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By Harold M. Feder, Irving Johnson

Tkermodynamic functions for dilute solutions of uranium in liquid cadmium were obtained from galvanic cell measurements. Deviations from Henvy's law were observed at concentvations down to 2 x 10-3 atom fraction. Unusually large negative values of the pavtial molal relative enthalpy and excess entvopy of uranium, suggestive of the occu,vvenctwe of partial ovdering of cadmium around uranium in these solutions, were found. The negative relative partial molal enthalpy of uranium at the liquidus accounts for the observed retrogvade solubility of metallic uranium between 473" and about 630°C. The standard free enevgy of formation of UCd,, from a-uranium and liquid cadmium is given by F,° THE constitutional diagram of the U-Cd system,' Fig. 1, is unusual in several respects. The near equality of the Goldschmidt atomic radii2 (Cd, 1.52A U, 1.56A) might be expected to give rise to extensive mutual solubility of the elements except for the restrictions imposed by differences in valence and electronegativity.3 The latter factors must be strongly influential because mutual solubilities in the terminal solid phases are probably negligible, and the solubility of uranium in liquid cadmium in the readily accessible range is only about 1 at. pct. Interestingly, the solubility of uranium in liquid cadmium actually decveases slightly with increasing temperature from 473" to about 630°C. Such a retrograde solubility in a liquid phase is a rare phenomenon in metallic systems; no other authenticated examples were found among the nearly 700 binary phase diagrams compiled by Hansen and Anderko.2 These observations suggested the existence of some unusual interaction between uranium and cadmium. Greater insight into the nature of this interaction was sought by measurement of the thermodynamic properties of the system. EXPERIMENTAL PROCEDURE The emf of cells denoted by the scheme was measured. Each cell consisted of two uranium and two alloy electrodes immersed in a molten lithium chloride-potassium chloride eutectic mixture containing uranium trichloride. The physical arrangement is shown in Fig. 2. The potential between any pair of electrodes could be measured with a Leeds and Northrup Type K-3 potentiometer. The measurements were made at points marked in Fig. 1. It should be noted that points on the phase boundaries represent the concentrations of uranium in the saturated liquid phases of heterogeneous alloys. Uranium Electrodes. Uranium, which is not a particularly soft metal, is capable of retaining residual stresses, and its potential may depend upon its physical condition. Electrodes were prepared from 3-mm diam rods of hot-rolled high-purity4

Jan 1, 1962

By C. E. Lundin, D. T. Klodt

The binary alloy systems, Y-Ti, Y-Zr, and Y-Hf, have been investigated throughout their entire composition regions. There is no compound formation in any of the systems, and each system is characterized by a single eutectic reaction. The eutectic compositions and temperatures are as follows: A eutectoid reaction pct Y and 870°C occurs in the Y-Ti system, whereas a peritectoid reaction,: pct Y and 880°C occurs in the Y-Zr system. Peri-tectic-type reactions at temperatures above the eutectic levels are postulated for the yttrium and hafnium transfovmations. The development of the technology of yttrium has been given considerable attention during the past few years, and studies of binary phase equilibria have, of course, taken a prominent position in this development. In many respects yttrium, in the third group of metals of the periodic table, is similar to the adjacent group of metals, titanium, zirconium, and hafnium, and the knowledge of the phase relationships of yttrium with these metals is basic to their technology. MATERIALS AND EXPERIMENTAL PROCEDURES Materials. The metals for this investigation were supplied by the General Electric Co., Aircraft Nuclear Propulsion Department. The yttrium was in the form of an arc-melted ingot, and the other metals were in the form of high-purity, iodide-Process crystal bar. Table I lists the purities of these materials. Alloy Preparation. Melting was done by conventional techniques in a nonconsumable electrode arc furnace in an atmosphere of purified argon. Melting conditions for each binary system were the same. Each alloy button was inverted and remelted several times to assure homogeneity. Accurate weights of the charges and resultant alloy buttons were obtained to indicate deviations from intended compositions. No chemical analyses were obtained since melting weight losses were consistently in the range of 0.1 to 0.2 pct of the total weight. 10- or 20-g buttons for each 5.0 wt pct composition increment were melted to survey the three individual alloy systems. Additional alloys differing in composition by 1.0 or 0.1 wt pct increments were also melted to study selected regions of the systems. Metallograpllic Techniques. Standard metallo-graphic techniques were followed for mounting and rough grinding. Preliminary polishing was accomplished using 6-u diamond paste as an abrasive on a Metcloth Lap. Final polishing was done on a Microcloth-covered wheel using 1-u diamond abrasive paste. Purified kerosene was used as a lubricant for both polishing stages. • sothermal- Annealing. Alloys were sectioned for as-cast structlure examinations and then homogenized in preparation for isothermal-annealing treatments. Homo{:enization was accomplished by cold pressing the alloy buttons followed by 72-hr anneals at 1100c. The alloys were encapsulated in Vycor or quartz for the homogenization treatments or for isothermal anneals. Resistance-wound or resistance-element tube furnaces were used for the annealing treatments. The homogenized alloy buttons were cold rolled until cracking occurred or until a -in. specimen thickness was obtained. Small -in. square) specimens for the isothermal anneals were then sawed from the alloys. Each specimen was wrapped in tantalum foil before being sealed in the capsule. Temperatures during the anneals were controlled The time at temperature necessary to equilibrate the structures during the anneals was determined for each alloy system by holding triplicate specimens of alloys at a constant temperature for three different periotls. The specimens were quenched and examined microscopically to determine the number and amounts of phases present in the micro-structure as a function of time. Melting Studies. Eutectic temperatures of the three alloy systems were established from the results of incipient-melting studies conducted on as-cast alloys. Specimens to be melted were suspended on a tungsten wire inside a graphite cylinder placed in a glass vacuum chamber. An optical pyrometer was used to follow the temperature of the specimen as it was inductively heated in a high vacuum. The temperatures were corrected for emissivity losses by standardizing the pyrometer with known-melting-point metals. Accuracy of the temperature measurements is estimated to be + 10°C. The melting point of the yttrium was determined to be 1550°C by this technique. The invariant-temperature levels were also checked by an anneal-quench technique. This technique consists of annealing a series of

Jan 1, 1962

By H. A. Baumann

Experimental data are presented showing the influence of size consist and firing rate upon the performance of bituminous coal-fired, single-retort, industrial underfeed stokers. Size segregation, degradation, and distributor data are also included. The conclusion is reached that size consist of the fuel as fired, is a critical factor in its performance on this class of equipment.

Jan 1, 1950

[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

By Marius S. Darrow, William B. White, Rustum Roy

The PbS-PbTe systen has been studied by quench-ing and D.T.A. techniques f?om 400' to 1150°C. Runs were made in evacuated silica tubes so that all equilibria are at the vapor pressure of the system. Lattice parameters of the quenched salnples , measured by X-ray diffraction, show a complete crystalline-solution series existing over a narrow temperature range between approximately 805" and 871°C. An exsolution dome extends from a maximum of about 805"C (approximately 30 mole pct PbTe) to 1 and 96.5 pet PbTe at 400°C. A narrow melting region, deternined by D.T.A., extends form 918c (mp PbTe), The shapes of the liquides and solidus curves imply the existence of a minimum at 871°C at approximately 65 pct PbTe. THe exact composition of the minimum could not be established due to the very narrow two-phase region. At compositions containing less than 50 pet PbTe, liquidus temperatures begin to increase, while the solidus remains almost flat to about 15 mole pet PbTe before beginning to vise toward the mp of PbS (1075 C). LEAD sulfide and lead telluride are isostructural (NaC1 type) semiconductors whose electrical and optical properties have been extensively studied and used in recent years. If appreciable crystalline solution exists between these compounds, the variation of physical properties with composition could be of interest. The purpose of this investigation was to determine the extent, if any. of crystalline solution, and to obtain the phase diagram for the system. To the knowledge of the authors, only three studies of the system PbS-PbTe have been reported, and, in chronological order, each investigation found an increasing amount of crystalline solution. In 1956, Yamamoto reported finding no evidence of crystalline solution between the compounds. Sindeyeva and Godov-ikov,' in 1959, found very limited crystalline solution. but only under conditions of excess tellurium concentration. Finally Melevski s3 investigation in 1963 indicated that one solid phase exists in the region from PbS to 7 pct PbTe and from 82 pct PbTe to PbTe at 886'C, with an eutectic at 55 pct PbTe at that temperature. Detailed data on the solvus boundary were not given. EXPERIMENTAL EQUIPMENT AND MATERIALS Commercially produced PbTe and PbS powders were used as starting materials. Batches of specific mole percent composition were accurately weighed and mixed in a plastic bottle, in a shaker mill. An analy- sis of impurity content is given in Table I for pure PbS and PbTe and for two randomly selected batches after the powders were mixed. Individual samples, ranging in weight from 0.2 to 0.5 g, were sealed in evacuated silica tubes which had been thoroughly washed and rinsed with acetone and distilled water. Thus all data taken were at the pressure of the system. Subsolidus relations were studied down to 400°C by heating the samples in a vertical tube furnace for 24 hr. The sealed tubes were quenched in water with quench time from the hot zone not exceeding 1 sec. Temperatures were measured by a chromel-alumel thermocouple and controlled to 53°C for most runs. The number and composition of phases present were determined from powder X-ray diffraction patterns taken at room temperature on a Norelco diffractome-ter, using silicon as an external standard. Above 850°C quenching techniques were, in general, found to be unsatisfactory, and differential thermal analysis (D.T.A.) was used to determine melting relations. The evacuated tubes were recessed about 1 cm at one end to accommodate the differential thermocouple. Al203 was used as the reference material in a similar tube containing the other side of the differential couple. For temperature measurements, a separate thermocouple was placed in the recess of the tube containing the sample to be measured, thus providing an opportunity to obtain thermal, as well as differential, analysis. All thermocouples for these measurements were Pt-Pt 10 pct Rh. Temperature and differential curves were recorded separately on synchronized strip-chart recorders. Thermocouples and recording equipment were calibrated using NaCl and gold standards, using the melting points 801" and 1063 C, respectively, which span most of the temperature range of interest. Heating and cooling rates generally were from 4 to 7°C per min. It was found, in fact. that rates ranging from 1.5 to 25°C per min did not significantly change the data obtained.

Jan 1, 1967

By William C. Hagel

Oxygen-18 exchange between gaseous oxygen, held at a pressure of 125 mm Hg in a PL-IORh chamber, and splzeres of a Fe2O3 containing three or less grains was determined from 9000 to 1250°C. Isotope equilibrum on crystal surfaces appears to be quickly established, and the rate-determining factor is self-difiusion confbvrning to the relation D = 2.04 esp(- 77,900/RT) sq cin sec-'. Changing sphere diameters caused no detectable variation in diffusion coefficients. Oxygen ions diffuse faster than cations at low temperatures, but a crossover may occur at about 1150°C. INVESTIGATIONS by Davies et al.' and Himmel et al2 have suggested that the mechanism of iron oxidation above 600°C involves a predominance of cation migration in the wüstite (FeO) and magnetite (Fe301) layers and oxygen-ion migration in the hematite (a Fe2O3) layer. Evidence for little cation migration during hematite growth consists of: 1) the disappearance of radioactive-silver markers, presumed to vaporize from the oxide-gas interface, and 2) a large discrepancy between parabolic rate constants for magnetite oxidation and those calculated from Lindner's3 data for cation self-diffusion, D:, using Wagner's theory.4 Reversing the calculations gave anticipated self-diffusion coefficients, D:, for oxygen ions of 3.6 x 10-9 sq cm sec-1 at 1100°C and 5.9 x 10-10 sq cm sec-1 at 1000°C. Since then Kingery et a1.5 reported three values for oxygen-ion diffusion in polycrystalline, sintered hematite. These were obtained near 1200°C, at an oxygen pressure of approximately 150 mm Hg, and could be represented by the Arrhenius expression, Dg = 1 x 10 11 exp(-146,000/RT) sq cm sec-1. Extrapolation to temperatures below 1100°C infers that oxygen ions are less mobile than cations. This contradicts the aforementioned oxidation evidence and also coble7s study of the initial sintering of hematite. From the latter, apparent diffusion coefficients for the slowest rate-controlling species could be calculated, and fair agreement was found with an extension of Lindner's data for cation diffusion. Fig. 1 depicts such comparisons graphically. Three points have been included for the determinations of Himmel et al. on cation diffusion in large, natural hematite crystals surrounded by pure oxygen at atmospheric pressure. No dependence on crystal log raphic direction was noted. Since the value of 10-l4 sq cm sec-' at 1000°C actually represents an upper limit, one might interpret that there is a small decrease in D: when single crystals are employed. On the whole, however, cation diffusion appears relatively well-defined,* while the few results tension to lower temperatures. After having gained experience measuring oxygen-ion diffusion in certain glasses7 and in the corundum oxide, a Cr2O3, the purpose of this work was to determine D; values for hematite and thus possibly assist a mechanistic understanding of the kinetics of the oxidation and reduction of solid iron oxides. I) EXPERIMENTAL PROCEDURE A) Material. Hematite powder of moderately high purity was received from the Columbian Carbon Co. An accompanying lot analysis listed 0.03 H2O, 0.008 weight percents, with the remainder Fe2O3. Subsequent treatments were ball milling, drying, prepressing, and hot-pressing for 60 min at 1350°C under 5000 psi. Since graphite dies coated with a slurry of alumina were used for hot-pressing, the surrounding atmosphere at temperature was sufficiently reducing to form some magnetite on the outer surface of each cylinder. After removing any attached alumina, a stabilizing anneal of 50 hr at 1300°C in oxygen was added. The final product was nonmagnetic and exceeded 97 pct of the density (5.24 g cm-3) usually given for FezO3. On polishing cylindrical ends, counts were made of the number of grain boundary intercepts per

Jan 1, 1967

By AIME AIME

THE program of government drilling, conducted jointly by the U. S. Geological Survey and the Bureau of Mines, has demonstrated the presence in Texas and New Mexico of potash-bearing beds of considerable importance. Information regarding the ex- tent and location of the potash deposits as presented at the non-metallic sessions was of great interest to many engineers. These subjects will be covered in greater detail in later paragraphs. The first session, with about 50 in attendance, convened at 10 a.m. on Feb. 18, with Oliver Bowles, chair- man of the Committee on Non-Metallic Minerals, pre- siding. The first paper was on "Soapstone Mining In Virginia," presented by C. W. Ryan of Lynchburg, Va. The nature and extent of the soapstone deposits of Nelson County were described in some detail. In origin, the soapstone is undoubtedly related to a basic peridotite rock though its mode of formation is some- what uncertain. This main soapstone deposit occurs in three veins, the western, middle, and eastern, the middle vein being of greatest economic importance. Methods of stripping, quarrying and milling the rock were described and the uses of soapstone were enum- erated. In discussing this paper, C. P. Berkey, of Co- lumbia University strongly favored the theory of igneous origin of the soapstone and the need for further detailed geological study. J. L. Gillson of Cambridge, Mass., stated that the Vermont and New York talc deposits were always associated with characteristic minerals, such as, a chlorite of one particular variety, siderite, amphibole, magnetite, and biotite. C. H. Behre of Cincinnati, Ohio, raised the question of parallelism in the soapstone structure and Mr. Ryan stated that such parallelism was in evidence in some parts of the deposits. H. A. Wheeler of St. Louis, Mo., also took 'part in the discussion.

Jan 1, 1929

By J. O. Betterton, D. S. Easton

A detailed investigation was made of the phase diagram of silver-zirconium, particularly in the region 0 to 36 at. pct Ag. The system was found to be characterized by two intermediate phases Zr2Ag and ZrAg and a eutectoid reaction in which the -zirconium solid solution decomposes into a-zirconium and Zr2Ag. It was found that impurities in the range 0.05 pct from the iodide-type zirconium were sufficient to introduce deviations from binary behavior, and that with partial removal of these impurities an increase in the a-phase solid solubility limit from 0.1 to 1.1 at. pct Ag was observed. The phase diagram of the silver-zirconium system is of interest as an example of alloying a transition metal from the left side of the Periodic Table with a Group IB element. Silver would normally act as a univalent metal, its filled 4d-shell remaining undisturbed during the alloying. However, there is a possibility that some of the 4d electrons might transfer to the zirconium. An insight into such a question can occasionally be obtained by comparison of phase diagrams. The silver-zirconium system forms part of a more complete review of various solutes in zirconium in which these valency effects were studied.' Earlier work on the silver-zirconium system was done by Raub and Enge1,2 who investigated the silver-rich alloys. After the start of the present experhents, work on this system was reported by Kemper3 and by Karlsson4 which for the most part agrees with the phase diagram presented here. EXPERIMENTAL PROCEDURE The alloys were prepared by arc casting on a water-cooled, copper hearth with a tungsten electrode and in a pure argon atmosphere. Uniform solute composition was attained by multiple melting on alternate sides of the same ingot. Progressive improvements in the vacuum conditions inside the apparatus during the course of the experiments reduced the Vickers hardness increase of the pure zirconium control ingot from 10 to 20 points, observed initially, to negligible amounts at the end of the experiments. Such hardness changes in zirconium are a well known indication of purity. For example, -01 wt pct additions of oxygen, nitrogen, and carbon increase hardness by 6, 10, and 3 VPN respectively. '9' Further verification that the final casting technique did not add a significant quantity of impurities was obtained when pure zirconium was arc cast and then isothermally annealed in the vicinity of the allotropic transition. The transition was always observed to take place over the same temperature range as in the original crystal bar. The alloy ingots were annealed in sealed silica capsules for times and temperatures which varied between 1 day at 1300°C and 60 days at 700°C. The best method found to prevent the reaction of the zirconium with the silica was foil wrapping of molybdenum or tantalum. With this method, samples of pure zirconium were found to be unchanged in hardness after annealing for 3 days at 1200°C. In most of the experiments the protection of these foils was supplemented by an additional layer of zirconium foil inside the molybdenum or tantalum foil. The alloys, foil, and the capsule were outgassed at pressures in the range 10 to l0-7mm Hg in the temperature range 800" to 1100°C before each anneal in order to remove hydrogen and other impurities, and to provide a suitable container for the high purity, inert atmosphere, which is essential in the annealing of zirconium. The temperature measurements were made with Pt/Pt + 10 pct Rh thermocouples calibrated frequently during the experiments against the melting points of zinc, aluminum, silver, gold, and palladium. For the longer anneals the sum of various temperature errors was generally well within ± 2°C. For short-time anneals and during thermal analysis the overall temperature error is considered to be within ± 0.5°C. The compositions of the alloys from the quenching experiments were determined by chemical analysis at Johnson Matthey and Company, Ltd., under the direction of Mr. F. M. Lever. The actual metallo-graphic samples were individually analyzed in every case, and prior to the analyses two or more sides of each specimen were examined to insure that the specimen was not segregated. The sum of the solute and solvent analyses was in each case within the range 99.9 to 100.1 pct. In the course of the experiments, minor impurities in the range 0 to 500 ppm were found to have significant effects on the zirconium-rich portion of the phase diagram. Similar effects had been encountered previously in other zirconium phase-

Jan 1, 1959

By D. W. Loucks

There is plenty of evidence to indicate that at least one of man'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'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.

Jan 1, 1949

By Colin Baker, G. C. Smith

Investigation of the initiation and propagation of ductile failure in OFHC copper was undertaken to determine the role of nonmetallic inclusions. The effect of inclusion initiated voids on the formation of the internal cavity and the final shear separation was studied by metallographic eranzination of strained test pieces. A strain anneal technique was used to enlarge the voids under uniaxial stress conditions to elinzinate triaxial stress effects. Measurements of void size us stress and strain were made to show the point at which void im'tiation begins and becomes an important factor in the deformation process. The work of separation of copper-cuprous oxide was determined to attempt to correlate the breakdown of the matrix inclusion interface with void initiation and propagation. The zloid shape and position relative to the tensile axis suggested an interface breakdown mechanisnz of initiation. Evidence is presented that shows a basic similarity between the central cavity propagation and the 45-deg shear portions of the failure. DUCTILE fracture has been studied by a number of workers1-lo and attention drawn to the importance of hard second phase particles in the initiation of the failure. Holes formed at the matrix-particle interface can elongate by plastic deformation and then subsequently expand sideways to link up and produce a major crack. This is usually observed first in the center of the macroscopically necked region of a test-piece where the hydrostatic stresses are at a maximum. As the crack spreads sideways towards the free surface of the specimen, well defined shear zones develop from the crack tip and the final separation is along a direction at approximately 45 deg to the stress axis. This shear failure may also be associated with voids formed adjacent to second phase particles. In this way a cup and cone type fracture is produced. The stage at which separation takes place between particles and the surrounding matrix has not been clearly identified. In addition, although researchers have dealt with anisotropy of tensile behavior" as a result of material fabrication variables, not much is known about the microstructural features of aniso-tropic behavior. In the present work evidence on these points is presented in relation to the behavior of copper containing second phase particles of cuprous oxide. I. MATERIALS AND PROCEDURES EMPLOYED The material used was +-in. diam or 2-in. sq cold-drawn OFHC copper bar which contained 0.6 pct by volume of cuprous oxide inclusions. These ranged in COLIN BAKER, Junior Member AIME, formerly at -mnF of Metallurgy, University of Cambridge, Cambridge, England, is presently Research Scientist Reynolds Metals Co., Richrnand, Va. G. C. SMITH, Member AIME, is Senior Lecturer, Department of Metallurgy, University of Cambridge. Manuscript submitted June 20, 1967. IMD size from approximately 1 to 6 p in length and 1 to 4 p in width. The shape was generally slightly ovoid. Tensile tests were made on specimens having a gage length of 2.5 cm and diameter of 0.643 cm. Metallographic examination was carried out by sectioning deformed and fractured specimens; in addition fracture surfaces were examined optically and with a scanning electron microscope. Some measurements of the work of separation between copper and cuprous oxide were made, using a sessile drop technique which was a modification of that used by Kingery and umenick." The best metallographic results were obtained by using a vibratory polisher, which minimized smearing of the surface. 11. RESULTS A) Initial Experiments. Specimens from the +-in. diam rod were annealed for 2 hr at 650°C in uacuo, at which temperature complete recrystallization occurred without any change in the form of the inclusion. They were then fractured at temperatures from -190" to 600°C. Cup and cone fractures were obtained at all temperatures from -196" to 400°C. With increase in temperature there was, however, a continuous increase in the extent of the central transverse area and a corresponding decrease in the shear portion of the fracture. Above 400°C, the fractures became intergranular. Sections of specimens tested below 400°C revealed extensive small voids which were always associated with inclusions. However, the voids only reached dimensions greater than the inclusion size in the region of the macroscopic neck, where they were many times longer. Lateral expansion was found only near the fracture surface of the test pieces. As observed by Puttick, the voids were either (a) triangular holes initiated in the direction of the tensile axis and elon-

Jan 1, 1969

By E. W. Shaw

Continued discussion of the paper of Roswell H. JOHNSON, presented at the New York meeting, February, 1915, and printed in Bulletin No. 98, February, 1915, pp. 221 to 226. See also Bulletin No. 101, May, 1915, pp. 1157 to 1162. E. W. SHAW, Washington, D. C. (communication to the Secretary+). -With the word petrology-literally the science of rocks-being used primarily for igneous rocks, and with geophysics coming to mean the study of lavas and the rocks into which they solidify, contributions to the knowledge of the physical chemistry of sedimentary rocks, even though only ideas which may be used as working hypotheses, become most welcome. The forces which control the formation and subsequent history of the stratified portions of the earth's crust are so little known that no one has yet been able to settle finally the questions as to whether petroleum is of organic or inorganic origin; whether it originated far from its present position, or nearby. Yet both the chemical and physical problems of the rocks in which oil occurs seem to be more simple than those of the igneous rocks. The oil-bearing rocks of western Pennsylvania, for example, have in all probability never been subjected to a pressure exceeding 3,000 or 4,000 lb. to the square inch, nor to a temperature higher than 100° or 200° C. These pressures are considerably below the crushing strength of rocks, and the temperature far below their melting point. The igneous rocks,, on the other hand, have been affected by enormous pressures and very high temperatures and yet steady progress is being made in reproducing in the laboratory the conditions of their formation and subsequent modification within the earth. The solution of the sedimentary-rock problems would seem to be fully as important as those of igneous rocks, and yet we must content ourselves with reasoning backward and our inferences as to what has happened are oftentimes little more than guesses.1 One of the fundamental problems is the origin of the salt water in oil fields. Is the salt water fossil sea water; has it been formed by the solution o-f salts of various kinds from distinct beds, from disseminated par-ticles, and from the weathering of suitable grains in the rock; or is it of deep-seated origin? Its general resemblance to sea water points to the first, but the principles held by some concerning the free circulation of water throughout the earth's crust, and certain peculiarities of composition indicated by the few analyses available, seem out of harmony with such an explanation.

Jan 7, 1915

By H. C. Rickaby

BY August 1944 Canada expects to be shipping 56 percent hematite ore from its new Steep Rock iron mine, via Port Arthur on Lake Superior, to the steelmaking centers in Canada and the United States. This is indeed welcome news to steel men, especially if they operate open hearth furnaces, as the Steep Rock ore is a high-grade lump and will be valuable as charge and feed ore. But better news is the fact that this first big producer of high-grade hematite ore in Canada, since the exhaustion of the Helen mine in the Michipicoten area north of Lake Superior in 1918, has a proved ore body of 16,757,000 long tons and a probable ore body of 14,000,000 long tons, thus giving an over-all total of 30,757,000 long tons and assuring production for a number of years to come.

Jan 1, 1943

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

Consolidation of hydride process, electrolytic, calcium reduced, and comminuted thorium powder, as well as saw chips and lathe turnings, by vacuum hot pressing and by cold pressing-vacuum sintering was studied. The mechanical properties of the consolidated material in the extruded form are compared with those of wrought castings. AT present there little little industrial use for thorium metal, although it has some important though small scale applications in electronic equipment. Despite its high inelting point—about 1750°C —a low modulus of elasticity, 11.4xl0 si at 20°C;' relatively low mechanical properties coupled with a high density, 11.7 g per cu cm; and an unusually high chemical activity with normal atmospheres limit any structural applications. The metal is utilized as an alloying element principally in magnesium. Pure thorium finds utility as electrodes in gaseous discharge lamps such as the high intensity mercury lamp' because its low work function and high electron emissivity provide lower starting potentials and more uniform operating characteristics than other available materials. The metal is also found in photoelectric tubes used for the measurement of the ultraviolet spectrum." Thorium metal has been used in germicidal lamps of the cold cathode type as sputtered coatings on nickel in order to provide a low work function surface and a low starting voltage. Other applications have involved the radioactive properties of thorium for the production of ionized particles." The potential value of thorium is much greater than its present use pattern because of possible utility in the field of nuclear power. Th may be converted through nuclear reaction to a fissionable element U which should be capable of acting similarly to U in the g'eneration of atomic power. Thorium has been reported to be about three times as plentiful as uranium in the earth's crust, placing it in the order of abundance of lead and molybdenum." Thus, it is of interest in augmenting the potential supply of fissionable material for nuclear power. Because of its high melting point, thorium is usually produced as a powder through the calcium reduction of its oxide or thermal reduction of halides by sodium, magnesium, and calcium. It may also be produced in flake form by electrolysis of fused alkali or alkaline earth chloricles and fluorides. Therefore, powder metallurgy assumes importance in the fab- rication of thorium metal shapes. Furthermore, it is rather difficult to obtain pure thorium by melting, as the molten metal reacts readily with graphite as well as oxide, carbide, and nitride refractories. These contaminate the melt with oxides, carbides, and metallic impurities." The current investigation was undertaken to examine the fabrication of thorium by powder metallurgy methods which have been used for the commercial production of beryllium and other metals.' A sparcity of data concerning the comparative cold and hot compaction of thorium powders of different derivation existed. Therefore, all commercially available types were examined along with other experimentally produced thorium powders in order to round out the comparison of consolidated thorium powders with melted reguline metal. Review of the Literature By heating a mixture of ThC1, with potassium, Berzelius made the first thorium metal as an impure powder in 1828. Improvements in the basic process, increasing thorium assay to 99 pct, were made by several investigators including Arsem," Lely and Hamberger10 and Von Bolton." Calcium reduction of Tho, to make powders was investigated by Berger," Huppertz,'" Kroll," and Kuzel and Wedekind.'" A thorium powder produced by this method using a CaC1, fluxing agent assayed 99.7 pct, as reported by Marden and Rentschler.'" Compacted and sintered, this product was found to be ductile, and could be fabricated into wire and sheet. Improvements of the calcium reduction process were made later" wherein CaCl, was eliminated from the reaction, producing metal assaying 99.8 pct Th. Further work by Lilliendah118 howed that a coarser metal could be obtained by the substitution of ThC1, or ThOC1, for oxide with consequent advantage of stability to atmospheric reaction. Reports on the technology of thorium developed in Germany during World War II have been made by Espe."' Thorium powder of 99.5 pct Th was obtained by reduction of the oxide by calcium. Screening to —200 mesh, compacting with about 20 tsi, and sintering in vacuo at 1320" to 1360°C for 3 hr resulted in a porous sinter cake. The sinter cake was sufficiently ductile to be worked into bar, wire, and sheet which could be employed as electrode materials.

Jan 1, 1957

By M. N. Pathasarathi, P. A. Beck, T. J. Koppenaal

EARLIER work1 indicated that in rolled and annealed copper the volume fraction of the cube-texture component may increase on continued isothermal annealing. Merlini found2 that in rolled copper the well-known increase in the amount of cube-oriented material with increasing annealing temperature3 is concurrent with grain growth, which takes place after recrystallization is complete. It was found that both in copper2 and in aluminum4 the texture resulting from primary recrystallization, even if this is followed by some grain growth, may in general comprise, in addition to the cube-texture component, four symmetrical texture components of the general type (123)[412], i.e., components not very far from the ideal orientations of the rolling texture. The volume fraction of the cube-texture component increases on further annealing at the expense of these four components.' The present work was undertaken to study quantitatively the increase in the volume fraction of the cube-texture component in the course of normal grain growth, under varying conditions. Since the grain-gr3wth behavior of A1-Mn alloys has been already investigated in some detaiL5 an A1 + 0.8 pct Mn alloy was chosen for this work, in which the extent of normal grain growth can be effectively controlled by the inhibiting effect of a dispersed second phase. EXPERIMENTAL PROCEDURE High-purity aluminum of the following composition was used: A1 99.997 pct, Cu 0.0004 pct, Fe 0.0005 pct, and Si 0.001 pct. A high-purity A1-Mn master alloy was prepared by dehydrating manganese chloride at 500°C and reacting it with molten high-purity aluminum at 750°C in a graphite crucible.5 The Mn metal reduced from the salt by the molten aluminum goes into solution in the latter. The master alloy? containing 13 pct Mn, was solidified under conditions suitable for minimizing segregation. An ingot of the final alloy, to be used in the experiments, was per pared by melting high-purity aluminum and the necessary amount of master alloy in a graphite crucible, and by pouring the molten alloy into a graphite mold preheated to 700°C through a box containing graphite baffles designed to intercept most of the aluminum oxide films floating in the melt. The melt was then solidified by placing the mold on a water-cooled copper plate and by keeping the top of the mold hot, in order to minimize piping. The 6 1/2 in. long, 11/4-in.diam ingot consisted largely of a single crystal. Chemical analysis showed that there was little segregation from the bottom (0.83 pct Mn) to the top (0.81 pct Mn). Spectrographic analysis of the ingot showed that the impurity content remained essentially the same as that of the aluminum used. The ingot was processed so as to obtain a uniformly small grain size. without banding. The ini-tial steps of rolling in the form of a flat bar and of annealing, down through a thickness of 0.4 in., are shown in Table I. At this point the bar was cut into four sections, each approximately 3 in. long, which were processed separately as shown in Table If. The table also gives the penultimate grain sizes obtained in each section by annealing prior to the final rolling of 90 pct RA. During the final rolling the strips were reversed end to end between passes. Annealing treatments were given in a salt pot furnace, with the temperature controlled to 1°C. All annealing of section "6s" was carried out above the solvus point to avoid the formation of second-phase precipitate. The penultimate annealing was sufficiently short to give a relatively fine grain size in spite of the high temperature. Section "6L" was processed in a similar manner, except that the penultimate annealing was much longer, so as to allow considerable grain growth. Section "4" was given the two final

Jan 1, 1961

By F. S., Mc Nicholas

A practical discussion of the theory of A block caving is presented which applies particularly to the physical conditions of the Climax orebody although the conditions are sufficiently characteristic of caving ore-bodies to provide valuable information applicable elsewhere.

Jan 1, 1950

By Charles C. Goddard

Since discovery of silver-gold lode deposits in 1864, the Butte district has produced more than $2.25 billion worth of copper, zinc, manganese, silver, and gold, an unprecedented value in the mining world. Exhaustion of the gold placer deposits along Silver Bow Creek, southwest of Butte, forced the early-day placer miners to turn their attention to the bold out- crops of the many veins exposed on the hillsides above the placer diggings. These outcrops bore silver and gold, and enough so that many lode claims were located. Such famous silver mines as the Alice, Moulton, Magna Carta, Nettie, and Blue Bird were developed. These and many smaller operations contributed to making Montana the leading silver-producing state in the 1880's. As depth was gained in the silver mines in certain parts of the district, occurrence of zinc minerals became troublesome. Zinc was not recoverable at the time, and in the chloridizing, roasting, and amalgamation of the ores, silver and gold recovery was greatly reduced. A period of active silver mining continued until 1892, when a decline in the price of silver brought the silver mining period to a close. Elsewhere in the district it was discovered that while some of the veins contained silver ores in the oxidized portions, the predominant minerals that were deeper were copper-bearing. Marcus Daly exposed rich copper ore on the 300 level of the Anaconda mine in 1891, and mining in the district disclosed that copper was destined to be developed in abundance. Early copper ore shipments were made to Swansea, Wales.

Jan 3, 1959

By Claus G. Goetzel

SOME of the reactions and procedures upon which modern techniques in the production of metal powders are based were used for 2000 years by the ancients to reduce iron and other metals from their ores. Despite this, however, the art of powder metallurgy is relatively new and probably stems from the introduction of incandescent electric lamp filaments. Attempts to improve upon Edison's carbon filaments led to the production, in order. of metallic filaments of osmium. tantalum.. and finally of tungsten, which ha, replaced the others and is the commercial product of today. These metallic filaments were originally manufactured by the extrusion and sintering of a mixture of the metal or its oxide with a reducing agent which also served as a binder. Further progress in this direction was in the pressing of a small percentage of nickel with the tungsten. The sintering operation was carried out in an atmosphere of hydrogen, at a tem-

Jan 1, 1944

||Abad, Leopoldo F., Min Engr, Div of Mines, Bureau of Science Manila, P I '23 Abadilla, Quirico A, Geol, Lago Pet Corp Box 172, Maracaibo, Venezuela '20 ||Abbey, Robert Graham, The W W Sly Mfg Co Train Ave, Cleveland, Ohio '21 Abbott, A. N., Mines Supt, Mazapil Copper Co, Ltd Concepcion del Oro, Mexico '23 Abbott, Clarence E., Mgr, Mines & Quarries, Tenn Coal, Iron & R R Co, 1242 Brown Marx Bldg, Birmingham, Ala. '04 Abbott, Louis Benjamin, Chief Engr , Consolidation Coal Co , Elkhorn Div Jenkins, Ky. '16 Abbott, Robert R., Met Engr , Peerless Motor Car Co Cleveland, Ohio '12 ||Abbott, Wells Osborn, Ray Consolidated Copper Co Hayden, Ariz. '23 Abeel, George H, Jr., Cons Min Engr 4612 West 17th St , Los Angeles, Cal '18 Abel, Albert E., Asst to Pres, Valley Mould & Iron Corp Sharpsville, Pa. '19 Abernathy, George Elmer, Prof of Geol & Min , Kansas State Teachers College, Pittsburg, Kans. '20 Abey, Hiroshi, Min & Met Engr, Min & Met Dept, The Higher Technical School, Osaka, Japan. '17 ||d'Ablaing, Philip R, Chem , Anaconda Copper Min Co Great Falls, Mont '25 Aborn, Robert H , Research Assoc., Mass Inst of Tech Cambridge, Mass '19 Abouchar, Sylvain Sley, Min. Engi & Geol , care of S H Sekaly, 13 Rue El Nimr, Cairo, Egypt '17

Jan 1, 1923

C. Edward Stafford, Chester, Pa.:—Doring all my business life, I have been engaged in the manufacture of Bessemer and open-hearth steels, but, during my long connection with the Shoenberger Steel Co. of Pittsburg, I had some experience in the manufacture of high-grade puddled iron for horseshoes, and in making, by Dr. Otto Wuth's process, extremely pure, low-phosphorus puddled blooms (analyzing from 0.005 to 0.01 per cent. of phosphorus and sulphur), which were melted with low-phosphorus pig-iron in acid open-hearth furnaces, to make extra locomotive fire-box steel. I have also seen the Danks puddlers in operation at different times and places, notably where they were most successful, at the Otis Steel Works, Cleveland, Ohio; then under the management of our friend, Mr. S. T. Wellman. These Danks blooms were made solely for open-hearth melting-stock, to which they were well adapted. (The unavoidable presence of bits of ore-fix imbedded in the mass of the metal always prevents the profitable manufacture of merchant iron from Danks' blooms.) With the experience just described, I was to some degree in position to value fairly the means, methods and results of Mr. Roe's mechanical puddling from the metallurgical or technical and economic points of view, when given an opportunity by Mr. Roe to see his puddling-furnace or machine in operation in Pottstown, Pa. Briefly, the furnace, with water-cooled bottom, is rectangular in plan, about 20 by 8 ft. in the clear, suspended by trunnions at the middle of the long sides, at a height of 17 or 18 ft. above the general level. The oscillation (65" each way from the vertical) is accomplished by geared segments (attached to the downward-projecting side or trunnion-plates) with which engage pinions driven by a reversing engine. The whole section

Jan 1, 1906

By C. A. Fisher

THE discovery of petroleum in Pennsylvania in 1859 marked the birth of an industry of paramount importance. Spreading from - Oil Creek, this remarkable industry may be said to have embraced the earth in a little more than half a century. Those who made the discovery little realized its deep significance or far reaching influence on our national life. For over sixty years, during which time this nation has created and developed the oil industry to a high state of efficiency and' carried its activities to all parts of the world, we have' at all times been the leaders in the production of crude oil and in the development of its technology. During the unprecedented growth and expanse of the oil industry there has been an increasing dependency of our basic industries on, petroleum, until at present it has become essential to our national existence. To meet the ever increasing demand for petroleum and its products, we have explored, at one time or another, for their oil possibilities, practically all parts of the sedimentary rock area in the United States. Furthermore, detailed surface and, in many places, subsurface studies have been made of all the promising regions; over 640,000 jewells have 'been drilled for. oil since the beginning of the industry; $12,000,000,000 have been spent in this work; seventeen major fields exceeding 100,000 bbl. daily production and more than a thousand minor pools have been opened up, and 8,000,000,000 bbl. 'of oil have been produced, or an amount nearly equal to the estimated future reserves of the United States made in 1921.

Jan 1, 1925