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By C. J. Rosa, W. C. Hagel

An attempt is made to determine the diffusion coefficients of oxygen ions in hypostoichiometric zirconium oxide. A phenomenological theory is developed for three-phase, unidirectional volume diffusion of a gaseous species from a planar source. Knowledge about oxygen diffusion in a and ß zirconium and experimentally measured rates of movements of interfaces permit the evaluation of oxygen ion diffusivi-ties in ZrO2-x. The results conform to the relationship: sq cm per sec, for the temperature range of 875" to 1050° C. DIFFUSION coefficients of oxygen ions in stoichio-metric oxides have been studied by many investigators. The obtained results not only supplement the knowledge about the lattice-defect structures of oxides and conduction mechanisms but also provide information of technological importance. Rate processes such as oxide sintering, high-temperature creep deformation, and oxidation of metals and their alloys are directly dependent on diffusion phenomena. Unfortunately, diffusion coefficients obtained from studies on stoichio-metric oxides cannot be treated without restraints when applied to oxidation kinetics, if precise evaluations of oxidation rates are desired. Oxides formed on metals are usually nonstoichiometric and exhibit nonuniform distribution of either cation or anion vacancies across their thicknesses. Debuigne and Lehr1 extended Danckwerts'2 mathematical analyses and furnished a semitheoretical treatment for evaluating oxygen diffusion coefficients in zirconium oxide in terms of weight gain measurements during oxidation of zirconium in the temperature range 400° to 850°C. Their calculations are based on theoretical partitioning3 of the total amount of oxygen between a zirconium and its oxide phase. An inherent discrepancy appears to continue throughout their calculations. The amount of oxygen confined to the oxide phase should be corrected by multiplying the calculated oxide thickness by the inverse of Pilling-Bedworth ratio, if expansion of zirconium dioxide is taken into account. The purpose of the present investigation is to provide a new semitheoretical treatment for evaluating diffusion coefficients of moving species in hypostoichiometric oxide. The analyses are relevant to unidirectional volume diffusion. Although the presented method is quite general, its applicability will be discussed in terms of kinetic measurements from oxidation of zirconium at temperatures above the a/ß transition, for reasons stated in the later part of this paper. EXPERIMENTAL Pure, 99.93 wt pct, zirconium samples of approximately 2 by 1 by 0.35 cm were exposed to oxygen for various times at four temperature levels: 875°, 950°, 1000°, and 1050°C. High-purity, better than 99.9 vol pct oxygen was passed through a cold trap and columns containing anhydrous CaSO4 to remove residual water vapor. Before exposing to oxygen at a pressure of 500 Torr, specimens were subjected to wet abrasion on 200- through 600-grit Sic papers and polished with 1—p diamond dust. Prior to oxidizing, all zirconium samples were vacuum-annealed at 10-6 mm Hg for about 15 min at the test temperature. The temperature variation across the uniform heat zone was ±2°C from the preset value. Final polishing, for phase thicknesses measurements, was performed by using 8- and 1-p diamond dust and followed by vibrator polishing with 0.05-µ ? Al2O3 solution. Measurements of phase thicknesses were made by projection on a metallographic viewing screen. Conventional powder X-ray analyses for the oxide were employed. RESULTS Fig. 1 is an example of the cross section of oxidized zirconium. Designations of phases given below this figure are the same as those used in the three-phase diffusion system represented by Fig. 5 in the following section. Zirconium oxidized for longer exposure times showed two types of oxides: white oxide at the surface and an underlaying layer of gray oxide. X-ray powder patterns of these oxides at room tern-

Jan 1, 1969

By D. A. Belforti, M. P. Lepie

Spectroscopically pure copper was melted on sapphire plaques in a zydrogen atmosphere. The surface tension of the liquid metal was determined using the sessile drop technique. Measurements were made by direct observation with the aid of a specially const,mcted telescope. The value obtained, 1268 dynes per cm, is compared to that found in the literature. THERE is at this time considerable interest in the use of ceramics for vacuum tubes. The crystalline material is superior to the more conventional glass in mechanical strength, chemical inertness, dielectric properties, ability to withstand high temperatures, and so forth. However, ceramics are much more difficult to seal hermetically with metals than are the glasses. For this reason an investigation was undertaken to determine the wetting and adhesion of metals to ceramics. The sessile drop technique offers a convenient means at elevated temperatures for measuring liquid surface tension, wetting angle, density, spread- ing coefficient, and work of adhesion. Thus, from the contour of a drop of liquid at rest on a solid surface one can obtain a quantitative evaluation of the degree to which the two substances will bond. To this end a special apparatus was constructed so that various molten metals could be observed. Standardization of the apparatus was done initially by measuring the surface tension of copper since this is well documented in the metallurgy literature. Although there are many methods available for the measurement of surface energy,'+ the sessile drop technique has been used most extensively for molten metals and ceramics.5"' Fig. 1 illustrates the dimensions to be measured. From these values, the surface tension of the liquid can be obtained using the Bashforth and bdams' equation and tables.

Jan 1, 1963

By R. W. Gurry

In a series of charts this paper presents the composition of all gas mixtures, composed of the elements carbon, hydrogen, oxygen and nitrogen, which at temperatures from 1000° to 1800°F are in equilibrium with (1) austenite of various carbon contents, (2) iron and iron carbide, (3) graphite, (4) iron and its oxide. THIS paper presents the results of calculations made to determine the proportions of CO, CO2, CH4, H2, H2O and N2 in gas mixtures which, at temperatures from 1000" to 1800°F, satisfy, individually, the following conditions: (1) equilibrium with carbon steel of specified carbon content throughout the stable 7 iron region; (2) equilibrium with iron and iron carbide, both above and below the eutectoid temperature; (3) equilibrium with graphite; (4) equilibrium with iron and its oxide. From these data a new type of chart has been prepared which permits one to determine, from a room-temperature analysis of the furnace gas in question, the effect of the gas upon the steel at furnace temperature. Thus a guide is provided as to the carbon content which will result and as to the possibility of oxidation or sooting. All of the atmospheres commonly used in the commercial heat treatment of steel are composed of some or all of the simple constituents CO, CO2, CH4, H2, H2O and N2, and also in some cases oxygen or higher hydrocarbons. As the gas mixture is heated certain alterations in the proportions of the constituents take place, and at the temperature of the furnace the composition is, in general, not at all that of the entering gas. If equilibrium in the gas phase is presumed a calculation involving the use of certain fundamental data predicts for a certain temperature the carburizing, decarburizing, or sooting characteristics of a given atmosphere, and, upon the additional assumption of equilibrium between gas and metal, also the oxidizing ability of the gas and the ultimate carbon content of the steel. The extent to which these predictions are fulfilled will depend upon how closely the assumptions of equilibrium are realized in any particular case. Although at lower temperatures equilibrium is often not reached, there is considerable evidence indicating that above about 1000°F the approach to equilibrium in the gas phase is generally substantially complete, particularly in the vicinity of the steel which acts as a powerful catalyst in promoting reactions in the gas phase. The extent of the gas-metal reactions is commonly affected essentially by the sojourn at temperature; equilibrium with respect to carbon, for example, is accomplished simply by continuing the treatment long enough. However close the approximation of equilibrium may be in any instance, the above mentioned calculation indicates the condition of the steel at equilibrium, and at the present time this is the only basis of control of a furnace atmosphere. The effect at elevated temperature of a gas of a certain composition at room temperature upon a given steel has customarily been judged by first calculating from gas equilibrium constants the proportions of the gas constituents at the temperature of the steel, then comparing certain of these with the proportions known to be in carbon or oxygen equilibrium. This process is tedious and time-consuming, in particular because the calculation generally involves a series of successive approximations; and since some knowledge and familiarity with this type of computation are required, not everyone needing the information has been, in the past, in a position to obtain it. By making a series of equilibrium calculations, combining with fundamental data for gas-metal reactions, and plotting the results in a special way, a chart has been prepared which enables anyone

Jan 1, 1951

By H. P. Willard, Conrad Martin

SINCE the deposits were found in 1927 in the Paradise Range of western Nevada, more than 1 mil- lion tons of magnesite and half a million tons of brucite have been mined and processed into a variety of granular refractory materials used as furnace linings by the steel industry. An additional million tons of magnesite were used during World War II to produce magnesium metal, and some magnesium oxide from the area is going into magnesia cements. Located near Gabbs, Nev., on the west flank of the Paradise Range, the principal bodies occupy an area a mile long by half a mile wide, and lesser occurrences have been found in a belt more than four miles long and in places almost two miles wide. Magnesite reserves containing less than 5 pct lime are estimated at more than 25 million tons. Reserves of better grade material are considerably less.

Jan 4, 1957

By Paul Giesecke

SINCE most modem metallurgical plants are operated continuously and on a large scale, successful operation at maximum efficiency demands that an accurate knowledge of the performance at each stage of the process be available at all times. Quantitative analyses provide the most practical process guides, and it is essential to have analytical procedures that combine accuracy and speed. In continuous plant operations, large losses may occur if the time interval between the development of trouble at any stage and its recognition and correction is great. Many metallurgical plants are using rapid colorimetric and spectrochemical methods of analyses for control purposes. So-called "color coppers" may be cited as an example of the colorimetric methods, in contrast with the routine use of the ultraviolet spectrograph for the analysis of steels.42 By means of this more refined spectrochemical procedure, a complete quantitative analysis of the molten metal is obtained every few minutes. During the past two years the Physics Division and the Ore Dressing Laboratory of the American Cyanamid Company's Stamford Research Laboratories have collaborated in a study of the use of spectrochemical methods for the analysis of various metallurgical products. New methods have been developed, which have proved of practical value in plant operation. The following pages give a general review of the principles of spectrochemical methods and also the details of several specific analyses. PRINCIPLES OF SPECTROCHEMICAL ANALYSIS In general, it can be said that a visible light spectrochemical analysis can be performed for any ion or molecule that is naturally colored, or that can be made to react with another to produce a colored salt or complex. Whereas transmission measurements in the ultraviolet and infrared portions of the spectrum are most useful for the analysis of organic molecules, visible light measurements are of particular value for metal salts. Such elements as copper, manganese, cobalt, nickel, iron, molybdenum, vanadium, chromium, phosphorus, mercury, zinc, lead, and a great many others, can now be determined with a high degree of sensitivity, accuracy and dispatch. From the simplest of qualitative determinations, color analyses have been improved to such an extent that, at the present time, through the use of recording spectrophotometers, hundreds of accurate quantitative analyses can be performed by a single analyst during an 8-hr. day after the standardization curves have been established for the ions to be determined.

Jan 1, 1944

By C. R. Van Hise

Introduction.............29 The Three Zones of the Lithosphere ..30 Zone of fracture............31 Zone of flowage............ 31 Factors influencing depth at which flowage occurs.. 32 Zone of combined fracture and flowage.. 33 The Water-Content and Openings in Rocks....36 Condition of rater in the zone of fracture.. 36 The openings in rocks...........38 Size and number of openings..... 40 Ore-deposits derived from zone of fracture..45 The source of underground water......... . 47 The cause of the flowage of underground water..47 Belts of underground circulation.. 51 Upper belt of underground circulation.. 51 Lower belt of underground circulation.. .... .52 Capacity of water for work in the lower belt of underground circulation........... 53 Movementsof water in the lower belt of underground circulation. 54 The preferential use by water of large channels.. 60 Physico-Chemical Principles Controlling the Work of Under ground Waters..........62 Chemical action............63 Underground aqueous solutions..64 The relations of solution and temperature..... 65 The relations of solution and pressure..66 Precipitation........... 67 Precipitation by change in temperature..68 Precipitation by change in pressure..69 Precipitation by reactions between aqueous solutions.. . 69 Precipitation by reactions between liquid solutions and solids. 70 Precipitation by reactions between gases and solutions. and solids............71 The General Geological work of Underground Waters.. . 71 Division of the zone of fracture into a belt of weathering and a belt of cementation............72

Jan 1, 1901

By William Colby

INCREASING governmental control of human activities seems inevitable. Within the present generation railroad rates and the public sale of water, gas and electricity have been subjected to rigid regulation. The field of control is slowly but surely being enlarged, and it is the object of this paper to outline in brief space this tendency toward increased governmental regulation, as far as mineral resources are concerned. Our, dual form of government complicates the problem. We must deal not only with the powers of the Federal Government, but also with those of the individual States. In order to approach this question intelligently we must have some conception of the powers and jurisdiction of the States and the United States, respectively, over mineral lands and mineral production. Starting with the Federal Government we find it never owned any public domain within the States that formed a part of the thirteen original colonies and, for historical reasons, the same is true of Tennessee and Texas. The Mid-Western States were erected out of the public domain which was acquired by the United States through cession from the original States or by purchase from foreign nations. Congress early in the last century adopted a policy of leasing public lands containing lead deposits in a portion of this Mid-Western territory, but later abandoned that policy and disposed of such public, lands, mineral and non-mineral, outright so that they long since have practically all passed into private ownership and become subject to the general jurisdiction of the respective State governments. In the great public domain lying west of the Mississippi River, and in portions of some of the Southern States, the Federal Government adopted a new mineral land policy following the discovery of gold in California. (Acts of Congress of 1866, 1870, and 1872.) The mineral lands within these States, instead of being disposed of on the game basis as agricultural lands, as occurred in the Mid-Western States, were segregated from agricultural lands and sold under special laws intended to encourage mining, giving the miner the free right to locate and work these mineral lands without paying any royalty to the Federal Government. A miner could also obtain at slight expense a complete

Jan 1, 1930

By Rodolfo V. de la Cruz

The in situ deformability of rock masses is determined by relating the applied load to the radial displacements of points on the borehole wall that are outside of the loaded surfaces. The external displacement method includes the steps in which: a) radial displacement sensors are installed to measure the change in length of a diameter of a borehole; b) unidirectional self- equilibrating pair of forces perpendicular to the direction of radial displacement measurements are applied on opposite sectors of the borehole wall, and; c) using elastic theory, the in-situ deformability of the rock mass can be related with the applied loads and measured radial displacements. The displacements outside the loaded surfaces are comparatively smaller in magnitude than displacements inside the loaded surfaces. These displacements, however, are sufficiently large and can be measured precisely by commercially available linear displacement sensors. Loads are applied by a conventional borehole jack. Existing methods for measuring the in situ deformability of rock masses yields unreliable results due to complex boundary stresses, small and varying contact areas, and the existence of fractures. It was shown that in the external displacement method, the effect of boundary pressure distribution and contact area are negligible. Also, since the displacements measured in the external displacement method were due to materials that are deeper inside the rock mass, borehole fractures have less influence on the calculated deformation modulus.

Jan 1, 1982

By Donivan L. Gordon, Fred H. Dorheim

Often, as viewed by the public and many in the mining industry, abandoned limestone and gypsum quarries offer a simple, economic solution to the twofold problem of solid-waste disposal and land reclamation. In a state where about 75% of the existing quarries are in hydrologic connection with carbonate aquifiers the rationale for considering the storage of solid waste in them must be critically examined. Consistent with the requirements of water resources protection, criteria are suggested to evaluate the potentiality of using abandoned limestone and gypsum quarries as sanitary landfill sites.

Jan 1, 1975

By Ralph K. Foster

During five underground mine fires which occurred in Arizona during 1980 and 1981, sealing the fire area became necessary. To minimize leakage into the fire area, ventilation control measures were instituted to balance pressure across the bulkheads. Problems en- countered in sealing the fire areas and measures taken to improve these conditions are discussed. The routing of the ventilation and ventilation control to en- sure the workers' safety were also important considerations in reopening the mines. The use of continuous CO monitors is discussed. One important consideration was the condition of the fire, and chromatographic analysis was used to establish this. Graphs comparing the Trickett ratio, carbon monoxide, carbon dioxide, and oxygen concentrations are given. The Trickett ratio was useful but needed to be augmented by the comparison of CO, C02, and 02. Problems with getting good samples from sealed areas and recommended procedures that were developed during these fires are discussed.

Jan 1, 1982

By Henry M. Howe

The natural effect of large ingot-size should be to increase segregation. I have previously pointed1 to the excessive segregation in many large ingots as tending to confirm this, but I have shown that in case of ingots less than 16 in. square this expected effect of ingot-size is liable to masked by that of Note.—The "maximum enrichment" of each ingot, i.e., the excess of the richest spot over the average of the whole ingot, is first calculated in percentage of that average. The average of the maximum enrichment of the several ingots of a given group is the abscissa in Fig. 1. The number beside each spot tells the number of cases which that spot represents. FIG. 1.—Influence of Ingot-Size on Maximum EnrichNent in Steel Ingots. other variables. Under these conditions we should expect that, if large ingot-size really does tend to increase segregation, this effect would be shown by taking the average of large numbers of cases, so that the effects of these other variables might off-set and cancel each other.

Jan 1, 1910

Executive SIDNEY J. JENNINGS, Chairman GEORGE D.-BARRON J. E. JOHNSON, JR. EDWIN LUDLOW ROBERT M. RAYMOND Membership KARL EILERS, Chairman LEWIS W. FRANCIS J. E. JOHNSON, JR. LOUIS D. HUNTOON ARTHUR L. WALKER Finance GEORGE D. BARRON, Chairman. CHARLES F. RAND BENJAMIN B. THAYER Library E. GYBBON SPILSBURY,1 Chairman ALEX C. HUMPHREYS3 GEORGE C. STONE2 J. H. JANEWAY4 BRADLEY STOUGHTON Papers and Publications BRADLEY STOUGHTON, Chairman

Jan 9, 1918

Executive SIDNEY J. JENNINGS, Chairman GEORGE D. BARRON J. E. JOHNSON, JR. EDWIN LUDLOW ROBERT-M. RAYMOND Membership LEWIS W. FRANCIS KARL EILERS, Chairman J. E. JOHNSON, JR. LOUIS D. HUNTOON ARTHUR L. WALKER Finance GEORGE D. BARRON, Chairman CHARLES F. RAND BENJAMIN B. THAYER Library E. GYBBON SPILSBURY.1 Chairman. ALEX C. HUMPHREYS3 GEORGE C. STONE2 J. H. JANEWAY4 BRADLEY STOUGHTON Papers and Publications BRADLEY STOUGHTON, Chairman

Jan 2, 1919

STANDING COMMITTEES Executive A, R. LEDOUX, Chairman HERBERT HOOVER EDWIN LUDLOW ARTHUR S. DWIGHT CHARLES F. RAND Membership J. V. W. REYNDERS, Chairman J. V. N. DOER W. H. ALDRIDGE EDGAR RICKARD R. M. RAYMOND Finance MARK L. REQUA CHARLES F. RAND, Chairman J. V. W. REYNDERS Library E. GYBBON SPILSBURY, Chairman ALEXANDER C. HUMPHREYS GEORGE C. STONE JOHN H. JANEWAY BRADLEY STOUGHTON Papers and Publications BRADLEY STOUGHTON, Chairman

Jan 1, 1923

Executive SIDNEY J. JENNINGS, Chairman GEORGE D. BARRON J. E. JOHNSON, JR. EDWIN LUDLOW ROBERT M. RAYMOND Membership KARL EILERS, Chairman LEWIS W. FRANCIS J. E. JOHNSON, JR. LOUIS D. HUNTOON ARTHUR L. WALKER Finance GEORGE D. BARRON, Chairman CHARLES F. RAND BENJAMIN B. THAYER Library E. GYBBON SPILSBURY,1 Chairman ALEX C. HUMPHREYS3 GEORGE C. STONE2 J. H. JANEWAY4 BRADLEY STOUGHTON Papers and Publications BRADLEY STOUGHTON, Chairman

Jan 11, 1918

For the year ending February, 1916 PRESIDENT WILLIAM L. SAUNDERS,1 NEW YORK, N. Y. PAST PRESIDENTS CHARLES F. RAND,1. NEW YORK, N. Y. BENJAMIN B. THAYER,3 NEW YORK, N. Y. FIRST VICE-PRESIDENT PHILIP N. MOORE,1 ST. Louis, Mo. TREASURER GEORGE C. STONE,1 NEW YORK, N. Y. SECRETARY EMERITUS ROSSITER W. RAYMOND, NEW, YORK, N. Y. SECRETARY BRADLEY STOUGHTON; NEW YORK, N. Y.

Jan 10, 1915

For the year ending February, 1916 PRESIDENT WILLIAM L. SAUNDERS,1 NEW YORK, N. Y. PAST PRESIDENTS CHARLES F. RAND,1 NEW YORK, N. Y. BENJAMIN B. THAYER,3 NEW YORK, N. Y. FIRST VICE-PRESIDENT PHILIP N. MOORE,1 . . . ST. Louis, Mo. TREASURER GEORGE C. STONE,1. NEW YORK, N. Y. SECRETARY EMERITUS ROSSITER W. RAYMOND, NEW YORK, N. Y. SECRETARY BRADLEY STOUGHTON NEW YORK, N. Y.

Jan 11, 1915

Executive SIDNEY J. JENNINGS, Chairman. GEORGE D. BARRON J. E. JOHNSON, JR. EDWIN LUDLOW ROBERT M. RAYMOND Membership KARL EILERS, Chairman LEWIS W. FRANCIS J. E. JOHNSON, JR. LOUIS D. HUNTOON ARTHUR L. WALKER Finance GEORGE D. BARRON Chairman CHARLES F. RAND BENJAMIN B. THAYER Library E. GYBBON SPILSBURY,1 Chairman ALEX C. HUMPHREYS3 GEORGE C. STONE2 J. H. JANEWAY4 BRADLEY STOUGHTON Papers and Publications BRADLEY STOUGHTON, Chairman

Jan 6, 1918

Executive SIDNEY J. JENNINGS, Chairman GEORGE D. BARRON J. E. JOHNSON, JR. EDWIN LUDLOW ROBERT M. RAYMOND Membership KARL EILERS, Chairman LEWIS W. FRANCIS J. E. JOHNSON, JR. LOUIS D. HUNTOON ARTHUR L. WALKER Finance GEORGE D. BARRON, Chairman CHARLES F. RAND BENJAMIN B. THAYER Library E. GYBBON SPILSBURY,1 Chairman ALEX C. HUMPHREYS3 GEORGE C.' STONE2 J. H. JANEWAY4 BRADLEY, STOUGHTON Papers and Publications BRADLEY STOUGHTON, Chairman

Jan 7, 1918

By R. P. Smith

The diffusivity of carbon in iron, cobalt, and alloys of 89.7 and 79.3 wt pct Co has been determined by a decarburization method for the temperature range 850° to 1100°C. The Plots of log D us 1/T for the two Fe-Co alloys are linear through the region of the Curie temperature, showing that, unlike some cases of substitutional diffusion, carbon diffusion in these alloys is not affected by electron spin order. RECENT investigations1-' have shown that for substitutional diffusion in iron the change in diffusivity with temperature does not follow an Arrhenius equation, at temperatures near the Curie temperature. Data on the diffusivity of carbon in a iron5"9 indicate that this anomaly does not exist for interstitial diffusion; however, this has not been definitely established. Since cobalt and Fe-Co alloys, 80 to 100 pct Co, have Curie temperatures in a temperature range convenient for carbon-diffusion measurements they are suitable systems for studying the relation of interstitial diffusion and the Curie temperature. EXPERIMENTAL The carbon diffusivity, D, was determined by a decarburization method. The diffusion cylinders, made from small vacuum melts of electrolytic cobalt and plastiron, were about 0.76 cm diam and 6.3 cm long. A small amount of carbon was added to each melt to keep the oxygen content as low as possible. The cylinders were first treated with a hydrogen-3 pct water vapor mixture at 1100°C to constant weight, then carburized to the desired initial carbon content with a suitable CO-C02 gas mix-

Jan 1, 1964