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A filled stope is one in which the support for walls and men and, at times, for the back of ore, is furnished by waste rock or sand tailings. The filling may be rock sorted out in the stope or from the walls, develop-ent, or the surface. The orebody is mined in sections, each practically an open or timbered stope, filled wholly or in part before adjacent ground is attacked. As a rule, the filled-stope method is limited to overhand flat-back, stepped-face, or rill stopes. The examples given are Copper Range, Iron Cap, Verde district, Zaruma district, Lucky Tiger, and Silver King Coalition.

Jan 1, 1925

By AIME AIME

TWO papers, "Calcium, Strontium, and Barium Metals," by Charles Hardy and Paul M. Tyler, and "The Mining of Gems and Ornamental Stones by American Indians," by Sydney H. Ball, were presented before the Rare Minerals and Metals group at its session Tuesday afternoon in the Auditorium. Donald M. Liddell, chairman, presided. Mr. Tyler summarized the first paper, outlining the uses, history, occurrence, manufacture, production and trade, markets and prices of the three metals. In discussion, in response to the chairman's query on "what are they doing in Russia with calcium, strontium, and barium," Guy C. Riddell replied that nothing is being done on a production basis. The great rare metals plant in Moscow is active, however, on other elements. "They are making radium chloride, uranium oxide, vanadium, cadmium, tungsten, molybdenum, selenium, antimony compounds; and mercury, nickel and arsenic are under production at interior plants. The rare metals plant is busily conducting research on beryllium, rhenium, lithium, bismuth, strontium and zirconium. These are the main rare metal activities. Much hard-alloy work. for cutting and facing, is under way:

Jan 1, 1933

By C. Y. Wang

China now leads the world in antimony production, having contributed during recent years something over 60 per cent. of the world's production. The history of the antimony industry of China dates back to 1897 when the Tai Shing Co. was formed, under contract with the Hunan Bureau of Mines, for the smelting of the ore to crude; and in 1908 the Wah Chang Mining & Smelting Co. was formed for the smelting and refining of the ore and crude to regulus. The writer was then asked to take charge of the erection and control of this first plant for regulus production in China and has, since then, been more or less connected with the antimony industry in this country. This paper contains the results of many years' experience in connection with the Wah Chang Mining & Smelting Co., Changsha; the Pao Tai Mining & Smelting Co., Wuchow; the Loong Kee Smelting Works and the To-Cheng Smelting Works, Hankow; as well as information gathered from various other small smelters, scattered in different parts of the Provinces of Hunan, Hupeh, Kwangsi, and Kwangtung. An idea of the growing importance of regulus production in this country can be gleaned from the fact that, within a period of about 8 years, the export of regulus from Hunan alone jumped from 3 tons in 1908 to about 6000 tons in 1915; that a production of about 23,000 tons of regulus per year could easily be effected from all the smelters, as tabulated below, most of which were erected a year or two ago under the stimulus of the war booms, if the price at Hankow were to stay somewhere about $900 (Mexican) per ton, half of what it was at its height, thus enabling the utilization of ores from the hinterlands of the provinces; and even under the present ruling of prices and the closing of the less favored smelters, the production of regulus should not be less than 12,000 tons per year.

Jan 1, 1919

Albin, B. R Billings, Mont. '28 Amster, Nathan L 25 Broad St., New York, N. Y. '28 Bache, Jules S 42 Broadway, New York, N. Y. '28 Barrett, C. P 5338 Harper Ave., Chicago, 111. '28 Bayless, William S Russ Bldg., San Francisco, Cal. '28 Bean, Louis, H 60 E. 42nd St., New York, N. Y. '28 Beatty, Ross J Room 604, 6 N. Clark St., Chicago, III. '28 Benwell, Oswald F Hold Mags. '28 Beymer, Albert S., V.P., Keystone National Bank Pittsburgh, Pa. '28 Blumenthal, Hugo 44 Pine St., New York, N. Y. '28 Boettcher. Charles Ideal Cement Bldg., Denver, Colo. '28 Bowlus, Thomas H., Banker, Pres., Allen County State Bank Iola, Ran. '28 Brown, Colvin B Chamber of Commerce, Washington, D. C. '28 Burt, Maxwell Struthers Southern Pines, N. C. '28

Jan 1, 1936

By Riki Kobayashi, Donald L. Katz

The dew point of natural gas which has been in equilibrium with gas hydrates has been reported to be lower than that obtained for natural gas in equilibrium with water1,? Hammerschmidt' reports a lowering of the dew point of 13 F for a natural gas in equilibrium with hydrate at 380 F and 525 psi. Records and Seely2 likewise show that the dew point of gas leaving hydrate separators' is as much as 150 F below the separator temperature. This paper presents the reasons for the observed differences between the equilibrium temperatures and the dew point temperatures. Descriptions of the dew point determination by the Bureau of Mines and ASTM tester3 indicate that the dew point is taken as the temperature at which liquid water droplets first begin to appear on the cooled mirror surface even though the temperatures involved are below that required for the formation of gas hydrates or ice. PRESSURE-TEMPERATURE DIAGRAM FOR METHANE-WATEK SYSTEM Fig. 1 presents a schematic pressure-temperature diagram for the methane-water system" for some constant pressure between the critical pressures of pure methane and pure water i.e., pressures frequently encountered in pipeline operations. The possible equilibrium relations are shown by the heavy solid lines. Curve AE represents the saturated water content or dew point of gas in equilibrium with a water-rich liquid solution while curve EF represents the dew point of gas in equilibrium with hydrates. In addition the dotted line DE labelled "metastable dew point" is introduced to explain the apparent discrepancy betwceen the dew point determination and gas-hydrate equilibria. Thermodynamics place certain restrictions on the location of line DE6, namely, that (1) the concentration of water along the line DE be greater than the concentration of water along EF or that the metastable line split the angle formed by the intersection of line GE and EF

Jan 1, 1956

By E. H. Jr. Dix

THE consideration of alloying elements for aluminum has led to a series of investigations of the equilibrium relations between aluminum and those alloying elements. Therefore, the aluminum end of the aluminum-antimony diagram has been studied. The general form of the aluminum-antimony equilibrium diagram has been worked out by Campbell and Mathews1 and by Tammann.2 Campbell and Mathews described principally the beginning of solidification. They found the curve of beginning of solidification to rise gradually from the melting point of pure aluminum to a maximum at about 67 per cent. aluminum. After a slight lowering of the curve at a little greater antimony concentration the curve again rises to a maximum at 18.4 per cent. aluminum, which corresponds to the compound AlSb. The curve then drops to the melting point of pure antimony. Tammann explained the maximum occurring at about 67 per cent. aluminum as the result of the slow formation of the single compound AlSb. The space lattice of the compound AlSb, according to Owen and Preston,3 is face-centered cubic, the antimony atoms being intermeshed with an identical aluminum lattice. Very little, if any, work has been done on aluminum alloys containing small amounts of antimony.

Jan 1, 1930

By G. C. Wallick

Since the appearance of the paper, "Solution of the Equations of Un-steady State Two-Phase Flow in Oil Reservoirs," by W. J. West, W. W. Garvin, and J. W. Sheldon,' a two-fold investigation of this subject has been carried out. One objective of the investigation has been to deter-mine the feasibility of solving such problems 7on a medium-size com-puter such as the Datatron*, and the other objective has been to in-vestigate the application of such cal-culations to experimental and theo-retical petroleum reservoir research. In the first Datatron calculations, the fluid and rock properties published by West, et al, were used, together with the published equations describ-ing the system. Details of the formu-lation not given in the original paper are discussed in the Appendix to this note. Reference should be made to the subject paper for the complete equations and defintion of symbols. An unexpected result of this in-vestigation was the discovery that the linear solution published by West was in error. Thus, in addition to describing the Datatron solutions and to discussing certain numerical diffi-culties which will be encountered if one uses the published method of solution, the purpose of this note is to indicate the nature of this error. LINEAR FLOW Since the linear case requires a minimum amount of scaling, a fixed-decimal point Datatron program was written for the one-dimensional flow problem and an attempt was made to duplicate the solution described by West. In the case described, fluid was produced at a constant rate, Q, until such time as well pressure reached 0.04. Production was then continued at constant pressure. From the constants and curves given by West it was determined that the ini-tial constant production rate could be approximated by Q = 0.007. An ini-tial dimensionless time step ?t = 0.434 X 10 - "as used, and each suc-cessive time step was doubled until a value of = 0.444 was reached. This constant interval was then used for the remainder of the solution. In subsequent solutions, several varia-tions in the time schedule were em-ployed, including smaller time steps and slower rates of increase in the time steps. In all cases, almost identical results were obtained regardless of the time schedule employed. However, as described below, it was noted that the time schedule had some influence on the rate of convergence of the solutions. As a check on the accuracy of the solution, the cumulative production at each time step was calculated using the two methods described in the Appendix. Satisfactory agreement was observed with the differences in these two values of the order of two parts in 50,000. It should be noted that the mass balance check as described is of questionable value, particularly with regard to the well pressure and saturation. This is especially true in the radial solution where pressure and saturation values near the wellbore would make only a negligible contribution to the numer-ical integration. It is believed, how-ever, that such a comparison is ot value in determining the over-all accuracy of a solution. In comparing the Datatron solu-tion with that published by West it was discovered that in the later stages of depletion, the pressures near the well declined more rapidly in our solution than in the West solution, and that the limiting well pressure of 0.04 was reached at an earlier time than that originally reported. It thus became evident that it would be impossible to duplicate the production schedule described by West and a constant rate of production was maintained until the well pressure was equal to 0.0. A representative comparison of the results published by West with those obtained in this investigation is shown in Fig. 1, which is a plot of GOR as a function of cumulative recovery. These two curves should be in agreement until a cumulative recovery is reached which corresponds to a well pressure of 0.04 — for the Datatron solution, a recovery of approximately 5.6 per cent. Actually, a major disagreement is evident. Subsequent correspondence

Jan 1, 1958

By E. S. Machlin, W. R. Yankee

IN a previous study1 of the effect of heating com-mercial titanium in air on its subsequent friction coefficient against other metals, as well as itself, it was found that the friction coefficient markedly decreased from a value of about 0.7 to about 0.3. A tentative explanation was given that surfaces normally produced at room temperature are not contaminated sufficiently to prevent seizing or welding of the titanium to the softer mating metals. The latter tend to cleanse themselves during rubbing over the harder titanium. It was thought that the lack of a contaminant protective film on the titanium was due to the high solubility of titanium for oxygen and nitrogen and hence an inability to form a contaminant oxide or nitride. This explanation requires the ratio of the surface absorption rate to the diffusion rate to become much lower at room temperature than it is at high temperatures. In order to check the phenomenon further, commercial titanium specimens were nitrided or oxidized at 800°C for 20 hr in flows of prepurified N2 and 01, respectively, at about 1/2 in. H2O above atmospheric pressure. Friction runs were made in argon using a freshly cut copper hemisphere (cut in argon) on surfaces cut successively into the diffusion layers in the titanium (cut in argon) using the techniques described in a previous publication.' DPH values (100 gram load) were made as a function of depth into the diffusion layer using a Tukon tester. Also, micrographs were taken at separate cross sections to indicate the diffusion layers. The results obtained are presented in Figs. 1 and 2, which show the "static" friction coefficient vs hardness for the nitrided and oxidized specimens, respectively. A separate measurement of the friction coefficient of clean copper vs iodide titanium also was made. From results reported in the literature' giving the oxygen and nitrogen contents as functions of the hardness, cross plots were made showing the friction coefficients as functions of the amount of interstitial solute. These plots are given in Figs. 3 and 4. From micrographs of the diffusion layers and the phase diagrams, it was deduced that the data in Figs. l through 4 correspond to the single phase a region. The points observed on the compound regions have been excluded from the figures. It is apparent that nitrogen or oxygen in solution in the a titanium markedly affects the friction coefficient against a softer mating metal. Discussion of Results These results are extremely interesting from both a practical and theoretical viewpoint. The theoretical implications will be discussed first. According to Bowden, the friction coefficient should be given to a good approximation by the relation where a is the fraction of contact area that has welded, a is the shear strength of weaker component, and H is the hardness of softer component. Using this relation alone, it is difficult to understand the results because none of the terms should be affected by a variation in the oxygen or nitrogen content of the harder and stronger metal, titanium. Even if the ratio of S/H for titanium is used in Eq. 1, the ratio has been shown to be independent of oxy-gen or nitrogen content.' If a more rigorous equa-tion is used combining Eq. 1 and a result given pre-viously" for the case where welding is absent, then the relation obtained is µ = a S/H + (1-a) a W aß/H where a is constant and Waß is the work of adhesion between the two metals comprising the friction couple. This relation states that if a is less than 1/2 or so, variation in the work of adhesion Waß between copper and the titanium should affect the friction coefficient markedly. It is reasonable to expect that the work of adhesion will depend on the oxygen or nitrogen content of the titanium. Available data4 show that clean metals and oxides have much lower works of adhesion than the same metals against the

Jan 1, 1955

By Robert K. Waits

The resistivity, temperature coefficient of resistance, stability at 200°C, and structure of annealed Si-Cr films have been studied as a function of film cowposition. Colorimetric analyses of the films indicated 20 to 60 wt pct Cr over the resistivity range of 1 to 10-4 ohm-cm. Resistors were delinealed by photolithographic etching, contacted with aluminum, and mounted in TO-5 packages. The average temperature coefjicient of resistance, a, between 50" and 150°C is related empirically to the film resistivity, p, by a (ppm per °C) = -2900 - 1140 log p (ohm-cm). Near a resistivity of 3.5 x 10-3 ohm-ctn (30 at. pct Cr) , the temperature coefficient changes from positive to negative. The temperature at which the resistance maximum occurs increases with decreasing resistivity. The conduction mechanism between —196" and +360 C appears to have two components—an activated conduction dominating a1 lord chromium content and higher temperatures and a linearly temperature-dependent conduction dominating at high chromium content and low temperatures. Electron diffraction patterns showed the films to consist of Cr3Si and amorphous silicon. Resistors thicker than 150A typically drifted less than 0.6 pct after 5000 hr stor-age at 200°C. Resistors as thin as approxinzately 80°A that had a silicon overlayer showed similar stability. Such films had sheet resistivities of 10 kilohm per square and temperature coefficients near —600 ppm per "c. THIN-FILM resistors having sheet resistivities greater than 1 kilohm per square are required in many integrated circuit applications. A process for producing such resistors should be compatible with present circuit fabrication and packaging, including exposure to maximum temperatures of 300° to 570°C during contact alloying, die-attach, and ceramic package sealing. In addition, the resistors should have a low temperature coefficient of resistance and change less than 1 pct during storage at temperatures up to 200°C for 1000 hr or longer. Reports of work beginning in 1949 at Battelle Memorial Institute indicated that, among other materials, the silicides of chromium, Cr-Co, molybdenum, tantalum, and tungsten were worthy of further study as high-stability resistive films. Later work on Si-Cr films vacuum-deposited by flash evaporation from a tungsten boat1 led to the conclusion that Si-Cr had "excellent properties for development into high- stability ... resistive elements". More recently, Si-Cr films have been vacuum-deposited from a tantalum boat,2 from a BeO-coated tantalum boat,3 by flash evaporation from an electron-beam-heated tungsten Source,4 and by triode sputtering.5 This paper describes a study of Si-Cr films vacuum-deposited by electron-beam heating of Si-Cr alloys. Resistivity, temperature coefficient of resistance, stability at 200°C, and structure were studied as a function of film composition. EXPERIMENTAL PROCEDURE Film Deposition. Si-Cr sources were prepared by vacuum-melting pressed pellets of mixtures of powdered chromium (99.9 pct, -100 mesh, Lunex Co., Pleasant Valley, Iowa) and silicon (99.99 pct, -325 mesh, United Mineral and Chemical Co., New York). A permanent-magnet focused electron-beam gun having a water-cooled copper crucible was used to heat the pellet until complete melting occurred. The mixture was then kept molten for an additional 5 min. The alloy thus formed was used as the source material for Si-Cr film depositions using the same electron-beam gun. Pieces of semiconductor-grade silicon ingots were used as sources for silicon depositions. The films were deposited within a standard vacuum evaporator having an 18-in.-diam Pyrex bell jar, a liquid-nitrogen-cooled trap, and a Consolidated Vacuum Corp. 6-in. diffusion pump containing Dow Corning DC-705 pump fluid. The substrates were thermally oxidized* silicon wafers 2 to 2.5 cm in diam. The

Jan 1, 1969

By S. J. CRAIGHEAD

IN 1912 the United States Smelting Refining and Mining Company made a large investment in a number of coal properties in Utah and in 1915 a subsidiary, the United States Fuel Co., was organized to take over these properties. Operations started in 1916 and the Company soon became, and remains, one of the major coal producers of the State. It now produces approximately one million tons of coal annually, which is about 22 per cent of Utah's output. The U. S. Fuel Co. owns large reserves of good coal and is in a position to expand operations with the industrial growth now taking place in the West. Traveling through the Western States, one is struck by numerous advertising signs portraying the picture of jovial Old King Cole of nursery rhyme fame. His rotund figure and beaming countenance are the symbols of Utah King Coal, the product of the King mine of U. S. Fuel Co. King Coal is a by-word of quality coal throughout all the Western States.

Jan 1, 1948

By Brian R. Castle, James J. Scott

INTRODUCTION Referring to a ground support system as a 'band-aid' borders on getting cute, but the application of cable slings in U.S. mining is somewhat analogous. Where problems in the roof or rib require additional support, the versatile cable sling is the answer in a variety of conditions. To fully understand how and why cable slings are used today we must briefly review their development history. Much of the thrust over the last five to seven years in ground support fixtures has been the development of hybrid systems. Taking the best of two or more existing roof bolt fixtures and marrying them into a new fixture which exhibits the good characteristics without the bad of the parent systems. Resin point anchored mechanical bolts, continuous threaded rebar bolts, and others have all be- come important fixtures in rock mass stabilization. HYBRID GROUND SUPPORT SYSTEM The cable sling system is also a hybrid, both in its parentage and in its ground support characteristics. See figure 1. Cable slings combine the techniques of cement. grouting high-strength cables, Friction Rock Stabilizers, and truss-like suspension into a versatile and high- strength ground support system. 1/2" high-strength cable is cement grouted in place in a manner similar to pre-

Jan 1, 1983

By H. Kenworthy, R. B. Fisher, R. G. Knicherbocker, M. M. Fine

The progress made to date in the mineral dressing of complex Arkansas titanium ores is reported in this paper. Concentrates of rutile, a dioxide of titanium, were produced by treating a submarginal ore from the Magnet Cove Rutile Co., Inc., Magnet, Ark. The rutile recovery at present is 45 to 50 pct of the total TiO2, with the possibility of increased recovery with additional research. The work reported herein is part of a general study which will later include results of investigation of other titanium ore bodies in the Magnet, Ark., area. The fragile character of the rutile minerals, the softness of the gangue, the occurrence of pyrite and leucoxene, and the considerable proportion of extremely small size rutile in the presence of montmorillonite- and illite-type clays in the Magnet Cove open-pit mine are the important factors in the mineral dressing of this submarginal rutile ore. History The occurrence of titanium minerals in the Magnet Cove area of Arkansas was recognized as early as 1890, but it was not until about 1912 that any appreciable prospecting for the minerals was undertaken. At that time drilling was begun, a shaft was sunk, and several drifts were driven, but beneficiation to recover the titanium minerals was not attempted. The only successful mining and milling operation of the Magnet Cove rutile deposit was begun in 1932 by the Titanium Corp. of America and continued until 1942. The ore was washed by means of a rotary scrubber and then deslimed in a drag classifier. The discharge was ground in a rod mill, classified, and tabled to recover a rougher rutile concentrate, which was screen-sized and retabled on cleaner tables. The cleaner concentrates were given a reducing roast, screen-sized, and magnetically separated to produce a finished rutile concentrate. Most of the rutile produced during this period was sold abroad. In 1942, the Titanium Alloy Corp. of Arkansas (a subsidiary of the Titanium Alloy Manufacturing Co. of New York) purchased the property and rebuilt the mill. Subsequently, the plant and property were acquired by the Magnet Cove Rutile Co., Inc., of Little Rock, Ark., the present owners. Very little titanium has been produced since 1942. Although the Titanium Corp. activities yielded enough returns to allow continued operation for approximately 10 years, certain factors must be recognized. These are: (1) production of rutile in that period was during a low in the economic cycle which permitted low-cost operation on a small scale, and (2) a considerable portion of the production was above the water level and no drainage problems existed. Prior to this paper there has been no published report of any mineral-dressing investigation of the lower levels of the ore body. Reference is made in another paper1 to an earlier investigation of Magnet Cove rutile by the Rolla laboratory, in which it is stated that recoveries of 12 to 17 pct of the rutile were obtained. The present investigation was undertaken to improve the known milling processes and to provide adequate metallurgical information about the ore treatment. Titanium Technology The titanium mineral of primary interest in the present investigation was the titanium dioxide, rutile. Rutile is one of the industrial minerals whose annual consumption is relatively small but strategically important. The domestic production of rutile was 7100 tons in 1948. The imports of rutile in the same year were approximately 8000 tons.2 A major use of rutile is in the production of welding-rod coatings, for which a product containing a minimum of 92 pct titanic oxide is desired. Other constituents, such as lime, silica, and sulphur, must be held to a minimum, but hard-and-fast specifications for these elements cannot be drawn. It is necessary to incorporate the rutile in a welding-rod coating, make a sufficient number of test welds, and then determine the tensile strength of the weld metal in the as-welded and stress-relieved conditions. Such a test gives

Jan 1, 1950

By W. R. Purcell, C. S. Brooks

The internal surfaces of rocks which are in contact with interstitial fluids are known to influence in some degree the recovery of hydrocarbons from pay zones. Despite the admitted importance of the influence of solid surfaces on hydrocarbon recovery, little information is available concerning the extent of surface of reservoir rocks. In this paper a description is given of the apparatus and procedure employed in the determination of the surface areas of sedimentary rocks, and values are reported for a variety of sandstone and limestone cores. In addition, consideration is given to the Kozeny equation, which relates surface area to porosity and permeability. A colliparison is made between the surface areas as calculated from this equation and the geometrical areas of a series of packs of spherical glass beads. Also, for a group of sandstone cores. Kozeny areas are compared with surface areas as determined by the gas adsorption method employed in this investigation. INTRODUCTION It has long been recognized that many processes which are of importance to hydrocarbon production are controlled in some degree by the extent of the surface of the reservoir rock through which the hydrocarbons move. For example, the recovery efficiency that is obtained in a given reservoir is certainly determined in part by the action of interfacial forces between the reservoir fluids and rock, and this action is influenced in turn by the extent of solid surface. Despite the admitted importance of surface effects to problems of petroleum recovery, little information is available concerning the extent of surface of reservoir rocks." It is the purpose of this paper to describe an apparatus which has been employed for the measurement of the surface areas of rock samples and to present the values which have been obtained for a variety of sandstone and limestone cores. In addition, the relationship of surface area to permeability and porosity, as given by the Kozeny equation, will be discussed. METHOD OF MEASURING SURFACE AREA The method of determining surface areas as employed in this work has previously found wide use in studies of porous solids such as catalysts. The method involves the measurement of the amount of physical adsorption of an inert gas, such as nitrogen or argon, on the bare surface of the solid at reduced pressure and constant temperature near the normal liquefaction temperature of the gas. With the aid of the theory of isothermal adsorption as developed by Brunauer, Emmett, and Teller,' it is possible to ascertain the amount of gas (and hence the number of molecules) which is required to cover the solid surface with a single layer of molecules. From a knowledge of the covering area per molecule the total surface ares of the solid can be computed. Since the Brunauer. Emmett, Teller (BET) theory has been adequately discussed elsewhere: it will suffice here merely to present their final equation as ordinarily employed for surface-area calculations. This equation relates the volume of gas, V, which is adsorbed at pressure, P, to the liquefaction pressure, Po, of the gas, and to the volume of gas, V.,, that is required to form a monomolecular layer: In this equation C is a quantity which is related to the heats of adsorption and liquefaction of the gas; for a particular solid-gas system at Constant temperature, C is considered to have a constant value. The basic adsorption data can be presented in the form of Equation (1) by plotting the quantity P/V(Po- P) as a func-

Jan 1, 1952

By J. S. Kasper, R. M. Waterstrat, B. F. Decker

THE existence of v phase in the Mn-Mo system was discovered in this laboratory several years ago,' but neither the conditions of its formation nor its composition were known, and preliminary attempts to reproduce the phase were unsuccessful. We wish now to specify the information appropriate to phase formation on the basis of experiments performed since that time. The starting materials were in every case electrolytic manganese and high purity molybdenum. Two methods of preparation were employed: l—arc-melting varying combinations of the elements in an inert atmosphere and subsequent heat treating, and 2—sintering compressed mixtures of finely divided powders of the elements. In the latter method, the powders were first passed through 200 mesh screen and then compressed into cylinders of % in. diameter and % in. length, which were sintered at elevated temperatures in an atmosphere of dry hydrogen. For some samples, the sintering temperature was 1200°C (for 1 hr), and these were then heat- treated at lower temperatures for times up to 24 hr. Eventually it was found, for the proper composition, that essentially pure a phase could be produced by sintering at 1125°C for 3 hr. Quenching to room temperature was effected by means of a stream of cold, dry hydrogen in a water-cooled chamber. The arc-melting procedure was found to be unsatisfactory after an investigation of many samples at different compositions and temperatures. Large quantities of manganese were vaporized during melting and none of the products were homogeneous or contained extended regions of pure phase. Nonetheless, these experiments established that no formation occurs in the Mn-Mo system below 1115oC, and indicated, at least roughly, the composition range of interest for further exploration. The more definite results obtained from samples produced by the second method are given in Table I. A portion of sample 2 heated for 16 hr at 1000°C in a Vycor tube transformed to molybdenum plus unidentified phases of complex X-ray pattern. From these few results it appears that the region of phase is quite narrow in composition. It is of interest that the composition is such as to make for difficulties in correlating this structure on an electron atom basis with other a structures of iron, cobalt, and nickel. In that respect Mn-Mo shows the same anomaly as Mn-Cr and Mn-V systems.' A second feature is that in common with the two other known molybdenum (Fe-Mo and Co-Mo), Mn-Mo v exists only at elevated temperatures. The X-ray powder pattern of the pure a phase of Mn-Mo is given in Table 11. It agrees well with the patterns established for other structures, especially with that for Fe-Mo as given by Goldschmidt.An attempt is being made to establish whether an ordering of the respective atoms occurs and such information will be reported in a future publication. Acknowledgment The authors acknowledge gratefully the assistance of Mrs. J. R. Belanger in some portions of this work. References 'J. S. Kasper, B. F. Decker, and J. R. Belanger: Journal of Applied Physics (1951) 22, p. 361. 2 A. H. Sully: Journal Inst. Metals (1951) 80, p. 173. H. J. Goldschmidt: Research (1949) 2, p. 343.

Jan 1, 1954

By E. R. Morgan, J. C. Shyne, V. F. Zackay

NITROGEN used as an alloying element in steel has received increased attention in recent years. Its merit as an austenite stabilizer and hot strengthener has long been recojinized, particularly by European investigators.' Recent work' indicates that nitrogen contents of 1/2 pet or more allow the addition of several percent of ferrite-forming hot strengtheners, such as molybdenum, without subsequent austenite decomposition at elevated temperatures. The room temperature properties of such alloys are characterized by high yield and tensile strengths with excellent ductility, even after cold working, as shown in Tables I and 11. The 1350°F creep-rupture properties of Cr-Mn-Mo-N steels are comparable to those of commercial alloys such as Timken's 16-25-6, containing 16 pct Cr, 25 pct Ni, and 6 pct Mo, as shown in Table 111. Cr-Mn steel containing 1/2 pet N must be made under pressure if ingot gassing is to be avoided. However, there are difficulties attendant to this practice. Pressure melting restricts the ingot size, and the equipment required is costlier and more complicated than comparable air melting facilities. An effort was made, therefore, to determine more economical methods of adding nitrogen. The pressures generated in centrifugal casting usually range from 5 to 10 atm and are sufficient to prevent the gassing of high nitrogen Cr-Mn steels. A centrifugal casting was made of an alloy containing 16 pct Cr, 18 pct Mn, 2 pct Mo, and 0.73 pct N. A risk, 8 in. diam and 11/2 in. thick, was cast at 1000 rpm. It has been calculated that a pressure of 9 atm was developed at the periphery of the disk at this speed. Metallographic inspection of specimens taken from the disk revealed no gas holes or other defects. The elevated temperature properties of radial and circumferential specimens taken from this casting are given in Table IV. The creep-rupture life of this cast nickel-free austenitic steel was equivalent to that of the wrought Cr-Mn-Mo-N steels. Although centrifugal casting appears to lend itself to the manufacture of high nitrogen austenitic steels, its applicability is limited to relatively small sizes. A process applicable to the production of large ingots of high nitrogen steels is suggested by low carbon rimming steel practice. Gas holes formed during ingot solidification are not detrimental so long as they weld shut during hot rolling. An economic advantage of gassing ingots is the increased ingot-to-slab yield, especially if the ingots are mechanically capped. Also, it is probable that higher nitrogen levels can be achieved with mechanically capped ingots than with hot-topped ingots. A series of gassy heats was made under both atmospheric and higher pressures, as indicated in Table V. Several of the air melted ingots were mechanically capped by chilling the molten ingot tops with a steel plate. The ingots were allowed to freeze in steel molds without hot-tops unless otherwise indicated. A comparison of Table 111 with Table V shows no significant difference in the creep-rupture properties of the gassy and the nongassy ingots after hot work- ing nor between the gassy ingots produced under different conditions. References 1 F. Rapatz: Application of Stainless and Heat Resisting Steels Alloyed with Nitrogen. Sinhl and Eisen ( 1941) 61, pp. 1073-1078. 'V. I?. Zackay, J. F. Carlson, and P. L. Jackson: High Nitrogen Austenltlc Cr-Mn Steels. Trans. ASM 119551 48, PP. 509-523.

Jan 1, 1957

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 L. F. Mondolfo

An investigation of the relationship between properties of the elements and type of binary diagram formed was conducted. It was found that, for each type of equilibrium diagram, the factors for the size, valence, electronegativity, period, melting point, entropies of fusion, and sublimation calculated for each pair of elements cover a range of values. However, these factors show sufficient relationship to the equilibrium diagram so that the correlation of several of them can be used to predict the type of diagram formed, or at least limit the choice to only a few types. ThE goal of the metallurgist concerned with alloy development has always been to find a method that predicts the properties that can be obtained when a certain metal is added to another one. In most cases a qualitative predictiton of properties can be made if the equilibrium diagram is known. However, this means that for new metals the alloy development has to start with the experimental determination of the equilibrium diagrams. Because this determination is at least as complicated and time-consuming as the determination of the properties themselves, most alloy development has taken place by trial and error, and the study of the equilibrium diagrams has followed rather than preceded the creation of new alloys. Alloy structures and properties depend on the interaction between electrons and a complete knowledge of these interactions would permit prediction of structure and properties of alloys. Unfortunately direct measurement of these interactions is extremely difficult and somewhat doubtful and only properties that depend on them can be measured easily and with certainty. Study of the relationship between properties of the elements and equilibrium diagrams is not new. Besides the well known Hume-Rothery rule of the necessity of an atomic diameter fit within 15 pct for extensive miscibility in the solid, and the wide knowledge of the effect of such factors as size, electronegativity, electron-atom ratio on solid state features,"' work relating to liquid state and liquid-solid reactions can be found in the literature. Of particular interest is the work by Axon,3 who investigated the effect of size and melting point on a selected number of eutectic and monotectic dia-

Jan 1, 1962

By K. P. Gupta

In ternary systems containing silicon and transition elements, silicon was found to stabilize the a phase.1 At 1000°C a broad a-phase region was found in the Cr-Mn-Si system,1 which extends very close to the Mn-Si binary line (within about 3 at. pct Cr). Later investigation showed that, if chromium was replaced by small amounts (3 to 5 at. pct) of v,1 Ti, Nb, Ta, Mo, or w,1 the a phase or the R phase was again stabilized. Whether stabilization of complex crystal structures is possible by small additions of iron, cobalt, or nickel to Mn-Si is not known. Investigation of the Co-Mn-Si system4 shows the presence of several ternary phases, but at cobalt concentrations higher than 10 at. pct. In the present work the ternary systems Fe-Mn-Si and Co-Mn-Si were investigated at low iron and cobalt concentrations (< 7 at. pct Fe or Co) in search of phases of complex crystal structure. Experimental Procedure. The alloys were pre-pared by induction melting Co (99.8 pct), Si (99.9 pct), electrolytic Fe (99.88 pct), and Mn (99.9 pct) in recrystallized alumina crucibles under an inert atmosphere of argon gas. The alloy specimens were wrapped in molybdenum foil, sealed in argon-filled (at 1/2 atm) silica capsules and annealed for 72 hr at 1000" 1°C, and water-quenched. The use of argon-filled capsules was found to reduce the losses during annealing and the molybdenum foil prevented reaction of the manganese with silica. The total weight loss due to annealing and melting was found to be less than 1 pct for each alloy. The alloys were not analyzed chemically. A part of each annealed specimen was polished and examined metal-lographically using etching solutions, a) 0.1 to 0.5 pct oxalic acid solution in water, or b) 0.5 pct HNOs in methyl alcohol. Even though the etching solutions were quite dilute, the specimens were heavily etched and stained if the etching time exceeded more than 5 sec. Etching times found suitable were usually 1 to 3 sec. For X-ray diffraction work, a part of each annealed specimen was powdered by crushing after the exposed surface was ground off. X-ray diffraction patterns were taken with powder specimens using a 20-cm-diam asymmetrical focusing camera and Fe K radiation. These powder patterns were found quite satisfactory for the purpose of phase identification. However, X-ray diffraction patterns of single-phase alloy powder specimens were also taken using a Siemens diffractometer and filtered Cr-Ka radiation for greater resolution of the diffraction lines. Results and Discussion. In the Fe-Mn-Si system a new ternary phase was found at 1000°C between the p manganese and the MnsSi phase regions. The approximate phase relationships in this region of the 1000°C isothermal section are shown in Fig. 1. The new ternary phase, designated as the K phase, was found to occupy a narrow region about 1 at. pct in width and extending from Fee.oMn74.5Silg.5 to Fe.Mn.Silg.. At the high-iron content region, the K phase was found in equilibrium with the p manganese and the MnsSi phases but, at the low-iron content end of the K-phase region, the phases in equilibrium with the K phase were the p manganese phase, the MnsSi phase, and another new phase, designated in Fig. 1 as the v phase. The v

Jan 1, 1964

By I. Havenaar

EXPERIMENTAL DATA In an article by C. K. Ferguson and J. A. Klotz,1 experiments on the filtration of drilling muds under borehole conditions are discussed. Experimental data on mud filtration through the wall and the bottom of the hole are presented. From the data on bottom-hole filtration it was concluded that the filtrate does not flow freely into the formation, but that the pores of the formation are plugged by the mud. A quantitative interpretation of the data can be civen, by using a formula for bottom-hole filtration, dehved below. This formula is based on the following assumptions, 1. Each time a blade of a drag bit, or a cone of a roller bit, moves along the bottom of the hole, the mud cake is completely removed. 3. A new mud cake is immediately formed on the freshly produced surface, and losses of "whole" mud into the formation are negligible (this is equivalent to an immediate plugging of the pores). 3. The filtration of the mud on the bottom of the hole follows the classic law: V = A +1—(Eq. I), where t is the time required to yield a volume of filtrate V, A is the surface area of filter cake, and C is a constant. The application of this equation means that any eroding effect of the mud stream on the mud cake is neglected. The formula for the calculation of the volume of filtrate, Q,, flowing in one second through the hole bottom (diam. d cm), when using a bit with n cones or blades rotating at a rate of rn revolutions per second, is derived as follows: The mud cake is formed on the bottom of the hole in the time t =1; the filtrate volume V which passes n through the bottom In this time 1s given by Eq. 1: After1/nmsec the mud cake is removed. In one m second this process takes place nm times. Therefore the volume of filtrate, obtained in one second is given by This equation has now been applied to the experiments of Ferguson and Klotz. The constants C were derived by means of Eq. 1 from the API filter losses of the muds used by the authors (t = 1,800 sec; A = 45.16cm2). A three-cone bit was used (n = 3) at 90 rpm (m = 1.5). The calculated figures are compared with the experimental data in the table below. The calculated values of Q, are usually lower than the experimental values. This may be due to the following causes. 1. The value of C used in the calculation is based on the API filter test (filtration pressure of 100 psi), whereas the experimental data were obtained with a filtration pressure of 200 psi. Although the effect of the pressure on C is not large, C decreases somewhat with increasing pressure, and this leads to a higher filtration rate. 2. Mud losses and the eroding action of the mud stream on the cake are not entirely negligible. 3. The values of Q, derived by Ferguson and Klotz from their experiments are too high, because of their assumption that all pore liquid within the formation drilled is picked up by the drilling mud. It is found, however, that the calculated values of Qf, except in the case of oil base muds, are of the right order of magnitude. ACKNOWLEDGMENT The author wishes to thank the management of the Koninklijke/Shell-Laboratorium, Amsterdam, for permission to publish this note.

Jan 1, 1957

By G. R. Gohn, S. M. Arnold

The results of stress-corrosion tests upon several non-ferrous sheet metals are presented in this paper. The metals include tough pitch copper, five binary brasses, two leaded brasses, one copper-silicon alloy, two tin bronzes, and two nickel-silver alloys. The tests indicate that for most of these sheet metals, externally applied bending stresses below the yield point (0.01 per cent offset) do not result in stress-corrosion cracking as determined by the A.S.T.M. Tentative Method of Mercurous Nitrate Test for Copper and Copper Alloys (B 154-41T).~ Only in the cases of low brass, high brass and medium leaded brass, all cold-worked 4 B & S numbers hard, was any corrosion cracking observed below the yield strength, and in all cases such failures occurred at stresses above the proportional limit for these materials. However, when some of the same materials which showed no evidence of stress-corrosion cracking at stresses below the yield strength, are stressed beyond the yield point, stress- corrosion cracking is quite apt to occur. Since experience has shown that some of these materials, particularly the brasses, are susceptible to stress-corrosion cracking under service conditions, these tests would indicate that, besides externally applied stress and corrosion, plastic deformation in addition to that resulting from the original cold working of the material is also required to produce conditions conducive to stress- corrosion cracking.

Jan 1, 1945