Search Documents

By Walter V. Knopp, Laurence Delisle

The aim of this work was the preparation of nickel-steels from elemental metal powders by powder metallurgy techniques. It was known that plain carbon steels could be made from a mixtufe of iron powder and graphite and that the effect of carbon on iron in powder form was of the same nature as that produced in fusion metallurgy. The problem in making nickel steels from elemental powders consisted therefore in finding out whether sufficient diffusion of the nickel and other incidental metals . normally present in such steels could be induced in the solid state to modify the properties of plain carbon steels made from powders and produce the beneficial effect of alloying. The composition selected originally was that of an S.A.E. 2330 steel. Metal powders, in the proportion correspending to that composition, were mixed with graphite, pressed, and heated at different temperatures for different periods of time, to produce bonding of the metal particles and mutual diffusion of the various elements without melting. Temperatures up to 1325°C and sintering periods as long as 6 hr were first investigated because it was expected.that such conditions would produce maximum diffusion with an accompanying improvement in the properties of the alloy. It was found that, although diffusion proceeded to a large extent under the conditions investigated, it would not be complete unless sintering were carried out at a high temperature for much longer than 6 hr. Relatively high temperatures and long sintering times are objectionable from a practical point of view, particularly when a low COSt material is to be produced, because they necessitate the use of special, costly equipment. Work could be done to improve the diffusion of iron and nickel by changing conditions other than the sintering temperature and time, that is, finer primary or alloy powders could be used. However, a marked change in the properties of the steel had been observed even with only partial diffusion. It was thought, therefore, that instead of trying to improve the diffusion, advantage might be taken of its incompleteness to produce a special structure consisting, in the unquenched condition, of a hard constituent, rich in nickel, dispersed in a tough pearlitic matrix. Steels with such a structure, not readily obtainable by fusion, should have desirable mechanical properties. Besides, it should be possible to prepare them from elemelltal powders under economical conditions. This latter alternative was therefore adopted for the second phase of this work. This report is divided into four parts: I. General Procedure. 2. Effect of Sintering Temperature. 3. Effect of Varying the Nickel Content. 4. Effect of Alloying Elements. General Procedure The general technique of cold pressing as used in powder metallurgy was applied.

Jan 1, 1949

By N. F. Dyson, T. R. Scott, M. R. Thornber, W. E. Ewers, M. Bussell

Leach liquors derived from the processing of nickel ores are generally highly contaminated and contain appreciable free acid. Methods are described for obtaining a commercial grade of concentrate from such solutions using pyrrhotite as the seed material to abstract nick- el, cobalt, etc. from solution. At temperatures in excess of 160° C., recoveries of 99% can be obtained from contaminated solutions where the free acidity is as high as 0.5 M in sulphuric acid. At lower temperatures down to 80° C., high recoveries can also be obtained either by adding H2S to the system with appropriate adjustment of the free acidity or by using "activated" pyrrhotite or artificial FeS in the system without prior addition of H2S. The methods are applicable to liquors derived from either oxide or sulphide ores, and the products are suitable for smelting or other known processes used to obtain pure metals. The mechanism of the reaction appears to vary with the operating temperature, and the results ye therefore discussed in the light of electron probe and optical microscopic studies.

Jan 1, 1973

By J. G. Bradley

On February 1, 1971, United States Steel Corporation, Lorain Works began operation of its first BOP facility equipped with a partial combustion gas cleaning system.- This shop consists of two 220 ton vessels. Figure I schematically describes this partial combustion gas cleaning system and highlights the necessary features for it-s safe and efficient operation. Waste gases are drawn into the membrane hood by a 2250 H.P. induced draft fan and are first quenched by the six inch bull nozzle at the top of the hood. Larger solid particles are separated from the gas in the quencher venturi and final scrubbing takes place in the P-A high energy venturi scrubber before the cleaned waste gas is burned in the flare stack. Scrubbing water is routed through a cyclone separator and then cycled into one of two 100' diameter thickeners. Underflow sludge which averages 20% solids is dewatered by 100 H.P. centrifuges. The clear overflow from the thickeners is recycled first to the P-A venturi and then to the quencher before returning to the thickeners.

Jan 1, 1972

(Members are urged to send in for this column, any notes. of interest concerning themselves or their fellow-members.) The following members registered at Institute headquarters during the month of May: Emil Gathmann, Baltimore, Md. Philip Argall, Denver, Colo. Albert H. Fay, Washington, D. C. A. C. Hodge, F.R.G.S., St. Austell, Eng. Alfred E. Barlow, Montreal, Canada. S. M. Marshall, Johnstown, Pa. B. C. Yates, Lead, S. D. Miltiades Armas, Paris, France. Leonard S. Austin, Salt Lake City. Albert Sauveur, Cambridge, Mass. Henry A. Wentworth, Boston, Mass. G. A. Reinhardt, Cambridge, Mass. Frank M. Leland, Mackay, Idaho. Fred Crabtree, Pittsburg, Pa. W. N. Crafts, Cleveland, Ohio. T. A. Rickard, London, England. Louis Hasbrouck, Kingston, N. Y. F. Lynwood Garrison, Philadelphia, Pa. F. V. Desloge, Desloge, Mo. S. B. Christy, Berkeley, Cal. E. C. Templeton, Palo Alto, Cal. H. A. Buehler, Rolla, Mo. L. D. Ricketts, Warren, Ariz. F. W. DeWolf, Urbana, Ill. J. E. Johnson, Jr., Ashland, Wis. Howland Bancroft, Denver, Colo. A. O. Granger, Cartersyille, Ga.

Jan 6, 1913

By AIME AIME

THE annual meeting of the Auxiliary to the A. I. M. E. was marked by the most delightful cordiality and warm spirit of welcome on the part of the members of the New York Section and an equally charming spirit of cooperation and appreciation on the part of the visitors. On Monday Mrs. Ernest H. Wolfes and Mrs. Charles A. Bohn had charge of registration and most efficiently .provided everyone with the necessary tickets and badges. The reception hall and regisfration booth were gay with beautiful flowers that reflected the welcoming spirit one found there. The smooth efficiency with which the whole program ran was due largely to the tireless efforts of Mrs. Donald M. Liddell and Mrs. Louis D. Huntoon, joint chairmen of the Ladies' Committee, and Miss Margaret Callow, chairman of the Junior Committee. After registering, the ladies proceeded to- the fifth floor, where they had luncheon with the members of the A. I. M. E. On that day Mrs. W. H. Bassett and Mrs. Lucius W. Mayer were the hostesses.

Jan 1, 1929

Colorado School of Mines Scientific Society held its first meeting on Friday evening, Jan. 14.1916. H. C. Parmalee gave an interesting talk on the Loss of Cyanide by Hydrolysis. F. E. BRIBER, Secretary. The School of Mines Society of the University of Minnesota held a meeting on Thursday evening, Jan. 13, 1916, at which Fred A. Jordan gave a talk on Magnetic Concentration of Iron Ores. Mr. Jordan is at present testing the new magnetic concentrator designed at the. School of Mines Experiment Station. This apparatus, if successful, will open up an enormous tonnage of ore on the Cuyuna and Mesabi ranges. ADOLPH DOVRE, President. At the College of Mines, University of Washington, Seattle, 33 mining men, with experience varying from one to 25 years, have enrolled in the 19th Annual Three Months' Short Session. At the annual smoker tendered the Short Session miners by the student branch of the American Institute of Mining Engineers, Capt. R. H. Stretch of the Alaska Bureau, Seattle Chamber of Commerce, delivered an address on The Mineral Belts of Alaska.

Jan 3, 1916

By S. C. Termes, R. L. Wilfong

As part of an effort to provide basic data on the fundamental scientific and engineering principles of minerals beneficiation, the Bureau of Mines is conducting research on the flocculation of mineral fines. This paper presents results of studies using cross-linked starches containing carboxyl, diethanolamine, iminodiacetic acid, and xanthate groups to flocculate hematite, goethite, chromite, manganite, pyrolusite, cuprite, and cassiterite fines. The carboxyl and xanthate derivatives flocculated all minerals except cassiterite; the latter was flocculated by only the diethanolamine derivative. The imlnodiacetic acid derivative flocculated hematite, goethite, chromite, cuprite, and pyrolusite fines. Zeta potential measurements were made to help define the reaction mechanism responsible for flocculation. These measurements indicate that electrostatic attraction probably is not involved, except possibly in the case of the diethanolamine derivative. The separation of hematite from quartz by selective flocculation with chelating crosslinked starches under two pH conditions and with two dispersing agents is described. Best recoveries and grades were found when either the carboxyl or xanthate derivatives was added at the natural pH of the pulp in the absence of a dispersing agent.

Jan 1, 1984

COMMITTEES. Iron and Steel. Albert Sauveur, Chairman. A. A. Stevenson, Vice-Chairman. Herbert M. Boylston, Secretary, Abbot Bldg., Harvard Sq., Cambridge, Mass. LOCAL COMMITTEES. Program Committee.-A. A. Stevenson, Chairman. Herbert A3. Boylston, J. E. Johnson, Jr., Henry D. Hibbard, E. Gybbon Spilsbury. Reception Committee.-J. R. Johnson, Jr., Chairman. Felix A. Vogel, William R. Walker. Dinner Committee.-E. Gybbon Spilsbury, Chairman. The opening session was held on Thursday morning, Oct. 16, 1913, at the Institute Headquarters in the Engineering Societies Building, 29 West 39th Street, New York, N. Y., and was called to order by President Rand, who addressed the meeting briefly before presenting Albert Sauveur, who responded to the President's address, and presided at the meeting. The following papers were then presented in oral abstract by their authors or authors' representatives: The Cleaning of Blast-Furnace Gas, by W. A. Forbes. Discussed by S. K. Varnes, H. N. Diehl, F. H. Wagner, Joseph Hartshorne, S. B. Marshall, J. W. Richards, J. E. Johnson, Jr., W. A. Forbes, and others.

Jan 12, 1913

By W. C. Snow

The plant of the Electrolytic Zinc Company of Australasia Limited, situated at Risdon on the estuary of the River Derwent, near Hobart, was designed and erected primarily to produce high-grade zinc from zinc concentrates produced by the mines of Broken Hill, N. S. W. Consequently the metallurgy of the process has been influenced in its development by the peculiar characteristics of the Broken Hill concentrate, which on treatment gives into solution relatively large amounts of cobalt, manganese and silica. The Risdon works (Fig. 1) produces high-grade electrolytic zinc, leaded electrolytic zinc, zinc dust, cadmium, sulphuric acid and superphosphate. This paper, however, is concerned only with the zinc plant and process. Roasting The roasting of raw concentrate is not a major feature of Risdon's process, and in this respect practice is unlike that of most zinc plants. The roasting is mostly done on the Australian mainland at centers where the sulphuric acid made from the roaster gases can be used for superphosphate manufacture. A small amount, approximately 40 tons per day, is roasted at Risdon, acid being manufactured from the gases. The amount that can be roasted there is limited by the acid requirements of the zinc plant and of the superphosphate plant. Roasting is not carried to completion at the mainland plants, and the product, known as preroast calcine, largely constitutes the raw material for the Risdon zinc plant. It contains about 6 per cent of sulphur as sulphide. Roasting is completed at Risdon for reasons that are set out later in this paper. The zinc plant proper is divided into four main divisions: (1) final roasting division, (2) leaching and purification division, (3) electrolytic division, (4) melting and casting division. There are two subsidiary divisions—the cadmium division and the preroast, acid and superphosphate division.

Jan 1, 1937

By W. W. Harvey, F. O. Dudas

Toward hot hydrochloric acid, the usual order of reactivities of the common copper sulfide and associated minerals is reversed, and the rates of H2S formation vary as [ ]. The iron component of chalcopyrite and bornite reports to the solution as ferrous chloride, while pyrite remains essentially unreacted. If a pressure of H2S is maintained in the reactor, copper solubilization is suppressed, and the primary copper sulfides are converted to finely divided secondary sulfides (principally covellite). The HCl leach reside then consists mainly of covellite, pyrite and acid-insoluble gangue. Copper can be selectively leached from this upgraded concentrate to yield a clean, strong copper sulfate solution for direct electrowinning. Preliminary analysis indicates competitive economics with respect to established hydrometallurgical processes. Other concentrate treatments based on an initial HC1 leach are proposed and relative advantages compared. The common denominator of the major process routes considered is the requirement to regenerate HC1 from an FeC12 solution. Five distinct concentrate compositions were employed in the experimental study, which included some attention to the fates of selected minor constituents of the copper concentrate, especially gold, silver, molybdenum, arsenic and selenium. Significant mineralogical features of reactants and products are described.

Jan 1, 1978

By John Peperakis, James Quigley

IN 1950 Kaiser Steel Corp. acquired control of the Utah Fuel Co., a pioneer Utah coal concern owning large reserves of high volatile coking coal near Sunnyside, Utah, and large reserves of coal elsewhere in Utah and Colorado. Kaiser Steel later disposed of the noncoking quality reserves included in the property and over the past six years has developed a group of three fully modernized mines and a central preparation plant at Sunnyside. This plant is geared to furnish 1.6 million tons per year of low ash coking coal to the byproduct coke ovens at its steel plant at Fontana, Calif., and to its beehive oven coking plant at Sunnyside. General Problems: Topographic and physical conditions under which Utah coals are found differ from those in most bituminous coal districts of the eastern and central states. Utah coal seams lie under deeper cover, generally at steeper pitches; consider- able distances are burned along the outcrop and back from the surface of the outcrop. Usually the coal seams lie high up on escarpments, accessible only through deep narrow canyons or long rock tunnels and tramways. The topography at Sunnyside is particularly rough, with great changes in cover over the coal in relatively short horizontal distances. This is due to the cliff-making sandstones of the cretaceous Mesa Verde group, the coal-bearing measures being in the Blackhawk formation. The thick massive Castle Gate sandstone of the Prince River formation overlies the coal-bearing rocks and is suspected to be the chief cause of roof control problems.

Jan 10, 1957

By George H. Eldridge

The existence of phosphate of lime within the State of Florida has been known for over a decade; but until the spring of 1887, the extent and value of its deposit.;, possibly with one exception, were unsuspected. In that year Col. T. S. Moorehead, induced by a statement made by Mr. J. F. Le Baron, examined the gravels of the Peace river, recognized the importance of the deposits, acquired such tracts as were regarded as desirable, and established the pebble-phosphate industry, making his first shipment in May, 1888, to the Scott Manufacturing Company, of Atlanta, Ga. The establishment of the pebble-phosphate industry upon Peace river was followed, a year later, by the discovery in Marion county of an entirely different class of phosphate, now commonly known as hard-rock phosphate. This discovery was made early in June, 1889, by Mr. Albertus Voght, in a well which he was sinking upon his place near the site of the present town of Donnellon, about 20 miles southwest of Ocala. To it, more than to any other cause, is due the rapid and remarkable development of the present great industry of the State. It was, however, Mr. John F. Dunn, of Ocala, who turned to advantage the accidental discovery of Mr. Voght. After acquiring a knowledge as to the chemical composition and value of the material, Mr. Dunn and hid associates purchased several thousand acres of land and organized the Dunnellon Phosphate Company for active operations. From Dunnellon as a center, prospecting rapidly extended in all directions, until at the present day important mines have been opened over a well-defined tract more than 200 miles long and about 6 miles wide. This tract lies par-

Jan 1, 1893

By I. H. Silberberg, R. L. Reed, O. K. Kimbler

interfacial films have frequently been observed at interfaces between certain crude oils and water. Several investigators have postulated that the presence of these films should influence the efficiency of oil recovery in water drive or waterflood operations. They may also influence the stability of emulsions which are sometimes a problem in petroleum production, and may be a factor in the fonation of paraffin deposits in oil well tubing and flow lines. This paper presents a technique with which a modified Langmuir film balance may be used to study the compressibility and collapse pressure of these natural interfacial films. Experimental data are presented for several nude oil-water systems. Data developed are used to infer the phase state of the film as a function of such variables as rate of reduction of interfacial area, ionic composition of the subtrate and pH of the subtrate. A film of known physical characteristics is shown to have a sinnificant effect on oil recovery from an unconsolidated sand pack. Possible applications of these results to petroleum production are discussed. INTRODUCTION The use of water to displace petroleum from reservoir rocks is of major importance both as a primary and a secondary recovery process. As water invades the rock, oil is completely displaced from some pores and left as a discontinuous phase in other pores. The manner in which water moves from pore to pore is strongly influenced by capillary forces. In view of the complexity of reservoir fluid systems, there can be little doubt that complicated interactions take place at both the liquid-solid and oil-water interfaces. One of the more interesting, and least understood, of the phenomena which take place at the oil-water interface is the formation of interfacial films. These films are believed to result from the adsorption of high molecular weight polar molecules at the interface.l.2 Presence of such molecules may cause a striking alteration in interfacial tension. When the oil-water interfacial area of certain crudes is rapidly reduced, a thin region (film) about the interface assumes the appearance of a solid membrane, and striations, wrinkles and gross distortions may occur. If such a film is solid, it should greatly alter the interfacial tension normally assumed to exist between the oil and water phases. If the membrane is continuous, a solid phase would separate the oil and water. Interfacial films between crude oil and water were observed in 1949 by Bartell and Niederhausers who commented upon the apparent rigidity of the films and their possible importance in the petroleum industry. Morrell and Egloff4 had earlier attributed the extreme stability of emulsions of sea water in fuel oil to very stable asphaltic films. Numerous investigators have observed rigid films in the course of crude oil-water interfacial tension determinations by the pendent drop method. Several investigators5,6,2 have separated inter-facially active materials from crudes and attempted to characterize them chemically. Reisberg and Doscher,2 using Ventura crude, showed the interfacial tension against water (as measured by the pendent drop method) to be affected by aging, contraction and expansion of the interface, and the pH of the water. These investigators attributed the adhesion of oil to a water-wetted surface and the distortions of flow paths in glass capillaries to the presence of rigid films. Dodd7 has studied the interfacial viscosity of adsorbed films and found them to be non-Newtonian in behavior. Craighead and Harvey8 reported a series of displacements in tubes packed with 60 mesh glass beads. They interpreted the results as indicating an effect of stearic acid films on waterflood recovery and imply that natural films may produce similar results.

Jan 1, 1967

By R. M. Rose, K. A. Jones

Resistive measurements ulere made on superconducting niobium single crystals in transverse magnetic fields. Crystals were grouln in both high and ulfrahigh vacua, doped with stnall quantities of oxygen, and annealed in ultrahigh vacua at temperatures from 900' to 1350°C. Maxima in the fluxoid pinr~ir~g force were observedfor the [100] and [210] directions. The increase of the critical current density with dissoved oxygen was seen to saturate at relatively low concentration. This behavior, and the variation of J, and residual resistivity (as a function of oxygen content and annealing) of both clean and dirty gassy) crystals, is seen as a consequence of the formation of clusters with (210)~b habit planes and (200)ffo common boundaries. These suboxide clusters are apparenlly stable at high temperatures and very low oxygen concentrations. It is generally known that dissolved oxygen at concentrations well below the solubility limit sharply increases the critical current density of superconducting niobium.' Such a result would not be expected if Nb-0 solutions were random, not even as the result of segregation on the scale usually encountered in solid solutions. According to the Kim-Anderson theory of flux creep,' the critical transport current density is determined by the pinning force Fp associated with some feature of the microstructure. As the Lorentz force. a or (J X R), of the transport current in the magnetic field approaches Fp, flux creep and then flux flow occur. The pinning force is expected to be quite small if the heterogeneity involved is significantly smaller than tte range of coherency which for niobium is circa 250~.~ Although the strain field of an individual oxygen atom in the niobium lattice is relatively large, it does not seem plausible that individual atoms could be so effective as to account for the data. Also, ~ramer~ found that straining and strain aging specimens containing small amounts of oxygen on occasion decreased the residual resistivity. A possible explanation for the above behavior may be found in the work of van Ooijen and van der Goot,= who found that annealing changed J, for niobium foils containing oxygen, and they attributed the changes to ordering of the oxygen atoms. This phenomenon has been observed by other investigators using X-ray and PROCEDURE Cylindrical 4-in.-diam niobium single crystals with axial orientations [ill], [110], [112], and [oo~] were grown from pure niobium, see Table I for analysis, in an ion-pumped ultrahigh-vacuum system using the electron beam floating zone technique. Total pressure during growth was lo-'9 torr: the oxygen partial pressure was less than lo-" torr, as determined by a mass spectrometer. These crystals will be referred to as the "clean" crystals. Similar crystals were also grown in another system at a pressure of 5 X 10"6 torr. These crystals will be referred to as the "dirty" crystals. Specimens 14 in. long were cut from the as-grown crystals and one end was polished down to no. 600 carbide paper smoothness. A back-reflection Laue photograph was then taken in order to fix the crystallo-graphic directions transverse to the crystal. The critical current density J,, the current density necessary to produce a voltage drop of 1.0 pv between voltage leads placed a in. apart, was determined as a function of the magnitude and direction of the transverse magnetic field and of the oxygen concentration. The technique and experimental arrangement was essentially similar to that of Tedmon et al.' In the remainder of this paper, the azjmuthal angle $ for the field H is referenced to the [ I101 direction in all four crystals, and oxygen was added in small equal increments by anodization and annealing.7 The resistivity ratio, RR, of the resistance at room ternperature to that at 4.2"K (H =7.00 kG) was determined as well.

Jan 1, 1970

By Franklin J. Hill, Theodore D. Tiemann

Sized fractions of Wisconsin Gogebic taconite were reduced with hydrogen over the temperature range from 600° to 1000°C. In general, the degree and rate of reduction increase with temperature. Particle size has no observable effect except in the smaller fractions at 900°C and above, where reduction is impeded, possibly due to the siliceous nature of the ore. Gaseous diffusion appears to be significant as a rate controlling factor at certain stages. THE depletion of high grade iron ore reserves in the United States has established the need to utilize all available iron ore deposits, both in long range planning and from the viewpoint of national emergency. This has led to extensive research and development in this field. The beneficiation of Wisconsin Gogebic taconite ore has been previously studied by investigators at the University of Wiscconsin, 1 the United States Bureau of Mines,, Battelle Memorial Institute, 3 and others. Methods investigated have included concentration by flotation processes, magnetic and gravity separation, magnetic roasting and various combinations of them. The foregoing studies have been concerned with the production of an enriched ore suitable for blast furnace use. If the ore could first be reduced to metallic iron and then beneficiated, the product could be used directly in the open hearth or electric steel-making furnace. The by-passing of the blast furnace should enhance the economic feasibility of the beneficiating process. The work reported here,4 was undertaken to establish data on the hydrogen reduction of Wisconsin taconite that would eventually lead to the development of an economic direct reduction process for this and perhaps other low grade siliceous ores. The volume of work on direct reduction can be judged by the fact that 240 direct reduction processes were patented in the United States alone up to 1951, 5 and numerous additional processes have since been developed. Some of the factors contributing to direct reduction development are: 1) The increasing capital cost of the blast furnace and its accessory equipment. 2) The decreasing availability of high grade domestic ore. 3) The high cost of steel scrap for use in the open hearth and electric furnaces. In general, direct reduction processes can be divided into two types; those using a solid reductant (coal, peat, lignite) usually carried out in a kiln, and those using a gaseous reductant (H2, CO) in a shaft furnace or a fluidized bed retort. As there is no low cost coal readily available in northern Wisconsin but natural gas could be quite easily obtained, it is believed a gaseous reductant process would offer the greater feasibility for use on Wisconsin taconite. It is hoped that this preliminary work will beof interest to other investigators in this increasingly important field. TACONITE ORE The ore used in the investigation was obtained originally from the U. S. Bureau of Mines, and consisted of a representative composite made up from trench samples of the Norrie, Pabst, Plymouth, Pence, and Yale members of the Wisconsin Gogebic range iron formation. Chemically, the ore contains approximately 52 pct SiO, and 30 pct Fe. X-ray diffraction and other studies indicate the principal minerals to be quartz (SiO2), hematite (Fe2O3), and goethite (Fe2O3. H2O). Minor amounts of iron containing silicates, siderite (FecO3), and magnetite (FeO-Fe2O3) are present. The iron minerals and quartz are so finely disseminated that the ore requires grinding to less than 200 mesh (74 µ) for essential liberation.l,2 The iron content of each of the several size fractions studied is shown in Table I. EXPERIMENTAL METHOD The method used throughout the investigation was based on that developed by the U. S. Bureau of Mines in Minneaopolis6,7 in which the course of reduction is followed by the loss in weight of the ore sample. More specifically, a 100-g sample of the size frac-

Jan 1, 1962

By Å. Sterten, R. Tunold, J. Brun, K. Dalatun

The subjects of this study are two corrosion phenomena familiar to operators of aluminum plants employing Soderberg anodes of the vertical type, namely the sul-fide scale formation observed at the steel contact spikes and the corrosion wear observed at the lower edge of the gas collecting skirts. The causes of these corrosion phenomena are discussed on the basis of observations from practice and measurements on commercial cells as well as on laboratory experiments. It is concluded that the anode spike corrosion is mainly due to the attack by sulfur compounds contained in the anodically evolved gases and that this attack is greatly promoted by cracks and pores in the anode carbon embedding the lower spike ends. The corrosion of the gas collecting skirt is mainly attributed to anodic dissolution of the iron during occasional contacts with the melt. ANODE SPIKE CORROSION The visible result of this corrosion is the formation of a brittle loosely adherent scale on the lower ends of the mild steel spikes maintaining the electric contact to the carbon anode, Fig. 1. The thickness of the scale usually varies from 0.5 to 3 mm, but in some cases scale of about 10 mm thickness has been observed by the writers. During the spike pulling, usually repeated every 3 weeks, part of the scale often loosens and remains in the anode carbon, resulting in contamination of the aluminum with iron. This corrosion has been attributed to reaction of the iron with gaseous sulfur compounds originating from the anode paste materials.'-4 This paste usually consists of 70 pct precalcined petroleum coke with 1.2 to 1.4 pct S and 30 pct coal tar pitch containing 0.5 to 0.7 pct S. During operation the gasification of the anode materials takes place in two ways: First, gases are evolved by the gradual baking of the anode paste added on top of the anode. Due to the sealing effected by the upper semifluid zone of the paste, these gases, containing sulfur compounds from the pitch, are forced downward through pores and cracks in the rigid anode carbon. At the temperatures of the zone of the lower ends of the spikes, 700" to 900°C, the original components of the baking gas must undergo decomposition, similar to that taking place with the production of coal gas, resulting in a gas mixture consisting mainly of H2 and CH4 with small percentages of H2S as the main sulfur compound.5 Second, the anodic reaction results in a mixture of C02 and CO, the total quantity of which is about 15 times that of the baking gas. These anode gases must carry the entire sulfur content of the carbon gasified by the anodic reaction. Henry and Holliday6 have shown that COS is the main sulfurous component of the anode gases from Soderberg cells. Soderberg anodes usually exhibit a network of vertical cracks, frequently traversing from one spike to the next one and to the outside of the block and widening downward to the working face of the anode. In addition the anode carbon, particularly that below the spike ends, is rather porous, as indicated in Fig. 1. It therefore seems probable that the anode gases also may partly penetrate to the spike ends. As the anode is partly immersed in the melt, the static pressure of this must forward this penetration. I) SPIKE SCALE COMPOSITION A great number of freshly extracted spikes from industrial plants were inspected and samples of the scale collected for examination. Before analyzing the samples a thin iron oxide layer, formed by air oxidation of the outside of the red hot scale immediately after spike pulling, was removed. On the average the Fe/S ratio found by these analyses corresponded to I the composition FeSl. oo7. X-ray powder patterns showed no oxide and otherwise agreed with those found by Haraldsen7 for iron sulfide with 50.00 at. Pct

Jan 1, 1970

By K. E. Brown, F. W. Jessen

It is deemed feasible to store atomic reactor fuel wastes in salt dome cavities when the differential pressure acting on the cavity does not exceed 3,000 psi and the temperature is less than 400°F. Tests at pressure increments of 1,000 psi were conducted on a 2-in, cylindrical cavity contained in a 6-in. long X 6-in. diameter salt core. The cavity exhibited stability under pressures up to 3,000 psi and temperatures to 300°F. At temperature ranges of 100 to 400°F and with pressures of 5,000 psi and above continuous deformation of the cavity resulted. Initial movement of the salt was observed at all pressares. This was evidenced by vertical deformation and cavity size reduction. INTRODUCTION The development of storage techniques for safe disposal of atomic reactor fuel wastes is a goal of the Atomic Energy Commission. Salt domes have been used successfully for storage of liquefied petroleum gases and hence should prove to be suitable for liquid waste products of atomic reactors. The purpose of the following work is to evaluate the practicability of utilizing salt dome cavities for such wastes and to de-termine particularly the effect of pressure and temperature on a salt cavity. This work represents a part of a comprehensive study covering the over-all problem of storing re- actor fuel wastes in salt domes and/ or salt beds. The problem of accurately determining the stresses which exist in rocks in the earth's crust is indeed a complex one. Theoretical studies have differed widely in many of the basic assumptions about the physical properties of the rock itself. Some solutions of problems in underground stress analysis assume that rock is elastic, homogeneous and isotropic in character; others assume that rock possesses plastic, viscous, elasticovis-cous properties, or a combination thereof. Experimental evidence has shown that salt possesses plastic, viscous and elasticoviscous properties.' Recent work has shown that salt becomes more plastic with temperature.' APPARATUS AND PROCEDURE For experimental study a cylindrical cavity was chosen for analysis since it provided maximum volume per unit of depth with constant diameter. This particular cavity shape, allowing for irregularities, can be easily leached out of salt domes in field operations. For the purpose of approaching underground storage conditions as nearly as possible, the following factors were considered: (1) control of pressure and temperatures, (2) measurements of temperature gradients throughout salt mass, and (3) measurement of structural stability of salt cavities. In order to obtain triaxial pressure on the salt cavity without resorting to the application of fluid pressure directly on the salt mass, a system was designed whereby the same effect could be produced through axial loading only. By cutting a core to close dimensions to fit a steel test cylinder and applying axial pressure, a lateral pressure was obtained. This equipment is shown in Figs 1 and 2. A steel cylinder was made from

By P. Shahinian, H. H. Smith, M. R. Achter

Crack growth rates are measured at elevated temperature in a resonant fatigue machine from vibration frequency decreases calibrated in terms of crack depth. Crack growth rates in Type 316 stainless steel at 500º and 800°C show a sharp increase with oxygen pressure in an intermediate pressure range and little or no change at high and low pressures. At 500°c, I torr of oxygen reduces the fatigue life by almost a factor of 100 in comparison to that in vacuum and raises the growth rate of shallow cracks by the same At At 800°C the effects are smaller. Changes in slope in the crack growth rate curves are discussed in terms of a model in which rates of surface production and of surface coverage by gas are compared. The use of a calculation method in which the surface exposure time is equal to X/v, where x is the interatomic spacing and v is the growth rate, makes it possible to obtain order of magnitude agreement at 500°C between the observed pressure and the predicted pressure at these slope changes. At 800°C oxidation becomes a .factor and the data cannot be treated by simple adsorption theory. THE decrease in the fatigue life of metals as a function of gas pressure usually follows a stepped curve with virtually all of the decrease concentrated in a sharp drop in a transition zone at intermediate pressures and little or no change at low and high ranges. A number of models, differing in the details of the mechanism, have been offered to explain the shape of the curve. Measurements of crack growth in aluminum as a function of gas pressure by Bradshaw and Wheeler' and Hordon2 demonstrated opportunities for quantitative comparison to evaluate the proposed models. Since comparable data were lacking at high temperatures, in the present work rates of crack propagation were measured in Type 316 stainless steel at 500" and 800°C as a function of oxygen pressure. Choice of this material was dictated by two considerations; it is stiff enough at these elevated temperatures to resonate with the regenerative drive on our fatigue machine and it is known to display a large effect of environment. A new method of calculation is described to predict the gas pressure at the critical point. EXPERIMENTAL PROCEDURE Because of the difficulty of measuring crack depths directly at high temperatures, an indirect method was developed based on the decrease in the resonant frequency with the growth of a crack. A reversed bending, constant amplitude fatigue machine, described previously,3 vibrates a specimen at its resonant frequency, automatically records any changes in it and shuts itself off after it has reached a preset value of frequency decrease. The record of frequency change is used to determine the rate of crack growth. Sheet type specimens of Type 316 stainless steel, Fig. 1, incorporated a sharp, shallow notch to localize the formation of a single crack. After machining, they were annealed in a vacuum of l0-6 torr either at 1066" (lot A) or 871°C (lot B) and then electropolished in an acetic-chromic acid solution. Bending strains were measured at 500" and 800°C by an optical technique4 and reported as total strain without correction for the notch. At 500°C, the 0.141 pct strain was 0.085 pct elastic and the remainder plastic. At 800°C the 0.062 pct strain was all elastic. To convert frequency decrease to crack length, calibration curves were obtained by interrupting the vibration at stated intervals of frequency decrease. The crack depth was measured microscopically at a magnification of X400 and reported as the average of the measurement on each edge. Some specimens were sectioned for crack measurement while others were returned to the machine and fatigued further. There was good agreement between the two methods. Before beginning the vibration, the vacuum chamber was first evacuated cold to 1 x 1O-6 torr, then heated to the operating temperature and held there until the pressure was again reduced to 1 x10-6 torr at which time oxygen was introduced to the desired pressure. In this investigation the vibration frequency was nominally 10 cps and a decrease of 0.6 cps was taken as the failure point. The choice of the frequency decrease to represent failure has no appreciable effect on the fatigue life because the crack is growing very fast at this point.

Jan 1, 1970

By A. L. Lee, M. H. Gonzalez, R. F. Bukacek

Experimental viscosity data for methane are presented for temperatures from 100 to 340F and pressures from 200 to 8,000 psia. A summary is given of the available data for methane, and a comparison is presented for that data common to the experimental range reported in this paper. Correlation of the data is presented, and predicted values are given for temperatures up to 460F and pressures up to 10,000 psia. INTRODUCTION The increasing ranges of temperature and pressure at which fluids are produced, transferred and processed in the petroleum and chemical industries stress the need for accurate information on physical properties, both for engineering calculation and for improving the methods used to estimate physical properties. A survey of the literature reveals that disagreements between published data on the viscosity of methane are common and that most investigations have been conducted over restricted temperature and pressure ranges. This situation made it desirable to undertake an investigation with a scope common to most of the literature data available. APPARATUS AND MATERIALS The apparatus used in this investigation was the capillary tube viscometer'described by Dolan,10 with modifications introduced in the general design and operation of the instrument. It has an effective pressure range from 14.7 to 10,000 psia and a temperature range from room temperature to 400F. The design of the viscometer is based on the establishment of a manometric head between two vessels containing the test fluid and a volume of mercury. The reservoirs are connected by a capillary tube through which the test fluid flows and a tube through which mercury flows. A pressure gradient is established by elevating one of the vessels above the other, the resulting flow of mercury displacing the test fluid through the capillary. The schematic diagram of the system (Fig. 1) shows the arrangement of the equipment auxiliary to the viscometer. The density cells assembly (E, Fig. 1) was not used in this investigation since reliable data are available on methane. 23 The assembly consists of a bank of eight 316 stainless steel pycnometers. Experimental values of the density of a natural gas19 and i-butane14 samples have been obtained for pressures up to 8,000 psia and temperatures up to 340F. The methane used was obtained from the Southern California Gas Co. Mass spectrometric analysis showed a composition of 99.8 percent CH4, 0.1 percent C2H6 and 0.1 percent C3H8. EXPERIMENTAL VALUES AND ACCURACY OF DATA Determinations were carried out at several temperatures. With the temperature in the cabinet controlled at a given level, a series of runs were made at various pressures. To establish pressures lower than that obtained from the methane cylinder, it was necessary to vent the gas slowly to the atmosphere until the desired pressure was reached. The consistency of the test run time for a particular condition can be used as a criterion for the accuracy of the data. A further check is obtained by comparison of the viscosity values obtained using different driving heads. To establish the instrument's reproducibility, a large number of runs were made at three completely different conditions of temperature and pressure. Data obtained were analyzed statistically to determine the most reliable value for the variance of the experimental data. It was found that the variances of the data taken at different experimental conditions were not statistically equivalent, but they were small. The largest variance was found at 8,000 psia and 100F, where the standard deviation was 0.385 micropoise. Therefore, 99.9 percent of the data can be expected to fall within 1.15 micropoises of the population mean, except for the intervention of systematic errors in operation.

By L. W. Davies

A problem often encountered is the provision of materials which have impurity contents below a certain specified level. This problem is in some cases solved by making use of the segregation of the impurity with respect to the liquid and solid states of the material: an ingot of the material is subjected to directional solidification and the ends of the ingot. which are richer in solutes which respectively raise and lower the melting point of the solvent, are removed. An important extension of this process is the zone-refining process invented by pfann,' in which molten zones are passed successively along the length of an ingot and displace solutes towards the ends. Pfann's process is particularly appropriate in cases for which the segregation coefficient k does not differ greatly from unity, or when the impurity content must be kept extremely low (-=,6 atom fraction); it is widely used, particularly in the purification of materials for use in semiconductor electronic devices. It is the purpose of this paper to investigate theoretically the efficiency of the above refining processes; that is! we determine the most economic method of attaining a given yield of solvent of specified purity, taking into account the variables of the process. One variable of interest is the effective value of the segregation coefficient. which depends on the rate of movement of the liquid-solid interface and on the degree of stirring in the liquid; in addition to this, in the zone-refining process we are also interested in the choice of zone length for most efficient operation. A mathematical determination is made here of the lengths of successive molten zones which give, for an initially uniform distribution, the most efficient removal of a solute of arbitrary distribution coefficient. In order to be able to give a quantitative treatment of efficiency, we first define figures of merit applicable to a given distribution of solute. FIGURE OF MERIT Let an ingot of length L contain a distribution y(x) of solute: we confine our discussion to mono-tonic distributions, in order to avoid inconsistencies in the subsequent analysis. The first moments of the distribution about the origin and x = L are respectively L F = hy{x)dx [I] G = f(L -x)y(x)dx = YoL2-F, [21 where yoL is the total amount of solute present. We shall see that the quantities F and G are useful figures of merit for a discussion of the efficiency of zone-refining processes. In the first place, it is

Jan 1, 1960