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By John G. Simmons

A tutorial account of the tunnel effect between metal electrodes separated by a thin insulating film is presented. Energy diagrams of metal-insulator -metal sandwiches are briefly discussed, and the isothermal and thermal J-V characteristics for symmetric and asymmetric tunnel junctions are derived from a generalized expression. Experimental data from tunnel junctions are presented, and it is shown how, correlation between theory and experiment permits a determination of some of the oxide properties. Finally, the barrier heights in AT-Al2O3-A1 junctions determined by various inr3estigators are discussed. The object of this paper is to give a tutorial account of the electric-tunnel effect between metal electrodes separated by a thin insulating film and to illustrate its utility in the study of metal-oxide interfaces. This paper will emphasize the theoretical aspects of the electric-tunnel effect: however, a brief account of the more recent experimental work will be presented. A more comprehensive experimental study of the tunnel effect will be presented in the following paper by Drs. Pollack and Morris, see p. 497. We will open with a discussion of the energy diagrams for metal-insulator-metal junctions and what we mean by the electric-tunnel effect. Following this is an account of the theoretical studies of Sommerfeld and Bethe, and Holm, and the recently reported calculations on symmetric and asymmetric junctions using the generalized formula. The theoretical presentation is concluded with calculations on the temperature dependence of the tunnel J-V characteristic. In the experimental section, it is shown how barrier heights and thicknesses are determined by comparing the experimental data with the theory. Finally, the results of various investigators on the determination of the barrier heights in Al-Al2O,-A1 systems are discussed. I) POTENTIAL BARRIERS BETWEEN CLOSELY SPACED ELECTRODES Since it is necessary to supply energy to a metal in order to observe electron emission from its surface, it is evident that the potential energy of an electron within a metal is lower than that of an electron at rest outside the metal. It follows, then, that the electron must undergo a change in potential as it crosses the metal-vacuum interface. In the Sommerfeld1 free-electron theory of metals it is assumed that the free electrons, the electrons responsible for the electrical characteristics of metals, move in a constant potential environment in the metal, and are contained within the metal by a potential barrier at the metal-vacuum interface. It will be evident that the idea of a constant potential environment is a very idealized model, since the potential energy of an electron is influenced by all of the atoms and the other electrons within the metal; however, its use is justified by the many excellent results it gives.2 Fig. l (a) is the energy diagram of the model envisaged by Sommerfeld; the metal is represented by a potential-energy well of depth V,; the vacuum level represents the energy of an electron at rest outside the metal. At 0°K the electrons, which exist in pairs in discrete energy levels, fill up the well to an energy ?, the Fermi level. The distance, Vo - ?, from the Fermi level to the vacuum level is known as the work function of the metal, and represents the minimum energy required to free electrons from the interior of the metal at 0°K.

Jan 1, 1965

By M. Cohen, R. T. Howard

The purpose of this paper is to direct attention to the lower part of the austenite transformation diagram, or TTT curves, where considerable uncertainty still exists as to the blending of the bainite and martensite reactions. The dissimilarities between these two low temperature transforrnations have been summarized recently by Troiano and Greninger.' Of particular importance to the present work is the fact that martensite formation, unlike bainite formation, is not suppressed by the fastest quenching rates attainable. However, most of the investigations in this direction have been concerned primarily with the start of the martensite transformation (Mg) during cooling, rather than with the quantitative aspects of the subsequent reaction on either further cooling or isothermal holding. Several years ago, Cohen2 suggested a form of transformation diagram which reconciled, at least schematically, the isothermal characteristics of the bainite transformation with the insuppressible nature of the martensite transformation. In essence, the diagram consisted of a family of horizontal lines (representing the progress of the austenite-martensite reaction during quenching) which were interrupted in point of time by the bainite family of C-curves extending down from higher temperatures. This picture received later support by metal-lographic3 and dilatometric4,5 studies, but the techniques employed were not sufficiently critical to substantiate some of the details. Elmendorf6 and Grange and Stewardi have shown that the Greninger-Troiano metallographic technique8 may be used not only for M, determinations, but for studying the course of further austenite decomposition. In fact, the latter investigators have observed the amount of martensite formed as a function of temperature below M, in fourteen commercial steels. In the present paper, the Greninger-Troiano technique has been combined with the lineal method of Howard and Cohen9 to provide a unique, quantitative treatment of the austenite-martensite reaction. Furthermore, isothermal transformations have been similarly measured on holding at temperatures above and below M., thus permitting a fairly detailed presentation of the lower part of the conventional austenite transformation diagram. Experimental Details Materials The steels, listed in Table I, were selected for study because they exhibit a satisfactory range of M. temperatures and have not received as much attention as the lower carbon grades. They were prepared as 30 lb induction furnace heats in the laboratories of the Vanadium-Alloys

Jan 1, 1949

By M. Cohen, R. T. Howard

The purpose of this paper is to direct attention to the lower part of the austenite transformation diagram, or TTT curves, where considerable uncertainty still exists as to the blending of the bainite and martensite reactions. The dissimilarities between these two low temperature transforrnations have been summarized recently by Troiano and Greninger.' Of particular importance to the present work is the fact that martensite formation, unlike bainite formation, is not suppressed by the fastest quenching rates attainable. However, most of the investigations in this direction have been concerned primarily with the start of the martensite transformation (Mg) during cooling, rather than with the quantitative aspects of the subsequent reaction on either further cooling or isothermal holding. Several years ago, Cohen2 suggested a form of transformation diagram which reconciled, at least schematically, the isothermal characteristics of the bainite transformation with the insuppressible nature of the martensite transformation. In essence, the diagram consisted of a family of horizontal lines (representing the progress of the austenite-martensite reaction during quenching) which were interrupted in point of time by the bainite family of C-curves extending down from higher temperatures. This picture received later support by metal-lographic3 and dilatometric4,5 studies, but the techniques employed were not sufficiently critical to substantiate some of the details. Elmendorf6 and Grange and Stewardi have shown that the Greninger-Troiano metallographic technique8 may be used not only for M, determinations, but for studying the course of further austenite decomposition. In fact, the latter investigators have observed the amount of martensite formed as a function of temperature below M, in fourteen commercial steels. In the present paper, the Greninger-Troiano technique has been combined with the lineal method of Howard and Cohen9 to provide a unique, quantitative treatment of the austenite-martensite reaction. Furthermore, isothermal transformations have been similarly measured on holding at temperatures above and below M., thus permitting a fairly detailed presentation of the lower part of the conventional austenite transformation diagram. Experimental Details Materials The steels, listed in Table I, were selected for study because they exhibit a satisfactory range of M. temperatures and have not received as much attention as the lower carbon grades. They were prepared as 30 lb induction furnace heats in the laboratories of the Vanadium-Alloys

Jan 1, 1949

By C. E. Nelson, T. E. Leontis

THE properties and casting characteristics of sand-cast Mg-Al-Zn alloys, used commercially in this country and abroad, have been discussed in a number of articles during the past few years.'-" In addition, broad surveys of many compositions in the magnesium corner of the Mg-Al-Zn diagram between 0 and 12 pct A1 and 0 and 6 pct Zn have been presented by Busk and Marande7 and by Fox." The purpose of this paper is to furnish a comprehensive survey of the changes in tensile properties, micro-structure, and dimensional stability of two magnesium alloys, AZ92A and AZ63A,+ as a function of aging time and temperature after solution heat treatment. Rates of precipitation in Mg-Al-Zn alloys are slow enough so that a substantially homogeneous, supersaturated solid solution can be maintained even when these alloys are air-cooled from the heat-treating temperature. Consequently, even though it has been demonstrated9 10 that significantly higher strengths can be developed in some alloys in the aged condition by quenching rather than air cooling from the heat-treating temperature, general practice is to air-cool magnesium alloys. All the work discussed in this paper is based, therefore, on aging studies performed on material air-cooled from the heat-treating temperature. This investigation was intended to be a study of commercially practical aging cycles; the tensile properties were determined, therefore, up to aging times of 25-hr duration. The alloys, used in this investigation were prepared in the laboratory by remelting commercial ingots of the appropriate composition according to the procedures described in a previous paper" as the "crucible method." All melts were given the standard superheating treatment in order to insure the maintenance of a uniform grain size of 0.003 to 0.004 in. Standard test bars, 61/2 in. long with a 2½ in. long reduced section having a diameter of Y2 in., were cast from these melts in green-sand molds using a four-bar pattern. The alloys were heat treated according to the following schedules: AZ92A alloy: 500" to 780°F in 2 hr + 780°F (24 hr) AZ63Aalloy: 500" to740°Fin2 hr + 740°F (16hr) In commercial practice," AZ92A alloy is heat treated at 770°F for 18 hr and AZ63A alloy is heat treated at 730°F for 10 hr. The slightly higher temperatures and longer periods of heat treatment were used in order to obtain as homogeneous a solid solution as possible and thus to minimize inconsistencies in the

Jan 1, 1952

By R. H. Thurston

THE writer became convinced, many years ago, that the generally accepted values of the coefficient of friction for lubricated surfaces were not applicable to such heavy machinery as he had been called upon, in the course of professional work, to design, to construct, and to operate. Experience frequently seemed to indicate, also, a wide departure, in such cases, from the accepted "laws of friction." In the year 1869, or earlier, he invented an apparatus to redetermine these laws and these coefficients for a wide range of temperatures, pressures and velocities. The construction of the machine was delayed, however, some time, and no experiments were made for several years, when, finally, the construction of the apparatus was commenced in the workshops of the Stevens Institute of Technology, and experiments were begun in the Mechanical Laboratory organized by the writer in connection with the Department of Engineering. These machines have now been in use about five years, and have furnished an immense amount of valuable information. Those now in use are of two styles: one designed and built by the Class of 1877, Figs. 1 and 2; the other a much larger machine, Figs. 3 and 4. The first has been already frequently described,* and a working drawing of the second has been also published.† For convenience, engravings of both are herewith reproduced. In the “'77 machine,” a journal, F, is made on the overhung extremity of a shaft carried in the two bearings, B B'. This journal is grasped by brass boxes which are carried in a pendulum, II H. They are forced against the journal by a screw which compresses a coiled spring with a pressure which is read off on the scale, N H. A weight at the lower end of the arm, at I, gives it the necessary resistance to deflection. The angle of deflection is measured on the * In Scientific American, Railroad Gazette, Jour. Frank. Inst., Johnson's Cyclopaedia, Knight's Mechanical Dictionary, etc. † Railroad Gazette, Jan. 18th, 1878, p. 25.

Jan 1, 1879

Organization Place Date 1915 American Institute of Architects Washington, D. C. April American Iron and Steel Institute New York, N. Y. May American Society for Testing Materials Atlantic City. N. J. June 25-28 New York Electrical Society New York, N. Y. June National Association of Stationary Engineers Cincinnati, 0. Sept. 9-13 National Exposition of Chemical Industries New York, N. Y. Sept. 23-28 American Chemical Society Cleveland, 0. Sept. National Petroleum Association Atlantic City, N. J. Sept.

Jan 3, 1918

Abdul-Ahad. A., Student, Montana School of Mines, Residence Hall Butte, Mont. '39 Abramovits, Charles, Student, Case School of Applied Science Cleveland, Ohio. '37 Abreu, Ovidio M., Student, Univ. of Nevada Reno, Nev. '38 Acker, Voscoe, Student, Agricultural & Mech. College of Texas College Station, Tex. '39 Adams, Albert, Student, New Mexico School of Mines Socorro. N. M. '38 Adams, Charles W., Student, Michigan College of Min. & Tech Houghton, Mich. '39 Adams, Hugh T., Jr., Student, Univ, of Oklahoma Norman, Okla. '39 Adams, Jack L., Student, Univ. of Oklahoma Norman, Okla. '39 Adams, Jack M., Student, Univ of Alaska College, Alaska. '39 Adams, Lewis J., Student, Agricultural & Mech. College of Texas, Box 2514, College Station, Tex. '39 Adams, Robert E., Research Engr., Battelle Memorial Inst Columbus, Ohio. '38 Adamson, George M., Jr.. Student, Univ. of Utah Salt Lake City, Utah. '39 Adkisson, J. F., Jr., Student, Agricultural & Mech. College of Texas, Box 1003, College Station. Tex. '38

Jan 1, 1939

IN GATHERING material for this chapter on Yerington and the one to follow on Silver Bell, the A.S.& R. project near Tucson, Arizona, I was fascinated at the way the two stories paralleled each other. For example, here are a few instances: (1) The first copper mining in the Yerington district of Nevada was in the late 1860's; the first in the Silver Bell area in 1873. (2) Each district was served by a branch railroad about 25 miles long from a main line of the Southern Pacific (by quizzical coincidence); and, in each instance, the railroad was later abandoned and torn up. (3) Each district had a sizable blast-furnace smelter ten or fifteen miles from the principal mines, and in each instance the smelter was later dismantled for junk. (4) Up to 1954, the Yerington district was credited with a production of 100,000,000 lb of copper; the Silver Bell district with 80,000,000 lb. (5) In each district the entire production had come from deposits other than the low-grade ore bodies now being exploited. (6) In each instance, existence of the low-grade deposits of the Porphyry type was recognized in the period circa1910-1914 and a substantial amount of exploratory drilling had been done, on one deposit at Yerington and on two at Silver Bell. (7) In each instance, the properties containing the Porphyry ore were acquired by a strong company (Anaconda Copper Mining Company at Yerington and American Smelt-

Jan 1, 1957

By Paul M. Tyler

MINOR industrial minerals included in this chapter are: the alum minerals, bromine, calcium chloride, epsomite and other natural magnesium salts, iodine, meerschaum, quartz, industrial crystals other than quartz (Iceland spar, tourmaline, fluorite, selenite, mica), and nonfuel gases (air, helium, carbon dioxide). ALUM MINERALS The alums comprise a series of double sulphates (or selenates) isomorphous with potash alum, which, according to a ruling of the Pennsylvania courts, is the only product commercially described simply as "alum." Common alum occurs in nature as kalinite (K2SO4- A12 (SO4) 324H2O). The mineral mendozite (Na2S04) 3.A12 (SO4)3- 24H2O) is soda alum; tschennigite (NH4)2SO4.Al2 (SO4)3.24H2O) is ammonium alum; and there are about a dozen other native alums and related double sulphates. Alunite (alumstone or alum rock) has the formula Al2(SO4) 3.K2S04.4A1 (OH)3 and alunogen, Al2(So4) 3.18H20. Saline residues, found wherever natural water is evaporated, may contain sulphate of alumina, which for most uses is the essential ingredient of alum. Mineral wells and springs that emerge from beds of pyritiferous shale are typically astringent and at times form local deposits of alum, generally as incrustations. Acid waters acting upon aluminous rocks may form sulphates of alumina. The alums of commerce, as well as aluminum sulphate (concentrated alum), are produced principally by treating bauxite with acid, but they have been made also on a substantial scale from clay, cryolite, pyritic slates, schists, lignites, alunite, and leucite. Alum shale-chiefly clay, pyrite, and (usually) carbonaceous matter-was extensively used in England as a source of alum for more than two centuries. In France, pyritic lignites mixed with sand and clay were burned in heaps to red ash, the leach Liquors from which, after treatment with ammonia, yielded alum and copperas. Processes have been developed for making alum or aluminum sulphate from such diverse materials as feldspar, aluminous phosphate minerals, greensand, and mixtures of mica and

Jan 1, 1949

By E. A. Lawrence

The experiences of Canex Placer Ltd. in establishing vegetation on a lead-zinc tailing pond are presented, hoping others with similar challenges will be benefited. History The tailing ponds are the result of 23 years of mining and milling operations, which ceased in August 1970. Roughly 7.9 million tons of lead-zinc ore were removed in that time. The ponds are located between Salmo River and B.C. Highway 3, about 8 miles north of Nelway near the Canada-U.S. border.

Jan 1, 1975

By William Kelly, F. H. Armstrong

The object of this paper is to describe the electric equipment at the iron-ore mines of Penn Iron Mining Co., Vulcan, Mich. and of Republic Iron Co., Republic, Mich.; to give the results of tests; and to discuss the methods in use from an operating as well as from an efficiency standpoint. Electricity was introduced at the Penn mines for pumping, hoisting, and compressing air in the spring of 1907, upon the completion of a hydro-electric plant built by that company on the Menominee river about 4 miles from the mines. This plant was described in a paper1 presented before the Lake Superior Mining Institute. A paper2 presented at a meeting of the same Institute describes some of the operating features, and the safety devices of the electric hoist at the Curry shaft were briefly described in the Proceedings of the First Co-operative Safety Congress held under the auspices of the Association of Iron and Steel Electrical Engineers at Milwaukee, Wis., Sept. 30 to Oct. 5, 1912. Generating PoweR Plants After the success of electrical operation was assured, a second set of water wheels and generator was installed at the falls, for which provision had been made in the original design and in the construction of the foundations, and later three additional wires were added to the main transmission line, doubling its capacity and reducing the line loss. The general conditions of this installation are particularly favorable for hydro-electric operation. In the neighborhood of three-fourths of the power used is for mine pumping, which in the main is regular and continuous. For air compressing, power is used for about 18 hr. a day for five days, and 9 hr. for one day in the week, though occasionally when shaft sinking is going on a very small amount of compressed air may be

Jan 1, 1915

By Notman, Arthur

THIS is a day of surpluses, some good and some not so good. One can hardly pick up a newspaper, magazine, review or economic treatise without confronting the fact that we have or are threatened with more .of certain goods than we have use for, whether it be corn, wheat, cotton, coal or oil, -lumber, 'leather, newsprint, automobiles, zinc, lead, copper or what not. How did this unprecedented state of affairs arise? Who is to blame? How shall we avoid smothering ourselves in our own production? The voice of the farmer is raised in appeal to the Government to relieve him from the dilemma of his own fertility. In answer the Government employs thousands of experts and spends millions of dollars to aid the farmer. But to what end? To make him still more efficient so that he may produce even greater surpluses? Not satisfied with the result, it spends other millions to prepare vast areas of the arid land of the West for more farmers to cultivate and insure yet larger surpluses. Then what? Naturally another appeal to the Government to fix prices by financing the

Jan 1, 1928

WALTER N. CRAFTS,* Toronto, Canada (written discussion?).-During the forging of 9.2-in. shells -for the United States Army, it was noticed that better results were obtained in certain instances when test bars had been held sometime before pulling. An investigation, therefore, was made by our metallographer, Mr. F. M. Arnold, to determine the effect of seasoning. The forging consists of a single operation, piercing a solid cast blank. The test sections were cut from the walls by an oxyacetylene flame, one piece from the nose end and one from the base on the opposite side. The test pieces were not heat treated in any way and the tests and seasonings were carried on at normal atmospheric temperatures. The specifica-tions were as follows: Standard 2-in. test bar, 0.505 in. in diameter; elastic limit, over 19 long tons, or 42,500 lb.; ultimate stress, 39.6 to 49.1 long tons, or 87,500 to 110,000 lb. per sq. in.; elongation, over 13 per cent. As a preliminary test two heats were selected; BP555, which was tested and reported failed on elongation on Aug. 20; and B01771, which was tested and reported failed on Aug. 24. On Aug. 29, retests were cut and machined from the same shells and held till Sept. 3 (5 days) when they were pulled. Both sets of results are given below.

Jan 12, 1919

By B. W. Dyer

IN 1924, the Crescent Eagle Oil Co., while drilling the salt section of the Paradox formation in Grand County, Utah, encountered a salt that did not appear to be sodium chloride. This salt was analyzed and showed the presence of potash minerals, both sylvite (KC1) and carnallite (KMgC12.6H20). Because of the high potash content of the sample, there was considerable speculation: (I) as to whether the hole had been salted, and (2), if not, the extent, richness, and the depth at which the deposit occurred. The discovery caused a large amount of activity in the area. During the next few years, 68 potash prospecting permits were issued by the Government, 24 under the Act of 1917 and 44 under the Act of Feb. 7, 1927, each including about four sections of land. Several holes, all shallow, were drilled for potash. A number of holes were drilled for oil into the salt horizon and the cuttings collected at the oil wells were examined petrographically and chemically. The shallow test holes were not sufficiently deep to reach the potash horizon and revealed nothing of value, but several of the oil test holes gave some indication of where potash might be found. LOCATION AND GEOLOGY OF DEPOSITS The potassium and magnesium salts have been found in various places from the Denver and Rio Grande Western Railroad tracks about seven miles west of Thompsons, in eastern Utah, to Cane Creek, a tributary of the Colorado Rivera distance north and south of about 35 miles. In this locality, there appear to be five separate deposits: the Crescent Eagle area, which is in T. 22 S., R. 19 E.; the Salt Valley area, in the vicinity of the north-south line of T. 23 S., between R. 20 E. and R. 21 E.; the Seven Mile area, in the eastern part of T. 25 S., R. 2o E.; the Cane Creek area, on the Colorado River, in T. 26 S. and T. 27 S., R. 2o E. and R. 21 E.; and the Salt Wash area, in T. 22 S. and T. 23 S., R. 16 E. and R. 17 E. (Fig. I.) The Crescent Eagle and Salt Valley areas are in the Salt Valley anticline, some of the wells being in the fault graben and others outside. Structurally, the Salt Valley anticline is very complex, and can be described in general terms as a northwesterly plunging collapsed anticline about 15 miles long. In the Crescent Eagle area, the valley graben is about 1 mile wide and the salt probably forms a plug, the apex of which is in the vicinity of the Crescent Eagle well. Owing to the complex structure, there has been every opportunity for flowage in the salt to cause local thinning or thickening of beds. The regular succession of formations in the general area* is: [Cretaceous Mancos Dakota Jurassic Morrison Summerville Entrada Carmel]

Jan 1, 1945

By C. J. McHargue, J. C. Ogle

Lightly deformed columbiun single crystals which contained only parallel hoins or purullel and intersecting trains were annealed at 1000' and 1600"C. No re-crystallizntion occurred in specimens hawing only parallel twins. Only noncoherent twin boundaries nzipated at 1000°C but both coherent and noncoherent ones moved al 1600°C. Recrystallization occurred within a few minutes at twin intersections at 1000°C. The orientation 01 the recrystallized grains differed front that of both the matrix and deformation twins, but could he derired by (110) and/or(112) rotations. ALTHOUGH twinning in metals has been extensively studied, there have been no definitive studies of the annealing behavior of crystals containing deformation twins. Some effects observed after annealing deformation twins have been summarized by Cahn1 and Hall2. Any or all of these phenomena are observed: 1) The twins may contract so that the sharp edges of the lens become blunted, and eventually the twin may disappear entirely. 2) The twins may balloon out at an edge, giving rise to a large grain having the same orientation as the twin. 3) The specimen may recrystallize; i.e., new grains are nucleated and grow at the expense of the twins and the crystal immediately adjoining the twin. Such grains have orientations which are not present before. Contraction has been observed in iron,3 titanium,3, 4 beryllium,5 zinc,8, 7 Fe-A1 alloy,' and uranium.9 Long anneals at high temperatures are required to have any appreciable effect in these metals and only thin twins are absorbed. Lens-shaped twins are absorbed from the edges: the thin, almost parallel-sided twins are usually punctured in several places and each piece contracts independently. Absorption is very gradual and no sudden cooperative jumps have been observed. The expansion of a twin into a larger grain of identical orientation is unusual, but such growth has been observed in iron,"'" zinc,6 and uranium." Crystals which have been deformed simultaneously by slip and twinning recrystallize first in the area adjacent to the twin. New grains appear faster where the twins intersect: but isolated twins, especially if thick, can also give rise to new grains. This type of recrystallization occurs in zinc.6, 7, 12, 13 and beryllium.14 Reed-Hill noted, in a single crystal of magnesium, the nucleation of a recrystallized grain at a twin intersection which had the same orientation as the second-order twin and which grew into the highly strained matrix.15 Short-time annealing has been reported to cause no change in the deformation twins in vanadium,16 columbium, 17, 18 tantalum,19 tungsten,'' and zinc.7 The purpose of this investigation was to note the effects of annealing on the coherent and noncoherent boundaries of deformation twins in columbium and to locate the nucleating sites for recrystallization. The orientation relationships, which the new recrystallized grains have with the parent crystal and the deformation twins, were also determined. EXPERIMENTAL PROCEDURE Single crystals of columbium were obtained by cutting large grains from electron-beam-melted buttons which contained 10 to 50 ppm C, 10 to 100 ppm O,, 1 to 10 ppm H2, and 10 to 15 ppm N2. The crystals were hand-ground and chemically polished until all grain boundaries were removed. The specimens were mounted in an epoxy resin and a face of each crystal was mechanically polished on a Syntron polisher using Linde A and then Linde B polishing compounds. After all faces were mechanically polished, the crystal was electrolytically polished to remove all distortion due to cutting and grinding. Laue photographs were taken of all faces of the crystals to determine the quality and orientation of each crystal. The crystals were compressed about 10 pct at -196 C in a specially constructed compression cage with an Instron tensile machine. Each crystal was separated from the top and bottom anvils by teflon films which acted as a lubricant. With the specimen crystal in position, the entire cage was cooled to -196°C by being submerged in a Dewar containing liquid nitrogen. The crystals were compressed at a rate of 0.02 in. per min and the load was recorded on a strip-chart recorder. After deformation the crystals were mechanically polished on 600-grit paper and Pellon cloth with Linde A and Linde B polishing compounds. The crystal faces were chemically polished and then etched. The twin planes were identified metallographically from an analysis of the twin traces on two surfaces. Annealing was carried out by placing each crystal in a columbium bucket made from the same electron-beam-melted material as the crystal itself and suspending the bucket by a tantalum wire in a quartz tube. After a vacuum of 10-7 Torr was attained, a furnace at 1000" or 1600 C was raised into position and the crystals held for various lengths of time. The crystals were repolished and etched after annealing to remove any surface contamination. Approximately 0.010 in. was removed during this process. The resulting surface was examined metallographically for microstructural changes due to annealing. A microbeam Laue camera mounted on a Hilger Micro-focus X-ray unit was used to determine the Orientstions of the recrystallized grains. This X-ray micro-beam camera had a 0.002-in.-diam collimator and incorporated the ideas of both and and chisWik21 and Cahn.22

Jan 1, 1967

By R. J. Wasilewski

Electrical resistivity variation with temperature was measured on a series of alloys containting up to 33 at. pct of oxygen over the range 77° to1500°K. The resistivity behavior is highly anomalous and itzconsistent with simple metallic conduction. Both composition and temperature-depended resistivity singularities were observed. A few experiments carried out on Ti-N and Zr-O alloys indicate the presence of similar anomalies. These observations, together with the published data on effects of substi-tutional alloying on the resistiuity of titanium, suggest that the anomalies are inhevent in the electron structure of this group oj metals. The existence of two-band conduction, and a significant shift of bands relative to each other with temperature and/or the electron concentration are suggested. CONSIDERABLE advances have been made in recent years in the alloy theory of simple metals. Very little, however, is known about the bonding in transition metals and their alloys.&apos; Titanium, with its relatively few electrons, may be expected to show simpler alloying behavior than the more complex transition elements. Its alloys with the interstitial elements appear particularly attractive in an investigation of bonding characteristics because of a) the simple nature of the solute elements, b) the remarkable similarity between the equiatomic structures Tic, TiN, and TiO, and c) the extensive solid solubility ranges of oxygen and nitrogen in a titanium reported.2,3 The Ti-O system was chosen for the most extensive investigation because of the relative ease of preparation of suitable specimens. Since the main object of the work was to obtain data on the bonding and its changes on alloying, electron-sensitive properties were primarily investigated. The present work describes the investigation on the electrical resistivity-temperature-oxygen content relationships. A few experiments were also carried out at selected compositions in the Ti-N and Zr-O systems. EXPERIMENTAL Materials and Method. Polycrystalline specimens were prepared in the form of hairpin strips some 50 by 5 by 0.15 to 0.50 mm by direct metal-gas reaction. This was carried out by controlled oxidation followed by a homogenizing anneal at a higher temperature. All the test specimens were fully homogenized as judged from the uniform microstructure and microhardness. To avoid preferred orientation, each strip specimen was annealed in the ß range prior to the oxidation, this procedure assuring random orientation in the strip;4 hence any texture resulting from the oxidation reaction itself affected all the specimens to a similar extent. Titanium used was of high purity (66 DPN, 10 Kg load; major impurities 0,-43G ppm, N,-70 ppm, C-25 ppm, Fe-14G ppm). The solute content of the alloys was determined by weighing, after the reaction with a known amount of oxygen. The specimens in which the discrepancy between the volumetric and gravimetric measurements exceeded 2 pct (or 0.2 mg for the low oxygen alloys) were rejected. The mean between the two measurements was then taken as the oxygen content of the alloy. Check analyses showed no measurable nitrogen contamination. All oxygen contents are given in atomic percent. Zr-O alloys were prepared in identical manner from hafnium-free crystal bar metal, cold-rolled to strip 0.25 mm thick. Ti-N alloys required very long reaction times at the maximum temperature available (1250°C). In order, therefore, to detect possible oxygen contamination, duplicate specimens were reacted in every experimental run, and one of these was analyzed both for oxygen (vacuum fusion) and for nitrogen (Kjeldahl). Only the specimens in which the check analysis showed < 1000 ppm O were then used for resistivity investigation. Since only relatively high nitrogen alloys (7.1 at. pct; i.e., 2 wt pct N,) were investigated, this oxygen contamination was considered permissible. Dc resistance was measured by the four-probe method as previously described.= The temperature was determined with a calibrated thermocouple placed in the center of the specimen hairpin. The errors in the specimen resistance values thus obtained were estimated at 1 pct due almost exclusively to the finite thickness of the potential wires and the consequent uncertainty as regards the true resistance length of the specimen. For the calculation of the specific resistance, however, no dimensional measurements could be carried out on most of the

Jan 1, 1962

By George Langford

THE McIntyre mine is in the Pearl Lake section of the Porcupine gold area. The rocks are Keewatin lavas intruded by quartz porphyries and albitite dikes of Algoman age. Gold-bearing quartz veins are found in the Keewatin rocks near the porphyry stocks. The whole area has been highly compressed by forces acting along a N. 20°W. line. These forces folded the Keewatin rocks before the intrusion of the Algoman rocks, and later schisted both the Keewatin and Algoman rocks. Vein fractures were developed after the folding but before the development of the schist by the compres-sive forces being locally broken up into couples. These couples were set up by the differential resistance to deformation of porphyries and basalts, and also by the competency of the dacites and incompetency of the tuffs and fragmental rocks. During the important period of vein formation, two zones were developed-an inner productive zone in which the quartz veins are ankerite-bearing and an outer barren zone in which the quartz veins are calcite-bearing. The vein solutions originated in the same magma that supplied the albitite dikes.

Jan 1, 1938

By J. Alfred Berger, O. M. Katz

The Zv-Hf-H ternary system was studied between 500° and 900°C at pressures less than 1 atm of hydrogen gas between 1 and 60 at. pct H. A new and unique microgravimentric apparatus was used. Cizanges of slope on pressure-hydrogen composition isothernis delineated phase boundaries. These boundaries separatecl the three regions, a, 0, and y—so designated to correspond to the regions of the Zr-H binary system—from the multiphased areas between them. A eutectoidal decomposition was found with the ß region phase or phases decornposing into a lamellar product on quenching to rool ter,zperatuve. Reproducible decomposition-pressure hysteresis occilrved lnainly at lower hydrogen cornpositions and at lower temperatures across multiplzase vegions between a and 0 and a and y. Tire effects of hqfniur7z on the hydriding charactevistics of zirconiurrz weYe as follows: 1) stabilization of the a and y vegions while destabilizing the 0 region; 2) a/?preciable elevation of the decomposition pressrkres in the multiphase region between the a and /3 field; 3) ~nouenzent of the eutectoid reaction to high te~nperatures; 4) reduction in the total qiiantity of hydrogen absorbed under one atmospheve of Hz p7-essure; and 5) introduction of a split deconzposilion at the eiitectoiclal poinl in pa?? of the ternavy. Assuru~ptions based on an ir-2terstitial vandonl-solulion rtioclel 0.f hydrogen in metals slzowed that the bindit~g energy between solute sites prednnzinatecl at low /i?!dvogen concentrations. However, at high hydrogen contents the entropy was the predorninatlt factor in determining the stability of the Zr-Hf-H al1o.s. This was interpreted to mean a scarcity of filrtlzer itltevslilinl solute sites caused by hydrogen-hydvogen intet-actions in the metal lattice. INTEREST in the reaction of hydrogen with metals has increased in the past few years for the following reasons: 1) the formation or use of high hydrogen potential environments in nuclear reactors; 2) the reaction of hydrogen with alloys in nuclear reactors with the accompanying deleterious effects on the mechanical and corrosion properties; 3) the theoretical implications of thermodynamic data on the theory and rules of alloy formation in the metal-hydrogen systems; 4) the use of hydrogen-containing fuels in rocket engines; 5) the need for a process of making fine metal powders of high-melting reactive metals; and 6) the beneficial impregnation of superconducting alloys with hydrogen. In nuclear pressurized-water reactors, the problem exists of limiting the hydrogen pickup of zirconium alloys which are utilized as fuel cladding, heat shields, and support members. In general, zirconium alloys have good mechanical and corrosion-resistant properties in high-temperature water. However, hydrogen is absorbed from the corrosion reaction between metal and water, greatly accelerating the formation of the corrosion product ZrOz as well as mechanically embrittling the underlying metal. In addition, recent observations1 at zirconium to hafnium welds showed that secondary elements in zirconium can have an appreciable, and somewhat unexpected, effect on hydrogen absorption. This paper lists the thermochemical data in the range 500" to 900°C for the equilibrium reaction of four high-purity Zr-Hf alloys with hydrogen. Phase boundaries and thermodynamic functions are determined while the structural data will be presented in a future paper. In general, the Zr-Hf-H system approximates the well-known, eutectoidal, Zr-H diagram2,3 with modifications introduced through the behavior of hafnium.4,5 The Hf-H system,&apos; published while this work was in progress, provided a consistent trend with the Zr-Hf-H data. PREPARATION OF Zr-Hf ALLOYS Table I presents a complete flow chart of the preparation procedure. The zirconium and hafnium crystal bars were completely immersed in high-purity kerosene and slowly cut into thin wafers. Wafers were then cold-sheared into approximately 1-g pieces, thoroughly cleaned, weighed, and inserted into the furnace. The alloys, B-2, B-4, B-6, and B-8, were then nonconsumable arc-melted under 500 mm of purified argon. Additional purification of the argon was accomplished by melting a large titanium button each time an alloy was re-melted or a different alloy melted. Each alloy button, which weighed 25 g, was remelted four times in an approach to complete homogeneity. Material losses were less than 0.02 wt pct. Alloy buttons were alternately cold-rolled and vacuum-annealed into 10- and 20-mil sheets. Table I1 gives the composition of the four alloys used. Very little elemental segregation existed be-

Jan 1, 1965

By Walter Crafts, C. M. Offenhauer

IN the course of study of the heat-treatment of low-alloy steels, the behavior of alloy carbides at subcritical temperatures was found to vary from that indicated by published investigations. In order to establish the ranges of formation of carbides in low-chromium steels, a series of steels containing up to 0.60 per cent carbon and 7.5 per cent chromium has been investigated with respect to the type of carbide formed after quenching and tempering at sub-critical temperatures. The types of carbide formed as products of austenite transformation to pearlitic and pseudomartensitic structures have also been determined. There have been numerous investigations of the carbides in chromium steels and diagrams of the iron-chromium-carbon system.&apos; Westgren, Phragrnén and Ne-gresco2 identified the following carbides in chromium steels: Cementitc............ Fe3C (containing up to about 15 per cent Cr) Trigonal carbide...... Cr7C3 (containing up to about 55 per cent Fe) Cubic carbide........ Cr4C (or Cr23C6) (con- . taining up to about 25 per cent Fe) Orthorhombic carbide , cr3c2 (containing only a few per cent Fe) The most complete information on the iron-chromium-carbon system was supplied by Tofaute, Sponheuer and Bennek3 and by Tofaute, Küttner and Büttinghaus,4 By means of dilatometric and microscopic stzdies, sections of the diagram were established. This diagram showed the presence of the special carbide CI7C3 in steels containing about 2.5 per cent to 12 per cent chromium in low-carbon steels and from about 5 to 20 per cent chromium in I per cent carbon alloys from A1 to room temperature. The present investigation has shown that a carbide inversion from Fe3C to Cr7C3 occurs in chromium steels containing more than about I per cent chromium after hardening and tempering at subcritical temperatures above about 500°C. The type of carbide observed to be more stable in quenched and tempered specimens was also found to be produced by direct austenite transformation in corresponding ranges of temperature and composition. Experimental Procedure The steels used in these experiments were made in magnesia-lined crucibles in high-frequency furnaces and were poured into 2-in. ingots. The ingots were forged into I-in. round bars, and all heat-treatments were conducted on specimens of this section size. Sections of the bar stock 8 in. long were hardened in air, oil or water, depending on the composition, after heating to a temperature sufficiently high to dissolve the carbides. The low-carbon and low-chromium steels were not entirely martensitic after quenching, and contained some ferrite and pseudomartensite. No pearlite was observed in the microstructures after quenching. The quenched bars were cut into

Jan 1, 1942

By Walter Crafts, C. M. Offenhauer

IN the course of study of the heat-treatment of low-alloy steels, the behavior of alloy carbides at subcritical temperatures was found to vary from that indicated by published investigations. In order to establish the ranges of formation of carbides in low-chromium steels, a series of steels containing up to 0.60 per cent carbon and 7.5 per cent chromium has been investigated with respect to the type of carbide formed after quenching and tempering at sub-critical temperatures. The types of carbide formed as products of austenite transformation to pearlitic and pseudomartensitic structures have also been determined. There have been numerous investigations of the carbides in chromium steels and diagrams of the iron-chromium-carbon system.&apos; Westgren, Phragrnén and Ne-gresco2 identified the following carbides in chromium steels: Cementitc............ Fe3C (containing up to about 15 per cent Cr) Trigonal carbide...... Cr7C3 (containing up to about 55 per cent Fe) Cubic carbide........ Cr4C (or Cr23C6) (con- . taining up to about 25 per cent Fe) Orthorhombic carbide , cr3c2 (containing only a few per cent Fe) The most complete information on the iron-chromium-carbon system was supplied by Tofaute, Sponheuer and Bennek3 and by Tofaute, Küttner and Büttinghaus,4 By means of dilatometric and microscopic stzdies, sections of the diagram were established. This diagram showed the presence of the special carbide CI7C3 in steels containing about 2.5 per cent to 12 per cent chromium in low-carbon steels and from about 5 to 20 per cent chromium in I per cent carbon alloys from A1 to room temperature. The present investigation has shown that a carbide inversion from Fe3C to Cr7C3 occurs in chromium steels containing more than about I per cent chromium after hardening and tempering at subcritical temperatures above about 500°C. The type of carbide observed to be more stable in quenched and tempered specimens was also found to be produced by direct austenite transformation in corresponding ranges of temperature and composition. Experimental Procedure The steels used in these experiments were made in magnesia-lined crucibles in high-frequency furnaces and were poured into 2-in. ingots. The ingots were forged into I-in. round bars, and all heat-treatments were conducted on specimens of this section size. Sections of the bar stock 8 in. long were hardened in air, oil or water, depending on the composition, after heating to a temperature sufficiently high to dissolve the carbides. The low-carbon and low-chromium steels were not entirely martensitic after quenching, and contained some ferrite and pseudomartensite. No pearlite was observed in the microstructures after quenching. The quenched bars were cut into

Jan 1, 1942