separations of rare earths by ion exchange were reported in a collection of papers which appeared in the November, 1947, issue of the Journal of the American Chemical Society.1'9 Some of this work was performed at the Ames Laboratory of the A.E.C., the remainder at the Oak Ridge National Laboratory. The processes developed at Oak Ridge, as well as some of the early Arnes methods, employed 5 pct citric acid-ammonium citrate eluant at low pH and were carried out on either H+-state or NH:-state resin beds. These techniques were successful for the separation of small quantities of either naturally occurring or radioactive rare earths and are still used for the isolation of rare-earth activities from fission products. Concentrated citrate is not economical, however, for use in moderate or large-scale rare-earth separations. For this reason, the Ames Laboratory turned its attention to lower concentrations and higher pH's in order to make more effective use of the eluting agent.10-14 Although elutions have been performed successfully over a wide range of conditions, 0.1 pct citrate at a pH of 8.0 is highly recommended for use on H+-state resin beds.15,16 Elu-tion with 0.1 pct citrate in the pH range from 5 to 9 brings about the separation of the constituent rare earths into a series of flat-topped elution bands which progress down the resin bed, head to tail, without actually pulling apart as do the rare-earth peaks which develop when trace quantities are eluted with 0.25M (5 pct) citrate at low pH's. Because of this, elution with 0.1 pct citrate at pH 8.0 do not produce pure rare earths unless sufficient quantities are present to provide developed bands which are at least several inches long on the columns. Although other eluting agents have proved more effective than citrate solutions, articles concerning the use of citric acid for separating rare earths still appear in the literature occasionally. For example, Ketelle and Boyd17 reported some further studies on the separation of rare earths with 5 pct citrate in 1951. They used 270 to 325 mesh Dowex-50 columns at 100°C and a pH of 3.28. vickery18 compared the effectiveness of a number of eluants for the separation of rare earths on NH+4 state Dowex-50 in 1952. He found that citric acid was more efficient than acetic, malic, tartaric, and aminoacetic acids. In 1953, Mayer and Freiling18 reported that citrate was inferior to malate, glycolate, lactate, and EDTA for the resolution of Sm-Eu and Y-Tb mixtures on 250 to 500 mesh, NH+4-state, Dowex-50 at 87°C. pinta20 used 5 pct citrate in the pH range 2.8 to 3.4 to obtain some rare earths for analytical work the same year. Trombe and Loriers21 reported the use of citric acid in their laboratory to separate rare earths in kilogram quantities. Lariers and Quesney22 reported some separations with citrate in 1954. They used 5 pct citrate at pH 2.8 to separate yttrium and the yttrium-group rare earths from the cerium-group rare earths. briers23 used 5 pct citrate at pH 3.2 and 90°C as late as 1956 to isolate thulium in fair purity. For the separation of tracer quantities of rare earths, Mayer and Freiling19 have recommended pH 5.00, 0.24M lactate at 87 °C on 250 to 500 mesh, NH+4-form Dowex-50. Freiling and Bunney24 have also employed lactic acid for the separation of fission-product rare earths. Cunninghame, Size-land, Willis, Eakins, and Mercer25 have reported a 4-hr separation of Y, Eu, Sm, Pm, Nd, and Pr with 1M lactic acid at pH 3.25 on Zeokarb-225 at 87°C. Stewart, et al.,26 reported separation factors for rare earths distributing between Dowex-50 and 0.25M glycolic acid. stewart27 also reported a 30-61 separation of Y, Tm, Er, Tb, and Lu tracers with buffered, 0.25M glycolic acid containing 0.05 pct Aerosol OT. The resin bed was 400-mesh Dowex-50 (X12). The pH of the ammonia-buffered eluant was 3.5. Various aminopolyacetic acids have also been used to obtain varying degrees of separation of the rare earths. In 1951, Fitch and Russell28 investigated iminodiacetic acid (IDA) and nitrilotriacetic

Jan 1, 1960

By S. H. Ash, J. J. Forbes

Probably the newest thing in mining safety, or safety for mines, is the apparent dissatisfaction on the part of the mineral industries, as represented by both management and labor, and the general public of the Nation, with the safety record of the mining industry. This is reflected by published comments and papers in the technical press;l-9 in labor periodicals,10,11 in popular journals and periodicals,l2, 13 and in the daily press; also by discussions of the Safety Committees sponsored by the National Safety Council,9, 14-15 the American Mining Congress,l.l6 the American Institute of Mining and Metallurgical Engineers,2,4 the Mine Inspectors' Institute of Amerthe Coal Mining Institute of America,5 19 the American Standards Association, and others.20.21 Mining safety is a joint problem of management and the individual workman. Safety is not attained and will not be attained solely by laws, decrees, and commands because, if it could be done in this manner, acceptable mining safety would have been achieved long ago by the individual states in our Nation and by the nations abroad. The best safety performance is found at plants where management provides a safe environment for the workers; where supervision is efficient and super- visors, others concerned with promoting safety, and the individual worker know through training, experience, and personal contact the safe and unsafe practices of their field; and where the trained individual worker has become safety-minded by experience, quiet influence, unconscious suggestion, and personal guidance. Despite what may be said to the contrary, progress has been and is being made in mining safety. This is shown in Fig 1 to 4. It is beyond the scope of this paper to give possible reasons for the valleys and peaks in the fatal-injury rates. Some recent factors that appear to be contributing to the improvement in these rates are briefly discussed. Aside from mining equipment, "what's new in mining safety" for some mines has been in effect or was tried by others long ago. A safety pro- gram is a living thing; as such, it must be vitalized and continuously fed with enthusiasm, constructive action, and improvements. Because safety is concerned with human conduct, it is necessary to practice safety at all times; if not, it is soon forgotten, and accidents occur. Mining-safety Records The large employment and production concerned with anthracite contribute much to the mining-safety records of the mineral industry. Approximately 81,000 persons are. employed in this industry having mines concentrated in an area of 480 square miles in northeastern Pennsylvania. Because of the achievement of the anthracite industry in safety during 1948, the other branches of the mineral industry can profit by a study of what has been done to achieve that record. Where one mineral is produced by other large groups having methods of mining that are similar in many respects to the anthracite-mining methods, an achievement in such a large industry is important. Salient factors concerned with safetye in the anthracite industry are: no radical change has occurred in the mining-safety regulations pertaining to anthracite mines. Because anthracite mining is a branch of the coal-mining industry,

Jan 1, 1950

By William E. Ford, Edward Salisbury Dana

5. Crystallography. - The subject of Crystallography includes the description of the characters of crystals in general; of the various forms of crystals and their division into classes and systems; of the methods of studying crystals, including the determination of the mathematical relations of their faces, and the measurement of the angles between them; finally, a description of compound or twin crystals, of irregularities in crystals, of crystal- line aggregates, and of pseudomorphous crystals. 6. Definition of a Crystal.- A crystal * is the regular polyhedral form, bounded by smooth surfaces, which is assumed by a chemical compound, under the action of its intermolecular forces, when passing, under suitable conditions, from the state of a liquid or gas to that of a solid. As expressed in the foregoing definition, a crystal is characterized, first, by its definite internal molecular structure, and, second, by its external form. A crystal is the normal form of a mineral species, as of all solid chemical com- pounds; but the conditions suitable for the formation of a crystal of ideal perfection in symmetry of form and smoothness of surface are never fully realized. Further, many species usually occur not in distinct crystals, but in massive form, and in some exceptional cases the definite molecular structure is absent. 7. Molecular Structure in General.- By definite molecular structure is meant the special arrangement which the physical units, called molecules, assume under the action of the forces exerted between them during the formation of the solid. Some remarks are given in a later article (p. 22 et seq.) in regard to the kinds of molecular arrangement theoretically possible, and their relation to the symmetry of the different systems and classes of crystals.

Jan 1, 1922

By Henry F. Herley

The New Orient mine, owned and operated by the Chicago, Wilmington & Franklin Coal Co., has caused a great deal of comment and interest because of its unusual features and huge daily production. It is in Franklin County, Illinois, adjacent to the town of West Frankfort. The seam being mined is the Illinois No. 6 which in this locality is 9 to 12 ft. thick and lies approximately 500 ft. below the surface. Without fear of contradiction, it can be said that this is one of the largest coal mines in the world from a daily production standpoint. During 1928, New Orient produced 2,400,000 tons, which amounts to over 10,000 tons each day the mine operated that year. The mine is built for a capacity of 12,000 tons but has actually hoisted over 15,000 tons in one 8-hr, shift. This enormous production can perhaps be better visualized if it is realized that each day's operation depletes over two acres of coal. The general features of this mine have already been fully covered in a paper by George B. Harrington,' President of the Chicago, Wilmington & Franklin Coal Co. In a paper of the nature of Mr. Harrington's, it was unnecessary to stress any particular phase of mining conditions, consequently the ventilation problems were touched upon but lightly. In this paper an attempt has been made to describe some of the problems which have been encountered in providing adequate ventilation for the mine. Ventilating Conditions The acreage allotted to New Orient mine has a length, north and south, of approximately 6 miles, and a width, east and west, of 2 to 4 miles. A number of important considerations caused the hoist shaft, air shaft and surface plant to be located near the southeast corner of the property, instead of near the center, as is usual. During the initial phase of the mine development, the mine was ventilated through these shafts, although there was a full realization that at some future date other shafts would be required.

Jan 1, 1930

By W. N. Carr, J. R. Biard, B. S. Reed

An analysis of the semiconductor injection laser is presented which is based on a phenomenological model using device and material parameters. The intent of the laser threshold analysis is not to predict from theory the actual threshold current density but rather to provide a logical means of interpreting experimental results. The device and material parameters have been selected such that they describe both the threshold conditions and quantum efficiency of the lasev. A technique is proposed whereby the current required to obtain a population inversion is predicted from device 1-V characteristics. Experimental data are presented which support the analysis. THIS investigation is concerned with the characteristics of GaAs lasers fabricated in this laboratory. However, the assumptions used in these calculations should not limit their application to GaAs alone. It is felt that the analysis is sufficiently general to be useful in describing the operation of other semiconductor-laser materials. ANALYSIS heavily doped semiconductors to be considered. The absorption and/or generation of optical radiation may be completely specified in terms of q(E) and the probability functions f,,(E) and f,(E) which define the occupancy of the valence-band and conduction-band levels, respectively. The symbols used in this analysis are listed at the end. Following the approach of all' it can be shown that the effective gain coefficient, g, in the plane of a forward-biased P -N junction is g(E)=-ai@)[1-fv(E)-fc(E)] [1I In particular Eq. [I] holds for the photon energy at which lasing occurs, Ep. Throughout the following discussion Eq. [I] is considered only for the lasing transition E = Ep. For simplicity the functional energy dependence of the various factors is omitted in subsequent equations. Unless otherwise stated the symbols used represent the values at Ep. If the analysis is limited to the P-type side of the laser junction, the function q(l -f,,) is recognized as the band-to-band absorption in the P-type material at thermal equilibrium. Under forward-bias conditions the function f, is determined by the electron quasi Fermi level in P-type material. For sufficiently large forward bias the second term in Eq. [3] will become dominant and net gain will result; i.e., g will become positive. In order to simplify the subsequent analysis several assumptions are in order at this point. a) No conductivity modulation occurs. /„ is independent of f, and therefore go is a constant. b) The P-type material is heavily doped such that the degeneracy of the valence band permits popu-

Jan 1, 1964

[Aamot, Clav Crone, (Member '29) Met., Det Norske Aktieselskab for Elektrokemisk, Industri, Inc., Oslo, Norway. Aamot, 0, Crone, (Member '29) c/o Elektrokemisk, Radhusgaten 23, Oslo, Norway. Aase, Glenn D., (Junior Member '40) Jr. Met., American Smelt. & Refin. Co., Selby, Calif. Abadie, Henry G., (Junior Member '43) Div. Petr. Engr., Union Pacific R.R. Co., 422 W. 6th St., Los Angeles 14, Calif. Abbott, Clarence E., (Member '04) Civil Engr., V.P., Tennessee Coal, Iron & R.R. Co., 1542 Brown Marx Bldg., Birmingham, Ala. Abbott, Fred E., Jr., (Member '44) Petr. Engr., c/o Arabian American Oil Co., A.P.O. 816, c/o Postmaster, New York, N. Y. Abel, Raymond L., (Member '28) Chem. Engr., 0. 0., Pittsburgh Chem. Warfare Procurement Dist., American Bank Bldg., Pittsburgh, Pa.]

Jan 1, 1946

For the year ending February, 1920 PRESIDENT HORACE V. WINCHELL.. . MINNEAPOLIS, MINN. PAST PRESIDENTS PHILIP N. MOORE ST. Louis, Mo. SIDNEY J. JENNINGS NEW YORK, N. Y. FIRST VICE-PRESIDENT A. R. LEDOUX NEW YORK, N. Y. TREASURER GEORGE D. BARRON NEW YORK, N. Y SECRETARY BRADLEY STOUGHTON NEW YORK, N. Y VICE-PRESIDENTS CHARLES W. GOODALE,1 . . . . District 5 BUTTE, MONT. MARK L. REQUA,1 District 6 SAN FRANCISCO, CAL. HENRY S. DRINKER, District 2 So. BETHLEHEM, PA. ROBERT M. RAYMOND,2 . . . . District 0 NEW YORK, N. Y. EDWIN LUDLOW,3 District 2 LANSFORD, PA. A. R. LEDOUX,3 District.0 NEW YORK, N. Y.

Jan 11, 1919

By A. T. Shurick

THE NRA Administrator's casual reference to the coal code as the next "pineapple" to be fixed was a conservative estimate of his job. This thorny and adamantine morsel now looms as a critical test of NRA. A failure in coal supplies would have the gravest potentialities in the Administration's program at this time. And the loss of prestige from a breakdown of the enforcement machinery in this initial large-scale test of strength would accentuate the incipient indications of insurrection in other directions. General Johnson has had a difficult task. It involves problems festering for a quarter of a century. A succes¬sion of Presidents have been glad to tide over their respective regimens with inconclusive expedients; they have been baffled by the complexities of the technical angles and hopelessly irreconcilable concepts of powerful conflicting interests with large issues at stake.

Jan 1, 1933

By R. J. Reynik, F. R. Meeks

IN the classical paper1 of Mehl and Rhines entitled "The Rates of Diffusion in the Alpha Solid Solutions of Copper", the authors state: "It has been mathematically demonstrated that the treatment of the data as though the diffusion were taking place between two flat plates instead of radially in a cylinder has no appreciable effect upon the results. Were the bars of a much smaller diameter, a modification of the analytical treatment would have been required." Unfortunately, the errors in the reported concentrations are much too large to neglect, as shown in the results below. A planar treatment of diffusion data assumes that the reference planes separated by a nominal distance (AX) have identical areas. An adjustment must be made on the concentration data should the successive diffusion planes differ in area. The Mehl-Rhines' diffusion samples were cylindrical with copper electroplated onto copper-based alloys. Successive surface areas through which diffusion occurs are in the ratio ri/r1, where ri is the radial distance between the center of the sample and the center of the i th shell to which the host (alloy) atoms diffuse, and r1 is the radial distance between the center of the sample and the center of the innermost (i = 1) experimentally reported shell from which the alloy atoms diffuse. Hence, ri/r1 (i = 1, ..., n layers) is a dimensionless correction factor to be multiplied by the reported concentration data before planar-data analysis is attempted. In the forty-seven samples reported, the original interface between the copper alloys and the electroplated copper was located at a mean distance of 8.255 mm from the center of the samples. The successive layers, machined off the samples, were approximately 0.0762 mm thick. The distance (xi) at which concentration (ci) was reported was always a distance measured with respect to the original interface, that is, with respect to the fixed distance of 8.255 mm. Hence, the as yet undiscovered Kirkendall Effect was precompensated. The values of ri and r1 are therefore given by ri = 8.255 + xi and Y, = 8.255 + x,. The illustrative table below lists the position xi (mm), ri (mm), the value of ri/r1, the reported concentration (ci) in weight percent (only valid for radial analysis of data), and the corrected concentration [c'i = (ri/r1)ci] in weight percent (only valid for planar analysis of data). Similar tables can be constructed for the remaining forty-six samples. The corrected data can be used to re-evaluate the diffusion coefficients for the reported systems.

Jan 1, 1965

By N. Tiner

The mechanical properties of magnesium-alloy castings are greatly improved by grain refinement, and at present considerable attention is being paid to methods of obtaining fine-grained castings. One method of achieving this end is the use of proper melting and superheating techniques. These have been employed com-rnercially to a great extent, but no comprehensive study of the subject appears to have been published at present. Numerous investigations found in the literature include some reference to superheating techniques,1"4 and Achenbach, Nippcr and Piwowarsky,% ased principally on thermal analysis, ascribe the grain-refilling action of superheating to the influence of solid foreign particles or dissolved gases present in the melt upon the course of crystallization. The primary purpose of this paper is to present the principal facts concerning the cffect of superheating on grain size of magilesium alloys. .ittempts are also made to explain the experimental results in terms of a general hypothesis. The investigations are limited chiefly to common commercial casting alloys. In order to carry on this work, it was necessary to determine the factors influencing grain size and to develop a proper technique for the preparation of samples. Thc preliminary tests made by the author indicated that the grain size of magnesium alloys resulting from the solidification of a melt is determined by alloy composition, presence of impurities, rate of cooling during solidification, thermal history of the melt and to some extent the structure of the charge used. The rate of cooling is in turn dependent upon the mass of the melt, pouring temperature, and dimensions, properties and temperature of the mold into which the melt is poured. The final grain size of the alloys is still further modified by heat-treatment subsequent to casting. It is not within the scope of the present paper to discuss all of these factors, and it would suffice to note here that when equal amounts of magnesium alloys are prepared from the same alloying materials, melted in graphite crucibles under the same thermal conditions, then cast into graphite molds at a constant temperature, the resultant solids have the same grain size. By maintaining all other factors constant, it is thus possible to vary thermal conditions of a melt and to examine the grain size of resultant castings. Preparation of Samples and Grain-size TestiNg The alloys investigated in this paper were taken from ingots made by Permanente the Or or prepared by the author with pure carbothermic magnesium and necessary alloying elements. Melting was carried out under a flux in a graphite crucible heated uniformly by an

Jan 1, 1946

By N. Tiner

The mechanical properties of magnesium-alloy castings are greatly improved by grain refinement, and at present considerable attention is being paid to methods of obtaining fine-grained castings. One method of achieving this end is the use of proper melting and superheating techniques. These have been employed com-rnercially to a great extent, but no comprehensive study of the subject appears to have been published at present. Numerous investigations found in the literature include some reference to superheating techniques,1"4 and Achenbach, Nippcr and Piwowarsky,% ased principally on thermal analysis, ascribe the grain-refilling action of superheating to the influence of solid foreign particles or dissolved gases present in the melt upon the course of crystallization. The primary purpose of this paper is to present the principal facts concerning the cffect of superheating on grain size of magilesium alloys. .ittempts are also made to explain the experimental results in terms of a general hypothesis. The investigations are limited chiefly to common commercial casting alloys. In order to carry on this work, it was necessary to determine the factors influencing grain size and to develop a proper technique for the preparation of samples. Thc preliminary tests made by the author indicated that the grain size of magnesium alloys resulting from the solidification of a melt is determined by alloy composition, presence of impurities, rate of cooling during solidification, thermal history of the melt and to some extent the structure of the charge used. The rate of cooling is in turn dependent upon the mass of the melt, pouring temperature, and dimensions, properties and temperature of the mold into which the melt is poured. The final grain size of the alloys is still further modified by heat-treatment subsequent to casting. It is not within the scope of the present paper to discuss all of these factors, and it would suffice to note here that when equal amounts of magnesium alloys are prepared from the same alloying materials, melted in graphite crucibles under the same thermal conditions, then cast into graphite molds at a constant temperature, the resultant solids have the same grain size. By maintaining all other factors constant, it is thus possible to vary thermal conditions of a melt and to examine the grain size of resultant castings. Preparation of Samples and Grain-size TestiNg The alloys investigated in this paper were taken from ingots made by Permanente the Or or prepared by the author with pure carbothermic magnesium and necessary alloying elements. Melting was carried out under a flux in a graphite crucible heated uniformly by an

Jan 1, 1946

By L. C. Graton, Joseph Murdoch

I. Introduction......................... 26 1. The Relations of Scale in Geologic Work........ 26 2. General Characteristics of Copper Sulphide Ores..... 29 3. Scope of Present Study................. 31 11. Description of the Important Minerals............ 36 1. Pyrite....................... 36 2. Pyrrhotite....................... 41 3. Chalcopyrite...................... 41 4. Bornite........................ 40 5. Covellite....................... 50 6. Chalcocite....................... 52 7. Enargite...................... 59 8. Tetrahedrite and Tennantite.............. 61 III. Conclusions.......................... 62 I. Introduction. The Relations of Scale in Geologic Work. Many features of human accomplishment rest upon the possibility of representing natural objects on a scale of different magnitude from the actual one. Most drawings, for example, are of very different scale from that of the object depicted, and indeed are useful mainly 011 this account. More important than the question of mere convenience, however, is that of meeting the physical limitations of vision.' Thus, a mural

Jan 1, 1914

By Leo J. Vogel, E. D. Hummer, David J. Akers

INTRODUCTION An efficient refuse-disposal system is a necessary part of the modem cleaning plant. The large-scale refuse system and disposal area, engineered for the lifetime of the plant, has become more important due to the greater tonnages of refuse produced from increased quantities of mechanically mined and prepared coal. Laws and increased government regulations have affected the design and operation of disposal systems. THE EFFECT OF MINE AND PLANT OPERATION Refuse disposal starts at the mining face. The mining system, the type of roof support, the machinery used, and the degree of discipline at the face contribute to the amount and type of refuse that must be removed through the disposal system. Economies gained through modification of the mining system or mining machinery may be partially offset by increased dilution of the mined coal with impurities from associated rock formations. In some cases the change in the mining system and equipment has reduced the dilution. In all cases the ratio of impurities that must be removed from the raw-coal feed to the plant not only affects the maintenance and

Jan 1, 1979

By Robert S. Archer

THE proper material of construction for a given purpose is that material which meets the requirements satisfactorily at the lowest ultirnatc cost. It is consistent with this principle that most aluminum castings are made of an alloy containing about 8 per cent. copper. This alloy possesses mechanical properties satisfactory for general engineering purposes together with manufacturing characteristics leading to the production of finished castings at low cost. It is to the aluminum industry what gray iron is to the iron and steel industry. Just as some services require "semi-steel," malleable castings or steel castings instead of gray iron, there is a certain and growing demand for aluminum castings of superior strength or ductility, or both. Since the beginning of .the industry producers and others have sought to develop alloys or processes by which such castings could be made. Out of these efforts have emerged many alloy compositions and special processes, of which only a few have had sufficient merit to survive. It is the purpose of this paper to describe those which seem to the authors to offer the greatest promise for the production on a commercial scale of aluminum castings of superior mechanical properties, with special reference to heat-treated castings. The suitability of an alloy or process for actual manufacture is affected by so many factors that the problem of appraisal is not a simple one. Since this is such an important part of the whole subject it is proposed to discuss briefly some of the requirements. The final verdict is of course the result of commercial trial and experience. It will therefore, perhaps, be profitable to employ a somewhat historical method of treatment in discussing the subject of alloy development. The alloys or processes to be used in the production of aluminum castings are to be considered from the standpoint of their effects on both the utility and the cost of the finished casting. Specific gravity and mechanical properties come under the first head, while the properties

Jan 1, 1927

By D. Harker, W. E. Seymour

CERTAIN alloys of iron and nickel, when rolled and annealed, possess a preferred crystal orientation: (001) in the rolling plane and [loo] in the rolling direction, when recrystallized at 850" to 1050°C after approximately 98 pct cold reduction. Since the preferred orientation makes a direction of easiest magnetization coincide with the rolling direction, these alloys, especially a 50 pct iron in nickel alloy, have found wide application in the electrical industry' for choke coils and special types of transformers. The rate of the recrystallization reaction was studied at temperatures ranging from 500° to 600°C. The heat of activation for the reaction was calculated from the observed rates, and crystal orientation determinations were made before and after re-crystallization. A vacuum melted iron-nickel alloy* analyzing 49.6 pct nickel, 0.018 pct carbon, and 0.30 pct manganese was used for the experiments. The alloy was cold-rolled 98 pct into strips 1/2 in. wide by 0.002 in. thick. Specimens 1 in. long were sealed under a vacuum (approximately 10-8 mm Hg) in 1/2 in. ID pyrex glass tubes. For heat treatment these tubes were fastened to Nicrohm wires and submerged in a molten salt bath controlled to ±2°C. (The maximum measurement error was within 3°C.) The time at temperature was varied logarithmically from one sample to another, and runs were made at 500°, 525", 550" and 575°C. A molten lead bath was used for a run at 600°C which was controlled to the same accuracy. To determine the extent of recrystallization after a particular time at a given temperature, a method was used suggested by the work of Decker, Asp, and Harker.3,4 This method employs an X-ray spectrometer whereby X rays are diffracted from crystallites whose diffracting atom planes are parallel to the rolling plane of the specimen. The intensities of the diffracted rays are measured by a Geiger counter. The counter can be rotated through a range of angle, and can be motor driven through this range at a speed of 2" per min. The measured intensities are plotted vs. angle by a potentiometer recorder. In a 50 pct iron-nickel alloy it was found that only (200) reflections were obtained from the rolling plane with recrystallized material, and that only (220) reflections were obtained from the rolling plane with unrecrystallized material. No other reflections were obtained under these conditions over a range of Bragg angle of 0 to 45" using either type of specimen. As a consequence, the intensity of the (200) reflections from the rolling plane was taken to indicate the amount of recrystallized ma-terial present in a specimen, and the corresponding intensity of the (220) reflections was taken to indicate the amount of unrecrystallized material present. To insure flatness and proper alignment of the reflecting specimen in the spectrometer, the sample was laid in a slot 1/2 in. wide x 0.001 in. deep which was machined in a 3/4x2x1/2 in. steel carrier. The specimen then was taped down with cellophane tape. This steel cradle was mounted vertically in the specimen holder of the spectrometer so that the bottom edge of the carrier rested against a horizontal shoulder. Intensity data used in plotting the percent of recrystallized material vs. time at temperature were obtained by directly counting the diffracted beam of nickel filtered copper Ka radiation used throughout the work. The X-ray spectrometer was employed also in obtaining pole figure data to be used for orientation determinations. At the beginning of this investigation a transmission pole figure holder was used." As a thickness of 0.002 in. of this alloy was found to be opaque to the copper Ka radiation, it was necessary to reduce the thickness of the pole figure specimen. A cold-worked sample was etched in a 50 pct HCl solution for 5 min and was found to transmit a

Jan 1, 1951

By Paul L. Russell

THIS is a progress report of an experiment being undertaken in cooperation with the Bethlehem Steel Corp., the Crucible Steel Co., and the Rock Bit Sales and Service Co., involving heat treatment of the shank ends of drill steel. This experiment is being conducted by the U. S. Bureau of Mines in its experimental mine, Mining Research Branch, Bluemont, Va. The purpose of the experiment is to determine the effect of an increase in the time the steel soaks in the furnace during the hardening heat. It has been thought that increasing this time produces a soft zone below the lugs resulting in a metallurgical notch that causes early failure. Each of the steel companies furnished enough 11/4 - in. straight carbon, hollow, round steel to make up 10 sets of drill steel, in each instance the steel bars were from the same heat. These sets of drill steel, consisting of 2-ft, 4-ft, 6-ft, and 8-ft lengths were fabricated by the Rock Bit Sales and Service Co. Special attention was given to the forging of the steel to produce the best rods possible. The heat treatment of all thread ends was identical and followed the best practice. The heat treatment of the shank ends of five sets of steel from each company produced a soft zone 2 to 4 in. in front of the lugs. It was decided that possibly the best way to obtain this effect was not to overlap the hardening heat but to let the steel soak for an additional 30 min before quenching. Therefore the only variable in the test steels is the length of time the shank ends were in the furnace. The remaining drill steel shanks were treated as follows: Heat treatment in pyrometer-controlled furnace at 1550°F. Quenching oil at 105°F to 125°F temperature. Areas for heat treatment were; shanks, 11 in.; threads, 9 in. Time at heat, standard practice, 20 min for 11/4-in. steel. Actual drilling tests were made in greenstone, (a metamorphosed basaltic rock), and in epidosite. Greenstone has a specific gravity of 2.96 and a compressive strength of 44,200 psi. Epidosite has a specific gravity of 3.26 and a compressive strength of 63,100 psi. All drilling tests were made using a 31/2-in. column-mounted, automatic feed drifter, with a controlled air pressure of 90 psi at the throttle. Tungsten-carbide bits of 2 in. diameter were used for all drilling. Contrary to expectations the drill steels that were allowed to soak for the additional 30 min before quenching performed better than the steels that were heat treated according to standard practice. This performance, as shown in Table I, was especially noticeable in the drilling of epidosite. The "longheat" drill steels furnished by Company "A" drilled 154 pct more minutes than the "standard-heat" steel. Expressed in feet, the "long-heat" steel drilled 114.60 ft more before failure than the "standard-heat" steel. The "long-heat" steel furnished by Company "B" drilled 37 pet more minutes or 60.39 ft more before failure than the "standard-heat" drill steel. The effect of the long heat treatment was not as evident when the steels were drilling in greenstone (Table II). In greenstone, the increase in minutes drilled by the "long-heat" steel over the "standard-heat" steel was 47 pet and 1 pet, respectively, for Companies "A" and "B."

Jan 1, 1952

By R. B. Moore

IN 1914 the writer and K. L. Kithil announced, through Bulletin 70 of the U. S. Bureau of Mines, that the United States possessed the largest deposits of radium-bearing ore in the world. At that time a small amount of this ore was being, mined and shipped to Europe, and one company was preparing to start the extraction and recovery of radium in this country. The importance of our carnotite deposits in Colorado and Utah up to the publication of Bulletin 70 was not, however, appreciated by anyone.. At that time the total supply of radium in the world was about 10 g., calculated as element, and when I estimated that at least 100 g. of radium element, and probably 200 g., would be produced from our carnotite deposits, there was a considerable amount of skepticism. Up to the present time almost 200 g. have come from this ore, and some writers put this figure a little higher. Uranium ore was found in the copper mines of the Union Minière du Haut-Katanga at Luiswishi in 1913. Later discoveries were made at other places in the Belgian Congo, and the Katanga ores now represent the largest supply of radium-bearing ore in the world. In fact, since 1923 very little radium has been produced from American carnotite, the Katanga ore representing practically the world's supply of. radium since that date.

Jan 1, 1930

By R. E. Hudrlik, G. W. Preckshot

The diffusion coefficients of silver from solid silver in molten lead were measured to within ± 0.8 pet in a columnar type diffusion cell ower, the temperature range of 326° to 530°C. Fick's law describes the process up to 530°C where the laminar mechanism appareltly breaks down. These is negligible resistance at the interface as shown by mathematical analyses. The diffusion coefficients are found concentration independent. IT would seem that diffusion in liquid metals would be free of such effects as molecular structure, dissociation. polarization. and compound formation. This view was taken by Gorman and preckshot in their study of diffusion of copper from solid copper into molten lead. They reported diffusion coefficients which were independent of the concentration over the range of 478° to 750°C. They found that the Stokes-Einstein equation with constant radius of the diffusing specie represented the diffusion data better than Eyring's rate theory equation and Sheibel's correlation. The radius of diffusion was found to be that of the doubly charged copper. There appeared to be no resistance across the solid-liquid boundary. In the present work the diffusion coefficients for silver in liquid lead were measured over a range of temperatures of 350° to 505°C. The solubility of silver in lead over the range of 303° to 630°C was also obtained. These results are compared with calculated or correlated values or with data in the literature. EXPERIMENTAL Procedure—The experimental equipment techniques and procedures were those reported in detail by Gorman and preckshot9 and will not be repeated here. Measured values of WT, Co, A. L were obtained for various diffusion times and the diffusion coefficient was computed for the case of no resistance at the interface9, 11 by: WT/CoAL = 1- 8/p2 n=1 1/(2n - 1)2 exp[-(2n - 1)2p2 Dt/4L2] [1] or where there was resistance at the interface by: WT = 1- ?n=1 2h2/ap2L [sxp [-Dan2t]/[(h2 + an2) L + h] The roots an are those of the transcendental equation3 tan (an L) = Iz/cun. The diffusion coefficient is that defined by Hartley and Crank.7 The total silver in the lead cylinder and equilibrium slug was determined by a cupellation technique' with proper correction for losses. Analysis of known samples showed that this method is surprisingly accurate. The amount of silver in the lead adhering to the silver cylinder was obtained in the same fashion as shown by Gorman and preckshot.9 The small errors involved in this determination are not critical since the silver in this adhering lead layer is only 3 to 15 pet of the total diffused. Materials—Electrolytic silver containing 99.9+ pet Ag obtained from General Refineries of Minneapolis, Minn. was used for all but runs 7 and 8. For the balance of the runs this silver was reduced with hydrogen at 1100°C and its oxygen content was found to be about 0.017 pet. For the runs. 7 and 8, phosphorous-reduced silver of the same purity was obtained from Handy and Harman Co. of Chicago, Ill. The densities of the phosphorus-reduced silver and the hydrogen-reduced electrolytic silver were 10.484 and 10.487 g per cm3, respectively. These values agree with those reported for pure silver. Silver which was reduced at 900 C had an average density of 9.998 g per cm3, indicating porosity. This silver was used for a number of runs which were not tabulated in Table I. These are indicated by crosses on Fig. 2. The 99.999 pet Pb was obtained from the National Lead Co. Research Laboratory of Brooklyn, New York. DISCUSSION OF RESULTS The diffusion and solubility results are reported in Table I for eleven runs using either phosphorus-reduced electrolytic silver or hydrogen-reduced silver at 1100° C. The solubility data shown in Fig. 1 show the excellent agreement with that reported by Heycock and Neville.8 The data of Friedrichs5 apparently are in error. The experimental solubility data of this work are reported to 0.3 pet. The experimental diffusion coefficients computed from Eq. [1] are reported within 1.2 pet of the mean and are plotted in Fig. 2. These are expressed within +0.8 pet of the experimental values over the entire temperature range by: D= 8.26 x 10 -5 e-1925/RT . [3] There appears to be little difference due to the

Jan 1, 1961

By S. T. Wlodek

The scale md subscale reaction products were identified and their rates of formation were studied in air over the range 1600" to 2000°F (871 " to 1149°C) for periods of up to 400 hr and for hoth the solution-annealed and aged conditions. The effect of prior sltrface preparation on suhscale oxidation was also studied The general oxidation behavior of both Ni-Cr-Mo-Al-Ti type alloys was similar. A surface film of a, Al2O3, forms immediately on exposure Subsequent oxidation continued at a linear rate (QL = 55 * 5 kcal per mole) as colonies of Cr2O3 nucleated at the A12O3/gas interface Further oxidation proceeded at a paraholic rate zvhiclz could he fitted to two successive rate constants. During paraholic oxidation, and depending on temperature, the scale consisted of Cr2O3, NiCr2O4 , and TiO2 with traces of NiO. In the case of Rene 41, the activation energy of both paraholic processes was 66 * 3 kcal per mole suggesting that diffusion of cations tlzrozrgh Cr2O3 was the rate -determining process. An unusual decrease in the oxidation of Udimet 700 at 1900°F where a spinel of Ni(A1,Crh0, zuas the predominant reaction product prevented the accurate assignment of activation energies for this composition. In both alloys internal oxidation of Al2O3 commenced shortly after parabolic scaling was observed. Prolonged exposure prod7tced intemal oxidation of TiN, and in Udimet 700 a complex Mo-Ni nitride was also found. At 1900oF, the subscale reactions in Udimet 700 undergo an inversion which parallels the decrease in surface oxidation; internal oxidation ceases hut is replaced by the formation of "spherodized" 3.' colonies. Surface-preparation techniqtles which introduce appreciable working, such as coarse surface grinding or grit blasting. increase the amount of alloy depletion and internal oxidation in Reni 41. The reverse is true of Udimet 700 for which electropolished or mechanically polished specimens show much more subscale oxidation than strongly worked stirfaces. The strongest commercial nickel-base alloys presently available are generic to the Ni-Cr-Mo-A1-Ti base which exploits the precipitation of Ni3(A1,Ti) as the main strengthening mechanism, while relying on solid-solution strengthening by molybdenum and chromium reinforced by the pre- cipitation of carbides to attain maximum properties. This study characterizes the oxidation behavior of Rene 41, the strongest alloy of the Ni-Cr-A1-Ti type commercially available in sheet form, and Udimet 700, whose higher aluminum and titanium content allows it to exhibit one of the more attractive combinations of high-temperature properties available in a wrought product. The scaling processes of complex, type nickel-base alloys have received relatively little attention. Malamand and vidal as well as Poulignier et al.2'3 have determined the composition gradients across the metal/oxide interface produced by high-temperature oxidation and considered the effect of surface perature, Limited weight-gain data has also been published by Fere 5 for alloys of this type and Radavich6 has identified the reaction products on Udimet 500 and Inco 702 after oxidation at 1832°F. Reference can, of course, be made to the excellent reviews of Kubaschewski and Hopkins7 or Ignatov and Shamgunova8 for a summary of the data available on the oxidation of binary and ternary alloy systems which are related to the more complex alloys considered here. EXPERIMENTAL The analyses of the different commercial heats studied are given in Table I. Using the experimental procedures previously established,9 continuous weight-gain data were obtained on both heats of Rene 41 sheet (A and B) and 150-mil-thick slices of cast Udimet 700. Subscale oxidation reactions were followed by static exposure of cylindrical specimens obtained from swaged Rene 41 (Heat C) and Udimet 700 (Heats E and F). In brief, continuous weight-gain tests were performed on specimens with a surface area of 10 to 12 sq cm. These were abraded through 600 grit Sic paper, electropolished to 2p rms in an electrolyte of 10 pct H2So4 in ethanol, and lightly etched in 10 pct HCl in ethanol before final washing and rinsing in ethanol. All continuous weight-gain data were obtained in dried (-70°F dew point) flowing (1 liter per min) air to an accuracy of +0.1 mg. Subscale oxidation processes were followed by the metallographic examination of 0.5-in-diam by 1.0-in.-long specimens. After an initial center-less grinding, various additional surface treatments were employed to determine the effect of surface preparation on subscale oxidation processes. Before exposure in zirconia crucibles, all samples were lightly etched in 10 pct HCl-ethanol, washed in ethanol, and dried. The depth of internal oxidation was measured to ±0.00025 in. on unetched specimens mounted so as to provide a taper mag-

Jan 1, 1964

By William L. Fink, Dana W. Smith

In parts I1 and II2 of this series, there were presented results of investigations on the age-hardening of an aluminum-copper and an aluminum-magnesium alloy. It was shown that the simple precipitation theory of hardening3 adequately explained the aging phenomena, including certain so-called "anomalous" behaviors which had caused other investigators to reject or modify the precipitation theory. However, these papers did not discuss the double aging peaks, which have been stressed in recent articles by Dr. M. Cohen4 and Dr. M. L. V. Gayler.6 The present paper is devoted to an explanation of this "anomaly." Fig. 1 is a generalized schematic representation of aging curves at different temperatures. Curve A corresponds to the aging at the lowest temperature, and D at the highest temperature. Certain previous investigators have explained curve A and the initial peaks

Jan 1, 1938